Alternating copolymerization of methyl acrylate with donor monomers having a protected amine group

Attempts were made to copolymerize p-aminostyrene, p-acetamidostyrene, N-methyl-p-aceta-midostyrene, N-(4-vinylphenyl) phthalimide, N-vinyl succinimide, and N-vinyl phthalimide with methyl acrylate complexed with ethyl aluminum sesquichloride. Only reactions involving N-(4-vinylphenyl)phthalimide and N-vinyl phthalimide yielded alternating copolymers. N-vinyl succinimide gave nonalternating copolymers insoluble in common solvents and the other monomers did not copolymerize. In some cases, the conventional radical copolymers were prepared for comparison purposes. The reactivity ratios of the free-radical initiated copolymerization of methyl acrylate (I) with N-(4-vinylphenyl)phthalimide (II) were r₁ = 0.14 and r₂ 1.56. The alternating copolymers were studied by ¹H-NMR and ¹³C-NMR spectroscopy. The alternating copolymer of N-(4-vinylphenyl)phthalimide with methyl acrylate was hydrazinolyzed to form the alternating copolymer of methyl acrylate with p-aminostyrene. Hydrazinolysis of the alternating copolymer of methyl acrylate with N-vinyl phthalimide removed the phthalimide moiety and generated vinyl amine units which readily cyclized with neighboring methyl acrylate units to form copolymers that contained five-membered lactam rings. The infrared (IR) spectra of the hydrazinolyzed products contain bands due to amine or amide groups and are devoid of the characteristic bands of the phthalimide ring.     

Polymerization systems driven by aromatization energy: Anionic polymerization of 4-allylidene-2,6-dimethyl-2,5-cyclohexadien-1-one and spiro[2,5]octadienone derivatives

To investigate the polymerization systems driven by aromatization energy, 4-allylidene-2,6-dimethyl-2,5-cyclohexadien-1-one ( Ia ), 5,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one ( Ib ), 4,7-dimethyl-1-vinylspiro[2,5]octa-4,7-dien-6-one [ Ic ], 2-vinyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] ( Id ), and 2-phenyl-2′-methylspiro[cyclopropane-1,4′-(1′-naphthalenone)] ( Ie ) were prepared and polymerized with sodium cyanide in N,N-dimethylformamide. Monomer Ia was highly polymerizable even at ?65°C. Monomers Ib–Ie also polymerized well, giving powdery polymers that were soluble in common solvents. All the polymerizations took place through the aromatization of the cyclohexadienone ring, suggesting that the aromatization energy is the driving force for the polymerization of these monomers.     

Preparation and Free-Radical Polymerization of 2,4-Dichloro-6-(p-Vinylphenyl)-1,3,5-triazine as a Reactive Monomer Containing Two Replaceable Groups

Abstract

A new monomer containing two replaceable groups, 2,4-dichloro-6-(p-vinylphenyl)-1,3,5-triazine (DCVT) was prepared by the reaction of p-vinylphenylmagnesium chloride with cyanuric chloride. This monomer was polymerized readily in benzene by AIBN at 60°C. From the copolymerization with styrene, Q and e values of DCVT were obtained as Q = 2.42 and e = 0.08. An insoluble terpolymer prepared from DCVT, styrene, and divinylbenzene was treated with several nucleophilic reagents, including sodium methoxide, sodium methylmercaptide, dimethylamine, and triethylphosphite, to afford the corresponding polymers in high conversions.     

Synthesis and polymerization of some optically active 2- and 1,2-substituted butadienes

Dehydration of (S)-3,5-dimethyl-1-hepten-3-ol gave: (3E)- (I) and (3Z)-(5S)-3,5-dimethyl-1,3-heptadienes (II) and 2-[(S)- 2-methylbutyl]-1,3-butadiene (III). 2-[(S)-1-Methylpropyl]-1,3-butadiene (IV) was also prepared similarly by dehydration of (S)-3,4-dimethyl-1-hexene-3-ol. Monomers I–IV we polymerized in the presence of the TiCl₄–Al(i-C₄H₉)₃ catalyst system and in emulsion with K₂S₂O₈ as initiator. Monomer IV was also polymerized in the presence of butyllithium. Specific rotations of polymers are of the same order of magnitude as that of monomers, with exception of polymers prepared by stereospecific polymerization of (S)-I and (S)-II. The acetone-soluble fraction of these polymers has a molar rotation similar to that of monomer, while the acetone-insoluble part has a lower rotation ([M]_D of monomer +53.2°; [M]_D of polymer, +5.9°).     

Poly(arylether amides) and poly(aryletherketone amides) via aromatic nucleophilic substitution reactions of self‐polymerizable AB and AB2 monomers

Two new extended self‐polymerizable AB monomers, N‐(4‐fluorobenzoyl)‐4‐amino‐4′‐hydroxydiphenylether and N‐(4‐fluorobenzoyl)‐4‐amino‐4′‐hydroxybiphenyl, were prepared. The monomers were homopolymerized and copolymerized to high‐molecular‐weight, linear poly(arylether amides) in N‐methylpyrrolidone (NMP)/toluene in the presence of potassium carbonate at elevated temperature. The polymers retained NMP up to 200 °C. Samples containing small amounts of the solvent (5–10 wt %) were soluble in polar aprotic solvents. However, after complete removal of the NMP, the polymers were only soluble in strong acids such as sulfuric acid and methanesulfonic acid (MSA). The polymers, which had intrinsic viscosities of 0.57–1.49 dL/g (30.1 ± 0.1 °C in MSA), were semicrystalline with melting temperatures above 400 °C. Two new self‐polymerizable AB₂ amide monomers, N,N′‐bis(4‐fluorobenzoyl)‐3,4‐diamino‐4′‐hydroxydiphenylether and N,N′‐bis(4‐fluorobenzoyl)‐3,5‐diamino‐4′‐hydroxybenzophenone, were also prepared and polymerized to give a hyperbranched poly(arylether amide) and a hyperbranched poly(aryletherketone) amide. The arylfluoride‐terminated, amorphous polymers had intrinsic viscosities of 0.34 and 0.24 dL/g (30.0 ± 0.1 °C in m‐cresol), glass‐transition temperatures of 210–269 °C, and were soluble in a wide variety of organic solvents. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis indicated that the components of the low‐molecular‐weight fractions contained cyclic structures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2374–2389, 2003     

Synthesis and polymerization of N‐(4‐tetrahydropyranyl‐oxyphenyl)maleimide

N‐(4‐Tetrahydropyranyl‐oxy‐phenyl)maleimide (THPMI) was prepared and polymerized by radical or anionic initiators. THPMI could be polymerized by 2,2′‐azobis(isobutyronitrile) (AIBN) and potassium tert‐butoxide. Radical polymers (poly(THPMI)r) were obtained in 15–50% yields for AIBN in THF at 65°C after 2–5 h. The yield of anionic polymers (poly(THPMI)a) obtained from potassium tert‐butoxide in THF at 0°C after 20 h was 91%. The molecular weights of poly(THPMI)r and poly(THPMI)a were M_n = 2750–3300 (M_w/M_n = 1.2–3.3) and M_n = 11300 (M_w/M_n = 6.0), respectively. The difference in molecular weights of the polymers was due to the differences in the termination mechanism of polymerization and the solubility of these polymers in THF. The thermal decomposition temperatures were 205 and 365°C. The first decomposition step was based on elimination of the tetrahydropyranyl group from the poly(THPMI). Positive image patterns were obtained by chemical amplification of positive photoresist composed of poly(THPMI) and 4‐morpholinophenyl diazonium trifluoromethanesulfonate used as an acid generator. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 341–347, 1999     

Preparation of molecularly imprinted polymers with thiourea group for phosphate

Molecularly imprinted polymers selective for phosphate were prepared with the two types of functional monomers, 1-allyl-2-thiourea and N-methyl-N′-(4-vinylphenyl)-thiourea, and the binding abilities of the polymers were evaluated. Phenylphosphonic acid or diphenyl phosphate were used as the template molecules and the imprinted polymers prepared with 1-allyl-2-thiourea as functional monomer showed high binding ability to phosphate in aqueous media and nearly 90% of phosphate could be recovered. Also, the imprinted polymer prepared with N-methyl-N′-(4-vinylphenyl)-thiourea as functional monomer had a high binding ability and specific interaction with phosphate in acetonitrile solution and over 90% of phosphate-derivatives could be recovered selectively.     

Liposome formation of selectively-polymerized diene-containing phospholipids and their postpolymerization

Small and large unilamellar liposomes composed of 1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphorylcholine (DODPC) are prepared by sonication and extrusion, respectively. They are polymerized with water-insoluble radical initiator, azobis(isobutyronitrile) (AIBN) which can selectively polymerize diene groups in 1-acyl chains of the lipids. Polymerized liposomes are freeze-dried to obtain the polymerized liposome powder. There are two methods to redisperse lyophilized liposomes into water. The extrusion is an effective method to disperse them because the energy at extrusion is necessary only for redispersion, whereas the excess energy at sonication gives damage on liposome structure. There is no difference in stability between polymerized liposomes before and after redispersion with extrusion. DODPC polymers, obtained from free radical-initiated polymerization with AIBN, are linear and have polymerizable diene groups in 2-acyl chains. The liposome powder is therefore soluble in organic solvents. Reconstruction of polymerized liposomes is performed with lipid polymers having low or high molecular weight. The lipid polymers having high molecular weight provide stable large unilamellar liposomes by ethanol injection, but unstable small unilamellar liposomes are formed by sonication. The liposomes reconstructed from lipid polymers having low molecular weight are unstable regardless of their size. After reconstruction of liposomes selectively polymerized by AIBN, diene groups in 2-acyl chains are polymerized by water-soluble radical initiator or UV-irradiation to yield highly crosslinked structure. Their stability is improved remarkably by this postpolymerization.     

Synthesis and thermal properties of liquid-crystalline polyacrylates containing a carbazolyl group in the mesogen

The new acrylate monomers 4-(ω-acryloyloxyalkyloxy)-N-(9-methyl-2-carbazolylmethylene) anilines containing from 2 to 11 methylenic units in their alkyl group and a carbazolyl group in the mesogenic unit were synthesized and polymerized by azobisisobutyronitrile (AIBN) as radical initiator and by low-energy electron beam (EB) initiation. The thermal properties of the resulting polymers were examined using differential scanning calorimetry and thermal optical polarizing microscopy. The polymer prepared by AIBN with a hexamethylene spacer exhibited a nematic phase from 73 to 170°C and with an undecamethylene spacer exhibited a smectic phase from 55 to 202°C. The isotropization temperature of the polyacrylates increased with increasing the number of carbons of the methylenic spacer. The yield of the resulting polymer was changed by EB irradiation temperature from 4.5 to 41%. The highest yield was obtained when the monomer was polymerized in a liquid-crystalline phase. The same tendency was observed in the molecular weight of the resulting polymers. © 1994 John Wiley & Sons, Inc.     

Synthesis and free radical polymerization of N-substituted citraconimides

N-phenyl and N-cyclopropylcitraconimides did not polymerize as free radicals with azobisisobutyronitrile (AIBN) as initiator. N-allylcitraconimide, however, depending on the temperature and concentrations of the reactions, readily polymerized to produce polymers of different molecular weights. These polymers contained as much as 85% cyclic repeating units when the polymer exhibited an average molecular weight of ca. 4000. The softening point of the polymer was higher than 350°C and the compound was highly soluble in many organic solvents. The allylic CH₃group in N-substituted citraconimides and in their corresonding citraconamic acids could not be brominated with N-bromosuccinimide.     

Studies of some new bioactive acrylic esters

Four typical bioactive esters of acrylic monomers, N-p-acryloxybenzoyloxysuccinimides, 3-ac-ryloxy-4-oxo-3,4-dihydro-1,2,3-benzotriazines, N-acryloxy-5-norbornene-2,3-dicarboximides, and I-p-acryloxybenzoyloxybenzotriazoles, were Synthesized and polymerized as reactive polymers. Twelve new monomers were prepared by coupling acrylic acid, methacrylic acid, p-acryloxybenzoic acid, or p-methacryloxybenzoic acid with four N-hydroxy compounds such as N-hydroxysuccinimide (HOSu), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB), and I -hydroxybenzotriazole (HOBT) in the presence of dicyclohexylcarbodimide. All monomers polymerized readily in solution with azobisisobutyronitrile (AIBN) as free radical initiator. The resulting reactive polymers with reactive ? OSu, ? OObt, ? ONB, or ? OBT group on the side chain are equally reactive toward n-butylamine at room temperature in the formation of corresponding polyacrylamides. Reactive polymers were used to immobilizetrypsin. It has been found that poly(N-p-methacryloxybenzoyloxy-5-norbornene-2,3-dicarboximide)-trypsin matrix had high activity around three times that of the poly(N-methacryloxy-5-norbornene-dicarboximide)-trypsin matrix. It is proposed that this activity may be due to the presence of a long spacer arm with a hydrophobic and rigid benzene ring between the ligand and matrix. The reactive poly(N-p-methacryloxybenzoyloxysuccinimide-p-methacryloxybenzoic acid) copolymer was used to immobilize the serum protein. This immobilized protein was a hopeful bioactive solid immunoadsorbent.     

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.     

Thermal reaction of ethynylphthalimides and hydration of N-(4-ethynylphenyl)phthalimide

Three ethynyl substituted phenylphthalimides were prepared and characterized by high pressure liquid chromatography, differential scanning calorimetry, and mass spectroscopy. When the preparation of N-(4-ethynylphenyl)phthalimide was attempted by the thermal cyclodehydration of N-(4-ethynylphenyl)-2-carboxybenzamide, N-(4-acetylphenyl)phthalimide was obtained as the major component. This unusual hydration of an ethynyl group was investigated and a mechanism was proposed to explain it.     

Monomers and polymers with silicon-containing functional groups

The novel monomer, p-vinylphenoxy(trimethyl)silane, has been prepared and copolymerized with styrene. The hydrolysis of the copolymer in dioxan has been examined briefly. Monomers of the type p-CH₂CHC₆H₄SiMe₂R (RH, OMe, OEt, OPr, CH₂Cl and NMc₂) have been prepared, polymerized and the resulting polymers cross-linked by hydrolysis.     

Preparation of polymers containing the 1,3,4-oxadiazoline-5-thione structure and their application to the activation of N-protected α-amino acids

Two new monomers with pendent 1,3,4-oxadiazoline-5-thione structures were prepared. Homopolymerization of 2-isopropenyl-1,3,4-oxadiazoline-5-thione (V) and copolymerization with styrene (M₁)(r₁ = 0.02, r₂ = 1.56, Q = 4.12, e = 1.06) were examined. Further, 2-(4-methacryloylaminophenyl)-1,3,4-oxadiazoline-5-thione (VIII) having a phenylcarbamoyl group between the isopropenyl and 1,3,4-oxadiazoline-5-thione ring as a spacer was also synthesized and polymerized. The resultant polymers were allowed to react with N-protected α-amino acids such as Z-AlaOH, Z-LeuOH and Z-PheOH by the DCC method. The polymers containing amino acids thus obtained were reacted with ethyl glycinate to give the corresponding dipeptides in excellent yields without racemization.     

New piperazine‐based polymerizable monoquaternary cationic surfactants: Synthesis,polymerization, and swelling characteristics of gels

Monoquaternary cationic polymerizable surfactants of type N‐acryloyl‐N′‐methyl‐N′‐alkyl piperazinium bromide based on piperazine heterocycle was synthesized by reacting N‐acryloyl‐N′methyl piperazine with the corresponding n‐alkyl bromide (decyl, dodecyl, tetradecyl, and hexadecyl) in anhydrous acetone at room temperature. The resulting surfactants were deliquescent to display any sharp melting points. The surface activity was studied by surface tension measurements. Due to the complex head group geometry of these surfactants, the critical micelle concentration value was high in comparison to the analogous alkyltrimethyl ammonium bromides of similar alkyl chain length. The surfactants were polymerized by micellar (in water) and isotropic (in benzene) conditions and the resulting polymers were characterized by solubility and viscosity studies. The polymers prepared in water showed higher viscosity than the ones prepared in benzene as a result of micellar aggregation in water. The reduced viscosity of the polymers in polar solvents such as methanol and dimethyl formamide (DMF) showed polyelectrolyte‐like behavior, whereas nonelectrolyte behavior was observed in chloroform. pH‐responsive hydrogels were prepared by polymerizing the surfactants in the bicontinuous phase of a microemulsion. The resulting polymers did not exhibit any definite micro/nanostructure due to cross‐polymerization of the hydrophilic oil in the bicontinuous network structure. The gels were highly responsive to changes in pH of the medium and showed high‐swelling degree in acidic media owing to the protonation of the tertiary nitrogen of the piperazine ring. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2059–2072, 2009     

Synthesis of novel polymer containing selenium by radical addition polymerization of 1,4-benzenediselenol to 1,4-divinylbenzene

A novel addition polymerization of 1,4-benzenediselenol (BDSe) to 1,4-divinylbenzene (DVB) was carried out with various azo radical initiators [dimethyl 2,2′-azobisisobutyrate (DAIB), 1,1′-azobis(1-acetoxy-1-phenylethane) (AAPE), and AIBN] in toluene at 65 and 75°C under a nitrogen atmosphere. The polymerization proceded without an induction period, and pale-yellowish powder polymers were obtained in 89% yields for 75 h (DAIB), 89% yields for 24 h (AAPE), and 60% yields for 8 h (AIBN). The molecular weight (M_w) of the insoluble polymers in toluene was about 4000 (IBN) to 14,000 (DAIB or AAPE) by GPC. The polymer had an alternating structure of BDSe to DVB units by ¹H-NMR, IR analyses, and selenium contents, but the polymer contained the diselenide linkage by Raman spectroscopy. By AIBN initiator, the yield of the polymers did not increase over 60% and higher molecular weight polymer was hardly obtained. According to the model addition reaction of benzeneselenol to styrene by AIBN, it was found that AIBN was consumed by the side reaction between dimethyl-N-(2-cyano-2-propyl)ketenimine derivedAppl 11 from AIBN and benzeneselenol to give the adduct C, MH⁺ 295 by DCI MS. On the other hand, DAIB and AAPE initiators, which do not form a ketenimine intermediate, gave the polymers of higher molecular weight in a higher yield. The polymer film exhibited high refractive index (n²⁵_D = 1.81) and a reversible phase transition between a transparency and an opaque by thermal mode. © 1994 John Wiley & Sons, Inc.     

Syntheses and reactions of optically active polymers. II. Preparations of optically active polymers containing quinine,L-ephedrine,and L-histidine residues and their reactions with α-cyanoethylaquocobaloxime

Preparations of polymers with bis(dimethylglyoximato)cobalt (cobaloxime) were investigated. 4-Vinylpyridine was reacted with α-cyanoethylaquocobaloxime to produce α-cyanoethyl-4-vinylpyridinatocobaloxime (I) in 72% yield. It did not, however, polymerize by the use of azobisisobutyronitrile (AIBN) as an initiator. Polymers containing α-cyanoethylcobaloxime were obtained by reactions of polymers with α-cyanoethylaquocobaloxime (II). Poly(9-O-methacryloylquinine) (III), poly(O-methacryloyl-N-methyl-L -ephedrine) (IV), poly[N^α-(o-vinylbenzyl)-L -histidine] (V), and poly(4-vinylpyridine) (VI) were prepared and used in these reactions. Polymers V and VI were reacted with II to give polymers X, XI, XII, and XIII containing α-cyanoethylcobaloxime.     

Synthesis and characterization of new soluble and thermally stable aromatic poly(amide-imide)s based on N-[3,5-bis(N-trimellitoyl)phenyl]phthalimide

A new dicarboxylic acid, N-[3,5-bis(N-trimellitoyl)phenyl]phthalimide (1a), bearing three preformed imide rings was synthesized from the condensation of N-(3,5-diaminophenyl)phthalimide and trimellitic anhydride in glacial acetic acid at 1:2 molar ratio. For study of structure-properties relationship 1,3-bis(N-trimellitoyl)benzene (1b, as a reference) was also synthesized in a similar manner. 1a and 1b were characterized by spectroscopic methods and elemental analyses.A series of wholly aromatic poly(amide-imide)s with inherent viscosities of 0.63-1.09 dl g⁻¹ was prepared by triphenyl phosphite-activated polycondensation from the triimide-dicarboxylic acid 1a and the reference monomer 1b with various aromatic diamines. All of the polymers were fully characterized by FT-IR and ¹H NMR spectroscopy. The effects of the phthalimide pendent group on the polymers properties such as solubility, crystallinity, and thermal stability were investigated by comparison of the polymers. The polymers obtained from triimide-dicarboxylic acid 1a exhibited excellent solubility in a variety of solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethylsulfoxide. These poly(amide-imide)s possessed glass-transition temperatures from 334 to 403 °C and exhibited excellent thermal stabilities and had 10% weight losses from 541 to 568 °C under a nitrogen atmosphere. Poly(amide-imide)s containing phthalimide pendent groups showed higher solubility, higher T_g and T_d10% values than those having no phthalimide pendent groups.     

Synthesis and asymmetric polymerization of (S)‐N‐maleoyl‐L‐leucine propargyl ester

A kind of N‐substituted maleimide (RMI), chiral (S)‐N‐maleoyl‐L ‐leucine propargyl ester ((S)‐PLMI) with a specific rotation of [α]₄₃₅ = ?27.5° was successfully synthesized from maleic anhydride, L ‐leucine, and propargyl alcohol. (S)‐PLMI was polymerized by three polymerization methods to obtain the corresponding optically active polymers. Asymmetric anionic, radical, and transition‐metal‐catalyzed polymerizations were carried out using organometal/chiral ligands, 2,2′‐azobisisobutyronitrile (AIBN) and (bicyclo [2,2,1]hepta‐2,5‐diene) chloro rhodium (I) dimer ([Rh(nbd) Cl]₂), respectively. Poly((S)‐PLMI) obtained by [Rh(nbd)Cl]₂ in DMF showed the highest specific rotation of ?280.6°. Chiroptical properties and structures of the polymers obtained were investigated by GPC, CD, IR, and NMR measurements. Two types of poly((S)‐PLMI)‐bonded‐silica gels as the chiral stationary phase (CSP) were prepared for high‐performance liquid chromatography (HPLC). Their optical resolution abilities were also elucidated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3722–3738, 2007