| Fluorinated poly(arylene ether)s polymers are attractive for optical communication field due to their low optical loss, tunable refractive index and easy processability, which have been recognized as a very potential for the application of optical waveguide during recent years. A novel kind of fluorinated poly(arylene ether) polymer optical waveguide material containing phthalazinone moiety having excellent thermal stability and good optical property was developed by our research team. However, the fluorinated poly(arylene ether) containing phthalazinone moiety also possess little larger birefringence owing to its rigid main chain, and the good solubility of the poly(phthalazinone ether)s make it difficuty to fabricate waveguide by muti-layer processing method. On the base of previous our study, different cross-linkable moieties have been introduced into the fluorinated poly(phthalazinone ether) and studied the structure and property of the obtained polymers systematicly.Three types of catalyst systems in the process of synthesis the fluorinated poly(phthalazinone ether) were studied in details firstly. The results show that, when CaH2 and KF as co-catalyst was used in the nucleophilic substitution polycondesation reaction, the reaction exhibits two stage, that is, the formation of the phenoxide anion is the rate-determining step in the first stage, and the formation of the intermediate complex is the rate-determining step in the second stag. The anhydrous condition in the system or appropriate increase of the reaction temperature can remarkably accelerate the reaction. The formation of the phenoxide anion is the rate-determining step in the K2CO3/CaH2 catalytic syatem. However, there exist some side reactions when using more ratio of K2CO3 or higher reaction temperature. In the later stage the formation of the intermediate complex is the rate-determining step with the NaH as catalyst. Unfortunely, the reaction time is too long and elevated temperature will result in cross-linking reaction. The reaction condition of CaH2 and KF as catalyst at 90℃is chose to syntheze the fluorinated poly(arylene ether)s without the side reaction.A serials of novel cross-linkable poly(phathalazinone ether)s bearing tetrafluorostyrene groups (FSt-FPPEs) were prepared by copolycondensation reaction, and the structure of the polymers obtained was confirmed by1H-NMR and 19F-NMR. The films could be cured at 160℃in the presence of 1 wt% dicumyl peroxide as an initiator for 4 h under vacuum. The curing polymers show good thermal stabilities (the temperatures of 1% mass-loss after curing: 478-490℃), and high glass transition temperatures (Tgs:177-283℃) which increase about 10℃than before thermal cross-linking. The curing FSt-FPPEs exhibit relatively low optical loss (<0.112 dB/cm at 1310 nm, <0.207 dB/cm at 1550 nm). By adjusting the feed ratio of the reactants, the polymers'refractive-indices of 1310 nm and 1550 nm (TE mode) could be well controlled in the range of 1.502-1.565 and 1.495-1.562, respectively. The birefringence of the curing FSt-FPPEs at 1310 nm and 1550 nm are in the range of 0.0031-0.0086 and 0.0028-0.0087, respectively, which is decrease by orders of magnitude compare to the FPPEs'.A kind of biphnol (BHPE) which containing 1,1-diphenylethylene group was synthesized and then introduced into poly(phathalazinone ether)s (PE-FPPEs) by copolycondensation reaction using CaH2 and KF as catalyst. The structure of the resulting polymers was confirmed by1H-NMR and 19F-NMR. The films could be cured in the present of photo initiator IHT-PI 184 for 10 min under nitrogen. The curing polymers show good thermal stabilities (the temperatures of 1% mass-loss after curing:472-496℃), and high glass transition temperatures (Tgs:183-262℃). The gel content is up to over 90%. The PE-FPPEs have relatively low optical loss (<0.207 dB/cm at 1310 nm, <0.287 dB/cm at 1550 nm) and high thermo-optic coefficient value (dn/dT) (TE mode,1310 nm:-0.91×10-4～-1.14×10-4℃-1, 1550 nm:-0.88×10-4～-1.17×10-4℃-1). By adjusting the feed ratio of the reactants, the polymers'refractive indices of 1310 nm and 1550 nm (TE mode) could be well controlled in the range of 1.505-1.568 and 1.502-1.566, respectively. The birefringence of the curing PE-FPPEs after heat treatment at 1310 nm and 1550 nm are in the range of 0.0044-0.0071 and 0.0037-0.0067, respectively, which is decrease by orders of magnitude compare to the FPPEs'. The more crosslinking density make them possible to fabricate waveguide by muti-layer processing method.A kind of biphnol (DA-DHBP) containing allyl group was synthesized, then was introduced into a serials of poly(phathalazinone ether)s (Allyl-FPPEs) by copolycondensation reaction, and the structure of the resulting polymers was confirmed by1H-NMR and 19F-NMR. The films could be cured at 280℃without any initiator for 2 h under vacuum. The curing polymers show good thermal stabilities (the temperatures of 1% mass-loss after curing:455-503℃), and high glass transition temperatures (Tgs:180-276℃). The Allyl-FPPEs exhibit relatively low optical loss (<0.163 dB/cm at 1310 nm, <0.297 dB/cm at 1550 nm) and high thermo-optic coefficient value (dn/dT) (TE mode,1310 nm:-0.86×10-4～-1.24×10-4℃-1, 1550 nm:-0.95×10-4～-1.20×10-4℃-1). By adjusting the feed ratio of the reactants, the polymers'refractive indices of 1310 nm and 1550 nm (TE mode) could be well controlled in the range of 1.502-1.565 and 1.499-1.561, respectively. The birefringence of the curing Allyl-FPPEs at 1310 nm and 1550 nm are in the range of 0.0050-0.0098 and 0.0044-0.0098, respectively, which is decrease by orders of magnitude compare to the FPPEs'. The more crosslinking density make them possible to fabricate waveguide by muti-layer processing method. The combination property of the Allyl-FPPEs superior to the fluorinated poly(aryl ether)s from literatures.Lithographic patterning was applied to fabricate inverted ridge waveguide using Allyl-FPPE-1 as core and PMMA-GMA as cladding. The resulting straight waveguide has achieved propagation light.
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