CN100393497C - Fluorine containing optical plastic perform-rod with gradient refractive index, preparing process and usage thereof - Google Patents
Fluorine containing optical plastic perform-rod with gradient refractive index, preparing process and usage thereof Download PDFInfo
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- CN100393497C CN100393497C CNB2005100246708A CN200510024670A CN100393497C CN 100393497 C CN100393497 C CN 100393497C CN B2005100246708 A CNB2005100246708 A CN B2005100246708A CN 200510024670 A CN200510024670 A CN 200510024670A CN 100393497 C CN100393497 C CN 100393497C
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Abstract
The present invention relates to a precast rod containing fluorine with gradient refractivity, a preparing method thereof and an application thereof. The precast rod is prepared by adopting the multiple-step aggregation of fluorine-containing acrylate monomer; firstly, a hollow pipe is prepared by aggregating monomer; secondly, monomer containing a right amount of inert dopant is put into the hollow pipe to obtain an optical precast rod with gradient refractivity through aggregation by swelling gel. The precast rod can be used as materials for preparing plastic optical fiber.
Description
Technical field
The present invention relates to a fluorine-containing optical plastic perform-rod with gradient refractive index, preparation method and purposes.
Technical background
Since successfully preparing first high-purity, low-loss silica fiber from Corning Incorporated in 1970, fiber optic communication is high-speed with it, big capacity and good interference free performance more and more are subject to people's attention.And especially obtaining application widely aspect the long haul communication in the modern communications field.It is thinner that but silica fibre lacks good toughness, diameter, usually below 100um, factor such as connection charge height and limited it in the short haul connection system especially optical fiber application in engineering of registering one's residence.In this case people begin one's study, diameter good, in light weight thick (500um-1mm) with macromolecular material processing machinery performance, be easy to connect and plastic optical fiber that production cost is low substitutes silica fibre.
Traditional plastic optical fiber mainly is a methyl methacrylate, and materials such as Merlon and polystyrene are made, and compares low many of the cost of plastic optical fiber with the chemical vapour deposition technique of producing the silica fibre costliness.Though plastic optical fiber has overcome some shortcomings of silica fibre, because the intrinsic defective of macromolecular material itself has hindered plastic optical fiber really to enter the communications field.Mainly there are some following shortcomings in traditional plastic optical fiber:
1, higher light loss consumption
The light loss consumption of plastic optical fiber mainly is made up of absorption loss and scattering loss two parts.Absorption loss comprises that the absorption of vibrations of chemical bond and electron transition absorb.In macromolecular material, exist c h bond, O-H key, the absorption of vibrations of chemical bonds such as C=O key, but because the number of c h bond is maximum in the molecule, and its absorption band broad, therefore, the temperature tolerance of c h bond in the infrared absorption of vibrations optical fiber that is plastics to visible region
Most of traditional plastic optical fibers all can only be worked below 100 degree, compare with silica fibre, and operating temperature is very low, and this also is the key factor that the restriction plastic optical fiber is used.2, the mismatch of operation wavelength and silica fibre
Because the operation wavelength of the backbone of plastic optical fiber and silica fibre is inconsistent, when therefore plastic optical fiber being connected with silica fibre, must change fiber-optic signal into the signal of telecommunication by converter, and then the signal of telecommunication is changed into the optical signal of another wavelength, need higher cost, especially for the optical fiber engineering of registering one's residence, required cost height.
In order to overcome the above-mentioned shortcoming of plastic optical fiber, make plastic optical fiber really enter optical communication field, people begin to attempt adopting new macromolecular material to prepare plastic optical fiber.Common method is that the monomer for preparing plastic optical fiber is carried out deuterate and halogenation.Though the loss of plastic optical fiber reduces greatly after the deuterate, the cost costliness in deuterium generation is abandoned by people gradually.And because again in the polymer, the too high levels of elements such as Cl, Br can make the stability of polymer reduce, so halogen mainly is based on fluoro to the replacement of hydrogen atom.
Fluoro is known by people already to the improvement of macromolecular material performance, and fluororesin industry is also very ripe already, fluoropolymer polymer in plastic optical fiber application and obtained important must the progress improving the plastic optical fiber aspect of performance.
1. reduce the wastage
At first, because the C-F key gets the absorption of vibrations fundamental frequency in the far-infrared band, and absorption is very little in the scope from the visible region to the near-infrared region, and the absorption loss of fluoro plastic optical fiber is reduced.Secondly, because the loss reduction that the red shift of optical transmission window makes scattering cause equally.In addition, the surface of fluoro-containing macromolecule material can be little, can reduce the absorption of water vapour on its surface, prevents the infiltration of water vapour in material, also plays the effect that reduces the wastage.
2. mate with the operation wavelength of silica fibre
Behind the fluoro, the red shift of absorption has improved the light transmission of material in the near infrared region, thereby has solved the problem that plastic optical fiber and silica fibre operation wavelength are complementary
3. high temperature tolerance
Fluoropolymer polymer is all more stable usually, has higher vitrification point, so the fluoro plastic optical fiber has temperature tolerance preferably usually.And fluoropolymer polymer is difficult aging, thereby make fluoroplastics optical fiber that be arranged long service life.
Summary of the invention
The object of the invention provides a kind of fluorine-containing optical plastic perform-rod with gradient refractive index.
Another object of the present invention provides the preparation method of above-mentioned fluorine-containing optical plastic perform-rod with gradient refractive index.
Purpose of the present invention also provides the purposes of above-mentioned fluorine-containing optical plastic perform-rod with gradient refractive index.
Fluorine-containing optical plastic perform-rod with gradient refractive index of the present invention, form by shell and inner core, shell is the polymer of fluorine-containing methacrylate compounds, inner core is the polymer of fluorine-containing methacrylate compounds of adulterant of inert molecule that contains the high index of refraction of 1-20% weight, the polymer of described fluorine-containing methacrylate compounds is a trifluoroethyl methacrylate, tetrafluoropropyl propyl ester or methacrylic acid hexafluoro butyl ester, described adulterant is an Ergol, ethyl benzoate, bromobenzene, the n-butyl phthalate methyl esters, benzyl phthalate, diphenyl sulfide, benzyl methacrylate, triphenyl phosphate or biphenyl.
A kind of graded index optical preform of the present invention, the weight ratio of its shell and inner core is 1: 0.25～4.Refractive index increases in the outlying islets gradually, and refractive index reaches maximum during to the center of prefabricated rods, tangible hop do not occur.
The preparation method of a kind of graded index optical preform of the present invention, be that the polymerization single polymerization monomer and the 0.2-1% initator that will contain the fluorine-containing methacrylate compounds adds in the glass tube sealing, preferably with its freeze drying, vacuumize, inflated with nitrogen is sealed tube sealing, horizontally rotates then, react the hollow tube that obtained polymerization in 24～100 hours down at 55～80 ℃, recommend high speed centrifugation to horizontally rotate; Add the fluorine-containing methacrylate compounds solution that contains 0.2-1% initator and 1-20% adulterant at hollow tube, recommend the initator of 0.2-0.5% and the adulterant of 5-10%, vertically place, 55～100 ℃ of reactions 100～170 hours.In order to obtain satisfied result, recommend the gradient increased temperature reaction, can prevent the generation of bubble, form optical plastic perform-rod with gradient refractive index preferably.As 55～70 ℃ of reactions 1 hour, be cooled to room temperature, 60～70 ℃ of reactions 50～80 hours, be warmed up to 75～85 ℃ and reacted again 24～50 hours, be warmed up to 90～100 ℃ of reactions 4～50 hours.Described glass tube is size arbitrarily, all is fine as length and diameter variation.
Described graded index optical preform as previously mentioned.Described initator is azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO).
Not only preparation method's progress of graded index optical preform of the present invention, and be monomer with methacrylic acid fluorinated ester class, by polymerization, the preform that obtains, its performance is significantly better than the prefabricated rods that obtains with the methyl acrylic ester polymerization.
This class graded index prefabricated rods can prepare the polymer optical fiber material of refractive index, has a wide range of applications in the communications field.
Description of drawings
Accompanying drawing 1 is the refractive index of fluorine-containing optical plastic perform-rod with gradient refractive index.
Wherein: r
pExternal diameter for optical plastic perform-rod with gradient refractive index; R is a distance of leaving the optical plastic perform-rod with gradient refractive index central shaft; n
0Refractive index for central axis; N is the refractive index at the r place.
The specific embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
In a tube sealing that is about 15cm diameter 14mm, add methacrylic acid hexafluoro butyl ester 4 grams that contain 0.3%AIBN.Freeze drying vacuumizes, and inflated with nitrogen three times repeatedly, is sealed tube sealing.The rotation of tube sealing horizontal positioned was reacted 72 hours down at 60 ℃.Obtain the hollow tube of polymerization.Cut the mouth of pipe, add the methacrylic acid hexafluoro butyl acetate solution that 12 grams contain 0.3%BPO and 5% Ergol.Vertically placed 2 hours, be warming up to 60 ℃, be cooled to room temperature after 1 hour, reacted 72 hours down at 60 ℃ again then, continue respectively to react 24 hours at 80 ℃ and 100 ℃.Reaction is placed on refrigerator and cooled but after finishing, and removes the glass of outside, promptly obtains transparent prefabricated rods.The refractive index of the fluorine-containing optical plastic perform-rod with gradient refractive index of this prefabricated rods as shown in Figure 1.
Embodiment 2
Add the tetrafluoropropyl propyl ester 8 gram freeze dryings that contain 0.3%AIBN in the tube sealing of a long 15cm diameter 14mm, vacuumize, inflated with nitrogen three times repeatedly, is sealed tube sealing.The centrifugal rotation of tube sealing horizontal positioned was reacted 48 hours down at 67 ℃.Obtain the hollow tube of polymerization.Cut the mouth of pipe, add the tetrafluoropropyl propyl ester solution that 8 grams contain 0.3%BPO and 8% bromobenzene.Vertically placed 1 hour, be warming up to 60 ℃, be cooled to room temperature after 1 hour, continue then to react 72 hours down, continue respectively to react 48 hours at 80 ℃ and 100 ℃ at 67 ℃.Reaction is placed on refrigerator and cooled but after finishing, and removes the glass of outside, promptly obtains transparent prefabricated rods.
Embodiment 3
Add the trifluoroethyl methacrylate 96 gram freeze dryings that contain 0.3%BPO in the tube sealing of a long 60cm diameter 28mm, vacuumize, inflated with nitrogen three times repeatedly, is sealed tube sealing.The rotation of tube sealing horizontal positioned high speed centrifugation was reacted 72 hours down at 65 ℃.Obtain the hollow tube of polymerization.Cut the mouth of pipe, add the tetrafluoropropyl propyl ester solution that 36 grams contain 0.3%BPO and 10% biphenyl.Vertically placed 0.5 hour, be warming up to 60 ℃, be cooled to room temperature after 1 hour, continue then to react 55 hours down, continue respectively to react 24 hours at 80 ℃ and 100 ℃ at 67 ℃.Reaction is placed on refrigerator and cooled but after finishing, and removes the glass of outside, promptly obtains transparent prefabricated rods.
Claims (7)
1. graded index optical preform, it is made up of shell and inner core, shell is the polymer of fluorine-containing methacrylate compounds, inner core is the polymer of fluorine-containing methacrylate compounds of adulterant of inert molecule that contains the high index of refraction of 1-20% weight, the polymer of described fluorine-containing methacrylate compounds is a trifluoroethyl methacrylate, tetrafluoropropyl propyl ester or methacrylic acid hexafluoro butyl ester, described adulterant is an Ergol, ethyl benzoate, bromobenzene, the n-butyl phthalate methyl esters, benzyl phthalate, diphenyl sulfide, benzyl methacrylate, triphenyl phosphate or biphenyl.
2. a kind of graded index optical preform as claimed in claim 1, the weight ratio that it is characterized in that shell and inner core is 1: (0.25～4).
3. a kind of graded index optical preform as claimed in claim 1 is characterized in that its refractive index increases from outside to inside gradually, reaches maximum during to the center of prefabricated rods, tangible hop do not occur.
4. the preparation method of an a kind of graded index optical preform as claimed in claim 1, it is characterized in that at first in a glass tube sealing, adding the polymerization single polymerization monomer and the initator of fluorine-containing methacrylate compounds, the polymerization single polymerization monomer of fluorine-containing methacrylate compounds and the weight ratio of initator are 1: (0.002-0.01), by horizontally rotating preparation polymer hollow tube, cut the mouth of pipe then, the polymerization single polymerization monomer and the adulterant that add the fluorine-containing methacrylate compounds that contains initator, described initator, the weight ratio of fluorine-containing methacrylate compounds and adulterant is (0.002-0.01): (0.01-0.2): (0.99-0.8), this system is vertically placed, and heated polymerizable forms prefabricated rods; The polymer of described fluorine-containing methacrylate compounds is trifluoroethyl methacrylate, tetrafluoropropyl propyl ester or methacrylic acid hexafluoro butyl ester, described adulterant is Ergol, ethyl benzoate, bromobenzene, n-butyl phthalate methyl esters, benzyl phthalate, diphenyl sulfide, benzyl methacrylate, triphenyl phosphate or biphenyl, and described initator is azodiisobutyronitrile or benzoyl peroxide.
5. the preparation method of a kind of graded index optical preform as claimed in claim 4, the preparation that it is characterized in that described polymer blank pipe is the glass tube sealing freeze drying that contains the polymerization single polymerization monomer of fluorine-containing methacrylate compounds and initator, vacuumize, inflated with nitrogen, tube sealing is sealed, horizontally rotate, reacted 24-100 hour down, obtain the hollow tube of polymerization at 55-80 ℃; Add the fluorine-containing methacrylate compounds solution of the adulterant of the initator contain 0.2-1% and 3-15% at hollow tube, vertically be placed on 55～100 ℃ of reactions 100～170 hours.
6. the preparation method of a kind of graded index optical preform as claimed in claim 4 is characterized in that described horizontally rotating is centrifugal or high speed centrifugation.
7. the purposes of an a kind of graded index optical preform according to claim 1 is characterized in that described prefabricated rods is used to make the material of plastic optical fiber.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100246708A CN100393497C (en) | 2005-03-25 | 2005-03-25 | Fluorine containing optical plastic perform-rod with gradient refractive index, preparing process and usage thereof |
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| CNB2005100246708A CN100393497C (en) | 2005-03-25 | 2005-03-25 | Fluorine containing optical plastic perform-rod with gradient refractive index, preparing process and usage thereof |
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| CN1669759A CN1669759A (en) | 2005-09-21 |
| CN100393497C true CN100393497C (en) | 2008-06-11 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10136286A1 (en) * | 2001-02-23 | 2002-09-12 | Ems Chemie Ag | Thermoplastic block copolymers with poly(meth)acrylate and polyamide segments, used for production of fibres, film, mouldings and hot-melt adhesives or as coupling agents for polyamides and acrylics or polycarbonates |
| CN1413307A (en) * | 1999-12-27 | 2003-04-23 | 三菱丽阳株式会社 | Plastic optical fibers, plastic optical fiber cables, optical fiber cables with plugs and copolymer |
| JP2004204018A (en) * | 2002-12-25 | 2004-07-22 | Hitachi Chem Co Ltd | Optical resin composition and optical element using the same |
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- 2005-03-25 CN CNB2005100246708A patent/CN100393497C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413307A (en) * | 1999-12-27 | 2003-04-23 | 三菱丽阳株式会社 | Plastic optical fibers, plastic optical fiber cables, optical fiber cables with plugs and copolymer |
| DE10136286A1 (en) * | 2001-02-23 | 2002-09-12 | Ems Chemie Ag | Thermoplastic block copolymers with poly(meth)acrylate and polyamide segments, used for production of fibres, film, mouldings and hot-melt adhesives or as coupling agents for polyamides and acrylics or polycarbonates |
| JP2004204018A (en) * | 2002-12-25 | 2004-07-22 | Hitachi Chem Co Ltd | Optical resin composition and optical element using the same |
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| CN1669759A (en) | 2005-09-21 |
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