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WO1998005721A1 - Revetement de fibres optiques a base de polyester - Google Patents

Revetement de fibres optiques a base de polyester Download PDF

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Publication number
WO1998005721A1
WO1998005721A1 PCT/US1997/011058 US9711058W WO9805721A1 WO 1998005721 A1 WO1998005721 A1 WO 1998005721A1 US 9711058 W US9711058 W US 9711058W WO 9805721 A1 WO9805721 A1 WO 9805721A1
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WO
WIPO (PCT)
Prior art keywords
group
vinyl ether
hbve
hydrogen
integer
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PCT/US1997/011058
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English (en)
Inventor
James Ronald Snyder
George David Green
Alvin Charles Levy
Raymond John Swedo
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Alliedsignal Inc.
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Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to AU36425/97A priority Critical patent/AU3642597A/en
Publication of WO1998005721A1 publication Critical patent/WO1998005721A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/141—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/106—Single coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates generally to the field of optical fibers and, more particularly, to the coatings applied to such fibers and the coated fibers
  • Optical fibers have become commonplace in recent years because of their ability to handle large volumes of data transmitted over long distances However, this is only possible because optical fibers have been developed which have extremely low transmission losses. These optical fibers are operated with light having wavelengths in the narrow regime between 0 6 and 1.6 microns to obtain the maximum transmission of light Losses have been attributed to scattering of light, absorption, and imperfections called "microbending", which refers to scattering of light caused by small deformations of the fiber axis. Such microbending has been attributed to coating defects, thermal contraction and external stresses. It has been found desirable to coat glass fibers in order to protect them and to give strength to the fibers and to alleviate the losses assigned to microbending.
  • the inner layer should have a low modulus down to -40°C, be thermally and hydrolytically stable, have good adhesion to glass and not evolve hydrogen (which can react with the fiber and reduce light transmission)
  • the outer layer of a two layer system serves to protect the fiber and the inner coating and thus must meet different requirements
  • the outer layer should be tough and abrasion resistant, be thermally and hydrolytically stable and not evolve hydrogen
  • the most commonly used coatings have been derived from acrylates, although silicones or rubber compounds have been employed
  • the most widely used acrylates are those which are capable of ultra-violet radiation curing at high speed since the coatings are normally applied immediately after the glass fiber has been drawn from the molten state and cooled to an appropriate temperature Typical of such acrylates are multifunctional acrylate terminated monomers and oligomers
  • the outer coating are most often urethane-acrylate or epoxy-acrylate copolymers which also can be cured bv ultra-violet radiation
  • the acrylates have inherent disadvantages since they are considered to present health hazards and also tend to be brittle and to absorb moisture.
  • Fiber optic coatings may be prepared from compositions which employ vinyl ether polyester oligomers, along with mono or multifunctional vinyl ether terminated monomers, which may be derived from esters or alcohols
  • the coating compositions include an effective amount of a photoinitiator to cause the vinyl ethers to react and produce the desired coatings
  • a moiety may be di, tri or tetra valent, they are defined as, for example, alkyl. aryl. etc which is to be understood as not implying a monovalent group, but a polyfunctional group having the general chemical nature indicated
  • the vinyl ether polyester oligomers are obtained by reacting (i) a polybasic ester having the formula
  • R7 is chosen from the group consisting of phenyl and an alkyl group containing from 1 to 6 carbons
  • X a , X , Y a , and Y5 are radicals having a molecular weight of from 25 to about 500, each X a , each X ⁇ , each Y a , and Y ⁇ being independently selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl radicals
  • z is an integer from 0 to 100
  • m is an integer from 0 to 100
  • w is 1 or 2 with the proviso that m and z may not both be zero
  • X a , X , Y a , and Y5 are radicals having a molecular weight of from 25 to about 500, each X a , each X ⁇ , each Y a , and Y ⁇ being independently selected from the group consisting of alkyl, aryl, aralkyl and
  • K ⁇ and R2 are monovalent radicals selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms.
  • K ⁇ is an alkyl group having 1 to 4 carbon atoms and R2 is hydrogen or Ri is hydrogen and R2 is an alkyl group having 1 to 4 carbon atoms.
  • Ri is hydrogen and R2 is an alkyl group having 1 to 4 carbon atoms.
  • both K ⁇ and R2 are hydrogen.
  • X a is a divalent radical having a molecular weight in the range of from 25 to about 500 and is independently selected from the group consisting of alkylene, cycloalkylene, and alkylene ether radicals;
  • X a and X5 are radicals having a molecular weight of from 25 to about 500, and each X a and X is independently selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl radicals, m is an integer from 0 to 100, preferably 1 to 10, and n is an integer from 0 to 100, preferably 1 to 10, it being understood that m and n may not both be zero
  • the vinyl ether polyester oligomers may be combined with one or more vinyl ether terminated ester monomers having the formula
  • w is an integer from 1 to 4 indicating the number of substituents of Y'
  • Y' is a mono-, di-, tri-. or tetrafunctional radical having a molecular weight of 15 to 500 and is independently selected from the group consisting of alkylene, arylene, aralkylene, and cycloaikylene radicals
  • X a is a divalent radical having a molecular weight of 25 to 500.
  • each X a being independently selected from t e group consisting of alkylene or cvcloalkylene radicals
  • R3 and R4 are monovalent radicals which are independently selected from the group consisting of hydrogen and alkyl groups having 1 -10 carbon atoms
  • the formulation optionally may also comprise one or more vinyl ether terminated monomers derived from an alcohol having the formula
  • w is an integer from 1 to 4 indicating the number of substituents of D, R5 and R ⁇ are monovalent radicals which are independently selected from the group consisting of hydrogen and alkyl groups having 1-10 carbon atoms, preferably independently selected from the group consisting of hydrogen and methyl, and D is a mono-, di-. tn-. or tetravalent radical consisting of alkyl. cycloalkyl, or alkyl ethers having a molecular weight of 26 to 1000
  • Both the primary and secondary coatings formulations typically will include additives such as thermal oxidation stabilizers, hydrogen stabilizers, light screens, color stabilizers, blocking agents, and coupling agents.
  • Primary optical fiber coatings generally will include oligomers having Tg equal to or less than -10°C while the oligomers used in secondary optical fiber coatings have a Tg greater than -10°C.
  • the coating formulations will have a viscosity of about 100 to 10,000 cps (mPa » s) at their application temperature
  • the primary coating will have a Tg at or below O°C, a modulus of about 80-800 psi (551-5510 kPa) at room temperature and an elongation greater than 50%
  • the cure secondary coating will have a Tg greater than 50°C. a modulus of at least 50.000 psi (344.735 kPa) at room temperature and an elongation greater than 5%
  • optical fiber coatings described in U.S. Pat. No. 5,139,872 have advantages over coatings derived from acrylates, particularly in cure speed, physical properties at low temperatures (i.e below 0°C), moisture resistance, and toxicity.
  • polyester-based vinyl ether oligomers rather than the vinyl ether oligomers based on urethanes of the '872 patent, we obtain further improved performance
  • polyester-based formulations cure more rapidly with a lower radiation dose required.
  • the polyester-based coatings can be cured at above ambient temperatures
  • glass fibers are drawn from heat- softened glass rod at a high speed in an elevated "draw tower" This means that the glass must be cooled rapidly from about 1800°F (982°C) so that the coatings can be applied and cured and the cooling is a critical factor in the design and operation of the draw towers
  • the speed of drawing glass fibers is increased in a given tower, it is evident that the temperature of the fibers rises Consequently, it is an important advantage if a coating formulation can be cured at higher temperatures with a lower radiation dose
  • Acrylate formulations require curing temperatures of about 50°C, while the vinyl ether oligomers may be cured at fiber temperatures of up to about 150°C
  • the polyester-based vinyl ether formulations are clearly superior
  • polyester-based formulations cure more rapidly, the amount of photoinitiator used can be reduced, which as will be shown, has advantages in improved thermal stability, color, and, particularly, in reduced hydrogen generation, which is a major concern in optical fiber coatings. Finally, the polyester-based coatings of the invention are superior in having lower water absorption and extractables.
  • the formulations comprise (a) vinyl ether polyester oligomers, plus either or both of (b) vinyl ether terminated ester monomers and (c) vinyl ether terminated monomers derived from an alcohol
  • oligomers are prepared by reacting (i) a polybasic ester (ii) a hydroxy monovinyl ether and (iii) a polyol
  • polybasic esters useful in the invention may be described by the formula
  • R7 is chosen from the group consisting of phenyl and an alkyl group containing from 1 to 6 carbons
  • X a , X5, Y a , and Yfc are radicals having a molecular weight of from 25 to about 500, each X a , each X5, each Y a , and Yf, being independently selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl radicals
  • j is an integer from 0 to 2
  • z is an integer from 0 to 100
  • m is an integer from 0 to 100, preferably 1 to 10
  • w is 1 or 2 with the proviso that m and z may not both be zero
  • Preferred structures for X a and X5 are independently selected from the group consisting of
  • q is an integer from 0 to 40
  • n is an integer from 2 to 20
  • E is chosen from the group consisting of bond, O, CH2, S, SO2, >C(CH3)2, and >C(CF3)2
  • Preferred structures for Y a and Y5 are those independently selected from the group consisting of.
  • n' is an integer between 0 and 20
  • E is chosen from the group consisting of bond, O, CH2, S. SO 2 , >C(CH3)2, and >C(CF3)2
  • R y is chosen from the group consisting of alkyl containing from 1 to 6 carbon atoms, and NO2
  • the vinyl ether terminated alcohols which are used in preparing the oligome ⁇ c esters of this invention have a structure corresponding to the adduct of an al yne and a diol.
  • these vinyl ether terminated alcohols also can be made in other ways, and the method of producing them is not pan of this invention
  • the structure is illustrated by the formula
  • Ri and 2 are monovalent radicals selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms
  • K ⁇ is an alkyl group having 1 to 4 carbon atoms and R2 is hydrogen or K ⁇ is hydrogen and R2 is an alkyl group having 1 to 4 carbon atoms.
  • both R] and R2 are hydrogen.
  • X a is a divalent radical having a molecular weight in the range of from 25 to about 500 and is independently selected from the group consisting of alkylene, cycloaikylene, and alkylene ether radicals. Preferred structures for X a are the same as those listed for the polyester (i) above.
  • the polyols which may be used in the process of the invention include diols described above and higher polyols. They may be generally described by the formula
  • X a and X are radicals having a molecular weight of from 25 to about 500, and each X a and X is independently selected from the group consisting of alkyl, aryi, aralkyl and cycloalkyl radicals, m is an integer from 0 to 100. preferably 0 to 10 and n is an integer from 0 to 100, preferably 1 to 10, it being understood that m and n may not both be zero Preferred structures for X a and Xb are the same as those listed for the polyester (i) above
  • the catalysts useful in preparing vinyl ether terminated polyester oligomers generally are transesterification catalysts.
  • Examples of such catalysts include dibutyl tin diacetate, dibutyl tin dilaurate, titanium tetra isopropoxide. lead oxide, antimony oxide, manganese diacetate.
  • cobalt diacetate hydrate, nickel diacetate hydrate, and lithium metal and mixtures thereof The amount required will vary but generally will be about 0 005 to 0 5 t % based on oligomer product weight Since the catalysts used for prepa ⁇ ng the oligomers remain in the products, they are present dunng cunng of the optical fiber coatings and may affect such curing although they are not the cationic initiators, which are discussed below Accordingly, the catalysts should be selected taking such effects into account
  • the process may be desc ⁇ bed as a sequential one in which the molecular weight of the oligomers produced is adjusted by varying the initial ratio of the ester to the polyol and in which by-products are continually vaponzed and removed
  • the reaction conditions are adjusted so that neither the ester nor the polyol are removed
  • the process involves contacting of a vinyl ether-terminated polyester with a polyol, or alternatively, the reaction of a polyester with a hydroxy monovinyl ether to form the vinyl ether terminated polyester, followed by reaction with a polyol
  • a vinyl ether is produced by the chain extension reaction and separated immediately from the reacting mixture
  • An example employing a dibasic ester is as follows
  • the reaction may be carried out in the liquid phase at temperatures in the range of about 50° to 250°C and at a vacuum selected to permit efficient removal of the hydroxy monovinyl ether by-product, typically about 0.01 to 200 torr (0.0013 to 26.7 IPa.abs). In general, the reaction will require about 1 to 20 hours to complete, depending upon the temperature, concentrations, catalyst 5 and other factors familiar to those skilled in the art.
  • the polybasic ester is chain extended with the polyol, followed by addition of a hydroxy monovinyl ether to cap the chain extended ester. This may be illustrated as follows:
  • the first step, chain extension, will be carried out in the liquid phase at temperatures of about 50° to 250°C and a vacuum selected to effectively remove alcohol (XOH).
  • XOH alcohol
  • the reaction requires about 0 5 to 10 hours to complete, depending on the temperature, concentrations, catalyst, and other factors familiar to those skilled in the art
  • the alcohol formed as a by-product is continuously removed dunng the reaction
  • the second step, end capping, will take place at temperatures of about 50° to 180°C and a vacuum selected to efficiently remove alcohol, generally about 0 01 to 500 torr (0 0013 to 66 7 kPa abs )
  • a vacuum selected to efficiently remove alcohol generally about 0 01 to 500 torr (0 0013 to 66 7 kPa abs )
  • the reaction requires about 0 5 to 10 hours to complete, depending on various factors as suggested above Again, alcohol is removed as formed
  • the objective of either reaction scheme is to provide a series of vinyl ether capped ester oligomers varying in molecular weight, viscosity, and reactivity
  • the molecular weight is generally controlled by the ratio of the ester to the polyol As the mol ratio approaches 1 0/1 0 the molecular weight becomes undesirably high and consequently mol ratios of about 1 5/1 are preferred, however, only exactly equal amounts of the reactants are excluded and ratios between 1 5/1 and 1 0/1 0 may be used As the mol ratio is raised still higher the product approaches a single molecule of the ester end capped with a vinyl ether (i e no polyol is present) Such materials are useful, but generally require the presence of higher molecular weight oligomers for most practical applications Alternatively, increasing the polyol so that it is in excess of the ester, i e less than 1 0/1 0, will produce an oligomer terminated with hydroxyl groups, which must be terminated with a vinyl ether terminated
  • the vinyl ether polyester oligomers may be combined with a vinvl ether terminated ester monomer havine the formula
  • w is an integer from 1 to 4 indicating the number of substituents of Y ⁇ Y' is a mono-, di-, tri-, or tetrafunctional radical having a molecular weight of 15 to 500 and is independently selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl radicals
  • X a is a divalent radical having a molecular weight of 25 to 500, each X a being independently selected from the group consisting of alkylene or cycloaikylene radicals
  • R3 and R4 are monovalent radicals which are independently selected from the group consisting of hydrogen and alkyl groups having 1-10 carbon atoms
  • compositions include those where X a is the same as given above for polyesters of (a)(i).
  • R3 and R4 are both hydrogen, and Y' is independently chosen from the group consisting of
  • n is an integer .. om 0 to 10
  • n' is an integer from 2 to 10
  • E is chosen from the group consisting of bond, O, CH2, S, SO2, C(CH3)2, and >C(CF 3 )2
  • Ry is chosen from the group consisting of alkyl containing from 1 to 6 carbon atoms, alkoxy containing 1 - 6 carbon atoms, and NO2
  • the formulation optionally may comprise a vinyl ether terminated monomer derived from an alcohol having the formula
  • R5 and R ⁇ are monovalent radicals which are independently selected from the group consisting of hydrogen and alkyl groups having 1-10 carbon atoms preferably independently selected from the group consisting of hydrogen and methyl, and D is a mono-, di-, t ⁇ -, or tetravalent radical consisting of alkyl. cycloalkyl, or alkyl ethers having a molecular weight of 26 to 1000
  • compositions include those where R5 and Rg are both hydrogen and D is ,
  • optical coatings are usually applied in two layers, the inner having much different physical properties than the outer
  • the inner or primary coating is softer and more elastic than the outer or secondary coating, which is intended to provide a tough barrier able to protect the inner coating and the glass fiber beneath it
  • the formulations used by the present inventors are selected from the same families of vinyl ether compounds, as will be seen quite different properties can be obtained It is an advantage to the formulator that both layers are chemically related
  • the coatings provide an important function in protecting optical fibers as has been discussed earlier In order to avoid damage to the fiber it is coated as soon as possible after it is drawn In effect, this means that the coating formulations must be able to be applied readily and that after curing certain physical properties must be satisfied
  • the coating formulations will include vinyl ether ester oligomers and one or both of the vinyl ether monomers derived from esters or alcohols as previously described.
  • the oligomers should have a Tg which is suitable for the properties of the inner or outer layers. If used for the inner resilient layer, the Tg of the oligomers should be equal to or less than -10°C, while for the outer rigid layer, the Tg of the oligomers should be greater than -10°C
  • the liquid formulation should have a viscosity at the application temperature (about 20° to 100°C) of about 100 to 10,000 cps (mPa»s) for both the primary or inner layer and the secondary or outer layer
  • the coating should not be so fluid as to flow significantly before curing or so viscous as to be difficult to coat the fiber surface
  • the cured coatings require certain physical properties consistent with their function.
  • the glass transition temperature (Tg) should be at or below 0°C and have a modulus of 80-800 psi (551-55 10 kPa) at room temperature with an elongation greater than 50%
  • the secondary layer should have a cured Tg greater than 50°C. a cured modulus of at least 50,000 psi (344 7 MPa) at room temperature and an elongation greater than 5%
  • the primary coating is to remain easily deformed under stress even at low ambient temperatures so that it can minimize the transfer of external forces to the glass fiber and thus limit the effect of "microbending" discussed earlier
  • the outer layer is seen to be much more ⁇ gid and provides protection to the inner layer and the glass fiber
  • the primary and secondary coating formulations will meet the requirements described above Within the limits set by the properties needed for applying the coatings and the cured properties, the proportions of the oligomers and monomers can be varied widely, depending upon the properties of the oligomers Thus, it is possible for the oligomers to make up only a minor fraction of the coating formulation, but up to nearly all may be oligomer In addition to the oligomers, one or both of the types of vinyl ether monomers may be used in formulating the p ⁇ mary and secondary coatings
  • a cationic photoinitiator is used to cause the vinyl ethers to react and produce the desired polymer
  • the recognized classes of cationic photoinitiators include various compounds which respond to irradiation by producing acid species capable of catalyzing cationic polymerization See Crivello, Advances in Polymer Science.
  • Onium salts of Group V, VI, and VII elements are stated to be the most efficient and versatile of the cationic photoinitiators They generate strong Lewis acids which can promote cationic polymenzation Curing of the vinyl ether compositions of the invention is not limited to a particular class of such photoinitiators, although certain types are preferred, including oruum salts based on halogens and sulfur More specifically, the onium salt photoinitiators described in Crivello's U S Pat No 4,058,400 and in particular iodonium and sulfomum salts of BF4-, PF6-, SbF ⁇ -, and SO3CF3- Preferred photoinitiators are t ⁇ arylsulfonium salts, and diaryliodomum salts Preferred anions are hexafluorophosphate and hexafluoroantimonate They are usually required in amounts from about 0 1 to 5 wt % in the blended formula of vinyl ether
  • X is SbFg- or PF6-
  • initiators include UVI-6974 (an SbF ⁇ - salt) and UVI- 6990 (a PF6- salt) supplied by Union Carbide
  • UVI-6974 an SbF ⁇ - salt
  • UVI- 6990 a PF6- salt supplied by Union Carbide
  • Other cationic photoinitiators are defined by the formulas
  • the formulations may also contain dyes, stabilizers, fillers, pigments, and antioxidants such as hindered phenols, wetting agents such as fluorosurfactants e g. FC-430 from 3-M, photosensitizers such as benzophenone, thioxanthone, perylene and other components familiar to those skilled in the art.
  • the formulations may also contain various stabilizers may be included as discussed in more detail below They include thermal oxidation stabilizers, hydrogen stabilizers, light screens, color stabilizers, blocking stabilizers (slip agents), and coupling agents (adhesion promoters)
  • Thermal Oxidation Stabilizer The thermal oxidation stabilizer is present in the coating in an amount up to about 5 wt %. preferably in the range of from about 0 25 wt % to about 3 0 wt %
  • hindered phenolic antioxidants such as octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)- propionate (Irganox 1076), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy- hydrocinnamate)]methane (Irganox 1010), and benzene propanoic acid, 3,5- bis( l, l-dimethylethyl)-4-hydroxy-,thiodi-2,l-ethanediyl ester (Irganox 1035)
  • stabilizers which are not hindered phenolic antioxidants are N.N'- (2-naphthyl
  • the hydrogen stabilizer may comprise one or more components chosen from the group consisting of hindered phenolic antioxidants, nitrogen-based stabilizers, aliphatic sulfides, aliphatic disulfides. aliphatic polysulfides, aromatic sulfides, aromatic disulfides, aromatic poly-
  • hindered phenolic antioxidants are Irganox 1076, 1010, and 1035 (see list of hindered phenolic antioxidants under (d) above for chemical formulas).
  • nitrogen-based stabilizers are phenothiazine, carbazole, and urethane protected hindered amine light stabilizers (HALS)
  • HALS hindered amine light stabilizers
  • R-S-R aliphatic sulfides
  • dodecyl sulfide octyl sulfide. octadecyl sulfide, sec-octyl sulfide. t-butyi sulfide, dilauryl thiopropionate (Irganox PS800).
  • aliphatic disulfides examples include dodecyl disulfide. octyl disulfide, octadecyl disulf ⁇ de, sec-octyl disulfide, and t-butyl disulfide
  • aliphatic polysulfides are di-octyl polysulfide, di-t- dodecyl polysulfide, and di-t-nonyl polysulfide.
  • aromatic sulfides are phenyl sulfide, benzyl sulfide, tolyl sulfide, and 6-hydroxynaphthyl sulfide.
  • aromatic disulfides are phenyl disulfide, benzyl disulfide, tolyl disulfide, 6-hydroxynaphthyl disulfide, and a mixture of amylphenol disulfide polymers (Vultac 3, marketed by Atochem).
  • aromatic polysulfides are benzyl trisulfide and phenyl trisulfide.
  • Examples of mixed aliphatic/aromatic sulfides are phenyl octyl sulfide, naphthyl octyl sulfide, and tolyl ethyl sulfide.
  • Examples of mixed aliphatic/aromatic disulfides are phenyl octyl disulfide, naphthyl octyl disulfide, and tolyl ethyl disulfide.
  • Examples of aliphatic nitro compounds are nitro- methane, 2-nitro-2-methyl-l-propanol, and 2-nitro-2-methyl-l,3-propanediol.
  • Examples of aromatic nitro compounds are 5-nitroisophthalate esters
  • transition metal salts of organic compounds They are believed to have broad usefulness and are the subject of another patent application These materials can act to decompose hydroperoxides believed to be associated with hydrogen generation, although their effectiveness may relate to other effects as well Examples of these salts include naphthenate octoate. 2-ethyl hexanoate. and cyclohexane butyrate salts, plus acetyl acetonate complexes of cobalt, manganese, nickel, iron, copper and
  • optical fiber coatings will include a mixture of hindered phenols, organics, sulfides or disulfides, and the organic salts of transition metals.
  • the light screen may be present in the coating at a range of 0 to 5 wt.%.
  • Examples of light screens include aromatic esters such as Cyasorb 2908 (2.6-di(t-butyl)-p-hydroxy-benzoic acid, hexadecyl ester), aryl salicylate esters, and esters of 2-cyano-3,3-di-phenyl-acrylic acid.
  • Color Stabilizer The color stabilizer may be present in the coating at a range of 0 to 5 wt.%.
  • color stabilizers are carbamates such as N,N'-dicarbomethoxybenzidine and blocked amines such as Tinuvin 440 (8-acetyl-3-dodecyl-7.7,9,9-tetramethyl-1.3,8-triazaspiro(4,5)decane-2,4- dione) Blocking Stabilizer
  • the blocking stabilizer is present in the secondary coating only at a range of 0 to 5 wt.%. of the secondary coating
  • blocking stabilizers are carnauba wax, polyether silicone copolymers such as SF 1 188, fluorinated copolymers, such as FC 430, micronized polyethylene waxes, and micronized celluloses.
  • the coupling agent is used in the coating to promote adhesion of the coating with the substrate.
  • coupling agents are used in the primary coating only and promote the adhesion of the primary coating with the glass fiber.
  • Typical coupling agents are substituted trialkoxy silanes such as epoxypropyltrimethoxy silane, acryloxy- propyltrimethoxy silane. allytriethoxysilane, and epoxycyclohexylethyltri- methoxy silane
  • Another coupling agent which has been found to be of particular usefulness is generally classified as vinyl ether urethane siloxanes. These compounds also have other uses and are the subject of another patent application They may be prepared by reacting mono hydroxy vinyl ethers with an isocyanate-containing alkoxy silane. Examples of such compounds are those obtained by reacting isocyanoto propyl triethoxysilane with 4-hydroxy-butyl vinyl ether 2-hydroxyethyl vinyl ether and hydroxy methyl cyclohex l methyl vinyl ethers The coupling agent may be present in the coating at a range of from 0 to 5 wt %.
  • the vinyl ether formulations of this invention may be cured or polymerized by methods known in the art.
  • the resins may be radiation cured, as for example by being subjected to an electron beam of an energy in the range from about 50 up to perhaps 500 KeV with a dosage from about 0.1 to about 10 0 Mrads
  • Electron beam curing may be performed advantageously in the presence of an iodonium or a sulfonium salt to afford high speed cationic polymenzation
  • Ultraviolet curing in the presence of an onium salt also may be used to produce cationic polymerization
  • the ultraviolet radiation from a mercury vapor lamp is commonly used
  • the coatings of the invention are applied by drawing the glass fiber from a heated glass rod and then passing a glass fiber through a die which applies the coating formula
  • a glass rod is heated to a temperature which softens it so that it can be pulled into a thin fiber
  • the hot fiber is cooled by air, it is coated with a primary vinyl ether formulation as described above and then cured by exposure to ultraviolet radiation Thereafter, the secondary coating formulation is applied and cured in a similar manner In some instances the curing of the primary coating is omitted and both coatings are applied before curing Once the coatings have been applied and cured, the glass fibers are ready for use
  • a vinyl ether terminated polyester oligomer for use in a p ⁇ mary optical fiber coating was prepared by reacting 890 g of hydroxy butyl monovinvl ether (HBVE) with 4452 g of dimethyl isophthalate (DMI) and 4056 g of polvtetrahydrofuran diol (PolyTHF-250) and 600 g of bishvdroxymethyltricvclodecane (BHTD) in a two-step procedure First, the DMI was reacted with the THF diol and BHTD at a temperature of 120°C and a vacuum of 300 torr (40 kPa) using 10 g of dibutyl tin diacetate (DBTDA) as a catalyst After 3 3 hours, the HBVE was added and the reaction earned out at 120°C with a vacuum of 190 torr (25 3 kPa) After 6 hours, the vacuum was reduced to less than 5 torr (0.67 kPa) and excess HB
  • VEX 8075-59 a primary optical fiber coating
  • VEX 8075-59 a primary optical fiber coating
  • x, y, and z represent the molar proportions of the chain-extended polyester
  • a vmyl ether terminated polyester oligomer for use in a secondary optical fiber coating was prepared by reacting 2699 g of HBVE with 4526 g of DMI and 3050 g of btshydroxymethyltricyclodecane (BHTD) in a two-step procedure as in Example 1 First the DMI and BHTD were reacted at a temperature of 120°C and a vacuum of 300 torr (40 kPa) using 10 g of DBTBA catalyst After 1 45 hours, the HBVE was added and the reaction carried out at 120°C with a vacuum of 105 torr (14 kPa).
  • BHTD btshydroxymethyltricyclodecane
  • VEX 8075-63 HBVE-[(DMI) x (BHTD)y]-DMI-HBVE where x and y represent the molar proportions of the chain-extended polyester
  • a fiber optic secondary (outer) coating was formulated as shown below:
  • This formulation had a viscosity of 1560 cps @ 60°C.
  • the formulation was coated on a glass plate with a 3 mil film applicator The film was heated to 60°C and cured by exposure to a mercury arc lamp with a dose of ca. 100 mJ/cm ⁇ in a nitrogen atmosphere. The cured film was removed from the glass plate for analysis.
  • Table A The results are summarized in Table A below
  • a fiber optic primary (inner) coating was formulated as shown below Component Pans by Weight
  • This formulation had a viscosity of 980 cps @ 60°C
  • the formulation was coated on a glass plate with a 6 mil film application
  • the film was heated to 60°C and cured by exposure to a mercury arc lamp with a dose of ca. 250 mJ/cm 2 in a nitrogen atmosphere.
  • the cured film was removed from the glass plate for analysis.
  • Table A The results are summarized in Table A below
  • polyester-based formulations cure more rapidly than do urethane-based formulations
  • Two secondary coating 15 compositions were prepared for comparison
  • Polyester-based formulations have been found to have superior physical properties relative to urethane-based formulations Two compositions were compared
  • Polyester Formulations Primary Coating Parts by Weight VEX 8075- 146(a) 80%
  • Example 6 The formulations of Example 6 were tested to compare their resistance to high temperature oxidation First, by Thermal Gravimetric
  • polyester-based coatings are more resistant to oxidation at high temperatures than are the polyurethane-based coatings.
  • Example 8 The polyester-based secondary formulations of Example 6 were tested again for high temperature oxidation resistance but the amount of photoinitiator was cut in half. This was possible since the polyester-based formulations cure very rapidly. The weight loss after exposure to 125°C in air was compared for samples of the secondary coatings of Example 6 with 0 8 pph and 0 4 pph of the photoinitiator UVI-6974 The results are as follows
  • the curing speed of the polyester-based formulation makes it possible to improve the high temperature resistance of the coatings by reducing the amount of the photoinitiator used in curing.
  • Optical fiber coatings should be insensitive to moisture However, increasing humidity results in an undesirable reduction in the modulus of the coatings. Cured films of the secondary coating formulations of Example 6 were exposed to humid air and the modulus measured as before The results were as follows
  • polyester coatings are superior to the polyurethane coatings.
  • Example 12 A primary (inner) coating for optical fibers was formulated as follows.
  • This formulation contained only two vinyl ether components and omitted alcohol-derived vinyl ester monomers
  • the viscosity was 1 1,652 cps (mPa «s) at 40°C and 3.737 cps (mPa « s) at 60°C
  • the Tg was -62 7°C
  • the modulus 569 psi 3923 kPa
  • Example 13 A secondary (outer) coating for optical fibers was formulated as shown below
  • This formulation contained only ester monomers - again, alcohol-derived monomers were omitted
  • the viscosity was 1548 cps (mPa » s) at 60°C and 320 cps (mPa»s) at 80°C
  • the Tg was 53°C.
  • the modulus was 76.406 psi (526 8 MPa), and the elongation 13 9%

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention permet de préparer des revêtements pour fibres optiques à partir de compositions contenant un ou plusieurs oligomères en polyester d'éther vinylique préparés par réaction d'un polyester ou d'un polyéther à terminaison hydroxyle, d'un polyol et d'un hydroxy éther monovinylique avec un ou plusieurs monomères multifonctionnels à terminaison éther vinylique qui peuvent être dérivés d'esters ou d'alcools.
PCT/US1997/011058 1996-06-24 1997-06-24 Revetement de fibres optiques a base de polyester WO1998005721A1 (fr)

Priority Applications (1)

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AU36425/97A AU3642597A (en) 1996-06-24 1997-06-24 Polyester based optical fiber coatings

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US67200796A 1996-06-24 1996-06-24
US08/672,007 1996-06-24

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006142A1 (fr) * 1994-08-19 1996-02-29 Alliedsignal Inc. Revetements de fibres optiques a base de polyester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006142A1 (fr) * 1994-08-19 1996-02-29 Alliedsignal Inc. Revetements de fibres optiques a base de polyester

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