# US 4,381,269 A · Fabrication of a low-loss plastic optical fiber

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- Number: US 4,381,269 A
- Document ID: US4381269A
- Status: Granted
- Kind: A
- Application number: 06/316,834
- Filed: 1981-10-30
- Granted: 1983-04-26
- Earliest claimed: 1980-11-11
- Assignees: Nippon Telegraph & Telephone Public Corporation
- Inventors: Toshikuni Kaino; Michiya Fujiki; Shigeo Nara; Shigeru Oikawa
- Web page: https://patentgrep.com/patent/US4381269A

## CPC

- G02B 1/045: {Light guides}
- B29C 48/05: Filamentary, e.g. strands
- D01F 8/10: with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
- G02B 1/046: {characterised by the core material}
- B29C 48/00: Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor (extrusion blow-moulding B29C49/04)
- Y10T 428/2907: with coating or impregnation
- Y10T 428/2929: Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- 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 (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

In a sealed system, a polymerization initiator and a chain transfer agent are added to a methyl methacrylate monomer distilled under reduced pressure condition via a distillation step of the former both ingredients, the methyl methacrylate monomer is successively polymerized to prepare a core polymer while maintaining the reduced pressure condition, then the resulting core polymer is subjected to melt spinning to form a core fiber while maintaining the sealed system, and a clad of a macromolecular compound having a refractive index lower than that of the aforesaid core fiber is adhered around the periphery thereof, whereby a low-loss plastic optical fiber with excellent optical transmission characteristics having a core-cladding structure is fabricated. Plastic optical fibers so made exhibit light attenuation as low as 60 dB/km or lower.

## Claims

### Claim 1

In a fabrication method of low-loss plastic optical fibers by using a polymer prepared from methyl methacrylate as the principal constituent for a core material, and forming a cladding of a synthetic macromolecular compound having a lower refractive index than that of said core material therearound, the improvement comprises, in a sealed system, the steps of
adding a polymerization initiator and chain transfer agent via a distillation step of said polymerization initiator and chain transfer to a methyl methacrylate monomer distilled under a reduced pressure condition,
subjecting succeedingly said monomer to polymerization to produce a core polymer while maintaining said reduced pressure condition, and then
subjecting said core polymer produced to melt spinning to form a core fiber.

### Claim 2 (depends on 1)

A fabrication method of low-loss plastic optical fibers as claimed in claim 1, wherein a cladding material of a fluorine macromolecular copolymer or a mixture of fluorine macromolecular polymers is adhered around said core fiber.

### Claim 3 (depends on 1)

A fabrication method of low-loss plastic optical fibers as claimed in claim 1, wherein a component of said cladding is a copolymer consisting of one type of fluoroalkyl methacrylate as first ingredient and another type of fluoroalkyl methacrylate as second ingredient, and a molecular weight of said copolymer is within a range of 20,000-100,000 in weight-average molecular weight.

### Claim 4 (depends on 3)

A fabrication method of low-loss plastic optical fibers as claimed in claim 3, wherein said cladding component is a copolymer which is prepared from two types of different fluoroalkyl methacrylates by subjecting said fluoroalkyl methacrylates to bulk polymerization in the absence of oxygen.

### Claim 5 (depends on 3)

A fabrication method of low-loss plastic optical fibers as claimed in claim 3, wherein said cladding component is adhered around said core fiber by coating the cladding component in molten state.

### Claim 6 (depends on 2)

A fabrication method of low-loss plastic optical fibers as claimed in claim 2, wherein said cladding component is a polymer blend prepared by fusing and admixing a first ingredient of a fluoroalkyl methacrylate polymer of a mixture of two types of different fluoroalkyl methacrylate copolymers with a second ingredient of vinylidene fluoride-tetrafluorethylene copolymer.

### Claim 7 (depends on 6)

A fabrication method of low-loss plastic optical fibers as claimed in claim 6, wherein said polymer blend comprises 10 to 50% by weight of said first fluoroalkyl methacrylate ingredient.

### Claim 8 (depends on 1)

A fabrication method of low-loss plastic optical fibers as claimed in claim 1, wherein said polymerization initiator is a radical polymerization initiator exhibiting a favorable activity at a temperature higher than the glass transition temperature of said core polymer, and bulk polymerization is effected at a temperature higher than said glass transition temperature in case of polymerizing said methyl methacrylate monomer.

### Claim 9 (depends on 1)

A fabrication method of low-loss plastic optical fibers as claimed in claim 1, wherein said core polymer after the completion of polymerization thereof is supplied to a melt spinning apparatus without lowering the temperature of said core polymer lower than the glass transition temperature thereof in case of melt spinning of said core polymer.

### Claim 10 (depends on 8)

A fabrication method of low-loss plastic optical fibers as claimed in claim 8, wherein said polymerization initiator is an alkyl azo compound.

### Claim 11 (depends on 10)

A fabrication method of low-loss plastic optical fibers as claimed in claim 10, wherein said polymerization initiator is azo-tert-butane.

### Claim 12 (depends on 1)

A fabrication method of low-loss plastic optical fibers as claimed in claim 1, wherein a component of said cladding is applied to said core fiber by coating said cladding component in molten state in case of forming said cladding around said core fiber.

### Claim 13

In a fabrication method of low-loss optical fibers consisting of a core and cladding each made of a synthetic macromolecular compound, the improvement comprises, in a sealed system, the steps of
supplying a core-forming monomer, polymerization initiator, and molecular weight modifier to a polymerization vessel via an atmospheric distillation or reduced pressure distillation step of all these ingredients under a reduced pressure condition, and
subjecting said distilled monomer to bulk polymerization in said polymerization vessel while maintaining said reduced pressure condition, thereby preparing a polymer for said core.

### Claim 14 (depends on 13)

A fabrication method of low-loss plastic optical fibers as claimed in claim 13, wherein said core-forming monomer, polymerization initiator, and molecular weight modifier are separately distilled, and then the so distilled ingredients are introduced into said polymerization vessel.

### Claim 15 (depends on 13)

A fabrication method of low-loss plastic optical fibers as claimed in claim 13, wherein at least two ingredients of said core-forming monomer, polymerization initiator, and molecular weight modifier are distilled in an admixed condition of said at least two ingredients, and then the so distilled ingredients are introduced into said polymerization vessel.

### Claim 16 (depends on 13)

A fabrication method of low-loss plastic optical fibers as claimed in claim 13, wherein said core-forming monomer consists of a core-forming main monomer and core-forming sub-monomer.

### Claim 17

In a fabrication method of low-loss plastic optical fibers by using a polymer prepared from methyl methacrylate as principal constituent for core material, and forming a cladding of a synthetic macromolecular compound having a lower refractive index than that of said core material therearound, the improvement comprises, in a sealed system, the steps of:
adding a polymerization initiator and a chain transfer agent to a methyl methacrylate monomer under a reduced pressure condition in such a manner that the number of dust in said methyl methacrylate monomer to which said polymerization initiator and chain transfer agent have been added is substantially 1 or less per 1 mm.sup.3 at any place in said monomer,
subjecting said methyl methacrylate monomer to which said polymerization initiator and said chain transfer agent have been added to bulk polymerization at a temperature higher than the glass transition temperature of said methyl methacrylate polymer, thereby preparing said polymer while further maintaining said reduced pressure condition in such a manner that each content of transition metallic ions in said polymer is 50 ppb or less for iron and manganese, 10 ppb or less for copper and nickel, 5 ppb or less for chromium, or 2 ppb or less for cobalt,
subjecting said polymer to melt spinning at such a temperature that voids are not generated to form a core fiber, and
applying said cladding of the substantially amorphous synthetic macromolecular compound having a lower refractive index than that of said core fiber around said core fiber.

### Claim 18 (depends on 17)

A fabrication method of low-loss plastic optical fibers as claimed in claim 17, wherein said polymerization initiator and said chain transfer agent are selected from the group consisting of polymerization initiators or chain transfer agents which can easily be distilled under atmospheric or reduced pressure, and the selected polymerization initiator and transfer agent are added to said methyl methacrylate monomer via the distillation step of both the ingredients under a reduced pressure condition in said sealed system.

### Claim 19 (depends on 17)

A fabrication method of low-loss plastic optical fibers as claimed in claim 17, wherein said polymerization initiator and said chain transfer agent are selected from the group consisting of polymerization initiators or chain transfer agents which can easily be distilled under atmospheric or reduced pressure, the selected polymerization initiator and transfer agent as well as said methyl methacrylate monomer are distilled under a reduced pressure condition in said sealed system, and only the fractions of said polymerization initiator and chain transfer agent are added to the so distilled methyl methacrylate monomer.

### Claim 20 (depends on 17)

A fabrication method of low-loss plastic optical fibers as claimed in claim 17, wherein said polymerization initiator is a radical polymerization initiator exhibiting a favorable activity at a temperature higher than the glass transition temperature of said polymer.

### Claim 21 (depends on 17)

A fabrication method of low-loss plastic optical fibers as claimed in claim 17, wherein said methyl methacrylate to which said polymerization initiator and said chain transfer agent have been added is subjected to bulk polymerization at a temperature higher than said glass transition temperature, and the resulting polymer is subjected to melt spinning without dropping the temperature of said polymer to the one lower than said glass transition temperature, thereby forming said core fiber.

### Claim 22 (depends on 17)

A fabrication method of low-loss plastic optical fibers as claimed in claim 17, wherein said core material comprises 50 mol% or more of methyl methacrylate monomer unit and another monomer the boiling point of which is within a range of 80.degree.-160.degree. C. under atmospheric pressure.