A novel synthesis of polyethers with pendant hydroxyl groups by polyaddition of bis(oxetane)s with bis(phenol)s

The polyaddition of 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (BEOB) with 3,3′,5,5′-tetrachlorobisphenol A (TCBPA) was examined with or without catalysts. High molecular weight polymer (polymers 1) (M_n = 13,600) with pendant primary hydroxyl groups was obtained in a 99% yield without any gel products when the reaction was performed with 5 mol % of tetraphenylphosphonium bromide as a catalyst in NMP at 160°C for 96 h. However, when the reaction was carried out without a catalyst under the same conditions, a low molecular weight polymer (M_n = 3200) was obtained in a 51% yield. The structure of the resulting polymer was confirmed by IR, ¹H-NMR, and ¹³C-NMR spectra. In this reaction system, it was also found that tetraphenylphosphonium iodide and crown ether complexes such as 18-crown-6 (18-C-6)/KBr and 18-C-6/KI have high catalytic activity. Polyadditions of 1,4-bis[(3-methyl-3-oxetanyl)methoxymethyl]benzene with TCBPA and BEOB with 3,3′,5,5′-tetrabromobisphenol-S were also examined, and corresponding polymers (polymers 2 and 3) were obtained in good yields. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2781–2790, 1999     

Synthesis and characterization of fluorine‐containing polyesters by the polyaddition of bis(epoxide)s with active diesters

The synthesis and optical properties of polyesters with pendant fluorinated phenoxy groups were examined. The polyaddition of bisphenol AF diglycidyl ether ( 1 ) with fluorine‐containing terephtalates ( 2a–f ) was carried out with tetrabutylphosphonium chloride (TBPC) as the catalyst in chlorobenzene to afford the corresponding polyesters with number‐average molecular weights (M_n's) ranging from 15,200 to 30,000 in 88–96% yields. Furthermore, the polyaddition of 1 with isophthalate 2g and phthalate 2h also produced high‐molecular‐weight polyesters with M_n's = 22,700 and 22,600 in 88 and 84% yields, respectively. The linear relationship was observed between the fluorine contents and refractive indices of the obtained polyesters. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 213–222, 2003     

Synthesis and characterization of fluoropolymers by the polyaddition of bis(epoxide)s with dicarboxylic acids and diols

The synthesis and characterization of the fluoropolymers poly 1a – 1d and poly 2a – 2d with pendant hydroxyl groups were examined. The polyaddition of bis(epoxide)s [2,2′‐bis(4‐glycidyletherphenyl)hexafluoropropane and bisphenol A diglycidyl ether] with dicarboxylic acids (tetrafluoroterephthalic acid and terephthalic acid) and diols [2,2′‐bis(4‐hydroxyphenyl)hexafluoropropane, 2,2′,3,3′,5,5′,6,6′‐octafluoro‐4,4′‐biphenol, 1,4‐bis(hexafluorohydroxyisopropyl)benzene, and 1,3‐bis(hexafluorohydroxyisopropyl)benzene] was carried out at 50–100 °C for 6–48 h in the presence of quaternary onium salts (tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium chloride; 2.5 mol %) as catalysts in dimethyl sulfoxide, N‐methylpyrrolidone, dimethylformamide, dimethylacetamide, dioxane, diglyme, o‐dichlorobenzene, chlorobenzene, and toluene to afford the corresponding polymers, poly 1a – 1d and poly 2a – 2d , with number‐average molecular weights of 11,000–59,400 in 45–97% yields. The solubility of the obtained polymers was good, and their thermal stability might be assumed from their structures. A linear relationship was observed between the contents of the fluorine atoms and the refractive indices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1395–1404, 2002     

Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (T_g's) and refractive‐indices (n_D's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T_g's and n_D's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007     

Synthesis of polymers with pendant hydroxyl groups by polyaddition of bis(oxetane)s with dithiols

Addition reaction of (3-methyl-3-oxetanyl)methyl acetate (MOMA) with bis(4-mercaptophenyl) sulfide (BMPS) was examined in certain organic solvents. When the reaction of MOMA with BMPS was performed without any catalyst in hexamethylphosphoric triamide (HMPA) and N-methyl-2-pyrrolidone (NMP) at 130°C for 24 h, conversions of the corresponding adduct were 96 and 36%, respectively, which was confirmed by ¹H-NMR spectra. On the other hand, when the reaction was carried out using tetraphenylphosphonium bromide (TPPB) as a catalyst under the same conditions, conversions of the adduct were 96 and 81% in HMPA and NMP, respectively. This result shows that although the addition reaction of oxetane compound with aromatic dithiol proceeds without any catalyst in HMPA, the reaction was strongly enhanced by adding TPPB in NMP. On the basis of the above results, polyadditions of bis((3-methyl-3-oxetanyl)methyl) terephthalate (BMOT) and bis((3-ethyl-3-oxetanyl)methyl) terephthalate with BMPS were performed using TPPB as the catalyst in NMP at 130°C for 24 h. As a result, the corresponding high molecular weight polymers 1 (M_n = 22,400) and 2 (M_n = 12,800) with pendant primary hydroxyl groups were obtained in 83 and 89% yields without any gel products, respectively. Furthermore, a low molecular weight oligomer was obtained from the polyaddition of BMOT with aliphatic dithiol, bis(mercaptomethyl)benzene, under the same reaction conditions. The catalytic activity on the polyaddition of BMOT with BMPS was also examined, and it was found that thermally stable TPPB and crown ether complexes at the reaction temperature (130°C) have higher catalytic activity than tetrabutylammonium bromide and tetrabutylphosphonium bromide to produce polymer 1 with high molecular weight. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2873–2880, 1998     

A novel synthesis of reactive polymers with pendant halomethyl groups by the polyaddition reaction of bis(epoxide)s with bis(chloroacetoxy)esters or bis(bromoacetoxy)esters

New reactive polymers with pendant halomethyl groups were successfully synthesized by polyaddition reactions of bis(epoxide)s with bis(chloroacetoxy)ester such as 1,4-bis [(chloroacetoxy)methyl]benzene (BCAMB) or 1,4-bis[(bromoacetoxy)methyl]benzene (BBAMB) using quaternary onium salts or crown ether complexes as catalysts. The polyaddition reaction of diglycidyl ether of bisphenol A (DGEBA) with BCAMB proceeded very smoothly with high yields (83–96%) by the addition of quaternary onium salts such as tetrabutylphosphonium bromide (TBPB) or crown ether complexes such as 18-crown-6/KBr as catalysts to produce high molecular weight polymers, although the reaction occurred without any catalyst to give low molecular weight polymer in low yield at 90°C for 48 h. It was also found that the reaction proceeded smoothly in aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) to produce high molecular weight polymers. Polyaddition reactions of DGEBA or digylcidyl ether of ethylene glycol (DGEEG) with BBAMB, other bis(chloroacetoxy)esters or bis(bromoacetoxy)esters using TBPB in DMAc also proceeded smoothly to give the corresponding polymers. The resulting poly(ether-ester)s contain reactive halomethyl groups as side chains, which were introduced during main chain formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3791–3799, 1997     

Synthesis of polyphosphonates containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with phosphonic dichlorides

The polyaddition of 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOBP) and phenylphosphonic dichloride (PPDC) with quaternary onium salts as catalysts proceeded under mild reaction conditions to afford a polymer containing phosphorous atoms in its main chain. A polyphosphonate with a high number‐average molecular weight (10,300) was obtained by the reaction of 4,4′‐BEOBP and PPDC in the presence of tetraphenylphosphonium chloride (TPPC) in o‐dichlorobenzene at 130 °C for 24 h. The structure of the resulting polymer was confirmed with IR, ¹H NMR, and ³¹P NMR spectroscopy. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with phosphonic dichlorides proceeded smoothly to give corresponding polyphosphonates with TPPC as the catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3835–3846, 2002     

Synthesis of poly(cyanurate)s by a novel polyaddition of bis(epoxide)s with triazine dichloride

Poly(cyanurate)s (P‐1–P‐4) containing triazine groups in the main chain and pendant chloromethyl groups in the side chain were synthesized by the polyaddition of bis(epoxide)s with 2,4‐dichloro‐6‐(diphenylamino)‐s‐triazine (DPAT) using quaternary onium salts as catalysts. The polyaddition of diglycidyl ether of bisphenol‐A (DGEBA) with DPAT proceeded smoothly in chlorobenzene at 100 °C for 12 h to give P‐1 with M_n = 19,000 in a 92% yield, when tetrabutylammonium chloride (TBAC) was used as a catalyst. However, no reaction occurred without a catalyst or with triethylamine alone under the same reaction conditions. Polyadditions of other bis(epoxide)s with DPTA also proceeded smoothly using 5 mol % of TBAC as a catalyst in chlorobenzene to produce corresponding polymers (P‐2≈P‐4) in high yields under similar reaction conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4006–4012, 2000     

Novel synthesis of polyethers by the polyaddition of bis(epoxide)s with bis(phosphinate)s

The polyaddition of bisphenol A diglycidyl ether with bis[4‐(P,P‐diphenylphosphinyloxy)phenyl] sulfone catalyzed by quaternary onium salt, such as tetrabutylammonium chloride afforded a new phosphorus‐containing polyether with good solubility in common organic solvents. Having studied various factors affecting the reaction, such as temperature, catalyst concentration, reaction time, etc., an appropriate polyaddition condition was suggested as using 5 mol % of suitable quaternary ammonium or phosphonium salt in polar solvent at 150°C within 25 h in an ampule for producing high molecular weight polymer. A number of polyethers bearing pendent phosphinate ester groups from the polyaddition of certain bis(epoxide)s and bis(phosphinate)s were synthesized under the above condition and characterized by GPC, IR, and NMR. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1009–1016, 1999     

Synthesis of poly(silyl ether)s containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with dichlorosilanes

The polyaddition of bis(3‐ethyl‐3‐oxetanylmethyl) terephthalate (BEOT) with dichlorodiphenylsilane (CPS) using tetrabutylammonium bromide (TBAB) as a catalyst proceeded under mild reaction conditions to afford a polymer containing silicon atoms in the polymer main chain. A poly(silyl ether) (P‐1) with a high molecular weight (M_n = 53,200) was obtained by the reaction of BEOT with CPS in the presence of 5 mol % of TBAB in toluene at 0 °C for 1 h and then at 50 °C for 24 h. The structure of the resulting polymer was confirmed by IR and ¹H NMR spectra. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with dichlorosilanes proceeds smoothly to give corresponding poly(silyl ether)s with TBAB as the catalyst. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2254–2259, 2000     

Novel synthesis of polyphosphonates by the polyaddition of bis(epoxide) with diaryl phosphonates

The polyaddition of bisphenol A diglycidyl ether (BPGE) with bis(4‐chlorophenyl) phenylphosphonate was carried out using quaternary onium salts or crown ether complexes as catalysts. When the polyaddition was performed using tetrabutylammonium chloride, tetrabutylphosphonium chloride, or 18‐crown‐6/KCl in N‐ methyl‐2‐pyrrolidone at 110°C for 48 h, the corresponding polyphosphonate with moderated molecular weights was obtained in 88–96% yields. The structure of the resulting polyphosphonate was confirmed by IR and ¹H‐NMR spectra. The polyaddition of BPGE with various diaryl phosphonates also proceeded very smoothly to produce the corresponding polyphosphonates with moderate molecular weights. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 959–965, 1999     

Synthesis of polyesters by the polyaddition of bis(oxetane)s with active di(ester)s

The polyaddition of bis(oxetane)s 1,4‐bis[(3‐ethyl‐3‐oxetanylmethoxymethyl)]benzene (BEOB), 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (4,4′‐BEOBP), 1,4‐bis[(3‐ethy‐3‐oxetanyl)methoxy] ‐benzene (1,4‐BEOMB), 1,2‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (1,2‐BEOMB), 4,4‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOMB), 3,3′,5,5′‐tetramethyl‐[4,4′‐bis(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (TM‐BEOBP) with active diesters di‐s‐phenylthioterephthalate (PTTP), di‐s‐phenylthioisoterephthalate (PTIP), 4,4′‐di(p‐nitrophenyl)terephthalate (NPTP), 4,4′‐di(p‐nitrophenyl)isoterephthalate (NPIP) were carried out in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in NMP for 24 h, affording corresponding polyesters with M_n's in the range 2200–18,200 in 41–98% yields. The obtained polymers would soluble in common organic solvents and had high thermal stabilities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1528–1536, 2004     

Synthesis of novel poly(hydroxyether terephthalate) via polyaddition of 2,5-difluoroterephthalic acid with aromatic bis(epoxide)s

A novel and more reliable synthetic route to 2,5-difluoroterephthalic acid was developed. A series of new poly(hydroxyether terephthalate) were prepared by the polyaddition of 2,5-difluoroterephthalic acid with various aromatic bis(epoxide)s catalyzed by tetrabutyl ammonium bromide.     

A novel polyaddition of bis(epoxide)s with triazine diaryl ether for the synthesis of poly(ether)s containing triazine group in the main chain

Poly(ether)s (P‐1–P‐4) containing triazine groups in the main chain and pendant phenoxy groups in the side chain were synthesized by the polyaddition of bis(epoxide)s with 2,4‐di‐(p‐chlorophenoxy)‐6‐(diphenylamino)‐s‐triazine (DCTA) with quaternary onium salts or crown ether complexes as catalysts. The polyaddition of diglycidyl ether of bisphenol A with DCTA proceeded smoothly in chlorobenzene at 120 °C for 24 h to give P‐1 with a number‐average molecular weight of 24,800 in a 95% yield when tetraphenylphosphonium chloride (TPPC) was used as a catalyst; however, no reaction occurred without a catalyst under the same reaction conditions. Polyadditions of other bis(epoxide)s with DCTA also proceeded smoothly with 5 mol % TPPC as a catalyst in chlorobenzene to produce the corresponding polymers (P‐2–P‐4) in high yields under similar reaction conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3604–3611, 2000     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis and properties of fluorine‐containing poly(aryl ether oxadiazole)s

Fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s were synthesized by the nucleophilic aromatic substitution reaction of 2,5‐bis(2,3,4,5,6‐pentafluorophenyl)‐1,3,4‐oxadiazole and various bisphenols in the presence of potassium carbonate. The polymerizations were carried out at 30 °C in 1‐methyl‐2‐pyrrolidinone to avoid the gelation caused by a crosslinking reaction at para and ortho carbons to the 1,3,4‐oxidiazole ring. The obtained polymers were all para‐connected linear structures. The obtained fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s showed excellent solubility and afforded tough, transparent films by the solution‐casting method. They also exhibited a high glass transition temperature depending on the molecular structure, and the glass transition temperature could be controlled by the bisphenols in the range of 157–257 °C. They showed good thermal stability and excellent hydrophobicity due to the incorporation of the 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2855–2866, 2007     

Synthesis of polyethers with unsymmetrical structures by the polyaddition of 3‐ethyl‐3‐(glycidyloxymethyl)oxetane with diacyl chlorides

Polyethers with unsymmetrical structures in the main chains and pendant chloromethyl groups were synthesized by the polyaddition of 3‐ethyl‐3‐(glycidyloxymethyl)oxetane (EGMO) with certain diacyl chlorides with quaternary onium salts or pyridine as catalysts. The unsymmetrical polyaddition of EGMO containing two different cyclic ether moieties such as oxirane and oxetane groups with terephthaloyl chloride proceeded smoothly in toluene at 90 °C for 6 h to give polymer 1 with a number‐average molecular weight (M_n) of 51,700 in a 93% yield when tetrabutylammonium bromide (TBAB) was used as a catalyst. The polyaddition also proceeded smoothly under the same conditions when other quaternary onium salts, such as tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylphosphonium chloride, and tetrabutylphosphonium bromide, and pyridine were used as catalysts. However, without a catalyst no reaction occurred under the same reaction conditions. Polyadditions of EGMO with isophthaloyl chloride and adipoyl chloride gave polymer 2 (M_n = 28,700) and polymer 3 (M_n = 25,400) in 99 and 65% yields, respectively, under the same conditions. The chemical modification of the resulting polymer, polymer 1 , which contained reactive pendant chloromethyl groups, was also attempted with potassium 3‐phenyl‐2,5‐norbornadiene‐2‐carboxylate with TBAB as a phase‐transfer catalyst, and a polymer with 65 mol % pendant norbornadiene moieties was obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 368–375, 2001     

Synthesis of polysulfonates containing reactive pendant chloromethyl groups by the polyaddition of bisepoxides with disulfonyl chlorides

Polysulfonates with reactive pendant chloromethyl groups were synthesized by polyadditions of bisepoxides with disulfonyl chlorides. The polyaddition of bisphenol A diglycidyl ether (BPGE) with m-benzene disulfonyl chloride (m-BDSC) occurred in anisole without any catalyst at 130°C for 24 h. However, polymer with high molecular weight was not obtained. On the other hand, the polyadditions of BPGE with m-BDSC proceeded very smoothly with high yield (81–91%) to give polymers with relatively high molecular weights in anisole at 130°C for 24 h when quaternary phosphonium salts were used as catalysts. The polyaddition was also enhanced by the addition of certain crown ether complexes. However, the catalytic activity of these compounds was less than those of quaternary phosphonium salts. Furthermore, polyadditions of certain bisepoxides with disulfonyl chlorides were also carried out to produce the corresponding polymers under the same reaction conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 249–256, 1998     

Synthesis of hetero‐telechelic polymers by self‐polyaddition of monomers containing both oxetanyl and carboxyl groups

The synthesis and self‐polyaddition of new monomers, o‐, m‐, and p‐[(3‐ethyloxetane‐3‐yl)methoxyethyl]benzoic acid (o‐EOMB, m‐EOMB, and p‐EOMB) containing both oxetanyl groups and carboxyl groups were examined. The reactions of o‐EOMB, m‐EOMB, and p‐EOMB in the presence of tetraphenylphosphonium bromide as a catalyst in o‐dichlorobenzene at 150–170 °C resulted in self‐polyaddition to give the corresponding hetero‐telechelic polymers poly(o‐EOMB), poly(m‐EOMB), and poly(p‐EOMB) with M_ns = 14,500–33,400 in satisfactory yields. The M_n of poly(o‐EOMB) decreased at higher reaction temperatures than 150 °C, unlike those of poly(m‐EOMB) and poly(p‐EOMB), possibly due to inter‐ or intraester exchange side reactions. It was also found that the thermal properties and solubilities of these polymers were supposed with the proposed structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7835–7842, 2008     

Preparation and characterization of fluorine‐containing aromatic condensation polymers. VII. Aromatic polyacetals and copolyacetals from 2,2‐bis(4‐hydroxyphenyl)‐1,1,1,3,3,3‐hexafluoropropane and/or 2,2‐bis(4‐hydroxyphenyl)propane and 2‐(trifluoromethyl)benzal chloride

A series of fluorine‐containing aromatic homopolyacetals and copolyacetals with a wide range of unit ratios were synthesized by the solution polycondensation of 2,2‐bis(4‐hydroxyphenyl)‐1,1,1,3,3,3‐hexafluoropropane (bisphenol AF), 2,2‐bis(4‐hydroxyphenyl)propane (bisphenol A), or both with 2‐(trifluoromethyl)benzal chloride, and the effect of fluorine substitution on the properties of these polymers is discussed in relation to the fluorine contents. High molecular weight polyacetals with reduced viscosities of 0.43–0.97 dL/g were obtained in high yields with potassium hydroxide as a base, 18‐crown 6‐ether as a catalyst, and N‐methyl‐2‐pyrrolidinone as a medium at 100 °C for 3 h. Regardless of the fluorine contents, these polymers all were highly soluble in various solvents, including benzene, chloroform, ethyl acetate, and tetrahydrofuran, and afforded colorless, transparent, and tough films by solution casting. The temperatures of 5% weight loss and 10% weight loss under nitrogen both increased significantly and monotonously with increasing fluorine content, whereas the glass‐transition temperatures were scarcely affected by fluorine substitution. The dielectric constant at 1 MHz of the bisphenol AF‐based homopolyacetal was 2.43, which was remarkably lower than the value of the bisphenol A‐based homopolyacetal, 2.68. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1873–1879, 2000