Synthesis and polymerization of N-[4-N′- (α-methylbenzyl)aminocarbonylphenyl]maleimide

A novel type of optically active N-[4-N′-(α-methylbenzyl)aminocarbonylphenyl]maleimide [(R)-MBCP] was synthesized from maleic anhydride, p-aminobenzoic acid, and (R)-methylbenzylamine. Radical homopolymerization of (R)-MBCP was performed in tetrahydrofuran (THF) at 50 and 70°C for 24 h to give optically active polymers having [α]²⁵_D = -141° and -129°, respectively. Anionic polymerization of (R)-MBCP with n-butyllithium in THF and N,N-dimethylformamide gave an optically active polymer having ?78 to ?81° of [α]²⁵_D. Radical copolymerizations of (R)-MBCP (M₁) were performed with styrene (ST, M₂) and methyl methacrylate (MMA, M₂) in THF at 50°C. The monomer reactivity ratios (r₁, r₂) and the Alfrey-Price Q-e values were determined as follows: r₁ = 0.009, r₂ = 0.091, Q₁ = 1.30, e₁ = 1.87 in the (R)-MBCP-ST; r₁ = 0.27, r₂ = 1.21, Q₁ = 0.93, e₁ = 1.46 in the (R)-MBCP-MMA system. Chiroptical properties of the polymers were also investigated. © 1992 John Wiley & Sons, Inc.     

Synthesis and Chiroptical Properties of Poly[N-(4-N′-(α-Methylbenzyl)-Aminocarbonylphenyl)-Mamaleimide]

Abstract

Radical homopolymerization of N-[4-N′-(α-methylbenzyl)-aminocarbonylphenyl]maleimide ((S)-MBCP) was carried out at 50 and 70°C for 24 h to give optically active polymers ([α]²⁵ _D = 159.8 to 163.4°). Radical copolymerizations of (S)-MBCP (M₁) were performed with styrene (ST, M₂, methyl methacrylate (MMA, M²) in THF at 50°C. The monomer reactivity ratios (r ₁, r ₂) and the Alfrey-Price Q, e values were determined as follows: r ₁ = 0.32, r ₂= 0.14, Q ₁ = 1.74, e ₁ = 0.96 in the (S)-MBCP-ST system; r ₁ = 0.54, r ₂ = 0.93, Q ₁ = 1.11, e ₁ = 1.23 in the (S)-MBCP-MMA system. Chiroptical properties of the polymers and the copolymers were also investigated, and asymmetric induction into the copolymer main chain is discussed.     

Intramolecular charge transfer complexes. VIII. Poly[N-(2-hydroxyethyl) carbazolyl acrylate-co-2,4-dinitrophenyl methacrylate]

Radical copolymerization of N-(2-hydroxyethyl) carbazolyl acrylate (HECA, M₁) with 2,4-dinitrophenyl methacrylate (DNPM, M₂) can be described by a simple terminal mechanism having the relative reactivities r₁ = 0.14, r₂ = 1.10 (at 60°C); 0.28, 0.96 (80°C); and 0.41, 0.79 (100°C), respectively. The dependence of the reactivity ratio values on copolymerization temperature, analyzed by Arrhenius equation, takes place mainly through the frequency factor. The copolymers obtained are intramolecular charge transfer complexes. The intramolecular interaction is evidenced by the shift of the aromatic protons from the DNPM structural unit in the copolymers' ¹H-NMR (nuclear magnetic resonance) spectra. This shift depends on sequence distribution and chain conformation, but is not affected by the copolymerization temperature.     

Synthesis,swelling properties,and network structure of new stimuli‐responsive poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels

Poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels were prepared by thermal free‐radical copolymerization of N‐acryloyl‐N′‐ethyl piperazine (AcrNEP) and N‐isopropylacrylamide (NIPAM) in solution using N, N′‐methylene bisacrylamide as the crosslinking agent. The gels were responsive to changes in external stimuli such as pH and temperature. The pH and temperature responsive character of the gels was greatly dependent on the monomer content, namely AcrNEP and NIPAM, respectively. The gels swelled in acidic (pH 2) and de‐swelled in basic (pH 10) solutions with a response time of 60 min. With increase in temperature from 23 to 80 °C the swelling of the gels decreased continuously and this effect was different in acidic and basic solutions. The temperature dependence of equilibrium water content of the gels was evaluated by the Gibbs–Helmholtz equation. Detailed analysis of the swelling properties of these new gels in relation to molecular heterogeneity in acidic (pH 2) and basic (pH 10) solutions were performed. Water transport property of the gels was studied gravimetrically. In acidic solution, the diffusion process was non‐Fickian (anomalous) while in basic solution, the diffusion was quasi‐Fickian. The effect was more evident in solution of pH 2 than in pH 10. Various structural parameters of the gels such as number‐average molar mass between crosslink (M_c), the crosslink density (ρ_c), and the mesh size (ξ) were evaluated. The mesh sizes of the hydrogels were between 64 and 783 Å in the swollen state in acidic solution and 20 and 195 Å in the collapsed state in basic solution. The mesh size increased between three to four times during the pH‐dependent swelling process. The amount of unbound water (free water) and bound water of the gels was also evaluated using differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Kinetic study of the radical polymerization behavior of N‐(1‐phenylethylaminocarbonyl)methacrylamide

Polymerization of N‐(1‐phenylethylaminocarbonyl)methacrylamide (PEACMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was kinetically studied in dimethyl sulfoxide (DMSO). The overall activation energy of the polymerization was estimated to be 84 kJ/mol. The initial polymerization rate (R_p) is given by R_p = k[MAIB]^0.6[PEACMA]^0.9 at 60 °C, being similar to that of the conventional radical polymerization. The polymerization system involved electron spin resonance (ESR) spectroscopically observable propagating poly(PEACMA) radical under the actual polymerization conditions. ESR‐determined rate constants of propagation and termination were 140 L/mol s and 3.4 × 10⁴ L/mol s at 60 °C, respectively. The addition of LiCl accelerated the polymerization in N,N‐dimethylformamide but did not in DMSO. The copolymerization of PEACMA(M₁) and styrene(M₂) with MAIB in DMSO at 60 °C gave the following copolymerization parameters; r₁ = 0.20, r₂ = 0.51, Q₁ = 0.59, and e₁ = +0.70. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2013–2020, 2005     

Radical polymerization of N-phenyl-α-methylene-β-lactam

N-phenyl-α-methylene-β-lactam (PML), a cyclic analog of N,N-disubstituted methacrylamides which do not undergo radical homopolymerization, was synthesized and polymerized with α,α′-azobis (isobutyronitrile) (AIBN) in solution. Poly (PML) (PPML) is readily soluble in tetrahydrofuran, chloroform, pyridine, and polar aprotic solvents but insoluble in toluene, ethyl acetate, and methanol. PPML obtained by radical initiation is highly syndiotactic (rr = 92%), exhibits a glass transition at 180°C, and loses no weight upto 330°C in nitrogen. The kinetics of PML homo-polymerization with AIBN was investigated in N-methyl-2-pyrrolidone. The rate of polymerization (R_p) can be expressed by R_p = k[AIBN]^0.55[PML]^1.2 and the overall activation energy has been calculated to be 87.3 kJ/mol. Monomer reactivity ratios in copolymerization of PML (M₂) with styrene (M₁) are r₁ = 0.67 and r₂ = 0.41, from which Q and e values of PML are calculated as 0.60 and 0.33, respectively.     

Living anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide: Synthesis of well‐defined poly(N‐isopropylacrylamide) having various stereoregularity

Anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide ( 1 ) was carried out with 1,1‐diphenyl‐3‐methylpentyllithium and diphenylmethyllithium, ‐potassium, and ‐cesium in THF at ?78 °C for 2 h in the presence of Et₂Zn. The poly( 1 )s were quantitatively obtained and possessed the predicted molecular weights based on the feed molar ratios between monomer to initiators and narrow molecular weight distributions (M_w/M_n = 1.1). The living character of propagating carbanion of poly( 1 ) either at 0 or ?78 °C was confirmed by the quantitative efficiency of the sequential block copolymerization using N,N‐diethylacrylamide as a second monomer. The methoxymethyl group of the resulting poly( 1 ) was completely removed to give a well‐defined poly(N‐isopropylacrylamide), poly(NIPAM), via the acidic hydrolysis. The racemo diad contents in the poly(NIPAM)s could be widely changed from 15 to 83% by choosing the initiator systems for 1 . The poly(NIPAM)s obtained with Li⁺/Et₂Zn initiator system possessed syndiotactic‐rich configurations (r = 75–83%), while either atactic (r = 50%) or isotactic poly(NIPAM) (r = 15–22%) was generated with K⁺/Et₂Zn or Li⁺/LiCl initiator system, respectively. Atactic and syndiotactic poly(NIPAM)s (42 < r < 83%) were water‐soluble, whereas isotactic‐rich one (r < 31%) was insoluble in water. The cloud points of the aqueous solution of poly(NIPAM)s increased from 32 to 37 °C with the r‐contents. These indicated the significant effect of stereoregularity of the poly(NIPAM) on the water‐solubility and the cloud point in water © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4832–4845, 2006     

Radical polymerization of benzyl N-(2,6-dimethylphenyl)itaconamate

The polymerization of benzyl N-(2,6-dimethylphenyl)itaconamate (BDMPI) with benzoyl peroxide (BPO) in N,N-dimethylformamide (DMF) was studied kinetically by ESR. The polymerization rate (R_p) at 70°C was given by R_p = k[BPO]^0.78[BDMPI]^1.1. The overall activation energy of polymerization was determined to be 83.7 kJ/mol. The number-average molecular weight of poly(BDMPI) was in the range of 1500–2000 by gel permeation chromatography. From the ESR study, the polymerization system was found to involve ESR-observable propagating radicals of BDMPI under practical polymerization conditions. Using the polymer radical concentration by ESR, the rate constants of propagation (k_p) and termination (k_t) were determined in the temperature range of 50–70°C. The k_p value seemed dependent on the chain-length of propagating radical. The analysis of polymers by the MALDI-TOF mass spectrometry suggested that most of the resulting polymers contain the dimethylamino terminal group. The copolymerization of BDMPI (M₁) and styrene (M₂) at 50°C in DMF gave the following copolymerization parameters; r₁ = 0.49, r₂ = 0.26, Q₁ = 1.2, and e₁ = +0.63. The thermal behavior of poly(BDMPI) was examined by dynamic thermogravimetry and differential scanning calorimetry. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1891–1900, 1997     

Copolymerization of N-Vinylcarbazole with 2-Dimethylaminoethyl Methacrylate

The thermal copolymerization of N-vinylcarbazole (VCz) with 2-dimethylaminoethyl methacrylate (DMAEM) initiated by α,α′-azobisisobutyronitrile (AIBN) in solution in tetrahydrofuran at 60°C has been studied. Different compositions of copolymer were prepared and characterized by UV, IR, and ¹H-NMR spectroscopy, viscosity measurements, and thermal studies. The estimation of the composition of VCz and DMAEM in the copolymer was carried out by UV spectroscopy. The reactivity ratio of VCz (r ₁) and DMAEM (r ₂) was determined by the methods of Mayo and Lewis, Kelen and Tüdös, and Tidwell and Mortimer.     

N-vinylpyrrolidone and 4-vinyl Benzylchloride Copolymers: Synthesis,Characterization and Reactivity Ratios

The copolymers prepared in this study by free radical copolymerization of N-vinylpyrrolidone (M ₂) with 4-vinylbenzylchloride (M ₁) using 2,2′-azobisisobutyronotrile (AIBN) initiator in 1,4-dioxane solvent at 70°C were characterized by FTIR, ¹H-NMR and ¹³C-NMR techniques. Polymer solubility was tested in both polar and nonpolar solvents. The thermal properties were studied by thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). Copolymer compositions were established by H¹-NMR spectra, while reactivity ratios of the monomers were computed using the linearization methods viz., Fineman-Ross (FR) (r ₁ = 1.67 and r ₂ = 0.67), Kelen-Tudos (KT) (r ₁ = 1.77 and r ₂ = 0.65) and extended Kelen-Tudos (EK-T) (r ₁ = 1.72 and r ₂ = 0.63) methods at lower conversion. Furthermore, reactivity ratios in nonlinear error-in-variables method (RREVM) also compute the reactivity ratios (r ₁ = 1.76 and r ₂ = 0.66); these are found to be in good agreement with each other. The distribution of monomer sequence along the copolymer chain was calculated using a statistical method based on the calculated reactivity ratios.     

Water-soluble copolymers. XLII. Cationic polyelectrolytes of acrylamide and 2-acrylamido-2-methylpropanetrimethylammonium chloride

The new monomer 2-acrylamido-2-methylpropanetrimethylammonium chloride (AMP-TAC, M₂) has been synthesized. Free radical copolymerization with acrylamide (AM, M₁) in feed ratios varying from 10 to 50 mol % AMPTAC gave the cationic ATAM series. Copolymer compositions were determined from ¹³C-NMR. The reactivity ratio product r₁r₂ was found to be 0.62. Molecular weights varied from 1.4 to 16.5 × 10⁶ g/mol for the copolymers. Turbidimetric studies showed aqueous solutions of the copolymers to be phase stable in the presence of CaCl₂ and Na₂CO₃ up to 100°C. Solution behavior was independent of pH in the range of 3 to 11, and temperature in the range of 25 to 60°C. Intrinsic viscosities of the cationic copolymers decreased with the addition of electrolytes; however, some samples showed curvature in plots of intrinsic viscosity versus the inverse square root of ionic strength. © 1993 John Wiley & Sons, Inc.     

Synthesis and Polymerization of Optically Active Di-L-Menthyl Itaconate

Optically active di-L-menthyl itaconate (DMI) was prepared from itaconic acid and L-menthol. DMI was polymerized in bulk at 80°C to give a chiral homopolymer having a specific rotation of -76.9°. DMI (M ₁) was copolymerized with styrene (ST, M ₂), N-cyclohexylmaleimide (CHMI, M ₂), vinyl acetate (VAc, M ₂) and methyl methacrylate (MMA, M ₂) with azobisisobutyronitrile in benzene at 50°C. The monomer reactivity ratios (r ₁, r ₂) and Alfrey-Price Q, e values were determined as r ₁ = 0.56, r ₂ = 0.55, Q ₁ = 0.76, e ₁ = 0.29 for DMI-ST; r ₁ = 0.0, r ₂ = 5.6 for DMI-MMA; r ₁ = 0.0, r ₂ = 0.25 for DMI-VAc; and r ₁ = 0.31, r ₂ = 0.56 for DMI-CHMI. The chiroptical properties of the polymers were investigated.     

Radical polymerization of 3-methylene-5,5′-dimethyl-2-pyrrolidinone: A cyclic analog of N-substituted methacrylamide

3-Methylene-5,5′-dimethyl-2-pyrrolidinone (α-MDMP), a cyclic analog of N-substituted methacrylamide, was synthesized and polymerized with α,α′-azobis (isobutyronitrile) (AIBN) in solution. Poly(α-MDMP) is only soluble in dimethyl sulfoxide (DMSO) at room temperature. Thermogravimetry of poly(α-MDMP) showed 10% weight loss at 355°C in air and 400°C under nitrogen, respectively. The kinetics of α-MDMP homopolymerization with AIBN was investigated in DMSO. The rate of polymerization (R_p) can be expressed by R_p = k[AIBN]^0.49[α-MDMP]^1.0 and the overall activation energy has been calculated to be 73.2 kJ/mol. Monomer reactivity ratios in copolymerization of α-MDMP (M₂) with methyl methacrylate (M₁) are r₁ = 0.71 and r₂ = 0.71, from which Q and e values of α-MDMP are calculated as 0.75 and -0.43, respectively. © 1993 John Wiley & Sons, Inc.     

Synthesis and Polymerization of N-(L-Menthylcarboxylatomethyl)maleimide

A new type of optically active N-(L-menthylcarboxylatomethyl)maleimide (MGMI) was synthesized from maleic anhydride, glycine, and L-menthol. Radical homopolymerization of MGMI was performed at 50°C for 24 h to give optically active polymer having [α]_D = -57°. Radical copolymerizations of MGMI (M ₁) were performed with styrene (ST, M ₂), methyl methacrylate (MMA, M ₂) in benzene at 50°C. From the results, the monomer reactivity ratios (r ₁, r ₂) and the Alfrey-Price Q, e values were determined as follows: r ₁ = 0.16, r ₂ = 0.006 for the MGMI-ST system; r ₁ = 0.15, r ₂ = 1.65 for the MGMI-MMA system, and Q ₁ = 0.72, e ₁ = 1.59 calculated from the MGMI-MMA system. Anionic homopolymerizations of MGMI were also carried out. Chiroptical properties of the polymers were investigated.     

Syntheses and radical polymerizations of novel optically active vinyl and isopropenyl carbamates having L-leucine structures

Syntheses and radical polymerizations of vinyl and isopropenyl carbamates having L -leucine methyl ester structures, N-vinyloxycarbonyl-L -leucine methyl ester (VOC-L-M) and N-isopropenyloxycarbonyl-L -leucine methyl ester (IOC-L-M), were carried out. VOC-L-M and IOC-L-M were prepared by the reactions of L -leucine methyl ester with vinyl and isopropenyl chloroformates in the presence of sodium hydrogen carbonate. The radical polymerization of VOC-L-M with AIBN (1 mol %) in bulk, chlorobenzene, methanol, and N,N-dimethylformamide afforded the corresponding polymer (poly(VOC-L-M)) with M _n 7,400–19,000. Meanwhile, IOC-L-M afforded no polymer with AIBN at 60°C but afforded a polymer having low molecular weight with BPO at 80°C. The glass transition temperatures of poly(VOC-L-M) and poly(IOC-L-M) were 53 and 65°C, respectively. The 10% weight loss temperatures of poly(VOC-L-M) and poly(IOC-L-M) under nitrogen were 255 and 173, respectively. The copolymerization parameters of VOC-L-M (M₁) and vinyl acetate (M₂) were evaluated as r₁ = 0.92 and r₂ = 0.63. © 1996 John Wiley & Sons, Inc.     

Radical polymerization of new functional monomer: Methacryloyl isocyanate containing 4‐chloro‐1‐phenol

New functional monomer methacryloyl isocyanate containing 4‐chloro‐1‐phenol (CPHMAI) was prepared on reaction of methacryloyl isocyanate (MAI) with 4‐chloro‐1‐phenol (CPH) at low temperature and was characterized with IR, ¹H, and ¹³C‐NMR spectra. Radical polymerization of CPHMAI was studied in terms of the rate of polymerization, solvent effect, copolymerization, and thermal properties. The rate of polymerization of CPHMAI has been found to be smaller than that of styrene under the same conditions. Polar solvents such as dimethylsulfoxide (DMSO) and N,N‐dimethyl formamide (DMF) were found to slow the polymerization. Copolymerization of CPHMAI (M₁) with styrene (M₂) in tetrahydrofuran (THF) was studied at 60°C. The monomer reactivity ratio was calculated to be r₁ = 0.49 and r₂ = 0.66 according to the method of Fineman—Ross. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 469–473, 2000     

Alternating copolymerization of bis(hexafluoroisopropyl) fumarate with styrene and vinyl pentafluorobenzoate: Transparent and low refractive index polymers

Bis(hexafluoroisopropyl) fumarate (BHFIPF) did not homopolymerize with free radical initiators. However, BHFIPF yielded alternating copolymers with styrene in bulk with Azobisisobutyronitrile (AIBN) as a radical initiator. The monomer reactivity ratios of BHFIPF (M₁) and styrene (M₂) were calculated as r₁ = 0.00 and r₂ = 0.02. BHFIPF also copolymerized with vinyl pentafluorobenzoate (VPFB) in bulk and in pentafluoroisopropanol solution to produce an alternating copolymer. The reactivity ratios of BHFIPF (M₁) with VPFB (M₂) were r₁ = 0.00 and r₂ = 0.05 in bulk and r₁ = 0.01 and r₂ = 0.11 in pentafluoroisopropanol, respectively. The glass transition temperatures (T_g) of the BHFIPF‐styrene and BHFIPF‐VPFB copolymers were 107 and 86 °C, respectively. The BHFIPF‐styrene copolymer was thermally stable, and the thermal degradation temperature (T_d) was 400 °C, whereas the T_d of BHFIPF‐VPFB copolymer was 240 °C. The films obtained by casting from tetrahydrofuran (THF) solutions of these copolymers were flexible and transparent. Their refractive indices were 1.4048 for the BHFIPF‐styrene copolymer, and 1.3980 for the BHFIPF‐VPFB copolymer at 633 nm, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Radical Copolymerization of Vinylidene Chloride with 3(2-Methyl)-6-methylpyridazinone in Several Solvents

The radical copolymerization of vinylidene chloride (Vc, M₁) with 3(2-methyl)-6-methylpyridazinone (I, M₂) was carried out in benzene, ethanol, phenol, and acetic acid at 60 and 80°C. The monomer reactivity ratios were found to vary with the reaction conditions. The linear correlationships were obtained by plotting the values of log r₁ against those of ^V C[dbnd]O and ^V C[dbnd]C of monomers determined in the solvents.     

Free Radical Copolymerization of N‐(4‐Carboxyphenyl)maleimide with Hydropropyl Methacrylate

Abstract

The free radical copolymerization of N‐(4‐carboxyphenyl)maleimide (CPMI) (M₁) with hydropropyl methacrylate (HPMA) (M₂) was carried out with 2,2′‐azobis(isobutyronitrile) (AIBN) as an initiator in ethyl acetate at 75°C. The composition of copolymer prepared at low conversion was determined by elemental analysis. The monomer reactivity ratios were found to be r ₁?=?0.31 and r ₂?=?1.11 as determined by the YBR equation. The number‐average molecular weight and polydispersity were determined by gel permeation chromatography (GPC). Furthermore, the solvent effect on this copolymerization system was also investigated. The resulting copolymer was characterized by FTIR and ¹H‐NMR spectroscopy. The thermal stability of copolymers was determined by thermogravimetric analysis (TGA). It was found that the copolymer shows step‐by‐step degradation, the initial decomposition temperature (T _i), and final decomposition temperature (T _f) increased with increasing the component of CPMI in copolymer.     

斯蒂芬酸氢铷的制备，晶体结构和热分解机理

A new compound,[RbHTNR]_∞[HTNR:C_6H(NO_2)_3(OH)O],was synthesized by the reaction of rubidium ni-trate and styphnic acid.The molecular structure was characterized using X-ray diffraction analysis,elementalanalysis and FTIR spectroscopy.The crystalline is monoclinic with space group P2_1/n and the empirical formulaC_6H_2N_3O_8Rb.The unit cell parameters are:a=0.4525 nm,b=1.0777 nm,c=1.9834 nm,β=90.47(2)°,V=0.96725 nm~3,Z=4,D_c=2.263 g/cm~3,Mr=329.58,F(000)=640,μ(Mo Kα)=5.165 mm~(-1).The thermal decompo-sition mechanism of the complex was studied by differential scanning calorimetry(DSC),thermogravimetry-derivative thermogravimetry(TG-DTG)and FTIR techniques.At the linear rate of 10 ℃/min,the thermaldecomposition of the complex showed three mass reducing processes between 60 and 500 ℃,and finally evolvedRbCN and some gaseous products.