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The polyaddition of bisphenol A diglycidyl ether (4a) with 2,2'-bis[(4-chloroformyl)oxyphenyl]-propane (5) was examined using quaternary onium salts as catalysts. When the polyaddition was performed using catalysts containing Br - as a counteranion such as tetraphenylphosphonium bromide in chlorobenzene at 100 °C for 48 h, the corresponding poly(alkyl aryl carbonate) with high molecular weight (M n = 59 000) was obtained. It was found from the 1 H NMR and 13 C NMR spectra of the obtained polymer that the reaction proceeded regioselectively at the epoxy group of 4a to provide the polycarbonate with pendant chloromethyl groups. The polyaddition of various bis(epoxide)s with 5 also proceeded smoothly to give the corresponding poly(carbonate)s with high molecular weight in good yields. The chemical modification of the obtained poly(carbonate)s with pendant chloromethyl groups by the phase-transfer method was also investigated using nucleophiles such as potassium thiocyanate and potassium 3-phenyl-2,5-norbornadienecarboxylate.

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 (Mn = 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

Nine polymers with kinked aromatic structures in the main chain and biphenylene-type mesogenic groups in the side chain were synthesized by the polyaddition of bis(epoxide)s and thio- and O-esters. Tetrabutylphosphonium chloride and tetraphenylphosphonium chloride effectively catalyzed the polymerization. The thermal behavior of the polymers was measured by DSC and polarizing optical microscopy. The effect of annealing time on the degree of crystallization was investigated by DSC analysis. Polymers containing 100% of the kinked aromatic groups and 1,3-propylene glycol in the main chain were amorphous. However, when half of the main-chain aromatic moieties were composed of kinked groups and the other half of the aromatics were linear rodlike groups, the polymers were crystalline. The incorporation of kinked groups into the main chain of side-chain liquid-crystalline polymers suppressed the formation of liquid crystallinity. The polymer with mesogenic aromatic structures in both the main chain and the side chain was capable of forming a liquid-crystalline phase.

側鎖にフェナシルエステル残基とビニルエーテル残基を有する新規な複合機能型の光機能性高分子の合成とその光反応特性について検討を行った. 光機能性高分子は, 1, 8-ジアザビシクロ- [5. 4. 0] -ウンデセン-7 (DBU) を塩基として用い, ポリメタクリル酸 (PMA) に2-クロロエチルビニルエーテル (CEVE) を反応させ, さらに種々のフェナシルブロミド類を反応させるワンポット反応によって合成した. この反応は, 温和な条件下で副反応を伴わず定量的に進行し, 目的とする光機能性高分子が得られた. また, 得られたポリマーの光反応特性は, UVスペクトルおよびIRスペクトルによって検討した. その結果, はじめに側鎖のフェナシルエステル残基が光照射により開裂して相当するカルボキシル基が生成し, そのカルボキシル基がビニルエーテル残基と反応し, アセタール化結合による架橋反応が進行することが判明した. また, この架橋反応の反応性は, ポリマー中のフェナシルエステル残基とビニルエーテル残基の組成比率やフェナシルエステル残基の構造によって著しく影響されることも明らかとなった.

主鎖および側鎖にノルボルナジエン残基を有するポリエステル (P-2) を合成し, そのフィルムの蓄熱量を測定した結果, このポリマーフィルムは光照射により290J/gの光エネルギーを蓄積したことが明らかとなった. P-2のフィルムを屋外暴露し, 耐候性について検討を行った. その結果, P-2フィルムを屋外暴露することによって蓄熱量の減少, Tgの上昇および分子量の低下がみとめられた. このことから, ポリマー間での架橋反応とともにポリマー主鎖の切断が進行したことが示唆された. また一方では, P-2のフィルム上にポリビニルアルコールをコーティングした場合には, 耐候性が向上することも明らかとなった.

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

The polycondensation of bis(4-mercaptophenyl) sulfide (BMPS) with bis(4-chloro-3-nitrophenyl) sulfone (BCNPS) was examined using various organic or inorganic bases in mixed solvents ofN-methyl-2-pyrrolidone (NMP) with water or in plain water. The reaction of BMPS with BCNPS proceeded smoothly to give the corresponding polysulfide in mixed solvents of NMP with water at 60 °C using 1,8-diazabicyclo[5.4.0]undecene-7 as a base, although the rate of the reaction decreased gradually as the water in the solvent increased. Polysulfide can also be obtained by reaction in plain water using appropriate organic bases such as tripropylamine (TPA) or quinoline. The polysulfide with a number-average molecular weight of 45,100 was synthesized in 62% yield when the reaction of BMPS with BCNPS was performed using TPA as a base at 60 °C for 48 h in plain water.

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 Mn = 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

We discuss the existence of a rational map whose Julia set is homeomorphic to a given topological self-similar set. We prove that a self-similar set K is homeomorphic to the Julia set of a postcritically finite rational map if and only if K is embedded in S 2 such that the dynamics of K can be extended to a postcritically finite branched covering on S 2 .

Six trimers with biphenyl mesogenic groups and polymethylene spacers were synthesized. From these trimers and biphenol diglycidyl ether (BPGE), a new series of combined liquid crystalline polymers (LCPs) with polyether backbone were synthesized by the polyaddition with quaternary phosphonium chloride as catalyst. The effects of flexible spacer length on the phase transition and mesomorphism of the resulting trimers and combined LCPs were studied using differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. The trimers with 1,3-propylene and 1,4-butylene spacers were absent of mesophase, and the trimers with odd-numbered spacers, 1,5-pentylene and 1,7-heptylene, were nematic. In contrast, the trimers with even-numbered spacers, 1,6-hexylene and 1,10-decylene, were smectic within very narrow temperature ranges. All the combined LCPs were thermotropically nematic, though the crystalline behavior was complex with varying side-chain spacer length. The combined LCPs ...

Polycondensations of bisphenols such as bisphenol-A (BPA), bisphenol-AF (BPAF) and bisphenol-S (BPS) with bis(4-chloro-3-nitrophenyl) sulfone (BCNPS) were examined using various organic or inorganic bases in mixed solvents of DMAc with water or in plain water. The reactions of bisphenols (BPA, BPAF and BPS) with BCPNS proceeded smoothly to give the corresponding polyethers (P-1, P-2 and P-3) in mixed solvents of DMAc with water at 60 °C using 1, 8-diazabicyclo[5.4.0]undecene-7 (DBU) as a base, although the rate of the reaction decreased gradually as the water in the solvent increased. Polyethers P-1, P-2 and P-3 can also be obtained by the reaction in plain water using appropriate organic bases such as DBU, triethylamine, and 4-( N, N-dimethylamino)pyridine. It was also found that P-1 with relatively high molecular weight was synthesized in high yield when the reaction of BPA with twice the amount of BCNPS was performed using DBU at 60 °C for 48 h in plain water.

Novel polyfunctional (meth)acrylates with a calixarene backbone [calixarene (meth)acrylates] were synthesized in good yields by certain reactions of p-methylcalix[6]arene (1a) or p-tert-butylcalix[6]arene (1b) with (meth)acrylate derivatives such as acryloyl chloride, methacryloyl chloride, (2-methacryloxy)ethyl isocyanate, and glycidyl methacrylate. Polyfunctional acrylate 6a having poly(oxyethylene) spacer chain between 1a and acrylate groups was also synthesized by the reaction of the poly(oxyethylene) modified 1a with acrylic acid. Calixarene acrylate 6a was liquid at room temperature, although the other calixarene (meth)acrylates were solid at room temperature. The initial decomposition temperature (IDT) of the resulting calixarene (meth)acrylates was measured by the thermogravimetric analysis to evaluate the thermal stability, and it was found that some of the IDTs of the calixarene acrylates were over 400°C. This means that calixarene (meth)acrylates have very good thermal stability. The photopolymerization of the resulting some calixarene (meth)acrylates with (2-phenyoxy)ethyl acrylate as a reactive diluent in the presence of photoinitiator proceeded smoothly upon irradiation with UV light. Therefore, polyfunctional (meth)acrylates with a calixarene backbone can be expected to be novel and thermally stable photoreactive acrylate oligomers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3071–3078, 1999

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) (Mn = 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 (Mn = 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

New photoreactive p-methylcalix[6]arene (MCA) derivatives containing cationically polymerizable groups such as propargyl ether (calixarene 1), allyl ether (calixarene 2), and ethoxy vinyl ether (calixarene 3) groups were synthesized with 80, 74, and 84% yields by the substitution reaction of MCA with propargyl bromide, allyl bromide, and 2-chloroethyl vinyl ether (CEVE), respectively, in the presence of either potassium hydroxide or sodium hydride by using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC). The p-tert-butylcalix[8]arene (BCA) derivative containing ethoxy vinyl ether groups (calixarene 4) was also synthesized in 83% yield by the substitution reaction of BCA with CEVE by using sodium hydride as a base and TBAB as a PTC. The MCA derivative containing 1-propenyl ether groups (calixarene 5) was synthesized in 80% yield by the isomerization of calixarene 2, which contained allyl ether groups, by using potassium tert-buthoxide as a catalyst. The photochemical reactions of carixarene 1, 3, 4, 5, and 6 were examined with certain photoacid generators in the film state. In this reaction system, calixarene 3 containing ethoxy vinyl ether groups showed the highest photochemical reactivity when bis-[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) (DPSP) was used as the catalyst. On the other hand, calixarene 1 containing propargyl ether groups had the highest photochemical reactivity when 4-morpholino-2,5-dibuthoxybenzenediazonium hexafluorophosphate (MDBZ) was used as the catalyst. It was also found that the prepared carixarene derivatives containing cationically polymerizable groups such as propargyl, allyl, vinyl, and also 1-propenyl ethers have good thermal stability. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1805–1814, 1999

One-pot synthesis of poly(cyclic ortho ester)s by the reaction of potassium perfluoroalkanoates with epibromohydrin (EBH) using quaternary onium salts is described. The reaction of potassium trifluoroacetate (KTFA) with EBH using quaternary onium salts such as tetrabutylphosphonium bromide (TBPB) produces the polymer with five-membered cyclic ortho ester structure in the backbone. This means that quaternary onium salts act as phase-transfer catalysts in the first step and polymerization catalysts in the second step during the reaction.

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.

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

N,N′-Bis[(3-carboxynorbornadien-2-yl)carbonyl]-N,N′-diphenylethylenediamine (BNPE) was synthesized in 70% yield by the reaction of 2,5-norbornadiene-2,3-dicarboxylic acid anhydride with N,N′-diphenylethylenediamine. Other dicarboxylic acid derivatives containing norbornadiene (NBD) residues having N,N′-disubstituted amide groups were also prepared by the reaction of 2,5-NBD-2,3-dicarboxylic acid anhydride with certain secondary diamines. When the polyaddition of BNPE with bisphenol A diglycidyl ether (BPGE) was carried out using tetrabutylammonium bromide as a catalyst in N-methyl-2-pyrrolidone at 100°C for 12 h, a polymer with number average molecular weight of 69,800 was obtained in 98% yield. Polyadditions of other NBD dicarboxylic acid derivatives containing N,N′-disubstituted amide groups with BPGE were also performed under the same conditions. The reaction proceeded very smoothly to give the corresponding NBD poly(ester–amide)s in good yields. Photochemical reactions of the obtained polymers with N,N′-disubstituted amide groups on the NBD residue were examined, and it was found that these polymers were effectively sensitized by adding appropriate photosensitizers such as 4-(N,N-dimethylamino)benzophenone and 4,4′-bis(N,N-diethylamino)benzophenone in the film state. The stored energies in the quadricyclane groups of the polymers were also evaluated to be about 94 kJ/mol by DSC measurement of the irradiated polymer films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 917–926, 1999

Novel sequence-ordered poly(S-alkyl thioester)s were synthesized on the basis of transformation of a backbone of the poly(S-aryl thioester) (P-1) using the regioselective insertion of thiiranes. The insertion reaction of 3-butoxypropylene sulfide (BPS) into P-1 using catalysts such as tetrabutylammonium chloride (TBAC), tetrabutylphosphonium chloride, or 18-crown-6-ether/potassium chloride in DMAc at 70 °C for 6 h proceeded completely and regioselectively to provide an ordered poly(S-alkyl thioester) (P-2a) with a new sequence. The molecular weight of P-2a was reasonably higher than that of the starting polymer P-1. The structure of P-2a including a head-to-tail sequence of BPS unit was well-characterized by IR, 1H NMR, 13C NMR spectroscopies, GPC, and elemental analysis. Various sequence-ordered poly(S-alkyl thioester)s were successfully synthesized by the insertion reaction of 3-phenoxypropylene sulfide, BPS, or cyclohexene sulfide using the TBAC catalyst under the same conditions. It was demonstrated t...

New photosensitive polyimides containing pendant propargyl ester group were synthesized, and the photochemical reaction of the resulting polyimides was investigated using photo-acid generators. The reaction of 4, 4′-diamino-3, 3′-dicarboxydiphenylmethane with 1.2 times amount of propargyl bromide was performed using 1, 8-diazabicyclo[5.4.0]-7-undecene (DBU), and the targeted diamine monomer containing pendant propargyl ester group was obtained with high yield. Poly(amic acid)s were prepared by the reaction of the diamine monomer containing propargyl ester group with various tetracarboxylic dianhydrides in dimethyl sulfoxide at room temperature for 8h. Poly(amic acid)s were then converted into polyimides using acetic anhydride I pyridine as a dehydrating agent at 90°C for 24h. The photochemical reaction of polyimide films was examined with various photo-acid generators (10mol-%). It was proved that the photoinitiated cationic polymerization of pendant propargyl ester group of the polyimides with photo-acid generator proceeded smoothly under UV-light irradiation to give insoluble polymer films in organic solvents.

We have demonstrated that the phase-transfer polycondensation of bisphenol A with 4,4'-dichlorodiphenyl sulfone catalyzed by 18-crown-6 provided poly(arylene ether sulfone)s with high molecular weights even in the non-dehydrated N,N-dimethylacetamide. The obtained poly(arylene ether sulfone)s showed similar or higher number average molecular weights (M n) compared with that prepared by the conventional polycondensation using azeotropic distillation.

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 (Mn = 22,400) and 2 (Mn = 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

Poly(ester-alt-sulfide) (polymer 1) was synthesized by the alternating copolymerization of glycidyl phenyl ether (GPE) with gamma-thiobutyrolactone (TBL) catalyzed by either quaternary onium salts or crown ether complexes. The copolymerization proceeded to produce polymer 1 with good yields in neat or in various organic solvents at 30-120 degreesC, in which quaternary onium salts having Cl- as a counteranion such as tetrabutylammonium chloride (TBAC) had higher activity than quaternary onium salts such as tetrabutylammonium bromide having Br- as a counteranion. It was also found that the alternate copolymer (polymer 1) of GPE with TBL was obtained selectively under different feed ratios of GPE and TBL, although ring-opening homopolymerizations of GPE and TBL did not proceed. Copolymerizations of various oxiranes such as butyl glycidyl ether, styrene oxide, and 1,2-hexene oxide with TBL catalyzed by TBAC also proceeded, and the corresponding poly(ester-alt-sulfide)s (polymers 2, 3, and 4) were obtained under the same conditions as for the synthesis of polymer 1.

Polyesters with pendant primary hydroxyl groups were synthesized by polyadditions of bis(oxetane) with dicarboxylic acids. The polyaddition of bis(3-methyl-3-oxetanylmethyl) terephthalate (BOMT) with adipic acid was carried out in hexamethylphosphorictriamide (HMPA) using certain quaternary onium salts as catalysts at 140°C for 12 h to produce the corresponding polyester, and tetraphenylphosphonium bromide (TPPB) showed the highest catalytic activity among quaternary onium salts used. However, the reaction did not occur without the catalyst or with triethylamine under the same conditions. The yield and the molecular weight of soluble polymer increased with increasing reaction temperature, reaction time, catalyst concentration, and monomer concentration. However, insoluble gel products were obtained when the reaction was performed under less than strict reaction conditions. Polyadditions of BOMT with sebacic acid, isophthalic acid, terephthalic acid, and 2,2′-bis(4-carboxylphenyl)hexafluoropropane were also carried out under similar reaction conditions, and corresponding polyesters with pendant primary hydroxyl groups were obtained in good yields.

Various epoxy monomers containing benzophenone (BP) groups were synthesized by reactions of potassium or lithium salts of BP derivatives with excess epichlorohydrin or epibromohydrin using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC). The copolymerization of glycidyl 3-(piperidylcarbonyl)-2,5-norbornadiene-2-carboxylate (GPNC), which was prepared by the reaction of epichlorohydrin with potassium carboxylate of a norbornadiene (NBD) derivative using a PTC, and (glycidyloxy)benzophenone with phthalic anhydride (PAn) proceeded in 93% yield using TBAB as a catalyst in sulfolane at 100 C for 24 h to give self-photosensitizing polyester P-1 containing a pendant NBD moiety and a pendant 4-oxybenzophenone group. Copolymerizations of various epoxy monomers containing certain NBD moieties and BP groups with PAn produced corresponding polyesters with pendant NBD moieties and BP groups in good yields. The photochemical valence isomerizations of the NBD moieties and the photosensitizing isomeri...

The heterogeneous oxidation of N-(2-phenylthioethyl)benzamide in a dispersion of water was performed with twice the amount of hydrogen peroxide at 60 °C for 72 h as a model reaction of the oxidation of poly(amide-sulphide) (polymer 1), and the corresponding N-[2-(phenylsulphoxy)-ethyl]benzamide and N-[2-(phenylsulphonyl)ethyl]benzamide were obtained in 5% and 95% yields respectively. This suggests that the alkyl phenyl sulphide group was easily oxidized with time via the alkyl phenyl sulphoxide group into the alkyl phenyl sulphone group. On the other hand, when heterogeneous oxidation of diphenyl sulphide in a dispersion of water was carried out with twice the amount of hydrogen peroxide at 60 °C for 72 h, the corresponding diphenyl sulphoxide and diphenyl sulphone were obtained in 77% and 23% yields, respectively. Therefore, the oxidation rate of the diphenyl sulphide group was much slower than that of the alkyl phenyl sulphide group, and the heterogeneous oxidation of diphenyl sulphide with excess hydrogen peroxide in a dispersion of water primarily produced diphenyl sulphoxide under the same conditions. On the basis of these model reactions, the heterogeneous oxidation of polymer 1, which was prepared by the polyaddition of bis(4-mercaptophenyl)sulphide with m-phenylenebis(2-oxazoline), was performed with one to three times the amount of hydrogen peroxide in a dispersion of water at 60 °C, and the Tg of the resulting polymers gradually increased with reaction time from 111 °C to 165 °C. When the oxidization was carried out with three times the amount of hydrogen peroxide for 48 h, the polymer with major structure, poly(amide-sulphone) (polymer 3), was obtained. Polymer 3 was also easily prepared by the oxidization of polymer 1 with equivalent amounts of sodium periodate in a dispersion of water at 60 °C for 48 h.

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.

2, 5-ノルボルナジェン-2, 3-ジカノレボン酸ジグリシジルエステル (NDGE) とテレフタル酸クロリドとの重付加反応により主鎖にノルボルナジエン (NBD) 残基と側鎖にクロロメチル基を有するポリマー (P-1) を合成し, 得られたP-1の側鎖クロロメチル基の化学修飾による自己増感型NBDポリマーの合成について検討を行った. ポリエステル (P-1) とカリウム4-ベンゾイルフェノキシド, カリウム4-ニトロフェノキシド, およびカリウム4-ニトロ-1-ナフトキシドとの反応を, 相間移動触媒としてテトラブチルアンモニウムブロミド (10 mol%) を用いて, N-メチル-2-ピロリドン中で48時間行った. その結果, 側鎖に種々の増感基を有する自己増感型のNBDポリマー (P-2～P-4) が高収率で得られた. 次に, 得られたポリマーの光異性化反応および光増感異性化反応について検討を行った. フィルム状態での光反応ではP-1の光反応速度は低分子増感剤 [1-メトキシ-4-二トロナフタレン (NN)] の添加により著しく促進されたが, THF溶液中では反応の促進効果は認められなかった. 一方, 自己増感型NBDポリマー (P-2～P-4) の光反応はフィルム状態およびTHF溶液中においても, P-1に対応する低分子増感剤を添加した系に比べて, 速やかに進行することが判明した. さらに, 光照射後の自己増感型NBDポリマーの蓄熱量は84kJ/molと, P-1と同等の蓄熱量 (88kJ/mol) を有することも判明した.

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

Silicon-containing divinyl ether monomers were synthesized by the addition reaction of glycidyl vinyl ether (1) with various silyl dichlorides using tetra-n-butylammonium bromide (TBAB) as a catalyst. The reaction of 1 with diphenyl dichlorosilane gave bis-[1-(chloromethyl)-2-(vinyloxy)-ethyl]diphenyl silane (3a) in 89% yield. Polycondensations of 3a with terephthalic acid were also carried out using 1,8-Diazabicyclo[5.4.0]-7-undecene (DBU) to afford silicon-containing polyfunctional vinyl ether oligomers (5). A multifunctional Si-monomer with both vinyl ether and methacrylate groups (7) was prepared by the reaction of 3a with potassium methacrylate using TBAB as a phase transfer catalyst. Photoinitiated cationic polymerizations of these vinyl ether compounds proceeded rapidly using the sulfonium salt, bis-[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophoshate (DPSP), as the cationic photoinitiator in neat mixtures upon UV irradiation. Multifunctional monomer 7 with both vinyl ether and methacrylate groups showed hybrid curing properties using both DPSP and the radical photoinitiator, 2,4,6-trimethylbenzoyl diphenylphoshine oxide (TPO).

The polycondensation of adipic acid with m-xylylene dibromide was performed using 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) as a base in mixtures of dimethyl sulfoxide (DMSO) with water or in plain water. The reactions proceeded smoothly even in water to give the corresponding polyesters, although the rate of the reaction decreased gradually with increasing water in the mixture. Polymers prepared in the aqueous solution had higher molecular weights (Mn, 7700–9200) than the polymers synthesized in DMSO (Mn, 6100–6400).

Poly(S-thioester)s were successfully synthesized by a new addition reaction of bis(thiirane)s with diacyl chlorides catalyzed by quaternary onium salts or crown ether complexes. The polyaddition of Bisphenol A bis(2,3-epithiopropyl) ether (BPTE) or butanediol bis(2,3-epithiopropyl) ether with certain diacyl chlorides proceeded smoothly using quaternary onium chlorides to give the corresponding poly(S-thioester)s with relatively high molecular weights. When the reaction of BPTE with terephthaloyl chloride or isophthaloyl chloride was carried out using 5 mol % of tetrabutylammonium chloride (TBAC) or tetrabutylphosphonium chloride (TBPC) in anisole at 90 °C for 24 h, the poly(S-thioester) with a number-average molecular weight of 40 000 was obtained. The reaction was enhanced more efficiently in aromatic solvents such as toluene or anisole than in aprotic polar solvents. It was proven that the reaction proceeded regioselectively to give the poly(S-thioester)s with the pendant chloromethyl group, which was i...

Polyaddition of bis(4-mercaptophenyl) sulfide (BMPS) with m-phenyl-enebis(2-oxazoline) (MPBO) proceeded very smoothly in the mixtures of aprotic ploar solvents such as N-methyl-2-pyrrolidone ( NMP) with water to produce the corresponding poly(amide-sulfide) with high molecular weights at 90°C under nitrogen. The reaction of BMPS with MPBO, p-phenylenebis(2-oxazoline), and 1,4-butylenebis (2-oxazoline) was also examined in water under the same conditions, and it was found that the reaction proceeds successfully to give the corresponding poly( amide-sulfide )s with high molecular weights. These results mean that water along as well as the mixed solvents of aprotic polar solvents such as NMP with water can be uses as suitable reaction media for the polyaddition of bis(oxazolines) with dithiol to synthesize poly(-amide-sulfide)s with high molecular weights.

N,N'-Bis[(3-carboxynorbornadien-2-yl)carbonyl]methylenedianiline (BNMA) was synthesized in 87 % yield by the reaction of 2,5-norbornadiene-2,3-dicarboxylic acid anhydride with 4,4'-methylene-dianiline. Other dicarboxylic acid derivatives containing norbornadiene (NBD) residues were also prepared by the reaction of 2,5-NBD-2,3-dicarboxylic acid anhydride with certain diamines. When the polyaddition of BNMA with bisphenol A diglycidyl ether (BPGE) was carried out using tetrabutylammonium bromide as a catalyst in NMP at 100 °C for 24 h, a polymer with a number average molecular weight of 18 000 was obtained in 91% yield. Polyadditions of other NBD dicarboxylic acid derivatives with BPGE were also performed under the same conditions. The reaction proceeded very smoothly to give the corresponding NBD poly(ester-amide)s in good yields. Furthermore, the photochemical reactions of the NBD poly-(ester-amide)s were evaluated in the film state or in solution. The photochemical valence isomerization of NBD residues in the polymer films proceeded smoothly to form the corresponding quadricyclane (QC) groups upon irradiation with sunlight. The photochemical reversion of the resulting QC groups in the polymer films proceeded efficiently by irradiation of 272 nm light. The stored energy in the QC groups of the polymers was evaluated to be about 84 kJ/mol by DSC measurement of the irradiated polymer films.

Synthesis of Photoreactive Imidazole Derivatives and Thermal Curing Reaction of Epoxy Resins Catalyzed by Photo-Generated Imidazole

The purpose of this study was to determine any discrepancies in the outputs of five commercial dental radiometers and also to evaluate the accuracy of these devices using a laboratory-grade spectroradiometer. The power densities of 12 different curing light sources were repeatedly measured for a total of five times using each radiometer in a random order. The emission spectra of all of the curing light sources were also measured using the spectroradiometer, and the integral value of each spectrum was calculated to determine the genuine power densities, which were then compared to the displayed power densities measured by the dental radiometers. The displayed values of power density were various and were dependent on the brand of radiometer, and this may be because each radiometer has a different wavelength sensitivity. These results cast doubt upon the accuracy of commercially available dental radiometers.

A convenient esterification reaction of poly(methacrylic acid) (PMAA) with certain alkyl halides was performed using 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as a base in aqueous solution or in water. The esterification reaction of PMAA with propargyl bromide (PB) proceeded very smoothly and quantitatively at 30°C to give corresponding poly(propargyl methacrylate), although the rate of the reaction decreased with increasing water. The reaction of PMAA with benzyl bromide, o-nitrobenzyl bromide, and p-nitrobenzyl bromide gave corresponding poly(methacrylic ester) using DBU under suitable reaction conditions in water. The esterification reactions of PMAA with PB were carried out using certain organic bases such as triethylamine, 4(N,N-dimethylamino)pyridine and pyridine. Inorganic bases such as sodium carbonate, sodium hydroxide, potassium carbonate, and potassium hydroxide were also tried under the same conditions as with DBU. However, the degrees of estrification with all these bases was much lower than that with DBU. © 1996 John Wiley & Sons, Inc.

Novel Thermal Curing Reactions of Epoxy Resin and Poly(glycidyl methacrylate) Using Photo-generated Difunctional Thiols

Polymers containing both pendant carboxyl and epoxy groups were synthesized by the radical copolymerization of p-vinylbenzyl glycidyl ether (VBGE) and itaconic acid monomethyl ester (IAME). The copolymerization proceeded smoothly under various conditions, and polymer soluble in 1,4-dioxane with no gel fraction was obtained. However, the carboxylepoxy addition reaction between VBGE and IAME was observed, when DMSO or DMF were used as polymerization solvents. The IR and 1 H-NMR spectrum of copolymers of VBGE and IAME showed the corresponding structure. The thermal crosslinking reaction of the resulting copolymers was examined under various conditions. Tetrabutylammonium bromide (TBAB) showed catalytic activity for the reaction. However, a 100% gel fraction of polymer was achieved after only 15 min without any catalyst, when the crosslinking reaction was performed at 150°C.

New polyethers with pendant chloromethyl groups were successfully synthesized by a polyaddition of bisepoxides with 4,4′-dichloro-3,3′-dinitrodiphenyl sulfone (DCNS) using quaternary onium salts or crown ether complexes as catalysts. The polyaddition of DCNS with diglycidyl ether of bisphenol A (DGEBA) was enhanced efficiently by the addition of tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), or tetrabutylphosphonium chloride (TBPC) as catalysts. It was also found that the reaction proceeded smoothly in amide-type polar solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) to give a high molecular weight polyether P-1. The polyaddition of DCNS with diglycidyl ether of ethylene glycol (DGEEG) using TBAB in DMAc also proceeded to give the polyether P-2 in good yield. The resulting polyethers contain reactive chloromethyl groups in a side chain, which was introduced during main chain formation.

New Chemical Modification of Polymers with Pendant Chloromethyl Groups Using 1,8-Diazabicyclo-[5.4.0]-7-undecene

Synthesis of Polymers in Aqueous Solutions. Selective Addition Reaction of Poly(2-isopropenyl-2-oxazoline) with Thiols and Carboxylic Acids in Aqueous Solutions

New hybrid vinyl monomers with both cationic- and radical-polymerizable vinyl groups were synthesized by the reaction of bis[1-(chloromethyl)-2-(vinyloxy)ethyl]terephthalate (3) with unsaturated carboxylic acids using 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU) as a base. The reaction of 3 with methacrylic acid 4a was carried out using DBU in DMSO at 70°C for 24 h to give an 86% yield of the hybrid vinyl monomer (5a). Polycondensation of 3 with unsaturated dicarboxylic acids was also performed using DBU to give hybrid vinyl oligomers with radical polymerizable C = C groups (V R ) in the main chain and cationic polymerizable vinyl ether moieties (V C ) on the side chain. The photopolymerization of these hybrid vinyl compounds proceeded smoothly in bulk using either a cationic photoinitiator such as a sulfonium salt or a radical photoinitiator such as acyl phosphine oxide under UV irradiation.

Various epoxy monomers containing norbornadiene (NBD) moieties were prepared by reactions of potassium salts of NBD derivatives with excess epichlorohydrin using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The copolymerization of glycidyl (3-phenyl-2,5-norbornadien-2-yl)carboxylate (GPNC) with phthalic anhydride (PAn) proceeded smoothly using TBAB as a catalyst in sulfolane at 100 °C for 24 h to give polyester P-1 containing pendant NBD moieties. Copolymerizations of various epoxy monomers containing certain NBD moieties with carboxylic anhydrides gave the corresponding NBD polyesters in good yields. The photochemical valence isomerizations of the NBD moieties in the polymers were carried out in the film state or in the solution. Rates of the isomerizations of some NBD moieties in the polymers were strongly enhanced by the addition of photosensitizers such as 4-(N,N-dimethylamino)benzophenone (DABP). The Tgs of the polyesters having NBD residues and stored thermal energy in the corresp...

A new acyl-group transfer polymerization of thiiranes using carboxylic acid derivatives and quaternary onium salts was investigated. 3-Phenoxypropylene sulfide (PPS) was polymerized efficiently by S-phenyl thioacetate in the presence of tetrabutylammonium chloride, bromide, or tetrabutylphosphonium chloride to give the corresponding polysulfide with a S-acetyl group at the polymer terminal. The polymerization of 3-butoxypropylene sulfide (BPS) and cyclohexene sulfide (CHS) also proceeded under the similar conditions to afford the corresponding polymers. It was found from the polymer structures and results of post-polymerization that the polymerization proceeded transferring an acyl group in each propagating step. It was demonstrated that the acyl-group transfer polymerization has living nature. Furthermore, di- and tri-block copolymers of a variety of thiiranes were successfully synthesized by the present acyl-group transfer polymerization.

主鎖にノルボルナジエン (NBD) 構造を有する光エネルギー変換・蓄積機能を有するポリエステルの合成について検討を行った. 2, 5-ノルボルナジエン-2, 3-ジカルボン酸無水物 (NBDA) とフェニルグリシジルエーテルとの開環共重合を, 触媒として二塩化スズを用い, 室温で3日間行った結果, 数平均分子量3500程度の主鎖にNBD構造を有するポリエステルが高収率で得られた. さらに, NBDAと種々のエポキシ化合物との開環共重合を行い, 対応するポリエステル類が得られた. これらポリマーのフィルムを光照射するといずれも約7時間でほぼ定量的にNBD残基からクワドリシクラン残基へと光原子価異性化反応が進行した. この光反応は4, 4′-ビス (ジエチルアミノ) ベンゾフェノンの添加で増感された. 光照射後のポリマーの蓄熱量は70～79kJ/mol程度であることが明らかにされた.

Certain new poly(silyl ether)s and a poly(germyl ether) were synthesized by the polyaddition of bisepoxides with dimethyldiphenoxysilane (MPS) and dimethyldiphenoxygermane (MPG). The polyaddition of Bisphenol A diglycidyl ether (BPGE) with MPS proceeded very smoothly and regioselectively using quaternary onium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylphosphonium chloride (TBPC) as catalysts at 100 °C to give the corresponding poly(silyl ether)s having high molecular weights, although the reaction did not occur without a catalyst under the same reaction conditions. The polyaddition also proceeded using either triphenylphosphine (TPP), triethylamine (TEA), or a complex of 18-crown-6 with potassium chloride as catalysts to give the poly(silyl ether)s, but with low molecular weights. The polyaddition of BPGE with MPG produced the corresponding poly(germyl ether) with good yield using TBAC as a catalyst; however, the molecular weight of the isolated poly(germyl ether) was lower than that ...