CN1195235C - Method for preparing gradation type plastic optical fiber - Google Patents
Method for preparing gradation type plastic optical fiber Download PDFInfo
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- CN1195235C CN1195235C CNB021510652A CN02151065A CN1195235C CN 1195235 C CN1195235 C CN 1195235C CN B021510652 A CNB021510652 A CN B021510652A CN 02151065 A CN02151065 A CN 02151065A CN 1195235 C CN1195235 C CN 1195235C
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- plastic optical
- penetrating fluid
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Abstract
The present invention relates to a method for preparing a gradation type plastic optical fiber, which adopts 90-100 portions of methyl methacrylate, 0-10 portions of styrene, or 100 % of styrene, initiating agent and chain transfer agent to prepare a fiber core with a high refractive index. Then, the fiber core is dipped in monomer solution with a refractive index lower than the refractive index of the fiber core for swell and infiltration. A plastic optical fiber core material swelled is initiated with polymerization or thermal polymerization under ultraviolet rays. According to a diffusion principle, a small molecule monomer of the present invention forms concentration gradation in the radial direction of a polymer rod. After polymerization, the concentration gradation is converted into refractive index gradation. Then, a plastic optical fiber having good refractive index distribution and thermal stability in a gradually changing type can be obtained.
Description
Technical field
The present invention relates to a kind of manufacture method of gradational plastic optical fibre, this type optical fiber index distribution radially is parabolic type, is mainly used in optical communication, belongs to the ICT (information and communication technology) field.
Background technology
Phase step type plastics optical fibre is because its transmission bandwidth makes its application in LAN (Local Area Network) be restricted for a short time, and gradational plastic optical fibre has been subjected to paying close attention to widely with its huge transmission bandwidth.
At present, states such as Japan and Korea S., U.S. have all applied for the multinomial patent of making gradually changing prefabricated rod of plastic optical fibre that relates at home, and China really has the patent of original creativity and few in this respect.
The patent of SUMITOMO CHEMICAL DENSO Corporation (application publication number CN 1197002A) discloses method and the device therefor of making graded refractive index plastic optical-fiber, this method need be furnished with multiple from low viscosity to more full-bodied monomer solution, method for making is more loaded down with trivial details.Simultaneously, this method is to form the gradual change plastic optical fiber by the micromolecule that adds refractive index regulating action that can not polymerization, and micromolecule in polymkeric substance because thermal motion, can spread to low concentration by high concentration, therefore when the time is longer, this graded index distribution can gradually change, and becomes even distribution until the refractive index of fibre core.The poor heat stability of index distribution is the disadvantage of this patent, and it directly limits the transmission bandwidth of plastic optical fiber.If the concentration of adulterant is excessive, the glass temperature of material is acutely descended, as the glass temperature of the polymethacrylate of 30% the diphenyl sulfide of mixing drop to 31 ℃ by 100 ℃ before mixing, badly influence the heat resistance of plastic optical fiber.
Japan is in the disclosed prefabricated rods of producing refractive index-distributed type plastic optical fiber with the interface gel method of another patent (notification number CN 1214454A) of China.This method is to make a polymkeric substance pipe (as polymethylmethacrylate) earlier, then its adulterant (as bromobenzene) higher but can not polymerization of monomers methyl methacrylate and a kind of refractive index ratio is filled up this polymer pipe, methyl methacrylate is the swollen polymer pipe at first, also begins reaction simultaneously in the gel of its swelling.Reaction advances to tube hub gradually from gel, forms gradually changing prefabricated rod of plastic optical fibre at last.This method is easy to generate bubble in the prefabricated rods process of making plastic optical fiber, easily broken when causing wire drawing.In addition, because this method is to make by the higher micromolecule of doping refractive index, the shortcoming that not only has the poor heat stability of above-mentioned index distribution, and be generally used for making the density of base monomer of plastic optical fiber prefabricated stick and the micromolecule of doping differs bigger, the micromolecular content that this prefabricated rods that has just caused utilizing this method to make is mixed on the direction of gravity field is inequality, at the upper end of prefabricated rods dopant content height, the lower end is then low, so the prefabricated rods length that this method is made is very limited.Also there is this shortcoming in Korea S in Chinese patents (notification number CN 1304051 A).In addition, make covering and the bigger prefabricated rods of sandwich layer refringence, must add more adulterant, this will cause the glass temperature of material to descend shortcomings such as the thermal stability variation of index distribution.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, proposed a kind of manufacture method of gradational plastic optical fibre, the preparation composition is evenly distributed, the gradual change plastic optical fiber of index distribution excellent in stability.
For realizing such purpose, the present invention at first prepares the higher fibre core of refractive index, then fibre core is immersed in swelling, infiltration in the lower monomer solution of refractive index ratio fibre core.According to diffusion principle, small molecule monomer will be in the radially formation concentration gradient of polymer rods, and concentration gradient will be transformed into refractive index gradient after polymerization.
The present invention can carry out as follows:
(1) preparation of fibre core
Adopting volume ratio is 90% methyl methacrylate, 10% styrene, add the initiating agent of total monomer weight 0.1% and 0.1% chain-transferring agent, under vacuum in 45 ℃ of stirred in water bath 40 hours, under vacuum, continue polymerization 20 hours again in 65 ℃, dry after the polymkeric substance pulverizing granulation, to extrude with extruder, the extruding dies diameter is 0.5～3 millimeter, the fibre core that obtains was worn out 30 minutes under 95 ℃ temperature, make fibre core.
Perhaps adopting volume ratio is 100% styrene, add the initiating agent of total monomer weight 0.05% and 0.05% chain-transferring agent, under vacuum in 50 ℃ of stirred in water bath 10 hours, under vacuum, continue polymerization 10 hours again in 70 ℃, dry after the polymkeric substance pulverizing granulation, to extrude with extruder, the extruding dies diameter is 0.5～3 millimeter, the fibre core that obtains was worn out 30 minutes under 100 ℃ temperature, make fibre core.
Methyl methacrylate in the core material of the present invention can adopt methyl acrylic ester, esters of acrylic acid, the fluoro acrylic ester class, a kind of replacement the in the fluoro methyl acrylic ester,, styrene can adopt phenylethylene, a kind of replacement in the N-alkyl maleimide class.The machining feature of this fibre core is, must at high temperature wear out to eliminate internal stress, make fibre core can be evenly during swelling in monomer solution from around infiltrate, form concentration gradient, promptly form refractive index gradient after the curing.
(2) preparation of penetrating fluid
Penetrating fluid is made up of one or more monomers, initiating agent, chain-transferring agent.To the feature request of monomer in the penetrating fluid is that refractive index behind the monomer polymerization is lower than the refractive index of the fibre core of preceding method (1) preparation.For the copolymer of methyl methacrylatestyrene fibre core, penetrating fluid employing volume ratio is 100% methyl methacrylate, adds the initiating agent 2-hydroxy-2-methyl-3-phenylacetone of monomer weight 0.05% and 0.1% chain-transferring agent lauryl mercaptan.For the polystyrene fibre core, it is 90% styrene, 10% methyl methacrylate that penetrating fluid adopts volume ratio, adds the initiating agent 2-hydroxy-2-methyl-3-phenylacetone of monomer weight 0.05% and 0.1% chain-transferring agent lauryl mercaptan.
Methyl methacrylate in the present invention's series penetrating fluid can adopt methyl acrylic ester, esters of acrylic acid, the fluoro acrylic ester class, a kind of replacement the in the fluoro methyl acrylic ester,, styrene can adopt a kind of replacement the in phenylethylene, the N-alkyl maleimide class.
The initiating agent that adds in the penetrating fluid can be light trigger or ordinary hot initiating agent, and light trigger is respectively: 2-hydroxy-2-methyl-3-phenylacetone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-methyl mercapto]-2-morpholinyl-1-acetone, 4-dimethylamino-ethyl benzoate, benzophenone and to methyldiphenyl ketone mixed liquor, 4-benzoyl-4-methyl-diphenyl sulfide, three-2-bromomethylphenyl sulfone or methyl o-benzoylbenzoate; The ordinary hot initiating agent is: dibenzoyl peroxide, azobisisobutyronitrile, dilauroyl peroxide etc.
The chain-transferring agent that adds in the penetrating fluid is a lauryl mercaptan.
(3) swelling
The fibre core of (1) preparation immerses in the penetrating fluid that is prepared by step (2) set by step, and the temperature of penetrating fluid is controlled between 40～80 ℃, and the immersion time was controlled at 0.1～30 minute.The difference of the solution levels concentration that causes for fear of its density variation and the influence of penetrating fluid self static pressure, but plastic optical fiber core level be immersed in the penetrating fluid, form the influence that difference and penetrating fluid infiltrate the fibre core degree of depth to reduce levels.
(4) polymerization
Through the plastic optical fiber core after the swelling can be under certain class ray initiated polymerization, also can thermal polymerization.Can solidify under ultraviolet ray as the plastic optical fiber core after the swelling, be 0.1～10 minute set time.Also can obtain gradational plastic optical fibre by temperature from 55 ℃ of segmentation thermostat thermal-initiated polymerizations up to 85 ℃.
The gradational plastic optical fibre of the present invention's preparation is because its index distribution is to form by refractive index two kinds of polymkeric substance just, promptly the polymkeric substance proportion that the higher polymkeric substance specific refractivity of refractive index is lower in the optical fiber fuse is bigger, and along radial direction, the high refractive index polymer proportion descends continuously, until arriving covering.And because the mutual entanglement of polymer chain makes the index distribution that obtains can not change in time, this is the present invention's advantage of giving prominence to just.This variation of refractive index is to realize by the diffusion of low-refraction monomer to high refractive index polymer.Because can be, make that the polymkeric substance of core polymkeric substance and penetrating fluid monomer polymerization gained can be compatible and be not separated the gradational plastic optical fibre of the index distribution good heat stability that can make by regulating the proportion of composing of core multipolymer.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Embodiment 1
(1) with volume ratio is 90% methyl methacrylate, 10% styrene, add the dibenzoyl peroxide of total monomer weight 0.05% and 0.05% chain-transferring agent lauryl mercaptan, in following 45 ℃ of stirring in water bath of vacuum 40 hours, after under vacuum, continued polymerizations 20 hours in 65 ℃ again, it is pulverized the back granulation.95 ℃ of dryings were extruded in 220 ℃ with extruder after 4 hours, and regulating the wire drawing wheel rotating speed, to make diameter be 0.8 millimeter transparent fibre core.The fibre core that obtains was eliminated the interior gravitation of staying in the silk in aging 30 minutes in 95 ℃, standby.
(2) with volume ratio be 100% methyl methacrylate, add the light trigger 2-hydroxy-2-methyl-3-phenylacetone of total monomer weight 0.05% and 0.05% chain-transferring agent lauryl mercaptan and mix, get final product penetrating fluid.
(3) the fibre core level that will make by step (1) by and be immersed in the penetrating fluid by step (2) configuration, the temperature of regulating penetrating fluid rises to 60 ℃, floods about 5 minutes.
(4) fibre core behind the dipping is by ultraviolet curing device, and the ultraviolet curing time is 4 minutes.Make the gradational plastic optical fibre of index distribution good heat stability.
Embodiment 2
(1) with volume ratio is 100% styrene, add the dibenzoyl peroxide of total monomer weight 0.05% and 0.05% chain-transferring agent lauryl mercaptan, in following 50 ℃ of stirring in water bath of vacuum 10 hours, after under vacuum, continued polymerizations 10 hours again in 70 ℃, it is pulverized the back granulation, extrude in 230 ℃ with extruder, port mould diameter is 1 millimeter.Regulating the wire drawing wheel rotating speed, to make diameter be 0.8 millimeter transparent fibre core.The fibre core that obtains was eliminated the interior gravitation of staying in the silk in aging 30 minutes in 100 ℃, standby.
(2) with volume ratio be 90% styrene, 10% methyl methacrylate, add the 2-hydroxy-2-methyl-3-phenylacetone of total monomer weight 0.05%, 0.01% 1-hydroxyl-cyclohexyl-phenyl ketone and 0.1% chain-transferring agent lauryl mercaptan mix, and are made into penetrating fluid.
(3) the fibre core level that will make by step (1) by and be immersed in the penetrating fluid by step (2) configuration, the temperature of regulating penetrating fluid rises to 60 ℃, floods about 5 minutes.
(4) fibre core behind the dipping is by a ultraviolet curing device, and the ultraviolet curing time is 4 minutes.Make the gradational plastic optical fibre of index distribution good heat stability.
Embodiment 3
(1) with volume ratio is 90% methyl methacrylate, 10% styrene, add the benzoyl peroxide of total monomer weight 0.1% and 0.1% chain-transferring agent lauryl mercaptan, in following 45 ℃ of stirring in water bath of vacuum 40 hours, after under vacuum, continued polymerizations 20 hours again in 65 ℃, it is pulverized the back granulation, the molecular weight that makes about 130,000～160,000.95 ℃ of dryings were extruded in 220 ℃ with extruder after 8 hours, and port mould diameter is 1 millimeter, and regulating the wire drawing wheel rotating speed, to make diameter be 0.8 millimeter transparent fibre core.The fibre core that obtains was eliminated the interior gravitation of staying in the silk in aging 30 minutes in 95 ℃, standby.
(2) with volume ratio be 100% methyl methacrylate, add total monomer weight 0.1% dibenzoyl peroxide, 0.1% chain-transferring agent lauryl mercaptan mixes, and is made into penetrating fluid.
(3) the fibre core level that will make by step (1) by and be immersed in the penetrating fluid by step (2) configuration, the temperature of regulating penetrating fluid rises to 60 ℃, floods about 5 minutes.
(4) fibre core behind the dipping passes through 60 ℃ of constant warm tube thermal polymerizations earlier, and then by 80 ℃ of constant warm tube thermal polymerizations, promptly curable.Make the gradational plastic optical fibre of index distribution good heat stability.
Claims (5)
1, a kind of manufacture method of gradational plastic optical fibre is characterized in that comprising the steps:
(1) adopting volume ratio is 90% methyl methacrylate, 10% styrene, add the initiating agent of total monomer weight 0.1% and 0.1% chain-transferring agent, under vacuum in 45 ℃ of stirred in water bath 40 hours, under vacuum, continue polymerization 20 hours again in 65 ℃, dry after the polymkeric substance pulverizing granulation, to extrude with extruder, the extruding dies diameter is 0.5～3 millimeter, the fibre core that obtains was worn out 30 minutes under 95 ℃ temperature, make fibre core;
(2) with volume ratio be 100% methyl methacrylate, add the initiating agent of monomer weight 0.05% and 0.1% chain-transferring agent and mix, be made into penetrating fluid;
(3) the polymkeric substance fibre core with step (1) preparation immerses in the penetrating fluid that is prepared by step (2), and the temperature of penetrating fluid is controlled at 60 ℃, and the immersion time was controlled at 5 minutes;
(4) through the plastic optical fiber core initiated polymerization under ultraviolet ray after the swelling, or thermal polymerization, gradational plastic optical fibre obtained.
2, a kind of manufacture method of gradational plastic optical fibre is characterized in that comprising the steps:
(1) the employing volume ratio is 100% styrene, add the initiating agent of total monomer weight 0.05% and 0.05% chain-transferring agent, under vacuum in 50 ℃ of stirred in water bath 10 hours, under vacuum, continue polymerization 10 hours again in 70 ℃, dry after the polymkeric substance pulverizing granulation, to extrude with extruder, the extruding dies diameter is 0.5～3 millimeter, the fibre core that obtains was worn out 30 minutes under 100 ℃ temperature, make fibre core;
(2) be 90% styrene, 10% methyl methacrylate with volume ratio, add the initiating agent of monomer weight 0.05% and 0.1% chain-transferring agent and mix, be made into penetrating fluid;
(3) the polymkeric substance fibre core with step (1) preparation immerses in the penetrating fluid that is prepared by step (2), and the temperature of penetrating fluid is controlled at 60 ℃, and the immersion time was controlled at 5 minutes;
(4) through the plastic optical fiber core initiated polymerization under ultraviolet ray after the swelling, or thermal polymerization, gradational plastic optical fibre obtained.
3, as the manufacture method of claim 1 or 2 said gradational plastic optical fibres, it is characterized in that polymerization is to solidify 0.1～10 minute under ultraviolet ray, or by the segmentation thermostat thermal-initiated polymerization of temperature from 55 ℃-85 ℃.
4, manufacture method as claim 1 or 2 said gradational plastic optical fibres, it is characterized in that the initiating agent that adds in the penetrating fluid is light trigger or ordinary hot initiating agent, light trigger is respectively: 2-hydroxy-2-methyl-3-phenylacetone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-methyl mercapto]-2-morpholinyl-1-acetone, 4-dimethylamino-ethyl benzoate, benzophenone with to methyldiphenyl ketone mixed liquor, 4-benzoyl-4-methyl-diphenyl sulfide, three-2-bromomethylphenyl sulfone or methyl o-benzoylbenzoate; The ordinary hot initiating agent is: dibenzoyl peroxide, azobisisobutyronitrile or dilauroyl peroxide.
5,, it is characterized in that the chain-transferring agent that adds in the penetrating fluid is a lauryl mercaptan as the manufacture method of claim 1 or 2 said gradational plastic optical fibres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021510652A CN1195235C (en) | 2002-12-05 | 2002-12-05 | Method for preparing gradation type plastic optical fiber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021510652A CN1195235C (en) | 2002-12-05 | 2002-12-05 | Method for preparing gradation type plastic optical fiber |
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| CN1415984A CN1415984A (en) | 2003-05-07 |
| CN1195235C true CN1195235C (en) | 2005-03-30 |
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| CNB021510652A Expired - Fee Related CN1195235C (en) | 2002-12-05 | 2002-12-05 | Method for preparing gradation type plastic optical fiber |
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| CN102070743B (en) * | 2009-11-20 | 2012-09-05 | 上海华明高技术（集团）有限公司 | Method for preparing polyacrylate copolymer resin for optical conduction |
| CN113480165B (en) * | 2021-07-29 | 2022-10-14 | 深圳市思珀光电通讯有限公司 | Quantum dot doped optical fiber material and preparation method thereof |
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