Study of photopolymers. XXX. Syntheses of new di(meth) acrylate oligomers by addition reactions of epoxy compounds with active esters

Some dimethacrylate oligomers were synthesized by new addition reactions of 2,2-(4-hydroxyphenyl)propane diglycidyl ether (BPGE) or glycidyl methacrylate (GMA) with phenyl methacrylates such as phenyl methacrylate (PMA), 4-nitrophenyl methacrylate (NPMA), 2,4-dichlorophenyl methacrylate (DCPMA), 4-methoxyphenyl methacrylate (MPMA), and (4-cinnamoyloxy)phenyl methacrylate (CIPMA) using tetrabutylammonium bromide as a catalyst at 120°C. The other new dimethacrylate or diacrylate oligomers were also prepared by the addition reactions of GMA or glycidyl acrylate with active esters such as di(S-phenyl)thioisophthalate (PTIP), di(4-nitrophenyl)isophthalate (NPIP), di(4-nitrophenyl)adipate (NPAD), and di(4-nitrophenyl)sebacate (NPSB) under similar reaction conditions. Furthermore, the rates of photochemical reaction of the obtained dimethacrylate oligomers were measured with 3 mol % of various photosensitizers such as benzoin iso-propyl ether (BIPE), 2-ethylanthraquinone (EAQ), and benzophenone (BP). The rate of photochemical reaction of BPGE-DCPMA oligomer was higher than those of BPGE-PMA, BPGE-NPMA, and BPGE-MPMA oligomers using BIPE as a photosensitizer. However, the photochemical reactivity of the unsensitized BPGE-CIPMA was almost the same as that of the sensitized BPGE-DCPMA. On the other hand, when EAQ was used as a photosensitizer, GMA-PTIP oligomer showed much higher reactivity than GMA-NPAD, GMA-NPSB, and GMA-NPIP oligomers. Also it was shown that the activity of EAQ as a sensitizer was higher than BIPE and BP in the photochemical reaction of BPGE-DCPMA oligomer.     

Novel synthesis of aromatic polysulfides from S,S′-bis(trimethylsilyl)-substituted aromatic dithiols and activated aromatic dihalides

A new method for the synthesis of aromatic polysulfides has been developed by the polycondensation of S,S′-bis(trimethylsilyl)-substituted aromatic dithiols with activated aromatic dihalides. The solution polycondensation of three S-silylated aromatic dithiols with bis(4-chloro-3-nitrophenyl) sulfone afforded readily aromatic polysulfides having inherent viscosities of 0.7 dL/g, and the polymerization with bis(4-fluorophenyl) sulfone gave the polymers with viscosity values of 0.3 dL/g. The silylation method was compared advantageously with a conventional route using parent dithiols and activated aromatic dihalides.     

Synthesis of multifunctional copolyamides with both cyclobutane ring and conjugated double bond in the main chain

Copolyamides 1,9 , and 10 containing both cyclobutane rings and conjugated double bonds in the main chain were synthesized by polycondensation of 1,3-di(4-piperidyl)propane (DPP) with β-truxinate (β-BNPT), with di(p-nitrophenyl) p-phenylenebis(acrylate) (p-NPDA), with di(p-nitrophenyl) p-phenylenebis (α-cyanoacrylate) (p-NPDC), and with di(p-nitrophenyl) p-phenylenebis (α-cyanobutadienecarboxylate) (p-NPDCB) in aprotic polar solvents at room temperature, respectively. Reduced viscosity of copolyamide 1 was strongly affected by the reaction process, the molar ratio of two ester monomers, and reaction time. The copolyamide 1 with the highest viscosity was prepared by the reaction of DPP with 70–50 mol % of β-BNPT for 24 h followed by the polycondensation of the resulting precursor with 30–50 mol % of p-NPDA for 24–96 h. Although copolyamide 9 with high viscosity was not obtained by the polycondensation with β-BNPT and p-NPDC, copolyamide 10 with relatively high viscosity was obtained by the reaction with β-BNPT and p-NPDCB under the same conditions applied for the synthesis of copolyamide 1 . The solubility of copolyamides 1,9 , and 10 decreased gradually with increasing p-NPDA, p-NPDC, and p-NPDCB units in the copolymers. Furthermore, it was found that copolyamides 1,9 , and 10 crosslinked upon irradiation with 313 or 365 nm light, and these copolyamides also decomposed upon irradiation with 254 nm light. That is, the photochemical property of these copolyamides can be controlled by the selection of wavelength of the photoirradiation.     

Synthesis of poly(dipeptide)s on the surface of functional micelle and reversed micelle

Amphiphilic active 4-dodecanoyl-2-nitrophenyl esters of dipeptide containing β-alanine ( 1 – 5 ) were prepared and their polycondensation was studied in detail. The critical micelle concentrations of the active esters 1 – 5 were determined in water by the dye method and the apparent mean aggregation number of reversed micelles formed by model compound 6 was determined by the osmotic method. The results of polycondensation can be explained by assuming that aggregations such as micelle and reversed micelle play an important role in polycondensation. The obtained new poly(dipeptide)s were examined by IR, ¹H NMR, x-ray diffraction, and circular dichroism spectra.     

Synthesis of polyamides from active 1-benzotriazolyl diesters and diamines under mild conditions

The effect of the solvent on the inherent viscosity of polyamides was investigated in the polycondensation of new active 1-benzotriazolyl diesters, such as 1,1′-(adipolydioxy)bisbenzotriazole and 1,1′-(isophthaloyldioxy)bisbenzotriazole, with diamines. The preferred polymerization media were polar aprotic solvents, including N-methyl-2-pyrrolidone and hexamethylphosphoramide. The solution polycondensation at room temperature afforded a series of polyamides having inherent viscosities as high as 1.8 from both aliphatic and aromatic diamines. The 1-benzotriazolyl diesters were more reactive than di(2,4-dinitrophenyl) isophthalate toward diamines. Prior to polymer synthesis, the aminolysis of some active monoesters was carried out as a model compound study.     

New thermo-crosslinking reactions of polymers containing pendant epoxide groups with various polyfunctional active esters

New thermo-crosslinking reactions of poly(glycidyl methacrylate), copolymers of glycidyl methacrylate with methyl methacrylate, styrene or ethyl acrlate with various active esters such as di[S-(2-benzothiazoly)] thioadipate (BTAD), di(S-phenyl) thioadipate (PTAD), di(4-nitrophenyl) adipate (NPAD), diphenyl adipate (PAD), and di(S-phenyl) thioisophthalate (PTIP), and other polyfunctional esters were carried out in the film state using various catalysts such as quarternary ammonium or phosphonium salts, tert amines, or the crown ether 18-crown-6 = potassium salts system. Addition reactions of pendant epoxide groups in the polymer with the active esters such as NPAD and PTAD proceeded selectively to give gel compounds without other side reactions. The rates of reaction with the thioesters such as BTAD and PTAD were relatively faster than those with the phenyl esters such as PAD and NPAD at 70°C. The rates of reactions with the esters having flexible segments such as PTAD were also faster than those with the esters having rigid skeletons such as PTIP. Furthermore, it was found that the rate of reaction was affected strongly by reaction temperature, catalyst concentration, length of alkyl chain in the catalyst, kind of counterion of quarternary ammonium salts as a catalyst, content of pendant epoxide groups in the polymer, and kind of copolymer unit in the polymer, respectively.     

Synthesis of polyester by means of polycondensation of diol ester and dicarboxylic acid ester through ester–ester exchange reaction

Based on our finding that the ester-ester exchange reaction between butyl benzoate and ethyl 4-phenylbenzoate in the presence of a metal alkoxide is faster than the ester-alcohol exchange reaction of butyl benzoate and ethanol, we investigated the synthesis of polyester through ester-ester exchange reaction under various conditions. The polycondensation of diol formate and methyl dicarboxylate in the presence of a catalytic amount of potassium tert-butoxide (^tBuOK) in diglyme at 120 °C under reduced pressure (90–100 Torr) afforded high-molecular-weight polyesters. Methyl dicarboxylate containing an amino group could be used for this polycondensation, although the corresponding diacid chloride containing an amino group was not isolable. The ester-ester exchange reaction could proceed even at the polyester backbone, and the reaction of poly(1,12-dodecamethylene isophthalate) ( PEs ₁ ) with poly(ε-caprolactone) (PCL) in the presence of ^tBuOK at 140 °C afforded a copolymer PEs ₁ -stat-PCL, the structure of which was confirmed by ¹³C NMR spectroscopy and DSC thermal analysis. A similar copolymer was also obtained by the polycondensation of dodecane-1,12-diol formate and dimethyl isophthalate in the presence of PCL and ^tBuOK at 120 °C under reduced pressure.     

Polyethylenimine catalysts containing an isolated apolar binding site: Solovolysis of p-nitrophenyl esters

The preparation dodecane-block-poly[ethylenimine-graft-4(5)-methylimidazole] copolymers and related model compounds has been described and such polymers have been described and such polymers have been demonstrated to be efficient catalysts for the hydrolysis of activated phenyl esters in aqueous solutions. Polymeric catalysts that contain isolated apolar blocks exhibited enhanced catalytic activity for the hydrolysis of the p-nitrophenyl esters of acetate and butyrate compared with polymer model compounds. This rate enhancement was atributed to the apolar binding of substrate within the apolar polymer regime. Twenty-to 100-fold increases in the second-order rate constants were observed for the hydrolysis of the longer-chain p-nitrophenyl esters. This is indicative of a significant hydrophobic interaction. The contribution of the apolar block to the hydrophobic interaction was masked in the hydrolysis of the p-nitrophenyl caproate and p-nitrophenyl laurate substrates. In both instances the dominant contribution to the hydrophobic interactions was ascribed to a substrate-imidazole intermediate rather than the apolar block of the catalyst. The pH-rate profiles for the hydrolysis of p-nitrophenyl esters by the various catalysts indicated an absence of any cooperative interactions between imidazole residues or amine groups.     

Syntheses and reactions of functional polymers. XCIII. Syntheses of polymers containing the N-(4-hydroxy-3-nitrophenyl)succinimide structure in the chain and the use of these activated polymer esters of N-blocked amino acids or peptides

Polymers containing the N-(4-hydroxy-3-nitrophenyl)succinimide residue were designed in order to achieve acyl activation of a reacting carboxylic acid in the solid phase. These polymers were prepared through the following three routes: (a) styrene was allowed to copolymerize with N-(4-hydroxy-3-nitrophenyl)- or N-(4-acetoxy-3-nitrophenyl)maleimide, (b) styrene was copolymerized with N-(4-acetoxyphenyl)maleimide in the presence of divinylbenzene (DVB), and the copolymer obtained was hydrolyzed and nitrated, (c) a copolymer of maleic anhydride and styrene was reacted with p-aminophenol, followed by nitration. The polymers prepared by routes b and c were converted to the activated polymer esters of N-blocked amino acids and peptides by using dicyclohexylcarbodiimide (DCC). The acylated polymers thus obtained were treated with amino acid esters and found to give peptides quantitatively without racemization.     

Effect of Chain Length on Enzymatic Hydrolysis of p-Nitrophenyl Esters in Supercritical Carbon Dioxide

The effect of chain length on the enzymatic hydrolysis of various p-nitrophenyl esters was investigated. Specifically, the hydrolysis of various esters p-nitrophenyl butyrate (PNPB), p-nitrophenyl caprylate (PNPC), p-nitrophenyl laurate (PNPL), p-nitrophenyl myristate (PNPM) and p-nitrophenyl palmitate (PNPP) was studied in supercritical carbon dioxide (ScCO₂) with lipase (Novozym 435). This indicates that the conversion of nitrophenyl esters decreases with increasing chain length. The effect of various parameters such as amount of water added, temperature, and enzyme loading was studied. The optimum temperature for the hydrolysis of PNPB and PNPC was 50°C but was 55°C for PNPL, PNPM, and PNPP in ScCO₂. The reactions were also conducted in acetonitrile as the solvent, and it was found that the reactions reach equilibrium much faster in ScCO₂ than in acetonitrile. The kinetics of the hydrolysis reactions were modeled using a Ping Pong Bi Bi model.     

Preparation and properties of aromatic polyamide-esters from aminophenols and aromatic diacid chlorides

Aromatic polyamide-esters of moderately high molecular weight were prepared from various combinations of three aminophenols (m- and p-aminophenol, and 4-(4′-aminophenoxy) phenol) and two aromatic diacid chlorides (isophthaloyl and terephthaloyl) by interfacial polycondensation in a cyclohexanone/water system and two-phase polycondensation in a dichloromethane/water system with phase-transfer catalysts. The solution polycondensation in dichloromethane/N,N-dimethylacetamide was also successful for the production of high-molecular-weight polymers. The solubility of the aromatic polyamide-esters varied markedly with polymer structure. Except for two polyamide-esters derived from terephthaloyl chloride, all the other polymers were almost amorphous. These polymers had glass transition temperatures at around 200°C and showed 10% weight losses at about 400°C in both air and nitrogen atmospheres.     

Azoles and Azines: CXIX. Alkylation of 5,5'-(4-Nitrobenzylidene)bis(2-thiobarbituric) Acid and 5-(4-Nitrophenyl)-2,8-dithioxo-5,7,8,9-tetrahydro-2H-pyrano[2,3-d:6,5-d']dipyrimidine-4,6(1H,3H)-dione with Haloacetic Acids and Their Esters

5,5'-(4-Nitrobenzylidene)bis(2-thiobarbituric) acid and 5-(4-nitrophenyl)-2,8-dithioxo-5,7,8,9-tetrahydro-2H-pyrano[2,3-d:6,5-d']dipyrimidine-4,6(1H,3H)-dione, similar to unsubstituted 2-thiobarbituric acid, readily react with haloacetic acids and their esters to form regioselectively the S-alkylation products. The alternative routes fo 5,5'-(4-nitrobenzylidene)bis[(4-hydroxy-6-oxo-1,6-dihydropyrimidine-5,2-diyl)sulfanyl]diacetic acids, based on condensation of 4,6-dihydroxypyrimidin-2-ylthioacetic acid with carbonyl compounds followed by cyclodehydration to [(5-(4-nitrophenyl)-4,6-dioxo-3,5,6,7-tetrahydro-4H-pyrano[2,3-d:6,5-d']dipyrimidine-2,8-diyl)di(sulfanyl)]diacetic acid derivatives, are less efficient. Alkylation of 2-thiobarbituric acid with ethyl bromoacetate in ethanol in the presence of alkali yields 5-(2-oxo-2,5-dihydro-1,3-thiazol-4-yl)-2-thiobarbituric acid.     

Polycondensation of bis(p-nitrophenyl) β-truxinate with diamine

Model reaction of bis(4-nitrophenyl) β-truxinate (BNPT) with aliphatic amines proceeded quantitatively at room temperature. Accordingly, polycondensation of BNPT with various diamines was carried out at room temperature or 80°C. During the polycondensation of BNPT with diamines, the precipitation of polymer or the observed gelation of polymerization solution occurred, which may limit the molecular weight of the polymer. On the other hand, the reaction of BNPT with 1,3-(4-piperidyl)propane (DPP) proceeded homogeneously to give the polymer with relatively high molecular weight, and the obtained polyamide (P-1e) showed excellent solubility in many solvents. The study of TG and DTA indicated that the obtained polymers were stable at lower temperature than around 270°C. The polymer prepared from the polycondensation of BNPT with hexamethylenediamine showed melting point and decomposition due to the imidation at 282°C. The photochemical reaction of these polymers was carried out in the film state. The irradiation of 254 nm light caused an absorption at 272 nm to appear and the molecular weight to decrease. This meant that the scission of cyclobutane ring in the main chain occurred to give cinnamamide structures. Also, the absorption at 272 nm decreased by the irradiation of 302.5 nm light. However, the UV spectrum of irradiated polymer did not agree with that of the original polymer. These results suggested that the dimerization of the resulting cinnamamide moieties occurred in the competition of their trans–cis-isomerization. On the other hand, the rate of scission of cyclobutane ring of P-1e was faster than that of the corresponding polyamide containing α-truxillamide structure.     

Synthesis of polyamides from rigid and sterically hindered dicarboxylic acids and diamines under mild conditions

The rate of polycondensation of piperazine with the 2,4-dinitrophenyl, succinimido, phthalimido, and 4-nitrophenyl esters of bicyclo[2.2.2]octane-trans-2,3-dicarboxylic acid was measured and found to decrease in this sequence. In the reaction of two moles of piperazine with one mole of diester, the reactivity of both ester groups was equal. In equimolar mixtures, the second ester group reacts with the second group about ten times slower because of steric hindrance. In the reaction of the esters with N,N′-dimethylethylenediamine no such effects were observed. The aminolysis of the N-hydroxyphthalimido ester stops at low conversions unless a very large excess of triethylamine is added. The catalytic effect of 1,2,4-triazole on the aminolysis was proportional to the triazole concentration. From the rate of ester consumption in the presence of pure triethylamine, the extent of possible racemization of the optically active dicarboxylic acid was estimated. In view of the rate data, the extent of polycondensation, and side reactions, only 2,4-dinitrophenyl and N-hydroxysuccinimido diesters are suitable for the synthesis of polyamides derived from rigid and sterically hindered dicarboxylic acids.     

Room-temperature polycondensation of β-amino acid derivatives VI. Synthesis of various N-(hydroxyethyl) nylons

Various N-(hydroxyethyl)amino acid esters having a methyl substituent or phenyl group between amine and ester groups have been synthesized and their polycondensation behavior was investigated. These substituted amino acid esters gave amorphous polyamides which were soluble in alcohol. A model reaction between N-(hydroxyethyl)-amine and carboxylic acid ester was carried out in order to elucidate the role of hydroxyethyl group on the polycondensation. It was found that the amidation reaction took place rapidly at room temperature when the alkyl group of the carboxylic acid was small. N-(Hydroxyethyl) polyamides were obtained from N,N′-(bishydroxyethyl)-dicamines and dicarboxylic acid esters. The reaction mechanism of the room-temperature polycondensation reaction is discussed.     

Polycyclic nitrogen compounds. Part I. Synthesis of new heterotricyclic quinoxalinones with bridgehead nitrogen atoms

New tricyclic quinoxalinone skeletons with a fully-reduced ring ‘C’ -1,2,3,3a-tetrahydropyrrolo[1,2-α]quin-oxalin-4-one (I-II) and 7,8,9,10-tetrahydropyrido[1,2-α]quinoxalin-6-one (III-IV) derivatives were obtained by selective hydrogen transfer reductive cyclisation of N-(2-nitrophenyl)pyrrolidine-2-carboxylic acid esters and N-(2-nitrophenyl)piperidine-2-carboxylic acid esters (VIa,b and VIIIa,b), respectively.     

Synthesis of aromatic polythioamide-oxothioxoquinazolines from bis(1,3,4-thiadiazoline-5-thione) and aromatic bis-o-amino esters

Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344–394°C in air.     

LCP aromatic polyesters by esterolysis melt polymerization

Polyarylates have previously been synthesized from acetate esters via esterolysis (loss of methyl acetate). This polycondensation can be extended to p‐substituted aromatic monomers for liquid crystal polyesters (LCPs). For AB‐type polymers, methyl p‐acetoxybenzoate and methyl 6‐acetoxynaphthoate were copolymerized to an LCP with reasonable molecular weights. Benzoate esters, methyl 4‐benzoyloxybenzoate (MBB) and methyl 6‐benzoyloxy‐2‐naphthoate (MBN), are also investigated. Several tin and antimony oxide catalysts were effective. The rate of esterolysis polymerization of MBB and MBN is slower than that of the corresponding acidolysis melt polymerization, but fast enough to give relatively high‐molecular‐weight polymers and similar thermal stability as commercial LCP prepared by acidolysis. Using these alternative benzoyloxy groups significantly reduced the color problem, because ketene loss cannot occur. Esterolysis melt polymerizations leading to AB/AABB‐type LCPs were performed using either dimethyl 2,6‐naphthalene dicarboxylate (DMND) or dimethyl terephthalate (DMT) with methyl 4‐acetoxybenzoate and phenylhydroquinone diacetate with tin and antimony catalysts. DMT‐based monomer compositions show much faster polymerization than DMND‐based compositions using antimony oxide catalyst. All these LCPs show a T_g in the 140–170 °C range as a result of the inclusion of the naphthalene and/or phenyl hydroquinone units in the polymer chain. Compositions completely off‐balanced on either side still lead to relatively high‐molecular‐weight copolyesters because either excess monomer can be removed during polymerization. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3586–3595, 2000     

Broad-line NMR and dynamic mechanical behavior of some aromatic polyesters

The dynamic mechanical properties of four aromatic polyesters were measured at temperatures in the 78–540°K region at 10³–10⁴ cps. The polymers studied were: poly(1,3 phenylene isophthalate), poly(1,4 phenylene terephthalate), poly(4,4′ diphenylene isophthalate), and poly(4,4′ diphenylene terephthalate). All four polymers had β loss peaks at about 280°K. Distinct β^* mechanical processes were found for the two terephthalate esters. Broad-line nuclear magnetic resonance measurements were carried out in the 150–440°K temperature range on the four polyesters mentioned above in addition to poly(4,4′ diphenylene 4,4′ biphenyl dicarboxylate). A change in NMR second moment takes place in the 190–330°K region, the magnitude of which is dependent on the polymer structure. The results are compared with those found for a series of aromatic polyamides and are discussed in terms of possible motional processes.     

Poly(butylene terephthalate‐co‐5‐tert‐butyl isophthalate) copolyesters: Synthesis,characterization, and properties

A series of poly(butylene terephthalate) copolyesters containing 5‐tert‐butyl isophthalate units up to 50 mol %, as well as the homopolyester entirely made of these units, were prepared by polycondensation from a melt. The microstructure of the copolymers was determined by NMR to be random for the whole range of compositions. The effect exerted by the 5‐tert‐butyl isophthalate units on thermal, tensile, and gas transport properties was evaluated. Both the melting temperature (T_m) and crystallinity were found to decrease steadily with copolymerization, whereas the glass‐transition temperature (T_g) increased and the polyesters became more brittle. Permeability and solubility slightly increased with the content in substituted isophthalic units, whereas the diffusion coefficient remained practically constant. For the homopolyester poly(5‐tert‐butyl isophthalate), all these properties were found to deviate significantly from the general trend displayed by copolyesters, suggesting that a different structure in the solid state is likely adopted in this case. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 92–100, 2005