Synthesis and Polymerization of Optically Active Mono-I-Menthyl Itaconate

Optically active mono-l-menthyl itaconate (MMI) was prepared from ita-conic acid and l-menthol. MMI was polymerized in bulk at 80°C to give a chiral homopolymer having -49.5° specific rotation. MMI (M₁ was copolymerized with styrene (ST, M₂), methyl methacrylate (MMA, M₂), and N-cyclohexylmaleimide (CHMI, M₂) by using 2,2′-azobisisobutyronitrile (AIBN) as the radical initiator and benzene as the polymerization solvent at 50°C. The monomer reactivity ratios (r₁, r₂) and Alfrey-Price Q, e values were determined to be r₁ = 0.28, r₂ = 0.32, Q₁ = 0.90, and e₁ = 0.75 in MMI-ST; r₁ = 0.09 and r₂ = 0.51 in MMI-MMA; and r₁ = 0.78 and r₂ = 0.39 in MMI-CHMI. The chiroptical properties of the polymers were investigated.     

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.     

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.     

Microstructure of the copolymers of methyl methacrylate with other methacrylates obtained by radical and anionic copolymerizations in tetrahydrofuran

Monomer reactivity ratios r₁ and r₂ were determined in the copolymerizations of methyl methacrylate (MMA, M₁) with 1, 1-diphenylethyl (DPEMA), α,α-dimethylbenzyl (DMBMA), tert-butyl (t-BuMA), diphenylmethyl (DPMMA), phenyl (PhMA), and 1-naphthyl (NpMA) methacrylates (M₂) in tetrahydrofuran (THF) by azobisisobutyronitrile (AIBN) at 60°C and butyllithium (n-BuLi) at ?78°C. The reactivities of the monomers were explained in terms of the polar effect of the ester groups in both copolymerizations. All the copolymers isolated in low yields were converted to PMMA either directly or by copoly(MMA—methacrylic acid) to determine the triad tacticities of the copolymers. Coisotactic parameters σ₁₂ and σ₂₁ were determined by assuming the terminal model statistics. The σ₂₁ values always accorded to the σ₂₁ values within experimental error, and in radical copolymerizations they were between isotactic parameters σ₁₁ and σ₂₂ of the homopolymerizations of MMA and M₂ monomers. In anionic copolymerizations, however, the σ₁₂ = σ₂₁ values varied, depending on the M₂ monomers. In copolymerization with DPEMA the values were less than both σ₁₁ and σ₂₂ with DMBMA they were between σ₁₁ and σ₂₂, with DPMMA, nearly equal to σ₁₁, and with PhMA and NpMA, greater than both σ₁₁ and σ₂₂. The application of these parameters to copolymerizations performed at high conversion was also investigated.     

Reactivity of methacrylates in anionic copolymerization with methyl methacrylate by n-BuLi

Monomer reactivity ratios, r₁ and r₂ were determined in the anionic copolymerizations of methyl methacrylate (MMA, M₁) with ethyl (EtMA), isopropyl (i-PrMA), tert-butyl (t-BuMA), benzyl (BzMA), α-methylbenzyl (MBMA), diphenylmethyl (DPMMA), α,α-dimethylbenzyl (DMBMA), and trityl (TrMA) methacrylates (M₂) by use of n-BuLi as an initiator in toluene and THF at -78°C. The order of the reactivity of the monomers towards MMA anion was DPMMA > BzMA > MMA > EtMA > MBMA > i-PrMA > t-BuMA > TrMA > DMBMA in toluene and TrMA > BzMA > MMA > DPMMA > EtMA > MBMA > i-PrMA > DMBMA > t-BuMA in THF. Except for the extremely low reactivity of TrMA and DPMMA in toluene due to steric hindrance, the order was explained in terms of the polar effect of the ester groups. A linear relationship was found between log (1/r₁) and Taft's σ* values of the ester groups, where the ρ* value was 1.1. The plots of log (1/r₁) vs. the ¹H_a (cis to the carbonyl) and ¹³C_ß chemical shifts of the monomers were also on straight lines. The polymer obtained in the copolymerization of MMA with TrMA in toluene by n-BuLi at -78°C was a mixture of poly-MMA and a copolymer, suggesting that there exist two kinds of growing centers.     

Self-crosslinkable polymers. IV. Copolymerization of 1-ethenyl-4-(2,3-epoxy-1-propoxy)benzene with vinylpyridines

Soluble and self-crosslinkable linear copolymers with pendant epoxy and pyridyl groups were obtained from 1-ethenyl-4-(2,3-epoxy-1-propoxy)benzene (M₁) and vinylpyridines (M₂) by the action of α,α′-azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C (r₁, r₂, and vinylpyridine given): 0.467, 0.638, 4-vinylpyridine; 0.556, 1.25, 2-vinylpyridine; 0.639, 1.38, 5-ethyl-2-vinylpyridine. The Q and e values for 1-ethenyl-4-(2,3-epoxy-1-propoxy)-benzene were calculated as 1.3–1.6 and ?1.1–?1.3, respectively, with the reported Q–e values for these vinylpyridines. The intrinsic viscosities of the copolymers were found to be 0.15–0.30 in tetrahydrofuran at 30°C and to be dependent on the copolymer composition. The copolymers with these vinylpyridines were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.     

Syntheses and thermostabilities of N-[4-(N′-substituted aminocarbonyl)phenyl]maleimide polymers

Three types of novel N-[4-(N′-substituted aminocarbonyl)phenyl] maleimide (RPhMI: N-substituent (R) = phenyl, cyclohexyl, and cyclododecyl) were synthesized and homopolymerized under several conditions. In the copolymerizations of RPhMI (M₁) with styrene (ST; M₂) or methyl methacrylate (MMA; M₂), monomer reactivity ratios and Alfrey-Price Q, e values were determined. All homopolymers decomposed without softening and melting points. The initial degradation temperatures (T_d) of poly(RPhMI)s were over 320°C. The glass transition temperatures (T_g) of RPhMI copolymers were much higher than those of N-phenylmaleimide (PhMI)–ST, PhMI–MMA, N-cyclohexylmaleimide (CHMI)–ST, and CHMI–MMA copolymers. Thermal stability of the terpolymers of RPhMI with ST and acrylonitrile (AN) was higher than that of ST–AN copolymers, i.e., AS resin. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2001–2012, 1998     

Polymerization of α-methylene-N-methylpyrrolidone

α-Methylene-N-methylpyrrolidone (α-MMP) was synthesized and homopolymerized by bulk and solution methods. The poly(α-MMP) is readily soluble in water, methanol, methylene chloride, and dipolar aprotic solvents at room temperature. Thermogravimetric analysis of poly(α-MMP) showed a 10% weight loss at 330°C in air. The kinetics of α-MMP homopolymerization and copolymerization were investigated in acetonitrile, using azobisisobutyronitrile (AIBN) as an initiator. The rate of polymerization R_p could be expresed by R_p = k[AIBN]^0.49[α-MMP]^1.3. The overall activation energy was calculated to be 84.1 kj/mol. The relative reactivity ratios of α-MMP (M₂) copolymerization with methyl methacrylate (r₁ = 0.59, r₂ = 0.26) in acetonitrile were obtained. Applying the Q-e scheme led to Q = 2.18 and e = 1.77. These Q and e values are larger than those for acrylamide derivatives.     

Polymerization of meta-naphthoquinone methide: 3,4-benzo-6-methylenebicyclo [3.1.0] hex-3-ene-2-one

Polymerization behavior of meta-naphthoquinone methide, 3,4-benzo-6-methylenebicyclo[3.1.0]hex-3-ene-2-one ( 1 ), was studied. Radical initiator 2,2′-azobis(isobutyronitrile) (AIBN) induced polymerization of 1 , but ionic initiators potassium tert-butoxide, butyllithium, and boron trifluoride etherate did not. Polymerization of 1 proceeded via ring-opening and aromatization to give a polymer with head-to-tail monomer unit placement. Compound 1 copolymerized with methyl methacrylate (MMA) in the presence of AIBN to obtain the monomer reactivity ratios r₁ ( 1 ) = 0.28 ± 0.07 and r₂(MMA) = 0.39 ± 0.02 at 60°C and Q and e values of Q = 1.04 and e = −1.03, indicating that 1 is a conjugative and electron-donating monomer. Ring-opening and aromatization of 1 also took place in the copolymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 741–746, 1997     

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.     

Self-crosslinkable polymers. I. Copolymerization of glycidyl methacrylate with 2-vinylpyridine and 2-vinyl-5-ethylpyridine

A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M₁) and 2-vinylpyridine (M₂) or 2-vinyl-5-ethylpyridine (M₂) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r₁ = 0.510, r₂ = 0.620 with 2-vinylpyridine and r₁ = 0.57, r₂ = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.     

Ferrocene-containing polymers. II. Radiation-induced copolymerizations of ferrocenylmethyl methacrylate with styrene,methyl methacrylate,and ethyl acrylate

Ferrocenylmethyl methacrylate (FMMA) was copolymerized with styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in benzene solution at 25°C by γ radiation. The reactions proceeded by a free radical mechanism, and monomer reactivity ratios were derived by the Tidwell–Mortimer method for St(M₁)–FMMA(M₂), r₁ = 0.35 and r₂ = 0.46; for MMA(M₁–FMMA)(M₂), r₁ = 0.85 and r₂ = 1.36; for EA(M₁)–FMMA(M₂), r₁ = 0.36 and r₂ = 3.03. The Q and e values of FMMA determined from copolymerization with St were 0.97 and 0.55, respectively. Terpolymerization of a MMA–FMMA–EA system based on the Alfrey–Goldfinger equations was studied. This is a typical terpolymerization system in which reactivities of the monomers obey the Q–e scheme. Comparing the results obtained here with those previously reported for other monomers, we concluded that FMMA is one of the most highly reactive monomers among alkyl methacrylates.     

Vinylhydroquinone. III. Copolymerization of vinylhydroquinone and vinyl monomers by tri-n-butylborane

The copolymerization of vinylhydroquinone (VHQ) and vinyl monomers, e.g., methyl methacrylate (MMA), 4-vinyl-pyridine (4VP), acrylamide (AA), and vinyl acetate (VAc), by tri-n-butylborane (TBB) was investigated in cyclohexanone at 30°C under nitrogen. VHQ is assumed to copolymerize with MMA, 4VP, and AA by vinyl polymerization. The following monomer reactivity ratios were obtained (VHQ = M₂): for MMA/VHQ/TBB, r₁ = 0.62, r₂ = 0.17; for 4VP/VHQ/TBB, r₁ = 0.57, r₂ = 0.05; for AA/VHQ/TBB, r₁ = 0.35, r₂ = 0.08. The Q and e values of VHQ were estimated on the basis of these reactivity ratios as Q = 1.4 and e = ?;1.1, which are similar to those of styrene. This suggests that VHQ behaves like styrene rather than as an inhibitor in the TBB-initiated copolymerization. No homopolymerization was observed either under nitrogen or in the presence of oxygen. The reaction mechanism is discussed.     

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     

Radical copolymerization of 3-tri-n-butylstannylstyrene with several vinyl monomers

The free radical homopolymerization and copolymerization of 3-tri-n-butylstannylstyrene (3-BTS) with styrene (ST), ethyl acrylate (EA), methyl methacrylate (MMA), vinyl acetate (VA), and acrylonitrile (AN) were carried out using 2,2′-azobisisobutyronitrile (AIBN) at 60°C. It was found that the yield of conversion to poly(3-BTS) increased with the molar ratio of initiator to monomer as well as with polymerization time. The conversion at equilibrium after 50 h was about 40%. The compositions of copolymer samples were determined from elemental analyses. Monomer reactivity ratio and Q-e values were calculated. The copolymers of 3-BTS-MMA and 3-BTS-AN were found to be alternating. The copolymers of 3-BTS with MMA, EA and AN were not soluble in any of a large number of organic solvents tested. The insolubility is believed to be due to formation of intermolecular coordination among the tributylstannyl moiety and the carbonyl or cyano groups of the polymer. These copolymers, however, were “soluble” in trihaloacetic acid, but this solubility was due to a cleavage of the trialkyltin moiety from the phenyl groups. The glass temperatures, T_g, and melting temperatures T_m, of the various polymers were also studied.     

Silyl enol ethers as monomer. III. Radical polymerization and copolymerizations of 2-trimethylsilyloxy-1,3-butadiene and desilylation of the resulting polymers

2-Trimethylsilyloxy-1,3-butadiene (TMSBD), the silyl enol ether of methyl vinyl ketone, was homopolymerized with a radical initiator to afford polymers with a molecular weight of ca. 10⁴. Radical copolymerizations of TMSBD with styrene (ST) and acrylonitrile (AN) in bulk or dioxane at 60°C gave the following monomer reactivity ratios: r₁ = 0.64 and r₂ = 1.20 for the ST (M₁)–TMSBD (M₂) system and r₁ = 0.036 and r₂ = 0.065 for the AN (M₁)–TMSBD (M₂) system. The Q and e values of TMSBD determined from the reactivity ratios for the former copolymerization system were 2.34 and ?1.31, respectively. The resulting polymer and copolymers were readily desilylated with hydrochloric acid or tetrabutylammonium fluoride as catalyst to yield analogous polymers having carbonyl groups in the polymer chains.     

Vinylhydroquinone. IV. Preparation and polymerization behavior of 2-methyl-5-vinylhydroquinone derivatives

As in the case of vinylhydroquinone (I), its alkyl-substituted derivative, 2-methyl-5-vinylhydroquinone (II) was found to copolymerize with methyl methacrylate by tri-n-butylborane in cyclohexanone at 30°C. II was prepared from the O,O′-bisether compound, 2-methyl-5-vinyl-O,O′-bis(1′-ethoxyethyl)hydroquinone (III). The monomer reactivity ratios (M₂ = II) were determined to be r₁ = 0.37 and r₂ = 0. No homopolymerization proceeded under the same conditions. Ordinary free-radical initiators, such as azobisisobutyronitrile and benzoyl peroxide, were not effective in the homopolymerization of II. 1:1 Copolymers were obtained from II and maleic anhydride by using tri-n-butylborane as an initiator. The copolymers exhibited no definite melting range and decomposed at 370–375°C endothermally (DSC). The polymerization behavior of III was also investigated. Although tri-n-butylborane did not initiate the homopolymerization of the monomer, azobisisobutyronitrile was capable of initiating the homopolymerization and copolymerization of III. The monomer reactivity ratios (M₁ = styrene) were determined to be r₁ = 0.83 and r₂ = 0.18. The ratios gave the following Q and e values; Q = 0.15 and e = ?2.2.     

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.     

Organometallic polymers. XIV. Copolymerization of vinylcyclopentadienyl manganese tricarbonyl and vinylferrocene with N-vinyl-2-pyrrolidone

N-Vinyl-2-pyrrolidone(I) has been copolymerized with vinylferrocene(II) and vinylcyclopentadienyl manganese tricarbonyl(III) in degassed benzene solutions with the use of azobisisobutyronitrile (AIBN) as the initiator. The polymerizations proceed smoothly, and the relative reactivity ratios were determined as r₁ = 0.66, r₂ = 0.40 (for copolymerization of I with II, M₁ defined as II) and r₁ = 0.14 and r₂ = 0.09 (for copolymerization of I with III, M₁ defined as III). These copolymers were soluble in benzene, THF, chloroform, CCl₄, and DMF. Molecular weights were determined by viscosity and gel-permeation chromatography studies (universal calibration technique.) The copolymers exhibited values of M?_n between 5 × 10³ and 10 × 10³ and M?_w between 7 × 10³ and 17 × 10³ with M?_w/M?_n < 2. Upon heating to 260°C under N₂, copolymers of III underwent gas evolution and weight loss. The weight loss was enhanced at 300°C, and the polymers became in creasingly insoluble. Copolymers of vinylferrocene were oxidized to polyferricinium salts upon treatment with dichlorodicyanoquinone (DDQ) or o-chloranil (o-CA) in benzene. Each unit of quinone incorporated into the polysalts had been reduced to its radical anion. The ratio of ferrocene to ferricinium units in the polysalts was determined. The polysalts did not melt at 360°C and were readily soluble only in DMF.