CA2282622A1 - Polymers comprising a fluorinated carbonate moiety - Google Patents
Polymers comprising a fluorinated carbonate moiety Download PDFInfo
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- CA2282622A1 CA2282622A1 CA002282622A CA2282622A CA2282622A1 CA 2282622 A1 CA2282622 A1 CA 2282622A1 CA 002282622 A CA002282622 A CA 002282622A CA 2282622 A CA2282622 A CA 2282622A CA 2282622 A1 CA2282622 A1 CA 2282622A1
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- refractive index
- polymer
- core
- cladding layer
- alkyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 125000005587 carbonate group Chemical group 0.000 title claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 46
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 150000002009 diols Chemical class 0.000 claims abstract description 6
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 4
- 239000010410 layer Substances 0.000 claims description 41
- 239000012792 core layer Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011162 core material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000001902 propagating effect Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- IMNRYXRWSHQJGH-UHFFFAOYSA-N 2-[2-(2,2-dihydroxycyclohexyl)propan-2-yl]-2,3,3,4,4,5-hexafluorocyclohexane-1,1-diol Chemical compound OC1(O)CC(F)C(F)(F)C(F)(F)C1(F)C(C)(C)C1CCCCC1(O)O IMNRYXRWSHQJGH-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZWDPULSRFPDFLR-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoro-1-[2-(1-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(F)(F)C(F)(F)C(F)(F)C1(O)C(C)(C)C1(O)CCCCC1 ZWDPULSRFPDFLR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- -1 methylene, ethylene, propylene Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RRFDUCXMRYNRLZ-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-4-methylpent-2-enoic acid Chemical compound CC(C)C(=C(CO)C(=O)O)O RRFDUCXMRYNRLZ-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 230000005374 Kerr effect Effects 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Optical Integrated Circuits (AREA)
Abstract
The invention pertains to a cross-linkable fluorinated polymer comprising the carbonate moiety having formula (I) wherein n=1-10 and m=0-9. Preferably, the polymer further comprises a cross-linkable moiety derived from a diol selected from (II) and (III) wherein A, A1, and A2 are independently a bond or C1-12 alkylene, or together with the carbon atoms to which they are bonded form a 5-or 6-membered ring; B is independently O or C1-4 alkyl; Q is -CO-C(=E)D, wherein D is H or C1-4 alkyl; and E is C1-6 alkylidene;and each of the alkyl, alkylene, and alkylidene groups may be halogenated. The polymers of the invention can be used in cladding layers or waveguides, in particular for thermo-optical devices.
Description
POLYMERS COMPRISING A FLUORINATED CARBONATE MOIETY
The present invention is in the field of optical components, more particularly, polymeric optical components. By optical components are ' S meant here, thermo-optical components, electro-optical components or passive components.
Both thermo-optical and electro-optical components are known. The working of thermo-optical components is based on the phenomenon of the optical waveguide material employed exhibiting a temperature dependent refractive index.
Polymeric thermo-optical components generally comprise a polymeric three-layer structure on a substrate. The three-layer structure comprises a low refractive index lower cladding layer, a high refractive index core layer, and a low refractive index upper cladding layer. On top of the upper cladding layer heating elements are provided (usually metal strips) to heat the polymeric cladding and core material, in order to change the refractive index for switching. The working of electro-optical devices is based on the phenomenon of the non-linear optically active material employed exhibiting an electric field dependent refractive index. Polymeric electro-optical components in general also comprise a polymeric three-layer structure.
The three-layer structure comprises a low refractive index lower cladding layer, a non-linear optically active, high refractive index core layer, and a low refractive index upper cladding layer. On top of the upper cladding layer electrodes are provided to apply an electric field to the non-linear optically active material to change the refractive index for switching.
Optical components having an at least yenta-layered polymer structure on ' a substrate comprising:
a) a low refractive index lower cladding layer, b) a core-matching refractive index lower cladding layer, c) a core layer,
The present invention is in the field of optical components, more particularly, polymeric optical components. By optical components are ' S meant here, thermo-optical components, electro-optical components or passive components.
Both thermo-optical and electro-optical components are known. The working of thermo-optical components is based on the phenomenon of the optical waveguide material employed exhibiting a temperature dependent refractive index.
Polymeric thermo-optical components generally comprise a polymeric three-layer structure on a substrate. The three-layer structure comprises a low refractive index lower cladding layer, a high refractive index core layer, and a low refractive index upper cladding layer. On top of the upper cladding layer heating elements are provided (usually metal strips) to heat the polymeric cladding and core material, in order to change the refractive index for switching. The working of electro-optical devices is based on the phenomenon of the non-linear optically active material employed exhibiting an electric field dependent refractive index. Polymeric electro-optical components in general also comprise a polymeric three-layer structure.
The three-layer structure comprises a low refractive index lower cladding layer, a non-linear optically active, high refractive index core layer, and a low refractive index upper cladding layer. On top of the upper cladding layer electrodes are provided to apply an electric field to the non-linear optically active material to change the refractive index for switching.
Optical components having an at least yenta-layered polymer structure on ' a substrate comprising:
a) a low refractive index lower cladding layer, b) a core-matching refractive index lower cladding layer, c) a core layer,
2 d) a core-matching refractive index upper cladding layer, and e) a low refractive index upper cladding layer, are also known in the art.
With this specific layer structure optimum transversal confinement can be obtained, which results in less loss of light and an improved switching efficiency.
For optical components preferably silicon substrates are used. These substrates are readily available on the market and are of homogeneous thickness. Furthermore, they are frequently used in integrated circuit techniques and apparatus. One disadvantage of silicon is its high refractive index. Due to this high refractive index the light of the propagating mode might leak into the silicon substrate. The low refractive index lower cladding layer a) is applied to prevent leaking of light from the propagating mode into the silicon substrate. When other substrates are used, the low refractive index lower cladding a) is also of advantage in controlling the confinement of the propagating mode. Using a low refractive index lower cladding a) of appropriate index and thickness gives ample freedom in designing the core-matching refractive index cladding layers b) and d) and the core layer c).
As described above, the optical components usually comprise metal electrodes on top of the upper cladding layer, either for use as heating elements or for applying an electric field. These electrodes are usually made of gold and/or other metals such as chromium, nickel, copper, platinum, or combinations or alloys thereof.
The low refractive index upper cladding e) is applied to prevent leaking of the light from the propagating mode into the attenuating (gold) electrodes.
The refractive indices of the low refractive index lower and upper cladding layers a) and e) are usually (approximately) the same.
WO 98/38237 PCTlEP98/00717
With this specific layer structure optimum transversal confinement can be obtained, which results in less loss of light and an improved switching efficiency.
For optical components preferably silicon substrates are used. These substrates are readily available on the market and are of homogeneous thickness. Furthermore, they are frequently used in integrated circuit techniques and apparatus. One disadvantage of silicon is its high refractive index. Due to this high refractive index the light of the propagating mode might leak into the silicon substrate. The low refractive index lower cladding layer a) is applied to prevent leaking of light from the propagating mode into the silicon substrate. When other substrates are used, the low refractive index lower cladding a) is also of advantage in controlling the confinement of the propagating mode. Using a low refractive index lower cladding a) of appropriate index and thickness gives ample freedom in designing the core-matching refractive index cladding layers b) and d) and the core layer c).
As described above, the optical components usually comprise metal electrodes on top of the upper cladding layer, either for use as heating elements or for applying an electric field. These electrodes are usually made of gold and/or other metals such as chromium, nickel, copper, platinum, or combinations or alloys thereof.
The low refractive index upper cladding e) is applied to prevent leaking of the light from the propagating mode into the attenuating (gold) electrodes.
The refractive indices of the low refractive index lower and upper cladding layers a) and e) are usually (approximately) the same.
WO 98/38237 PCTlEP98/00717
3 Employing a low refractive index upper cladding layer e) with a larger thickness than that of the low refractive index lower cladding layer a) makes it -possible to use a core-matching refractive index upper cladding layer d) which is thinner than the core-matching refractive index lower cladding b). In this case the resulting combined thickness of the low refractive index upper cladding d) and the core-matching refractive index upper cladding e) is smaller than the combined thickness of the low refractive index lower cladding a) and the core-matching refractive index lower cladding b). As a consequence, the structure is transversally asymmetric, with the core layer being close to the electrodes and thus experiencing stronger induced thermo-optical or electro-optical effects, resulting in a more efficient component.
The core-matching refractive index lower cladding b) and the core matching refractive index upper cladding d) are applied to obtain transversal confinement of the propagating mode. The refractive index can be chosen in a relatively wide range to achieve the required properties, such as: monomode behavior, good overlap with a Standard Single Mode Fiber (SMF).
Lateral confinement can be achieved by all known methods for defining channels in planar waveguiding components. Suitable methods are:
1. shaping the core layer by etching techniques (for instance reactive ion etching with oxygen plasma) to obtain a buried channel waveguide, 2. bleaching the core layer to obtain a buried channel waveguide, 3. shaping either of the core-matching refractive index upper and lower cladding layers b) and d) to obtain a ridge (strip loaded) or an inverted ridge waveguide,
The core-matching refractive index lower cladding b) and the core matching refractive index upper cladding d) are applied to obtain transversal confinement of the propagating mode. The refractive index can be chosen in a relatively wide range to achieve the required properties, such as: monomode behavior, good overlap with a Standard Single Mode Fiber (SMF).
Lateral confinement can be achieved by all known methods for defining channels in planar waveguiding components. Suitable methods are:
1. shaping the core layer by etching techniques (for instance reactive ion etching with oxygen plasma) to obtain a buried channel waveguide, 2. bleaching the core layer to obtain a buried channel waveguide, 3. shaping either of the core-matching refractive index upper and lower cladding layers b) and d) to obtain a ridge (strip loaded) or an inverted ridge waveguide,
4. bleaching either of the core-matching refractive index upper and lower cladding layers b) and d) to obtain a ridge (strip loaded) or an inverted ridge waveguide.
_ WO 98/38237 PCT/EP98/00717 All these techniques are known to the artisan and need no further elucidation here. When using technique 1, the core layer is etched away, leaving only the channel waveguide. Subsequently, core-matching refractive index upper cladding material is applied both on top of the core layer c) and onto the areas where the core material was etched away. This technique and also technique 2 are preferred because they can result in symmetrical channel waveguides. Symmetrical channel waveguides show low polarization dependence of the modal properties. When the bleaching technique is used, the refractive index of the core-matching refractive index cladding layers b) and d) should be adapted to the refractive index of the bleached parts of the core. When the shaping of the core technique is used, the refractive index of the core-matching refractive index upper cladding layer material is chosen such as to give the required properties, such as: monomode behavior, good overlap with a Standard Single Mode Fiber (SMF), low polarization dependence, low bend losses.
The polymers used for thermo-optical devices according to the invention are so-called optical polymers. Many optical polymers are known in the art, but there is still need for improvement. A particular problem of polymeric waveguides is the difference between the refractive indices of the core layer and the surrounding cladding layers. Typically, these index differences are in the range of 0.003 to 0.008. In waveguide switches switching is induced by index differences of 0.001 (digital switches) to 0.0001 (interferometer switches). These small index differences can be induced by thermo- or electro-optical properties of polymeric materials. In a thermo-optical switch the core index is lowered by focally heating the layer stack by means of a heating element. The closer the heater is to the core, the more efficiently this index lowering can be performed by a lower switching power. To prevent unwanted light absorption by the heater elements, it is advantageous to apply a low-index cladding layer between the waveguide and the heating element. The lower the index of the a ~;
. , , . ,, -, ... .. ..' leakage to the substrate, this material must have a low absorption at the operating wavelengths (1.3 and 1.5 ~~m). Low refractive index polymers have been disclosed in WO 96128493, but their optical loss is relatively high. It is therefore an object of the invention to provide
_ WO 98/38237 PCT/EP98/00717 All these techniques are known to the artisan and need no further elucidation here. When using technique 1, the core layer is etched away, leaving only the channel waveguide. Subsequently, core-matching refractive index upper cladding material is applied both on top of the core layer c) and onto the areas where the core material was etched away. This technique and also technique 2 are preferred because they can result in symmetrical channel waveguides. Symmetrical channel waveguides show low polarization dependence of the modal properties. When the bleaching technique is used, the refractive index of the core-matching refractive index cladding layers b) and d) should be adapted to the refractive index of the bleached parts of the core. When the shaping of the core technique is used, the refractive index of the core-matching refractive index upper cladding layer material is chosen such as to give the required properties, such as: monomode behavior, good overlap with a Standard Single Mode Fiber (SMF), low polarization dependence, low bend losses.
The polymers used for thermo-optical devices according to the invention are so-called optical polymers. Many optical polymers are known in the art, but there is still need for improvement. A particular problem of polymeric waveguides is the difference between the refractive indices of the core layer and the surrounding cladding layers. Typically, these index differences are in the range of 0.003 to 0.008. In waveguide switches switching is induced by index differences of 0.001 (digital switches) to 0.0001 (interferometer switches). These small index differences can be induced by thermo- or electro-optical properties of polymeric materials. In a thermo-optical switch the core index is lowered by focally heating the layer stack by means of a heating element. The closer the heater is to the core, the more efficiently this index lowering can be performed by a lower switching power. To prevent unwanted light absorption by the heater elements, it is advantageous to apply a low-index cladding layer between the waveguide and the heating element. The lower the index of the a ~;
. , , . ,, -, ... .. ..' leakage to the substrate, this material must have a low absorption at the operating wavelengths (1.3 and 1.5 ~~m). Low refractive index polymers have been disclosed in WO 96128493, but their optical loss is relatively high. It is therefore an object of the invention to provide
5 polymeric material with very low refractive index, and very low optical loss, preferably less than 0.15 dB/cm. However, the polymeric material must also display high Tg because of chemical and optical stability, and be cross-linkable to obtain cladding layers suitable for thermo-optical waveguides. Moreover, when polymeric material is used as a waveguide core, it is advantageous to use material with an index similar to that of the optical fiber attached to said waveguide, which effective index for standard single mode fiber is 1.467 at 1.3 ~m and 1.468 at 1.5 Vim. When doped silica is used as a core, the polymers of the invention can be used advantageously as cladding because their refractive indices can be lower than that of the glass core, which has the advantage that these hybrid waveguides can be rendered athermal.
It has now been found that a cross-linkable fluorinated polymer comprising the carbonate moiety having the formula:
F3C CFa FaC CF7 0 ~ O
~0 0 0 0 n m wherein n = 1-10 and m = 0-9 meets these demands. Preferably n =1-3 andm=0-3.
The various layers can be applied by spin-coating. In order to be able to spin-coat layer-on-layer, it is often necessary to cross-link one layer before applying the next. Therefore, the optical polymers or NLO polymers are AMENDED SHEET
WO 98/38237 PCT/EP9$/00717
It has now been found that a cross-linkable fluorinated polymer comprising the carbonate moiety having the formula:
F3C CFa FaC CF7 0 ~ O
~0 0 0 0 n m wherein n = 1-10 and m = 0-9 meets these demands. Preferably n =1-3 andm=0-3.
The various layers can be applied by spin-coating. In order to be able to spin-coat layer-on-layer, it is often necessary to cross-link one layer before applying the next. Therefore, the optical polymers or NLO polymers are AMENDED SHEET
WO 98/38237 PCT/EP9$/00717
6 rendered cross-linkable either by the incorporation of cross-linkable monomers or by mixing cross-linkers such as polyisocyanates, polyepoxides, etc. into the polymer.
Preferably, the polymer further comprises a cross-linkable moiety derived , from a diol selected from:
g B D
A A~
H \ /OH ~a HO~ OOH
A N A~
i o Q
wherein A, A~, and A2 are independently a bond or C~_~2 alkyiene, or together with the carbon atoms to which they are bonded form a 5- or 6-membered ring;
B is independently O or C~~ alkyl;
Q is -CO-C(=E)D, wherein D is H or C~.~ alkyl; and E is C~.~ alkylidene;
and each of the alkyl, alkylene, and alkylidene groups may be halogenated.
More preferably, the cross-linkable moiety is derived from the diol with the formula HO-CH2-CH(OH)-CH2-O-CO-C(=CH2)CH~.
The term C» alkyl means an alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tent butyl, and the like. Methyl is the preferred alkyl group.
The term C~_~2 alkylene means an alkylene group with 1 to 12 carbon atoms, such as methylene, ethylene, propylene, 2,2,-dimethylpropylene,
Preferably, the polymer further comprises a cross-linkable moiety derived , from a diol selected from:
g B D
A A~
H \ /OH ~a HO~ OOH
A N A~
i o Q
wherein A, A~, and A2 are independently a bond or C~_~2 alkyiene, or together with the carbon atoms to which they are bonded form a 5- or 6-membered ring;
B is independently O or C~~ alkyl;
Q is -CO-C(=E)D, wherein D is H or C~.~ alkyl; and E is C~.~ alkylidene;
and each of the alkyl, alkylene, and alkylidene groups may be halogenated.
More preferably, the cross-linkable moiety is derived from the diol with the formula HO-CH2-CH(OH)-CH2-O-CO-C(=CH2)CH~.
The term C» alkyl means an alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tent butyl, and the like. Methyl is the preferred alkyl group.
The term C~_~2 alkylene means an alkylene group with 1 to 12 carbon atoms, such as methylene, ethylene, propylene, 2,2,-dimethylpropylene,
7 dodecylene, and the like. A, A~, and A2 are preferably a bond or an alkylene group with 1-3 carbon atoms.
The term C~-s alkylidene means an alkylidene group with 1 to 6 carbon atoms, such as methylene, ethylidene, propylidene, 2-methylpropylidene, and the like. Methylene and ethylidene are the preferred alkylidene groups.
When the alkyl, alkylene, or alkylidene groups are halogenated, chlorine and fluorine are the preferred halogens. Fluorine is the most preferred halogen. The index of the polymer can be fine-tuned by selecting the number, the type, and the combination of halogens.
The polymer of the invention can be prepared by standard methods known in the art for the preparation of similar polymers. For instance, the bischloroformate of hexafluorobisphenol A or hexafluoroisopropylidene-dicyclohexanediol bischloroformate can be polymerized in suitable solvents with the hexafluoro-perhydro-bisphenol A, the synthesis of which has been disclosed in EP 0,279,462, optionally in the presence of suitable cross-linkable moieties, such as the above-mentioned diols.
Non-linear electric polarization may give rise to several optically non-linear phenomena, such as frequency doubling, Pockets effect, and Kerr effect. In order to render polymeric non-linear optical material active (obtain the desired NLO effect macroscopically), the groups present in the polymer, usually hyperpolarizable side-groups, first have to be aligned (poled). Such alignment is commonly effected by exposing the polymeric material to electric (DC) voltage, the so-called poling held, with such heating as will render the polymeric chains sufficiently mobile for orientation.
In order to enhance the stability of the thermo-optical component, oxygen scavengers and radical scavengers and the like may be added to the optical polymers.
The term C~-s alkylidene means an alkylidene group with 1 to 6 carbon atoms, such as methylene, ethylidene, propylidene, 2-methylpropylidene, and the like. Methylene and ethylidene are the preferred alkylidene groups.
When the alkyl, alkylene, or alkylidene groups are halogenated, chlorine and fluorine are the preferred halogens. Fluorine is the most preferred halogen. The index of the polymer can be fine-tuned by selecting the number, the type, and the combination of halogens.
The polymer of the invention can be prepared by standard methods known in the art for the preparation of similar polymers. For instance, the bischloroformate of hexafluorobisphenol A or hexafluoroisopropylidene-dicyclohexanediol bischloroformate can be polymerized in suitable solvents with the hexafluoro-perhydro-bisphenol A, the synthesis of which has been disclosed in EP 0,279,462, optionally in the presence of suitable cross-linkable moieties, such as the above-mentioned diols.
Non-linear electric polarization may give rise to several optically non-linear phenomena, such as frequency doubling, Pockets effect, and Kerr effect. In order to render polymeric non-linear optical material active (obtain the desired NLO effect macroscopically), the groups present in the polymer, usually hyperpolarizable side-groups, first have to be aligned (poled). Such alignment is commonly effected by exposing the polymeric material to electric (DC) voltage, the so-called poling held, with such heating as will render the polymeric chains sufficiently mobile for orientation.
In order to enhance the stability of the thermo-optical component, oxygen scavengers and radical scavengers and the like may be added to the optical polymers.
8 The invention is further illustrated by the following examples.
EXAMPLE I
Hexafluoro-perhydro-bisphenol A (150.0 g), hexafluorobisphenol A
bischloroformate (398.7 g), and 2,3-dihydroxypropyl methacrylate (68.9 g) were dissolved in a mixture of anhydrous dichloromethane (1.5 I) and anhydrous tetrahydrofuran (1 I). After cooling to 0°C, anhydrous pyridine (133.4 g) was added dropwise. After the addition, the reaction mixture was allowed to warm to room temperature and stirred overnight. The pyridine hydrochloride was filtered off and the filtrate was precipitated in 50 I of methanol. The precipitate was filtered off and washed with methanol. The polymer was dried overnight in vacuo at 5 kPa at 50°C. Yield 460 g. Mw 26,000; Mn 13,000; Tg 119-126°C; TGA 190°C.
EXAMPLE II
The optical loss and the Tg of prior art polymers (A-C) with normal refractive indices were compared with the optical loss of the very low refractive index polymer of Example I:
Compound Refractive IndexOptical Loss Tg (1565 nm) (dB/cm) (C) A 1.5170 0.1 168/193 B 1.5111 0.1 168/190 C 1.4837 0.12 163/183 Example 1 1.4676 0.15 167/195 The optical loss and the Tg of prior art polymers (D-E) with very low refractive indices were compared with the optical loss of the very low refractive index polymer of Example I:
EXAMPLE I
Hexafluoro-perhydro-bisphenol A (150.0 g), hexafluorobisphenol A
bischloroformate (398.7 g), and 2,3-dihydroxypropyl methacrylate (68.9 g) were dissolved in a mixture of anhydrous dichloromethane (1.5 I) and anhydrous tetrahydrofuran (1 I). After cooling to 0°C, anhydrous pyridine (133.4 g) was added dropwise. After the addition, the reaction mixture was allowed to warm to room temperature and stirred overnight. The pyridine hydrochloride was filtered off and the filtrate was precipitated in 50 I of methanol. The precipitate was filtered off and washed with methanol. The polymer was dried overnight in vacuo at 5 kPa at 50°C. Yield 460 g. Mw 26,000; Mn 13,000; Tg 119-126°C; TGA 190°C.
EXAMPLE II
The optical loss and the Tg of prior art polymers (A-C) with normal refractive indices were compared with the optical loss of the very low refractive index polymer of Example I:
Compound Refractive IndexOptical Loss Tg (1565 nm) (dB/cm) (C) A 1.5170 0.1 168/193 B 1.5111 0.1 168/190 C 1.4837 0.12 163/183 Example 1 1.4676 0.15 167/195 The optical loss and the Tg of prior art polymers (D-E) with very low refractive indices were compared with the optical loss of the very low refractive index polymer of Example I:
9 Compound Refractive Optical Loss Tg Index {1565 nm) (dBlcm) (C) D 1.4622 N.D. 88/97 E 1.4640 0.25 78/93 Example I 1.4676 0,15 167/195 N.D. = not determined Key (monomer composition in mole%):
S T U V W
A 50 25 (R=H) - - 25 B 40 25 (R=H) - - 25
S T U V W
A 50 25 (R=H) - - 25 B 40 25 (R=H) - - 25
10 (R=COCI) C - 25 (R=H) _ _ 25 50 (R=COCI) D 50 (R=COCI) 25 - 25 E - 50 (R=COCI) - 25 25 legenda:
S=
Br CIO( OCOC1 SUBSTITUTE SHEET (RULE 26) 9a T=
F3C~ ~CF3 RO~ v v FOR
U=
CFg CFg Ho-cl~-cl-~-o ~ ~ o-cl-~-ct-~-off CF3 CFg V=
HO-CH 2-(CF 2)4-CH 2-OH
w=_ OH
OOH
O O
X Y Z
Example I 50 25 25 SUBSTITUTE SHEET (RULE 26) 9b legenda:
X=
C~oCO
Y=
Z=
OH
OOH
O O
It may be concluded that the polymer of the invention has a Tg and an optical loss which are comparable with those of higher refractive index materials, whereas the Tg of the polymer of the invention is substantially higher than the Tg of other very low refractive index materials.
1~
SUBSTITUTE SHEET (RULE 26) Example III
A solution of 22.5 g of the polymer of Example I and 1.13 g of dicumyl peroxide in 77.5 g of cyclohexyl acetate was filtered through a 0.2 p,m filter.
5 The solution was spin-coated at 1000 rpm for 30 sec and then cured in a vacuum oven which was heated from 20°C to 200°C in 1.5 h and then kept at 200°C for 30 min. The resulting product was cooled slowly to give a cladding layer having a refractive index of 1.4676 and an optical loss of 0.15 dB/cm which was used in a penta-layered thermo-optical device 10 according to PCT application WO 97/01782.
Example IV
A reactor was charged with 122 g of hexafluoroisopropylidenedicyclo hexanol, 100 g of triphosgene (bis(trichloromethyl) carbonate), and 1 I of dry toluene, under a nitrogen atmosphere.
The temperature of the reactants was lowered to approx. -3°C with stirring, after which 86.3 g of N,N-dimethylaniline diluted in 100 ml of dry toluene were added dropwise in 80 min.
The reaction mixture was diluted with 200 ml of dry toluene, the temperature was raised to ca. 70°C, and the mixture was stirred for approx.
50 h more under a stream of nitrogen to remove the excess phosgene and other volatile products.
After working up (extraction with 10% hydrochloric acid, water, and brine, drying on sodium sulfate, evaporation of toluene in vacuo, recrystallization from toluene/n-hexane 1/1.35 v/v, 0.28 g/ml, and drying) pure hexafluoro isopropylidenedicyclohexanediol bischloroformate was obtained in approx.
33% overall yield.
To a stirred solution of 11.45 g of hexafluoroisopropylidenedicyclohexane diol bischloroformate, 4.17 g of hexafluoroisopropylidenedicyclohexanol, and 1.95 g of dihydroxy-isopropylmethacrylate dissolved in 70 ml of tetra WO 98/3$237 PCT/EP98/00717
S=
Br CIO( OCOC1 SUBSTITUTE SHEET (RULE 26) 9a T=
F3C~ ~CF3 RO~ v v FOR
U=
CFg CFg Ho-cl~-cl-~-o ~ ~ o-cl-~-ct-~-off CF3 CFg V=
HO-CH 2-(CF 2)4-CH 2-OH
w=_ OH
OOH
O O
X Y Z
Example I 50 25 25 SUBSTITUTE SHEET (RULE 26) 9b legenda:
X=
C~oCO
Y=
Z=
OH
OOH
O O
It may be concluded that the polymer of the invention has a Tg and an optical loss which are comparable with those of higher refractive index materials, whereas the Tg of the polymer of the invention is substantially higher than the Tg of other very low refractive index materials.
1~
SUBSTITUTE SHEET (RULE 26) Example III
A solution of 22.5 g of the polymer of Example I and 1.13 g of dicumyl peroxide in 77.5 g of cyclohexyl acetate was filtered through a 0.2 p,m filter.
5 The solution was spin-coated at 1000 rpm for 30 sec and then cured in a vacuum oven which was heated from 20°C to 200°C in 1.5 h and then kept at 200°C for 30 min. The resulting product was cooled slowly to give a cladding layer having a refractive index of 1.4676 and an optical loss of 0.15 dB/cm which was used in a penta-layered thermo-optical device 10 according to PCT application WO 97/01782.
Example IV
A reactor was charged with 122 g of hexafluoroisopropylidenedicyclo hexanol, 100 g of triphosgene (bis(trichloromethyl) carbonate), and 1 I of dry toluene, under a nitrogen atmosphere.
The temperature of the reactants was lowered to approx. -3°C with stirring, after which 86.3 g of N,N-dimethylaniline diluted in 100 ml of dry toluene were added dropwise in 80 min.
The reaction mixture was diluted with 200 ml of dry toluene, the temperature was raised to ca. 70°C, and the mixture was stirred for approx.
50 h more under a stream of nitrogen to remove the excess phosgene and other volatile products.
After working up (extraction with 10% hydrochloric acid, water, and brine, drying on sodium sulfate, evaporation of toluene in vacuo, recrystallization from toluene/n-hexane 1/1.35 v/v, 0.28 g/ml, and drying) pure hexafluoro isopropylidenedicyclohexanediol bischloroformate was obtained in approx.
33% overall yield.
To a stirred solution of 11.45 g of hexafluoroisopropylidenedicyclohexane diol bischloroformate, 4.17 g of hexafluoroisopropylidenedicyclohexanol, and 1.95 g of dihydroxy-isopropylmethacrylate dissolved in 70 ml of tetra WO 98/3$237 PCT/EP98/00717
11 hydrofuran/dichloromethane 2.4/1 v/v were added dropwise 3.83 g of pyridine in 10 ml of tetrahydrofuran/dichloromethane 2.4/1 v/v at 20°C
in approx. 60 min.
The reaction mixture was stirred overnight, the precipitate (pyridine.HCl salt) was removed by filtration. The polymer was precipitated by vigorous stirring in 1 I of methanol, collected, and stirred with fresh methanol. The product was collected by filtration and left to dry in a vacuum oven at 65°C
to yield 11.2 g (approx. 70%) of a polymer the recurring unit of which has the formula:
O
O O O
HaC
Mw = 13,460 ; Mn = 6,470; polydispersity 2.08.
Refractive index at 1550 nm 1.4428 and at 1300 nm 1.4443.
in approx. 60 min.
The reaction mixture was stirred overnight, the precipitate (pyridine.HCl salt) was removed by filtration. The polymer was precipitated by vigorous stirring in 1 I of methanol, collected, and stirred with fresh methanol. The product was collected by filtration and left to dry in a vacuum oven at 65°C
to yield 11.2 g (approx. 70%) of a polymer the recurring unit of which has the formula:
O
O O O
HaC
Mw = 13,460 ; Mn = 6,470; polydispersity 2.08.
Refractive index at 1550 nm 1.4428 and at 1300 nm 1.4443.
Claims (9)
1. A cross-linkable fluorinated polymer comprising the carbonate moiety having the formula:
wherein n = 1-10 and m = 0-9.
wherein n = 1-10 and m = 0-9.
2. The polymer of claim 1 wherein n = 1-3 and m = 0-3.
3. The polymer of claim 1 or 2 further comprising a cross-linkable moiety derived from a diol selected from:
wherein A, A1, and A2 are independently a bond or C1-12 alkylene, or together with the carbon atoms to which they are bonded form a 5- or 6-membered ring;
B is independently O or C1-4 alkyl;
Q is -CO-C(=E)D, wherein D is H or C1-4 alkyl; and E is C1-6 alkylidene; and each of the alkyl, alkylene, and alkylidene groups may be halogenated.
wherein A, A1, and A2 are independently a bond or C1-12 alkylene, or together with the carbon atoms to which they are bonded form a 5- or 6-membered ring;
B is independently O or C1-4 alkyl;
Q is -CO-C(=E)D, wherein D is H or C1-4 alkyl; and E is C1-6 alkylidene; and each of the alkyl, alkylene, and alkylidene groups may be halogenated.
4. The polymer of claim 3 wherein the cross-linkable moiety is derived from the diol with the formula HO-CH2-CH(OH)-CH2-O-CO-C(=CH2)CH3.
5. A film comprising the polymer of any one of claims 1-4.
6. A waveguide comprising the polymer of any one of claims 1-4.
7. A cladding layer comprising the polymer of any one of claims 1-4.
8. A thermo-optical device comprising the polymer of any one of claims 1-4.
9. The thermo-optical device of claim 8 having an at least penta-layered polymer structure on a substrate comprising:
a) a low refractive index lower cladding layer, b) a core-matching refractive index lower cladding layer, c) a core layer, d) a core-matching refractive index upper cladding layer, and e) a low refractive index upper cladding layer, wherein the low refractive index upper cladding layer and, optionally, the low refractive index lower cladding layer comprise the polymer of any one of claims 1-4.
a) a low refractive index lower cladding layer, b) a core-matching refractive index lower cladding layer, c) a core layer, d) a core-matching refractive index upper cladding layer, and e) a low refractive index upper cladding layer, wherein the low refractive index upper cladding layer and, optionally, the low refractive index lower cladding layer comprise the polymer of any one of claims 1-4.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL97200511.0 | 1997-02-24 | ||
EP97200511 | 1997-02-24 | ||
PCT/EP1998/000717 WO1998038237A1 (en) | 1997-02-24 | 1998-02-04 | Polymers comprising a fluorinated carbonate moiety |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2282622A1 true CA2282622A1 (en) | 1998-09-03 |
Family
ID=31502872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002282622A Abandoned CA2282622A1 (en) | 1997-02-24 | 1998-02-04 | Polymers comprising a fluorinated carbonate moiety |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0963395A1 (en) |
CA (1) | CA2282622A1 (en) |
-
1998
- 1998-02-04 EP EP98909428A patent/EP0963395A1/en not_active Withdrawn
- 1998-02-04 CA CA002282622A patent/CA2282622A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP0963395A1 (en) | 1999-12-15 |
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