CN104671676A - An improved low-refractive index coating for optical fiber, a method for manufacturing the same and a product comprising the same - Google Patents
An improved low-refractive index coating for optical fiber, a method for manufacturing the same and a product comprising the same Download PDFInfo
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- CN104671676A CN104671676A CN201410550917.9A CN201410550917A CN104671676A CN 104671676 A CN104671676 A CN 104671676A CN 201410550917 A CN201410550917 A CN 201410550917A CN 104671676 A CN104671676 A CN 104671676A
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Abstract
The invention relates to an improved low-refractive index coating for optical fiber, a method for manufacturing the same and a product comprising the same. A composition of the invention contains 65-95wt% of fluorination mono-functional monomer, 5-35wt% of fluorination multi-functional monomer, and 0.5-3wt% of a silane coupling agent, wherein the weight percentage is based on the total weight of the composition; the fluorination mono-functional monomer and the fluorination multi-functional monomer contain no tri-functional perfluorocarbon containing part when containing 6 or more perfluorocarbon containing repetitive units; the perfluorocarbon containing repetitive units are CF2 or CF parts. The cross-linked composition has a Shore D hardness of 56-85 and has a refractive rate (RI) satisfying the formula of RI<=1.368+10.8/X, wherein the X represents the wavelength based on nanometer.
Description
The cross reference of related application
The right of priority of the U.S. Provisional Application submitted in application claims on October 16th, 2013 numbers 61/891,556, its full content is incorporated herein by reference.
Background technology
The present invention relates to the low refractive index coating of the improvement for optical fiber, its manufacture method and the goods comprising it.Especially, the present invention relates to and fluoridize low refractive index coating for optical fiber, it does not comprise and has borontrifluoride carbon atom (CF
3) long chain molecule and not containing with the fluorinated molecule of Types Below:
·CF
3(CF
2)
n-CH＝CH
2；
CF
3(CF
2)
n-C (=O)-X, wherein X is any chemical part;
CF
3(CF
2)
m-CH
2-X, wherein X is any chemical part;
Wherein n>5 or m>6.
Use perfluorinated polyether (PFPE) oligopolymer to obtain in the past and fluoridize low refractive index coating for optical fiber.Principle example is with trade(brand)name
with
sold by Solvay and have the UV-curable of the ethoxylation PFPE glycol of following general formula derivative:
X-CF
2-O-(CF
2-CF
2-O)O-(CF
2O)
q-CF
2-X
Wherein X end group comprises one or more-CH usually
2bridged group and one or more alcohol (-OH) parts of (such as, to become acroleic acid esterification) can be derived.These PFPE generally have relatively high number-average molecular weight (order of magnitude is 1500-2600 gram/mol), usually carry out leverage to obtain " height " viscosity and to make it possible to hopefully use conventional high-pressure fibre coating applicator easily by described number-average molecular weight.Hopefully, PFPE has low-refraction inherently, but its use has some shortcoming, and these shortcomings mainly PFPE itself are soft and do not bring hardness when may wish hardness.PFPE derivative, such as, PFPE (methyl) acrylate or urethane (methyl) acrylate, demonstrate low thermo-oxidative stability (after solidification) compared to the fluorocarbon material that contains not being polyether-based.In addition, PFPE oligopolymer more may be difficult to purifying compared to lower molecular weight fluorinated monomer, and some evidences show that hydrophilic impurities causes the performance of PFPE base coating layer in wet environment bad.(methyl) acrylate is methacrylate or acrylate as the term is employed herein.
PFPE derivative due to its high molecular, and is characterised in that significant polymolecularity; Its molecular weight distribution may be difficult to when producing continuous batch control and reproduce.Polymolecularity and then can cause the difference of viscosity and the consistency with other coating ingredients between different batches; Such difference may reduce the consistence of the fiber using PFPE based polyalcohol coating layer to prepare.
Other polymer covering layer be purchased has depended on such chemical composition, its purposes chemical balance motion mechanism disables or strict restriction (that is, having the structure that with perfluorination sad PFOA and its precursor and higher homologue forbid).Have been found that PFOA is biopersistence and biological accumulation.Although be not that biopersistence and the biological accumulation of whole all components of the present invention is all proved, target of the present invention is the component not using US EPA ' s Long-Chain Perfluorinated Chemicals (PFAC) Action Plan (2009) to describe.
Therefore wish the friendly coating of environment for use, it has low-refraction, lower oxidative degradation susceptibility, and more consistent characteristic (production profile) (that is, the nature difference owing to working condition change is minimum).In addition, the use wished has the coating of applicable balance of properties, and described character comprises hardness (or modulus) and specific refractory power.
Summary
Disclosed herein is composition, it comprises the fluorinated monofunctional monomer of 65-95wt%; 5-35wt% fluoridizes polyfunctional monomer; With the silane coupling agent of 0.5-3wt%; Wherein all weight percents are all based on composition total weight; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when it has 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF
2or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting formula RI≤1.368+10.8/X restriction, wherein X represents the wavelength in nanometer.
Also disclose method herein, it comprises and being blended together by following material: the fluorinated monofunctional monomer of 65-95wt%; 5-35wt% fluoridizes polyfunctional monomer; The silane coupling agent of 0.5-3wt%, to form composition; Wherein all wt per-cent is all based on composition total weight; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when y has 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF
2or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting equation RI≤1.368+10.8/X and limit, wherein X represents the wavelength in nanometer.
Also the goods comprising optical fiber are disclosed herein; Comprise the coating layer of the reaction product of such composition, described composition comprises the fluorinated monofunctional monomer of 65-95wt%; 5-35wt% fluoridizes polyfunctional monomer; With the silane coupling agent of 0.5-3wt%; Wherein all wt per-cent is all based on composition total weight; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when y has 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF
2or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting equation RI≤1.368+10.8/X and limit, wherein X represents the wavelength in nanometer; Wherein coating layer contact optical fiber; With the buffer layer be placed on coating layer.
Accompanying drawing explanation
Fig. 1 (A) is the figure of the relation describing Shore D hardness and contrast the numerical aperture with regard to commercially available polymer covering layer with regard to the present composition (sample 7 and sample 8) and other; Remove indicated, with reference to silica core, numeric aperture values is by following calculating: under 633nm, measure specific refractory power (the curing dose 14J/cm on coated tunic
2, non-optical fiber base material); Shore D hardness is measured there is no the form of the film of optical fiber base material;
Fig. 1 (B) is the figure describing the specific present composition (sample 13), and described composition exhibiting to go out than two kinds other and contrasts commercially available polymer covering layer 1-A and 1-B (from table 4) and have higher thermostability; Data in Figure 1B are that the life standard of the weight loss of use 25% produces;
Fig. 2 is the figure of the dynamic elastic modulus (not being placed on silica optical fiber) of display film, and it compares commercially available polymer covering layer 1-A and 1-B (from table 4) and the present composition (sample 13);
Fig. 3 is the figure of the dynamic elastic modulus (not being placed on silica optical fiber) of display film, and it compares some commercially available polymer covering layers (from table 4) and the present composition (sample 13);
Fig. 4 is for showing the figure of attenuation change for the 100-m fiberoptic coil when standing temperature and humidity circulation/FOTO-72 and measuring under the wavelength of 630 nanometers and the relation of time;
Fig. 5 is the figure showing attenuation change for the 100-m fiberoptic coil when standing the thermal cycling of-65 to 125 DEG C of temperature and measuring under the wavelength of 630 nanometers and the relation of time;
Fig. 6 is the figure of the relation showing attenuation change for the loose 100-m coil before and after aging 1 day at 150 DEG C and wavelength.
Fig. 7 be showing fiber fault when being transmitted in high power laser light radiation and the figure of bending radius funtcional relationship.During fracture, bending radius is less shows that intensity is higher; With
Fig. 8 compares fiber and the commercially available fiber of the contrast fade performance change under 850nm in hot-water soak process with coating layer of the present invention.Fiberoptic coil length is 15 meters.
Describe in detail
The curable polymeric composition of the improvement as optical fibre packages coating is disclosed herein.Composition comprises fluorinated monofunctional and fluoridizes polyfunctional monomer.The composition exhibiting of solidification goes out unique combination of properties, is that it is combined with high rigidity (and high elastic coefficient) and low-refraction (and high-NA).The composition of solidification (sometimes also referred to as through crosslinked composition or coating or coating layer) defines comparatively low refractive index coating (when compared to other commercially available contrast coating layer) on optical fiber therefore, for optical fiber (such as, there is the fiber of silica core) provide height to the higher numerical aperture (NA) of about 0.50, maintain high rigidity (Shore D of 56-85) simultaneously and show the Young's modulus being greater than 300MPa at 23 DEG C.Stand aging, the thermal cycling in thermal ageing and wet environment, hot-water soak for composition during coated fiber, and demonstrate the improvement of (being better than other commercially available coating) environmental resistance when being exposed to the superpower in sharp turn.
In the preferred embodiment described in Fig. 1 (A), produce through crosslinked composition when being arranged on optical fiber and be greater than 0.46, be preferably greater than 0.47, and more preferably greater than 0.48 numerical aperture, demonstrate 56-85, the Shore D hardness of preferred 60-80 and more preferably 65-75 simultaneously.
In addition, the chemical composition of composition drops on outside the PFOA-similar varieties class of US EPA ' s Long-Chain Perfluorinated Chemicals (PFCs) the Action Plan restriction of announcing on December 30th, 2009 technically.This is not because namely composition comprises trifluoro carbon (-CF
3) group and/or have and get rid of molecular chain length outside limited kind.Select the component of composition to have Low acid, to maximize the staging life containing silane liquid, and there is low alkalinity, so as in minimum wet environment glass fibre tractive after (post-draw) corrosion.In an exemplary embodiment (it describes in detail afterwards), when fluorine-containing carbon number of repeat unit is greater than 6, fluorinated monofunctional monomer and fluoridize polyfunctional monomer not containing trifluoro carbon (-CF
3) group and be less than 6 in fluorine-containing carbon number of repeat unit and make or monofunctional monomer and any one or both that fluoridize polyfunctional monomer optionally can comprise trifluoro carbon (-CF
3) group.Fluorine-containing carbon repeating unit is CF
2or CF part.Coating layer does not especially contain with the fluorinated molecule of Types Below:
·CF
3(CF
2)
n-CH＝CH
2；
CF
3(CF
2)
n-C (=O)-X, wherein X is any chemical part;
CF
3(CF
2)
m-CH
2-X, wherein X is any chemical part;
Wherein n>5 or m>6.
Crosslinking reaction for generation of the coating layer on optical fiber can be the general free radical reaction by using uv-radiation to activate.Crosslinking reaction also can be brought by being used for by cationoid polymerisation implementing the crosslinked of composition.Fluorinated monofunctional monomer disclosed herein and fluoridize polyfunctional monomer have by during radioactivation use free radical reaction solidify functional group's (such as olefinic unsaturated functional group, acrylate-functional groups or methacrylate functional).But other monomer with reactive functional groups (such as epoxide functional group or vinyl ether functional group) can use cationoid polymerisation to be cross-linked.When fluoridizing the radical polymerization of (methyl) acrylate, the fluorinated comonomers with functional group's (mercaptan and/or vinyl and/or vinyl ether) of other particular type can finite quantity use (wherein its molar fraction is compared to acrylate and/or methacrylate based number) be less than 0.5.When the cationoid polymerisation of epoxide or vinyl ether, fluorinated comonomers containing alcohol functional group also can finite quantity use (again, wherein compared to the molar fraction of epoxide or vinyl ether group, its molar fraction is much smaller than 0.5).
Fluorinated monofunctional monomer comprise there is at least one reactive group fluoridize material, described reactive group allows it at covalent bonding in crosslinked composition.In preferred embodiments, fluorinated monofunctional monomer comprises and has at least one reactive group and fluoridize material, and described reactive group allows it covalently bonded to coating.Fluoridize material when " n " number of repeating unit is more than or equal to 6 in following formula do not contain the fluorine-containing carbon part of any trifunctional and optionally can comprise the fluorine-containing carbon part of trifunctional when n is less than 6.Fluoridize that material can comprise straight chain fluoro material, cyclic fluorinated material, branching fluoridize material or its combination.Preferred straight chain fluoro material.Straight chain fluoro monofunctional monomer is represented by chemical formula (1A):
R
1-(CF
2)
n-R
2(1A)。
Cyclic fluorinated monofunctional monomer is represented by chemical formula (1B):
In its Chinese style (1A) or (1B), R
1be non-reactive end groups, it comprises CH when n is more than or equal to 6
2f or CHF
2but do not comprise CF
3, and wherein R
1be non-reactive end groups, it comprises CH when n is less than 6
2f, CHF
2or CF
3; Wherein R
2monofunctional reactant, group, it comprises olefinic unsaturated functional group, such as acrylate, methacrylic ester or vinyl ether functional group; Epoxide functional group, hydroxy functional group, vinyl ether functional group or thiol functionalities.In monofunctional reactant radicals R
2comprise acrylate or methacrylate functional, this material is preferably cross-linked via free radical reaction.
In above formula (1), n is 1-15, preferred 6-10.In preferred embodiments, R
2comprise olefinic unsaturated functional group, preferred acrylate methacrylate functional.
In preferred embodiments, fluorinated monofunctional monomer has and is less than 1200 grams/mol, is preferably less than 1000 grams/mol, and is more preferably less than the number-average molecular weight of 700 grams/mol.The fluorinated monofunctional monomer of wishing has the flash distillation point being greater than 60 DEG C.
In preferred embodiments, the straight chain fluoro monofunctional monomer represented by chemical formula (2A) can also be used.
R
1-(CF
2)
n-(CH
2)
m-R
2(2A)
Cyclic fluorinated monofunctional monomer is represented by chemical formula (2B) or (2C):
In its Chinese style (2A), (2B) and (2C), R
1, R
2with n as above concrete definition and wherein m be 1-10, preferred 1-5 and more preferably 1-2.In embodiments, R
2group is bonded to main structure by C-O-C some covalent, except at R
2when being mercaptan, alcohol or epoxide.
Also branched fluorinated monofunctional monomer can be used and it is represented by chemical formula (3),
Wherein R
1and R
3be non-reactive end position group, it comprises CH when the summation of n and o is more than or equal to 6
2f or CHF
2, but do not comprise CF
3, and comprise CH when the summation of n and o is less than 6
2f or CHF
2or CF
3; Wherein R
2be monofunctional reactive group, it comprises olefinic unsaturated functional group (such as acrylate-functional groups, methacrylate functional or vinyl ether functional group), epoxide functional group, hydroxy functional group or thiol functionalities.
In above formula (3), n or o is 1 to 15 separately independently of one another, preferably 2 to 12 and be more preferably 6 to 10, and p is 1 to 6, is preferably 1 to 2.It should be noted that branched fraction can along fluorine carbon molecular backbone stochastic distribution.In a preferred embodiment, R
2be olefinic unsaturated functional group, be preferably acrylate-functional groups or methacrylate functional.
In another embodiment, the fluorinated monofunctional monomer of the side chain with following formula (4) can also be used
Wherein R
1, R
2, R
3, n, o and p as described in above-mentioned formula (3), and m is as described in above-mentioned formula (2).The fluorinated monofunctional monomer of formula (1A), (1B), (2A), (2B), (2C), (3) and (4) can combinationally using with any hope each other.
The fluorinated monofunctional monomer that may be used for composition comprises 1,1-dihydro perfluorocyclohexane Trivalin SF acrylate (being also referred to as perfluoroethyl cyclohexylmethyl herein), 1,1-dihydro perfluorocyclohexane Trivalin SF methacrylic ester (being also referred to as methacrylic acid perfluorocyclohexyl methyl esters herein), 1,1-dihydro Decafluorocyclopentane Trivalin SF acrylate, 1,1-dihydro Decafluorocyclopentane Trivalin SF methacrylic ester, vinylformic acid 1H, 1H, 5H-octafluoro amyl group ester, methacrylic acid 1H, 1H, 5H-octafluoro amyl group ester, vinylformic acid 1H, 1H, 11H-perfluor undecyl ester, 1H, 1H, 9H-ten hexafluoro nonanylmethyl acrylate, vinylformic acid 1H, 1H, 9H-ten hexafluoro nonyl ester, vinylformic acid 1H, 1H, 7H-ten difluoro heptyl ester, vinylformic acid 2-(perfluoro hexyl) ethyl ester, methacrylic acid 2-(perfluoro hexyl) ethyl ester, 2-vinylformic acid 3,3,4,4,5,6,6,6-octafluoro-5-(trifluoromethyl) polyhexamethylene, vinylformic acid 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluoro decyl ester, vinylformic acid 2,2,3,3,4,4,5,5-octafluoro amyl group ester etc. or comprise the combination of at least one of above-mentioned fluorinated monofunctional monomer.
Preferred is vinylformic acid 1H for the straight chain fluoro monofunctional monomer in composition, 1H, 11H-perfluor undecyl ester or vinylformic acid 1H, 1H, 9H-ten hexafluoro nonyl ester.Preferred cyclic fluorinated monofunctional monomer is perfluorocyclohexyl methacrylic ester and perfluorocyclohexyl methylmethacylate.Above-mentioned straight chain fluoro monofunctional monomer and above-mentioned cyclic fluorinated monofunctional monomer can use with the combination of any hope.
Fluorinated monofunctional monomer can be used, based on the total weight of composition with the amount of 65 to 95 % by weight (wt%).In a preferred embodiment, fluorinated monofunctional monomer can be used, based on the weighing scale of composition with the amount of 75 to 85 % by weight.
Composition also comprises fluoridizes polyfunctional monomer.Fluoridize polyfunctional monomer and can have 2 or more functional groups.In one embodiment, it can be Bifunctionalized, trifunctional, four functionalized, five functionalized etc. for fluoridizing polyfunctional monomer.In preferred embodiments, it is Bifunctionalized for fluoridizing polyfunctional monomer.Fluoridizing polyfunctional monomer can be straight chain, ring-type or straight chain.
In one embodiment, fluoridize polyfunctional monomer and can have the structure shown in formula (5) to (8)
R
2-(CF
2)
n-R
2(5)
R
2-(CH
2)
m-(CF
2)
n-(CH
2)
m-R
2(6)
Wherein R
2be reactive group, it comprises olefinic unsaturated functional group (such as acrylate, methacrylic ester or vinyl ether functional group).When preparing coating layer by free radical reaction, use acrylate or methacrylate reactive group; In this case, thiol functionalities or vinyl ether functional group also can be used in fluorinated comonomers with the molar ratio much smaller than 0.5.If when preparing coating layer by cationoid polymerisation, the reactive group R comprising epoxide functional group or vinyl ether functional group can be used
2; In this case, can use with little amount the reactive functional groups comprising hydroxyl or organoalkoxysilane.Referring now to formula (5)-(8), except when R
2be mercaptan or hydroxyl or epoxy group(ing) time, reactive group R
2be covalently attached on ethylidene key by C-O-C chain.
In above-mentioned formula (5) in (8), n and o is 1 to 15, preferably 2 to 12, and be more preferably 4 to 10, and m is 1 to 10, is preferably 1 to 5, and be more preferably 1 to 2.In formula (7), p is 1 to 6, is preferably 1 to 2.It should be noted that the branched group of formula (7) can along the main chain stochastic distribution of fluorine carbon oligopolymer.R in formula (7)
3can be reactive or non-reacted.In preferred embodiments, R
2for olefinic unsaturated functional group, be preferably acrylate-functional groups or methacrylate functional.
Preferred fluorinated monofunctional monomer has the structure of formula (9),
R
2-(CH
2)
m-(CF
2)
n-(CH
2)
m-R
2(9)
Wherein, in formula (9), R
2be acrylate group, n is 1 to 15, be preferably 4 to 10, and m is 1 to 10, is preferably 1 to 2.Preferably fluoridizing polyfunctional monomer is fluoro-1, the 8-ethohexadiol diacrylate of 2,2,3,3,4,4,5,5-octafluoro-1,6 hexanediol diacrylate and 2,2,3,3,4,4,5,5,6,6,7,7-12.
Fluoridize polyfunctional monomer to use, based on the total weight of composition with the amount of 5 to 35 % by weight.In preferred embodiments, fluoridize polyfunctional monomer to use, based on the total weight of composition with 10 to 25 % by weight.
Composition also comprises the silane coupling agent not containing amine functional group.Silane coupling agent contributes to applying period and after forming coating, composition being attached to optical fiber at curing composition.When based on (methyl) acrylate formulation (formulation), wish that silane coupling agent comprises at least one and can participate in the functional group with the Raolical polymerizable fluoridizing single and many unsaturated monomers, and wish silane coupling agent have at least one can condensation to form the alkoxysilane groups with the Si-O-Si bonding of optical fiber.When the composition based on epoxide or vinyl ether, wish that silane coupling agent comprises at least one and can participate in the functional group with the cationic polymerization of each fluorinated monomer type, and also comprise at least one can condensation to form the alkoxysilane groups with the Si-O-Si bonding of optical fiber.
When being subject to radiation or by heating, silane coupling agent and fluorinated monofunctional monomer reaction, or react with difunctional monomer.Silicon dioxde reaction on some and optical fiber in silane functional is to provide the combination improved with optical fiber.As mentioned above, when monomer has the reactive functional groups for epoxide or vinyl ether, usually cationoid polymerisation is used.
The silane be applicable to for radically curing preparation is gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-acryloxypropyl Trimethoxy silane, gamma-methyl allyl acyloxypropyl three ('beta '-methoxy oxyethyl group) silane, γ-acryloyl-oxy oxygen base propyl group three ('beta '-methoxy oxyethyl group) silane, γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane; The example of silane be applicable to for cationic epoxy base curing composition be applicable to is glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl diethoxy silane, β (3,4-ethoxycyclohexyl) ethyl trimethoxy silane etc. or comprise the composition of at least one of above-mentioned silane coupling agent.Preferred silane coupling agent is γ-acryloxypropyl Trimethoxy silane.The silane with glycidoxy groups is used to cationoid polymerisation, and described cationic polymers adopts by the monomer of epoxy functional.The silane comprising vinyl ether reactive group is similarly applicable to the vinyl ether composition based on cationically curable.
Silane coupling agent can use, based on the total weight of composition with the amount of 0.5 to 3 % by weight (wt%).In preferred embodiments, silane coupling agent can use (wt%), based on the total weight of composition with the amount of 1.0 to 2.0 % by weight.
Composition can also comprise optional mercaptan synergistic agent.Mercaptan synergistic agent is mostly just used in radical-cured acrylate or methacrylate compositions.Mercaptan synergistic agent improves curing speed, but sometimes may reduce cross-linking density and undesirably increase specific refractory power.Therefore, when deployed, mercaptan synergistic agent uses with very little amount usually.Illustrative mercaptan synergistic agent is disclosed in US4,511, in 209, is incorporated to herein by its full content by introducing.The example of mercaptan synergistic agent is γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane, tetramethylolmethane four (3-mercaptopropionic acid ester) etc., or comprises the combination of at least one of above-mentioned mercaptan synergistic agent.Mercaptan synergistic agent preferably uses, based on the total weight of composition with the amount up to 3 % by weight and more preferably with 0.1 to 1 % by weight.
Composition can also comprise one or more of following additive: initiator, antioxidant, thermo-stabilizer, UV stablizer, surface modification additive, slip(ping)agent or comprise the combination of at least one of above-mentioned additive.Preferred additive is light trigger and antioxidant.
Can with 0.01 to 5 % by weight, the amount of 0.5 to 1.5 % by weight that is more preferably to use light trigger, based on the total weight of composition.Light trigger can be free radical type or cation type, and this depends on that whether monomer is acrylate or methacrylic ester (for free radical type) or epoxide or vinyl ether (for cation type).Exemplary light trigger is
1173.
In one embodiment, in a kind of method preparing composition, by fluorinated monofunctional monomer, fluoridize polyfunctional monomer, silane coupling agent, light trigger and optional mercaptan synergistic agent and be blended together to form composition.Composition can be prepared with partial or continuous method.
Composition simply can mix by mixing simple on such as magnetic agitation dish or with the spiral scraper of large volume such as on Stirring bar possibly.Heating may be needed also may not to need heating.If monomer is not at room temperature liquid, then need heating.Such as, the vinylformic acid 1H of the sample 13 in embodiment, 1H, 11H-perfluor undecyl ester is solid wax, and it is about 45 DEG C of fusings.
Then composition to be placed on optical fiber and to be cured or crosslinked.Usual use electromagnetic radiation is cross-linked.Electromagnetic radiation comprises ultraviolet (UV) radiation, microwave radiation, electron beam irradiation or its combination.Forms of radiation preferably for cross-linked composition is uv-radiation.
Before crosslinked, composition is less than 100 centipoises applying to have at temperature, is preferably less than the low viscosity of 20 centipoises.When not being subject to theoretical constraint, because of the characteristic (lower concentration of considerable Oil repellent, relatively low molecular weight and hydrogen bond group) of the component of selection, low viscosity is present in composition.These coating can with open (open up) spreader or in the US6 of Lindholm, and 958, the spreader described in 096 easily applies.Applying of the coating of other types can send use with such as spray transmission or aerosol.Before crosslinked, the composition of composition has relatively low volatility all at atmosheric pressure to realize processing stable when coated fiber.Their " flash-point " value is more than or equal to 70 DEG C, usually preferably greater than or equal to 100 DEG C.
After being placed in optical fiber, crosslinked can the utilization of composition has 0.1 to 15 joules per cm (J/cm
2) the UV radiation dose of energy density carries out.In preferred embodiments, crosslinked can the utilization of composition has 0.5 to 1.5 joules per cm (J/cm
2) the UV radiation dose of energy density carries out.Uv-radiation can be the combination of ultraviolet light,long wave, UV-B, ultraviolet-C radiation, or comprises the combination of at least one of above-mentioned uv-radiation form.
Be typically used as the coating on optical fiber through crosslinked composition and have the specific refractory power of the specific refractory power of the glass part being less than optical fiber, this makes it possible to use fiber direct light in fiber core.For the optical fiber based on silicon-dioxide, use the crosslinked composition with the specific refractory power less than the specific refractory power based on silica core to contribute to it and be used as at the optics coating layer based on silicon-dioxide in-core light conducting.The commercial polymer coating layer comparative relative to other, has specific refractory power and the outstanding balance of mechanical property (comprising hardness, Young's modulus and the adhesivity to glass) through crosslinked composition.
Cross-linked composition preferably has the specific refractory power lower than the specific refractory power of silicon-dioxide (such as, preferably under 850nm lower than about 1.45).In one embodiment, this cross-linked composition (such as, coating) has the specific refractory power lower than about 1.38 under 850nm.More preferably cross-linked composition has through type RI≤1.368+10.8/X specific refractory power relevant to wavelength (RI), and wherein X represents the wavelength of nanometer unit.Hereafter table 1 shows specific refractory power how as the change of function of wavelength.
Table 1
| Wavelength (nm) | The maximum RI of solidification coating |
| 400 | 1.395 |
| 589 | 1.386 |
| 633 | 1.385 |
| 790 | 1.383 |
| 850 | 1.381 |
| 1538 | 1.375 |
| 2100 | 1.373 |
Crosslinked composition is polymerization and is therefore viscoelastic, and this shows that this coating modulus depends on time and temperature.Elasticity modulus value is determined by the dynamic mechanical analysis (DMA) under the frequency of selected cyclic strain.In one embodiment, coating to illustrate the dynamic elastic modulus being greater than 200MPa under the frequency test of 1 Radian per second, is preferably greater than 350MPa at 23 DEG C, and more preferably within the scope of 400-1000MPa.Corresponding glass transition temperature, Tg, (under cyclic strain rate is 1rad/s by DMA tan δ peak temperature measure) higher than 30 DEG C, preferably higher than 40 DEG C.Shore D hardness, uses internal specimen technology of preparing to measure, should within the scope of 56-85, preferred 60-80.
The optical fiber with the coating composition of invention can being more than or equal to 75kpsi (kip is per square inch), preferably greater than or equal to 150kpsi, under carry out proof test and obtain low Break frequency or the formation of point defect.The optical fiber with 200 urn glass diameters can be stood by conventionally test the pulling force proof test that load is greater than 150kpsi, and the optical fiber with 400 microns can be stood load and be greater than the pulling force proof test of 100kpsi by conventionally test or use the wheel of bending radius 38.4mm radially bending under 100kpsi verifies load.The optical fiber with 400 microns and the glass diameter that is up to 2000 microns can be tested and bear and use the wheel of the bending radius selected according to glass diameter to verify radially bending under load being greater than 75kpsi.
The optical fiber of coating can carry out outer coating or buffering with the second layer.Mainly the coating of (of the present disclosure) is applied and with the monolayer immobilization of relative thin on optical fiber, then uses the second layer (such as, extruded thermoplastic or UV solidified coating) to carry out outer coating or buffering.Optical fiber is designed so that the second layer provides additional soundness (abrasion resistance; Optional, flame resistivity) and prepare in end type in termination or other fiber and be removed, and polymer covering layer is not removed.The thickness of polymer covering layer (main coating) is 2-30 micron, and 10-15 micron typically depends on diameter and the drawing condition of optical fiber base material.The second layer (such as, buffer layer) can comprise ethylene tetrafluoroethylene (ETFE) thermoplastics, although fiber design is not limited to use this material.The buffer layer substituted comprises extrudes nylon thermoplastic's plastics or UV-cured acrylate, UV-curing epoxides, the UV-of resistance to combustion solidified coating, heat or UV-curing silicone, multi-buffering-layer or analogue.The thickness of the second layer can be made to be suitable for glass diameter.Such as, the thickness being buffer layer on 230 micron polymer coating layers at diameter is about 135 microns.
In one embodiment, coating can be used as the auxiliary coating layer on the optical fiber of glass fluxing technique, in peak power restriction with under transmitting.This includes the wavelength that scope is 350-2200nm.
The optical fiber (have or do not have the second layer) of coating illustrates the tolerance to polymer covering layer layering, to bear through capstan winch in wire drawing, taking-up (take-up) and recoil and to draw wheel.When using the second layer (or buffer layer), fiber illustrates ability that machinery divests and uses traditional fibre to divest instrument and removes skin and do not scrape or the ability (being expressed as " the anti-wiping tolerance of nail ") of its lower polymer covering layer of tearing, and this ability is other the comparative commercially available optical fiber commercially available being better than applying by commercially available coating.
With the fiber exhibits of composition coating be
" crispatura and divide " technology that fiber is founded terminates the ability of optical fiber, makes polymer covering layer in place.By the ability of fiber exhibits epoxy/polishing method termination fiber of composition coating, make coating layer perfect, make optical fiber connector carry out polishing for end-use application simultaneously.
Compared with all the other local disclosed polymer covering layers and compared with other commercially available composition, solidified coating provides excellent heat and heat-oxidative stability and illustrates lower yellow trend.With based on urethane or based on polyethers coating layer compared with time especially like this.
When being used as polymer covering layer on optical fiber, compared with all the other local disclosed polymer covering layers and compared with other comparative commercially available composition, the coating of solidification provides the attenuation change tolerance under optical attenuator low especially in visible wavelength range and good environmental exposure.This is embodied by exemplary fiber under following environmental exposure type:
Thermal cycling is carried out-65 DEG C to+125 DEG C scopes
Humidity aged according to the heat of FOTP-72, be circulated to+85 DEG C under being included in 85% relative humidity, then thermal cycling is extremely lower than 0 DEG C (-10 DEG C)
Thermal ageing (24 hours) is carried out at 150 DEG C
Fiber bending under laser power
Soak in the hot water
In addition, coating provides excellent heat-oxidative scission tolerance, as in thermogravimetric test, (weight loss, relative to temperature and/or time, shows in atmosphere).
Composition and its purposes are in a fiber described in detail in the following non-limiting examples.
Embodiment
Embodiment 1
Carry out the present embodiment to show the composition comprising fluorinated monofunctional monomer (monoene) and fluoridize difunctional monomer.Obtain as in table 2 listed a series of fluoridize single-with two-(methyl) acrylate monomers.These comprise straight chain and cyclic aliphatic monoene.Selectable liquid property (specific refractory power, light absorptive, and viscosity) is measured at feasible 30 DEG C.F20 mono acrylic ester is at room temperature wax-like; Therefore, its liquid property is 50 DEG C of measurements.DDFODDA is at room temperature mainly liquid, but (former state) has the crystallising part producing some mist degrees, and therefore its light absorptive is measured at 30 and 50 DEG C; Mist degree minimizes at a higher temperature.PFHXEMA and PFHXEA, former state, shows the yellowing higher than other monomer.All abbreviations are introduced in detail in following table 2.
In order to characterize the factor that may affect final performance, often kind of monomer homopolymerization in the following manner: add 1wt.% light trigger (2-hydroxy-2-methyl-1-phenyl-propyl-1-ketone, Irgacure1173, BASF), then in nitrogen environment, be exposed to dosage 1J/cm
2uV radiation.By the liquid (there is between slide glass thin interval) between curing glass and quartz slide (top slide glass is quartz), then pry open slide glass after hardening, thus prepare film.The film of solidification keeps preferentially being attached on one of slide glass, then for measuring specific refractory power.The specific refractory power of film uses Metricon prism coupler to measure under three kinds of wavelength.By to little aluminium dish (such as by such as TA Instruments or Perkin Elmer sold for those of dsc) on drop carry out UV and solidify the sample coming to measure for the preparation of Shore D hardness.
All fluorinated monomers are refractive index value after scope shows the solidification of scope at 1.37-1.43 under the wavelength of 633-1538 nanometer, far below the specific refractory power of silica core (RI about 1.4585), as shown in table 3.All mono acrylic esters show the low mechanical integrity as homopolymer.Wherein, F20 acrylate (sample 1) is the most manageable, and create soft vaporific film, but not easily shift out from substrate when not breaking, its Shore D hardness is 42.Compared with the mono acrylic ester of short chain, DDFHPA (sample 2), only produces thick liquid, so there is no the specific refractory power after measuring solidification.Fluoridize cyclic aliphatic mono acrylic ester, PFCHMA (sample 4), create the film that can carry out the softness of RI measurement, but its Shore D hardness is not easily measured.Its methacrylic ester counterpart, PFCHMMA (sample 3), is not easy homopolymerization under original light trigger level and UV dosage, therefore various factors is improved five times to produce the film being used for RI test.OFHDDA and DDFODDA diacrylate, per molecule all has Liang Ge functional group, can give crosslinked; This generates high rigidity homopolymer (being respectively Shore D 88 and 94, sample 5 and 6), but gained film is crisp.
Then study monomer mixture (also see table 3), add 1.5wt% γ-acryloxypropyl Trimethoxy silane (APTMS) (a kind of silane couplent), as SIA0200.0 purchased from Gelest.Select APTMS be because: (i) it contain can easily with the reactive acroleic acid class group of other acrylic monomer copolymerization; (ii) it can not significantly improve the specific refractory power of formulation; (iii) it and other silane (such as, hydrosulphonyl silane) are compared and are produced relatively long storage time when being used for the coating thing based on acrylate.In the composition of test, the balance that some F20 mono acrylic esters with the combination of fluoridizing diacrylate create excellent hardness (69-72) and estimate NA value (0.47-0.49).
The sample 1-6 of table 3 shows comparative composition, and what they comprised the crosslinked fluorinated monofunctional monomer of 100wt% or the crosslinked of 100wt% fluoridizes difunctional monomer.
The sample 7-12 of table 3 all comprises fluorinated monofunctional monomer and fluoridizes the mixture of difunctional monomer.Sample 7 has low-refraction, and this specific refractory power estimates the numerical aperture NA that can produce about 0.47 on silica fiber.F20 fluorinated mono-acrylate is fluoridized diacrylate with OFHDDA and is combined with the ratio of 80:20 by sample 7, and adds light trigger and silane couplent further.At room temperature, said composition is half wax-like, and becomes clear liquid when being heated to above 40 DEG C.Crosslinked composition is limpid (that is, it is transparent, does not have mist degree).Table 3 shows the main character of crosslinked composition.
Crosslinked composition is than most of comparative commercial polymer coating layer, those hard (see table 3 and the Fig. 1) particularly with equal refracting power.The gained Shore D hardness (70) of sample 7 (composition of the present invention) with for more commercially available OFS Medium NA
coating layer on coating layer (the sample 1-A in table 4) is identical, but the specific refractory power of sample 7 significantly lower (that is, NA is higher).Based on the coating layer hardness measured, it is believed that corresponding fiber (having the crosslinked coating of sample 7, and if cushion with ETFE) is that machinery is strong, and provide gratifying crispaturaing and the termination that ftractures.
Do not measure the viscosity of liquid formulation.Such as, but based on the viscosity of each component, it estimates the scope falling into 5-8cP, makes it be suitable for coating, uses open cup coating applicator or U.S. Patent No. 6,958, the low pressure adverse current spreader of the type described in 096.
Comparative sample 1-A to 5-Q obtains from outside business supplier and from OFS inside.As can be seen from Table 3, when after the UV being subject to erg-ten/square centimeter dosage when the wavelength measurement of 600-1600 nanometer, the specific refractory power from about 1.36 to about 1.38 of the composition that the example of sample 7-12 is cross-linked changes.
Embodiment 2
Carry out the present embodiment to show the composition comprising fluorinated monofunctional monomer (monoene) and fluoridize difunctional monomer.
Sample 13 is similar to sample 7 (table 3) preparation, and wherein formulation has the ratio in table 5.
Table 5
| Composition | wt％ |
| F20 (fluoro acrylic ester) | 80 |
| OFHDDA | 20 |
| APTMS silane | 1 |
| Irgacure 1173 | 1 |
Film (being labeled as sample 13) is at 2J/cm
2lower UV solidification, its thermo-oxidative stability adopts thermogravimetric analysis to measure.Testing method is according to disclosed method (A.A.Stolov, D.A.Simoff, J.Li, Thermal Stability of specialtyoptical fiber, J.Lightwave Tech., 2008, Vol.26, pp 3443-3451).Fig. 1 (B) is such figure, which depict composition of the present invention (sample 13) and demonstrates and compare commercial polymer coating layer than other: the thermostability that 1-A and 1-B (from table 4) is high.Dynamic elastic modulus under room temperature is measured as 425MPa, between coating layer 1-A and 1-B, and is significantly higher than other business coating layer (see Fig. 2 and 3) in such index region.Fig. 2 is such figure (by carrying out the acquisition of dynamic mechanically spectrography), it compares the Young's modulus of commercial polymer coating layer 1-A and 1-B and composition of the present invention (sample 13), and Fig. 3 is such figure (by carrying out the acquisition of dynamic mechanically spectrography), it compares the Young's modulus of other commercial polymer coating layer (from table 4) and composition of the present invention (sample 13).
Embodiment 3
Carry out the present embodiment to show that coating (covering) has crosslinked comprising fluorinated monofunctional monomer (monoene) and fluoridize the composition of difunctional monomer and have the character comprising the fiber of the buffer layer of ETFE be arranged on this coating layer further of the present disclosure.
Fiber uses two kinds of formulation wire drawings of NA of the present invention about 0.47, is similar to those (samples 7 and 10 especially in table 3) of describing in detail in table 3.In order to compare, fiber also uses more commercially available coating layer wire drawing, is similar in table 4 the composition 1-A' with lower NA (about 0.44).Nominal fi diameter is 200/230/500 μm/μm/μm (being respectively glass/coating layer/ETFE buffer layer outside diameter), adopts Heraeus F300 pure silicon dioxide precast body.Amount to fiber length ranges at 1-2.2km.Optical attenuator low after all three kinds of fiber mass have wire drawing, under the wavelength of 850nm, scope is at 2.2-3.3 decibel/km (dB/km).Compared with the coating layer of lower NA, the coating layer of new higher NA produces (lower) decay (being respectively 3.7 and 4.1dB/km, contrast 6.0dB/km) slightly improved under 980nm.The crosslinked composition of these fibers and the details of buffer layer provide in following table 6.
Table 6
* comparative sample
100-rice (100-m) coil unclamped of often kind of fiber is subject to three kinds of different severe rugged environments and exposes.One group is exposed to and circulates according to the temperature/humidity of FOTP-72, monitors the decay (see Fig. 4) under visible wavelength 630nm simultaneously.Second group of thermal cycling from-65 DEG C to+125 DEG C, monitors (see Fig. 5) equally under 630nm.3rd group to be subject at 150 DEG C thermal ageing one day, and measures the Spectrum attenuation (see Fig. 6) before and after exposing.Fig. 4 is such figure, which show when loose 100-m coil is subject to the change of decling phase when measuring under temperature and humidity circulates in 630 nanometers for the time according to FOTP-72.Fig. 5 is such figure, to which show when the 100-m coil loose when measuring under 630 nanometers is subject to the thermal cycling of-65 to 125 DEG C decling phase for the change of time.Fig. 6 is showing the decay of loose 100-m coil thermal ageing one day front and back at 150 DEG C to the figure of wavelength.
Sample 16 shows excellent environmental stability (see table 6) at these test periods; This fiber adopts F20 fluorinated mono-acrylate and OFHDDA to fluoridize the polymer covering layer of the weight ratio 80:20 of diacrylate monomer, and wherein this weight ratio only fluoridizes the gross weight of diacrylate monomer based on F20 fluorinated mono-acrylate and OFHDDA.
As can be seen from Table 6, the fiber with described crosslinked composition shows maximum attenuation under 630nm when measuring according to FOTP-72 and adds 0.4-4.2 decibel/100 meter after temperature humidity circulation.As can also be seen from Table 6, this fiber shows maximum attenuation under 630nm and adds 0.6-3.4 decibel/100 meter after the thermal cycling of-65 DEG C to+125 DEG C.
Embodiment 4
Carry out another embodiment to show that coating (covering) has crosslinked comprising fluorinated monofunctional monomer (monoene) and fluoridize the composition of difunctional monomer and have the character comprising the fiber of the buffer layer of ETFE be arranged on this coating layer further of the present disclosure.
Following table 7 discloses the fiber adopting composition of the present disclosure to manufacture and the fiber adopting comparative composition to manufacture.Comparative composition is disclosed as the sample 1-A' of table 4, and the details of composition of the present disclosure is similar to the sample 11 of table 3.Nominal fi diameter is 200/230/500 μm/μm/μm (being respectively glass/coating layer/ETFE buffer layer outside diameter), adopts Heraeus F300 pure silicon dioxide precast body.Amount to fiber length ranges at 1-2.2 km (km).Optical attenuator low after two fiber mass all have wire drawing, scope is 3.1-3.3dB/km at a wavelength of 850 nm.Numerical aperture is measured under 633nm, is respectively 0.48 and 0.44 for new with prior art coating layer.Above-mentioned three kinds of environmental exposure are carried out to fiber, the results are summarized in following table 7.
Table 7
* comparative sample
Embodiment 5
Carry out the present embodiment to show flexural strength, high power laser light is irradiated to the core of fiber simultaneously.Utilize with three kinds of different polymer covering layers and there is pure silicon dioxide core and fluorine silicon silicate glass internal coating
glass preform wire drawing fiber.The nominal geometrical dimension (in micron) of glass core, glass fluxing technique layer, polymer covering layer and ETFE buffer layer is respectively 272/299/330/400.Calculate relative to silica core, the corresponding nominal NA value of polymer covering layer is 0.37,0.43 and 0.47.But the actual NA of fiber measures mainly through its glass fluxing technique layer in this case.Result is shown in table 8 and Fig. 7.
Table 8
Fiber is subject at 2 and bends, and before using, disclosed method transmits laser power simultaneously, and the method is described in detail in Xiaoguang Sun; Jie Li; Adam Hokansson; Study of optical fiber damage under tight bend with high optical power at 2140nm.Proc.SPIE 6433, Optical Fibers and Sensors for Medical Diagnostics and Treatment Applications VII, 643309, February 15,2007.The laser apparatus used in fiber test is Pulse Nd: YAG laser, from Lee Laser.The centre wavelength of laser is positioned at 1064nm, and pulse repetition rate is set in 6kHz.This measurement device fibre breakage diameter is delivering power simultaneously, and wherein parallel plank moves thus together with constant 2mm/s fixture speed curved fiber.Mean power is 83W, and peak power is 170kW.
Probability of failure is determined (see Fig. 7) as the function of bending radius.Fig. 7 is such figure, which show the figure lost efficacy as the function of bending radius.During less fracture, bending radius shows higher intensity.The coating layer of higher NA (comparatively low-refraction) of the present disclosure can bend to less compared with coating layer radius frequently, shows excellent intensity and bends the mechanical resistance of period to laser power.
Embodiment 6
The present embodiment compares the performance of the fiber during hot-water soak with coating layer of the present invention and more commercially available fibre property.The sample 20 with composition of the present disclosure uses the coating layer composition identical with sample 16 (see table 6) and manufactures to fill a prescription and manufactures.Relatively fiber sample 21 uses coating layer 1-A (see table 4) to manufacture.Their nominal geometrical dimension is 200/230/500 glass/coating layer/ETFE, and wherein size is in micron.They are all dipped in water, make temperature cycle to as high as 80 DEG C simultaneously, and monitoring decay under wavelength 850nm.Result is shown in Fig. 8.The decay of sample 20 still keeps very stable between exposure period, and the rising at test period of sample 21.Sample 20 shows the attenuation change lower than 0.05dB/ (15 meters) in this test.
Embodiment 7
The present embodiment compares the performance balance of fiber of the present invention and the performance balance by the fiber using a series of commercial polymer coating layer to manufacture.Those listing in detail from table 4 are selected some business coating layer and have the optical fiber of 200 urn glass diameters for wire drawing.In some cases, fiber uses the low OH glass spinning of Heraeus F300, and other fiber uses Heraeus Spectrasil F2000 height OH glass spinning.Business coating layer all has " height " viscosity being at room temperature greater than 1000 centipoises.When polymer covering layer is greater than about 50MPa at the Young's modulus of 23 DEG C, the wire drawing when there is single coating and do not assist buffer layer of some fiber.The urethane acrylate assistant coating that other fibers use UV-to solidify carries out wire drawing as outer buffer layer.These buffer layers are usually used in the representative type in communication fibres, and are called as UrAcr1 and UrAcr2 in table 9.The environmental exposure of three types is utilized to test fiber in the mode identical with the fiber sample of the present invention disclosed in embodiment 3 and 4.In the exposure of the first type, the loose fiberoptic coil of 100-m at 150 DEG C aging a day, and the attenuation measurement of aging front and back under wavelength 630nm, the inverting method adopting optical bench and know.The results are summarized in table 9, the decay of wherein unaged and aging fiber under 630nm is tabulated respectively.In the exposure of the second type, the loose fiberoptic coil of 100-m circulates according to the temperature and humidity of FOTP-72 at-10 DEG C to+85 DEG C and the highest being subject to for 85% time of rh value in temperature range, as shown in Figure 4.In the exposure of the third type, the loose fiberoptic coil of 100-m is subject to the thermal cycling of-65 DEG C to+125 DEG C under ambient moisture, as shown in Figure 5.For temperature-humidity circulation and thermal cycling, between exposure period, measure the transmittance under 630, and maximum for the decay of often kind of fiber change is tabulated in table 9.
Compared with often kind of business coating layer, coating layer of the present invention provides excellent performance balance.Coating layer of the present invention provides the transmittance lower than 15dB/kmat under 630nm for unaged fiber, and wherein sample 16,19 and 20 provides before ageing lower than 10dB/km.Coating layer of the present invention provide 150 DEG C after aging one day under 630nm lower than the transmittance of 45dB/km, wherein sample 16,19 and 20 provide aging after lower than the preferred value of 20dB/km.Even if commercially available coating layer 4-N and 2-E still provides high especially and extremely undesirable decay (be respectively 64.9 and 77.9dB/km) before ageing.Other business coating layer produces the undesirable high pad value being greater than 50dB/km under 630nm in aging one day afterwards at 150 DEG C; These comprise the coating layer 2-C when being coated with as single-layer coating, with coating layer 4-N, 1-B and the 2-D when being coated with together with the buffer layer of UV-curable.When being exposed to temperature-humidity circulation or thermal cycling, coating layer of the present disclosure creates to be increased lower than the decay of 4.5dB/ (100-m) under 630nm, and wherein sample 16 and 20 provides the particularly preferred increased value lower than 1dB/ (100-m).On the contrary, commercially available coating layer 3-G, 4-J, 4-N and 4-J are greater than 10dB/ (100-m) and up to about 48dB/ (100-m) in the decay increase that temperature-humidity cycle period shows, and show similar undesirable increase when thermal cycling.Coating layer 1-B shows the performance of change, sometimes produces the relatively good low decay that environmental exposure produces, but is producing height decay poor especially At All Other Times.
Be not wishing to be bound by theory, the decay increase of various fiber when standing these three kinds dissimilar environmental exposure it is believed that it is due to one or more mechanism, such as produce the chemical degradation of yellow, being separated of uncrosslinked composition causes scattering of light, due to the microbend that the buffer layer shrinkage above more soft polymer covering layer causes, because of water suction by the swelling microbend that causes and optical absorption, or the specific refractory power caused to glass/coating interface migration by coating due to the uncrosslinked composition of movement or the moisture of absorption is increased.In addition, data show, poor performance in most cases to there is the coating layer of relatively low Young's modulus and/or not relevant containing the coating layer of silane adhesion promoter.When business coating layer 5-P and 5-Q, for unaged fiber and during three kinds of environmental exposure with all recorded relative good transmittance afterwards.But coating layer 5-P with 5-Q shows the nail of going on business and to swipe tolerance compared with disclosed coating layer of the present invention.Finally, coating layer 3-F, 3-G, 3-H and 3-I are not satisfied, because they have employed the component be restricted due to the similarity with PFOA.
Embodiment shows transmittance that coating layer of the present invention provides after aging one day at 150 DEG C lower than 45dB/km under 630nm, preferably under 630nm lower than 35dB/km, preferably under 630nm lower than 35dB/km, and preferably under 630nm lower than 20dB/km.
As can be seen from previous embodiment, crosslinked composition creates the fiber with peculiar property combination.Described fiber shows numerical aperture and is greater than 0.46, is preferably greater than 0.47, more preferably greater than 0.475.It is the highest by 0.50 that described fiber shows numerical aperture when being arranged on silicon-dioxide optical fiber.Described fiber also shows resistance to sharp turn (tight bending) ability excellent under high laser power.
When wavelength 630 nano measurement, described fiber also shows (under the state of the complete former state of their wire drawings, when curling with the tension force of 100-gm) decay of 5.5-12 decibel/km, and when when wavelength 630 nano measurement, as a child showed the decay of 17-45 decibel/km in the temperature 24 being exposed to 150 DEG C.
It should be noted that the scope of all detailed description herein all comprises endpoint value.Numerical value from different range can combine.
Connect term " comprise " cover connect term " by ... composition " and " substantially by ... form ".
Term "and/or" comprises " with " and "or".Such as, " A and/or B " is interpreted as A, B, or A and B.
Term (methyl) acrylate comprises methacrylic ester and acrylate.
Although with reference to some embodiments describing the present invention, it is understood to one skilled in the art that, can various change be made to the present invention and to the present invention's replacement equivalent elements wherein, but can not deviate from scope of the present invention.In addition, much remodeling can be made to adapt to specific situation or material to instruction of the present invention, also can not deviate from base region of the present invention.Therefore, the present invention is not intended to be defined in disclosed as the particular implementation for implementing optimal mode of the present invention, and the present invention will comprise all embodiments fallen within the scope of claims.
Claims (10)
1. a composition, it comprises
The fluorinated monofunctional monomer of 65-95wt%;
5-35wt% fluoridizes polyfunctional monomer; With
The silane coupling agent of 0.5-3wt%; Wherein all wt per-cent is all based on composition total weight meter; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when having 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF
2or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting formula RI≤1.368+10.8/X restriction, wherein X represents the wavelength in nanometer.
2. the composition of claim 1, wherein fluorinated monofunctional monomer is linear fluorinated monofunctional monomer, and it is represented by chemical formula (2A)
R
1-(CF
2)
n-(CH
2)
mR
2(2A)，
Wherein R
1be non-reactive end groups, it comprises CH when n is more than or equal to 6
2f or CHF
2but do not comprise CF
3, and when n is less than 6 R
1comprise CH
2f, CHF
2or CF
3; Wherein R
2be monofunctional reactant group, it comprises olefinic unsaturated functional group, acrylate-functional groups, methacrylate functional or vinyl ether functional group; Wherein n is 1-15 and wherein m is 1-10.
3. the composition of claim 1, wherein fluorinated monofunctional monomer is 1, 1-dihydro perfluorocyclohexane Trivalin SF acrylate, 1, 1-dihydro perfluorocyclohexane Trivalin SF methacrylic ester, 1, 1-dihydro Decafluorocyclopentane Trivalin SF acrylate, 1, 1-dihydro Decafluorocyclopentane Trivalin SF methacrylic ester, vinylformic acid 1H, 1H, 5H-octafluoro amyl group ester, vinylformic acid 1H, 1H, 11H-perfluor undecyl ester, methacrylic acid 1H, 1H, 9H-ten hexafluoro nonyl ester, 1H, 1H, 7H-ten difluoro heptyl methacrylates, vinylformic acid 2-(perfluoro hexyl) ethyl ester, methacrylic acid 2-(perfluoro hexyl) ethyl ester, 2-propionic acid 3, 3, 4, 4, 5, 6, 6, 6-octafluoro-5-(trifluoromethyl) polyhexamethylene, vinylformic acid 1H, 1H-perfluor (2-methyl-3-oxa-octyl group) ester, vinylformic acid 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluoro decyl ester, or comprise the combination of at least one of above-mentioned fluoro monofunctional monomers.
4. the composition of claim 1, wherein fluorinated monofunctional monomer is cyclic fluorinated monofunctional monomer, and it is represented by chemical formula (2B) or (2C):
In its Chinese style (2B) and (2C), R
2comprise monofunctional reactant group, it comprises olefinic unsaturated functional group, acrylate-functional groups, methacrylate functional or vinyl ether functional group, and wherein n is 1-15, and wherein m is 1-10, and wherein x is 0-2.
5. the composition of claim 1, wherein fluorinated monofunctional monomer is side chain monofunctional monomer, and it has formula (4):
Wherein R
1and R
3be non-reactive end groups, it is n and o's and comprise CH when being equal to or greater than 6
2f or CHF
2but do not comprise CF
3, and wherein R n and o's and when being less than 6
2comprise CH
2f, CHF
2or CF
3; Wherein R
2be monofunctional reactant group, it comprises olefinic unsaturated functional group, acrylate-functional groups, methacrylate functional or vinyl ether functional group; Wherein n and o is 1-15, and wherein p is 1-6 and wherein m is 1-10.
6. the composition of claim 1, wherein fluoridize polyfunctional monomer and there is the structure shown by formula (5)-(8):
R
2(CF
2)
nR
2(5)
R
2-(CH
2)
m-(CF
2)
n-(CH
2)
m-R
2(6)
Wherein R
2be reactive group, it comprises olefinic unsaturated functional group, acrylate-functional groups, methacrylate functional or vinyl ether functional group, and wherein n is 1-15, m is 1-10, and p and o is 1-10 independently of one another.
7. the composition of claim 1, wherein polyfunctional monomer is 2,2,3,3,4,4,5,5-octafluoro 1,6 hexanediol diacrylate, 2,2,3,3,4,4,5,5,6,6,7,7-ten difluoro 1,8-ethohexadiol diacrylates, or its combination.
8. a method, it comprises:
By the fluorinated monofunctional monomer of 65-95wt%; 5-35wt% fluoridizes polyfunctional monomer; The silane coupling agent of 0.5-3wt% is blended together to form composition; Wherein all wt per-cent is all based on composition total weight meter; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when having 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF
2or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting formula RI≤1.368+10.8/X restriction, wherein X represents the wavelength in nanometer;
Described composition is placed on optical fiber; With
Make described composition through raying to form coating layer.
9. goods, it comprises:
Optical fiber;
Coating layer, it comprises the reaction product of such composition, and described reaction product comprises:
The fluorinated monofunctional monomer of 65-95wt%;
5-35wt% fluoridizes polyfunctional monomer; With
The silane coupling agent of 0.5-3wt%; Wherein all wt per-cent is all based on composition total weight; Wherein fluorinated monofunctional monomer and fluoridize polyfunctional monomer when having 6 or more fluorine-containing carbon repeating units not containing the fluorine-containing carbon part of any trifunctional; Wherein fluorine-containing carbon repeating unit is CF2 or CF part; And wherein have the Shore D hardness of 56-85 through crosslinked composition and have the specific refractory power (RI) meeting equation RI≤1.368+10.8/X and limit, wherein X represents the wavelength in nanometer; Wherein coating layer contact optical fiber; With
Be placed in the buffer layer on coating layer.
10. the goods of claim 9, wherein said goods demonstrate the numerical aperture being greater than 0.45, under the tension force of 100-gm as demonstrated the decay of 5.5-12 decibel/km when measuring under the wavelength of 630 nanometers under tractive condition and demonstrating the decay of 17-45 decibel/km when the temperature being exposed to 150 DEG C is measured after 24 hours under the wavelength of 630 nanometers.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| US61/891,556 | 2013-10-16 | ||
| US14/515,118 US10035915B2 (en) | 2013-10-16 | 2014-10-15 | Low refractive index coating for optical fibers, methods of manufacture thereof and articles comprising the same |
| US14/515,118 | 2014-10-15 |
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| CN112759961A (en) * | 2021-02-09 | 2021-05-07 | 上海先权光纤科技有限公司 | Low-refractive-index optical fiber coating and preparation method thereof |
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| US5239026A (en) * | 1991-08-26 | 1993-08-24 | Minnesota Mining And Manufacturing Company | Low loss high numerical aperture cladded optical fibers |
| JPH07218734A (en) * | 1994-01-28 | 1995-08-18 | Sumitomo Electric Ind Ltd | Resin composition and plastic clad optical fiber formed by using the same |
| JPH09281346A (en) * | 1996-04-16 | 1997-10-31 | Sumitomo Electric Ind Ltd | Plastic clad optical fiber |
| CN101466744A (en) * | 2006-06-12 | 2009-06-24 | 旭硝子株式会社 | Curable composition and fluorine-containing cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5822489A (en) * | 1996-12-31 | 1998-10-13 | Lucent Technologies, Inc. | Low refractive index photo-curable composition for waveguide applications |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5239026A (en) * | 1991-08-26 | 1993-08-24 | Minnesota Mining And Manufacturing Company | Low loss high numerical aperture cladded optical fibers |
| JPH07218734A (en) * | 1994-01-28 | 1995-08-18 | Sumitomo Electric Ind Ltd | Resin composition and plastic clad optical fiber formed by using the same |
| JPH09281346A (en) * | 1996-04-16 | 1997-10-31 | Sumitomo Electric Ind Ltd | Plastic clad optical fiber |
| CN101466744A (en) * | 2006-06-12 | 2009-06-24 | 旭硝子株式会社 | Curable composition and fluorine-containing cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759961A (en) * | 2021-02-09 | 2021-05-07 | 上海先权光纤科技有限公司 | Low-refractive-index optical fiber coating and preparation method thereof |
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| JP6382676B2 (en) | 2018-08-29 |
| JP2015078369A (en) | 2015-04-23 |
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