Poly(alkylene oxide) ionomers IX. Polymerization of methyl ω-epoxyalkanoates and characterization of the polymers

Polymerization of linear methyl ω-epoxyalkanoates of C-3 to C-10 carboxylic acids (0 to 7 methylene groups between oxirane ring and carbomethoxy group) was accomplished with a triethylaluminum/water/acetylacetone (1.0/0.5/1.0) initiator system to yield polymers of high molecular weight, apparently via a coordinative anionic mechanism. The rate of polymerization increased as the number of methylene groups between the oxirane ring and the carbomethoxy group increased, up to three methylene groups. When more than three methylene groups separate the polymerizable oxirane group and the carbomethoxy group, the rate of polymerization becomes essentially constant. The polymers were characterized by their infrared and ¹³C-NMR spectra, DSC, GPC, and inherent viscosity. The lower members of the series (ω-epoxyalkanoates of n < 3) gave polymers of lower molecular weight and wider-molecular-weight distribution (M _w/M _n > 2), while the higher members had molecular weight distributions between 1.5 and 2. The glass transition temperatures of the polymers also decreased from ?26°C for n = 1 to around ?50 to ?55°C for n ≥ 3.     

Coordination polymerization of ω-alkenoates and ω-epoxyalkanoates

As functional polymers have become more and more used, the need for a general synthesis of addition polymers with functional groups became greatly important. We have achieved the polymerization of ω-alkenoates with coordination initiators of the Ziegler-Natta initiation type using titanium trichloride-based transition metal initiators modified with dialkylaluminum chloride. To accomplish this polymerization required that the ω-alkenoates be precomplexed with dialkylaluminum chloride. High molecular weight homopolymers and copolymers with olefins have been obtained. The polymerization of ω-epoxyalkanoates with coordinative anionic polymerization systems based on triethylaluminum/water/acetylacetone (1.0/0.5/1.0) has also been accomplished. Homo- and copolymers of high molecular weight and of relatively narrow molecular weight distribution have been prepared. All polymers and copolymers of functional olefins and epoxides have been characterized and the study of the reactivity of the functional groups attached via a flexible spacer to the polymer main chain has been started. Special attention was given to the classical cationic copolymerization of trioxane with derivatives of ω-epoxyundecanoate to prepare novel functional polyoxymethylenes of potential commercial interest.     

Functional polymers. XLIX. Copolymerization of ω-alkenoates with α-olefins and ethylene

The 2,6-dimethylphenyl ester of 10-undecenoic acid was copolymerized with 1-dodecene, 1-octene, 1-hexene, propylene, and ethylene using coordination initiation systems based on “aluminum-activated” titanium trichloride and dialkylaluminum chlorides. The copolymerizations with higher α-olefins proceeded smoothly and gave copolymers incorporating from 60 to 90% of the 10-undecenoate feed. Copolymerization with propylene gave incorporation of 5 mol % of 2,6-dimethylphenyl 10-undecenoate; with ethylene only 3 mol % of the ω-alkenoate was readily incorporated. All copolymers were characterized by elemental analysis, dilute solution viscosity, and by their IR ¹H- and ¹³C-NMR spectra.     

Functional polymers. XLVIII. Polymerization of ω-alkenoate derivatives

Esters of ω-alkenoic acids have been homopolymerized with transition metal initiating systems. The key to the successful polymerization was the complexation of the monomer prior to its addition to the initiating system. Titanium trichloride, aluminum activated, was found to be best as the transition metal part of the initiator systems, with diethyl-, or better, diisobutylaluminum chloride as the reducing agents and n-hexane or toluene as the solvents. Best results for polymerizations were obtained with 2,6-dimethylphenyl esters of the functional α-olefin monomers; however, other phenyl esters also polymerized well. Attempts to polymerize methyl 10-undecenoate gave the corresponding polymer in only low yields. Polymers of the 2,6-dimethylphenyl esters, obtained in high molecular weight, were characterized. Polymers were also obtained from 2,6-dimethylphenyl 7-octenoate, but not from ω-alkenoates with less than three methylene units between the ester group and the terminal olefin group. Poly(2,6-dimethylphenyl 10-undecenoate) was hydrolyzed in an aqueous sodium hydroxide/1,4-dioxane solution to poly(sodium 10-undecenoate) that in turn was neutralized with acetic acid to poly(10-undecenoic acid).     

Cationic polymerization of γ-methyl- and α-methylphenylallene

The cationic polymerizations of γ-methylphenylallene ( 1 ) and α-methylphenylallene ( 2 ) were carried out with some Lewis acids at 25 and 0°C in dichloromethane to obtain the corresponding polymers through allyl cations, respectively. Tin (IV) chloride was found to be an effective catalyst for the cationic polymerization of both allenes 1 and 2 compared with other Lewis acids. Thus, in the polymerization of 1 , methanol-insoluble polymer was only obtained using Tin (IV) chloride, and M?_n of methanol-insoluble polymer obtained by Tin (IV) chloride was the highest in the polymerization of 2 . From the analysis of ¹H- and ¹³C-NMR spectra of the obtained polymers, the polymer from 1 consisted of two kinds of units polymerized by each double bonds of allene 1 , whereas the polymer from 2 consisted of only one unit polymerized by terminal double bond of allene 2 . Moreover, effect of solvent on the cationic polymerizations of 1 and 2 were discussed.     

Functional polymers. XLVII. Synthesis of various derivatives of ω-alkenoates

A number of derivatives of ω-alkenoates were synthesized in preparation for the synthesis of functional polymers based on α-olefins. For the preparation of most of the methyl esters, the regular esterification of ω-alkenoic acids, specifically 10-undecenoic acid with methanol and sulfuric acid as the catalyst, was most effective. For the preparation of the tert-butyl- and 2-ethylhexyl esters of 10-undecenoic acid, the acid chloride route was found to be most convenient, whereas for the preparation of the corresponding esters of 5-hexenoic acid, our method of choice was the synthesis via the imidazolyl derivative of the acid. 2,2,2-Trifluoroethyl 10-undecenoate and the 2,2-dimethyloxazolidine derivative of 10-undecenoic acid were prepared from the acid and 2,2,2-trifluoroethanol or 2-amino-2-methyl-propanol with p-toluene sulfonic acid as the catalyst. Esters of phenol, 2,6-dimethylphenol, and 2,6-diphenylphenol were synthesized from 3-butenoic and 10-undecenoic acid with trifluoroacetic anhydride.     

Study of the synthesis of poly(isobutylene-b-amide-11) by polycondensation α,ω-dianhydride oligoisobutylene with α,ω-diamino oligoamide-11. II. Synthesis of the block copolymers by reaction in solution

Several di-, tri- or multiblock poly(isobutylene-b-amide-11)s are prepared by reaction of α-mono or α,ω-dianhydride oligoisobutylenes with α-mono or α,ω-diamino oligoamides, in o-dichorobenzene at 140°C. They are characterized mainly by ¹H- and ¹³C-NMR spectroscopy and GPC, using the trifluoroacetylation technique. Their thermal differential chromatograms are reported and analyzed.     

Synthesis of halogenated monodispersed telechelic oligomers. III. Bistelomerization of allyl acetate with telogens which exhibit α, ω-di(trichloromethyled) end groups

The redox bistelomerization of allyl acetate with telogens which exhibit α, ω-di(trichloromethyled) end groups catalyzed by copper, iron salts, or a ruthenium complex led to monoadducts and telechelic oligomers. These diacetates were quantitatively changed into diols. Such compounds have been characterized by both ¹H- and ¹³C-NMR. A reactivity series has been determined and shows that both end groups must be activated to obtain the expected telechelic products in satisfactory yields.     

Synthesen von ω-substituierten ω-Nitrocarbonsäureestern aus α-Nitrocycloalkanonen

Synthesis of ω-Nitroalkanoates Substituted in ω-Position from α-Nitrocycloalkanones α-Nitrocycloalkanones substituted in α-position by a functionalized alkyl residue underwent ring opening to the corresponding chain derivatives by intermolecular nucleophilic attack; ω-nitroalkanoates substituted in ω-position were obtained (Scheme 1). The so formed methyl 6-nitro-9-oxodecanoate ( 3 ) was used to prepare methyl 8-(2-methyl-1,3-dioxolan-2-yl)octanoate ( 15 ), an intermediate in the synthesis of the sex phermone of the honey bee.     

Preparation of polymandelide by reaction of α-bromophenylacetic acid and triethylamine

Polymandelide was prepared in 77% yield by reaction of α-bromophenylacetic acid and triethylamine. The product was characterized by ¹H- and ¹³C-NMR and IR spectra and isolation and identification of mandelic acid from hydrolysis of the polymer. The NMR spectra indicate the presence of tacticity at CH in the polymer. Molecular weights were determined by GPC and viscosity measurements; n values of 12–20 are comparable to those reported for polymandelides prepared by other methods. The x-ray powder diffraction pattern showed the product to be completely amorphous. Thermal decomposition was studied using DSC.     

13N-NMR spectroscopy. XXXV. Sequence analysis of alternating and random copolyamides made up of aliphatic and aromatic ω-amino acids

Alternating copolyamides of various ω-amino acids were synthesized by base-catalyzed polycondensation of N-isothiocyanatoacyl ω-amino acids in solution. Derivatives of the following amino acids were used: glycine, β-alanine, γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, D ,L -β-aminobutyric acid, trans-4-aminocyclohexane 1-carboxylic acid, 4-aminophenyl acetic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-4-methyl benzoic acid, and 4-amino-3-methyl benzoic acid. The base-catalyzed polycondensation at lower temperatures gave purer products than the bulk condensation at 180–200°C. ¹³C-NMR and natural-abundance ¹⁵N-NMR spectra measured in trifluoroacetic acid demonstrate that in most cases undisturbed alternating sequences were obtained. Strong neighboring residue effects and long-range sequence effects were found in the ¹⁵N-NMR spectra, and structure/shift relationships are discussed. The sequences of copolyamides obtained by copolymerizations of lactams or β-amino acid N-carboxyanhydrides were investigated by both ¹⁵N-NMR and ¹³C-NMR spectroscopy. ¹³C-NMR spectroscopy was found to be more useful if the copolyamides consist of ω-amino acid units of different chain length. However, ¹⁵N-NMR spectroscopy is more suited if the monomer units differ exclusively by their substituents.     

Poly(alkylene oxide) ionomers. X. Copolymerization of methyl ω-epoxyalkanoates and characterization of the polymers

Selected methyl ω-epoxyalkanoates ranging from methyl 3,4-epoxybutanoate to methyl 7,8-epoxyoctanoate were copolymerized with a number of oxiranes and with oxetane. Tetrahydrofuran did not take part in the attempted methyl ω-epoxyalkanote–tetrahydrofuran copolymerization, but acted only as the solvent. The oxirane copolymers had polymer compositions similar to the comonomer feed ratio. Oxirane comonomers used were propylene oxide (1,2-epoxypropane), butylene oxide (1,2-epoxybutane), 1,2-epoxyhexane, epichlorohydrin, and phenylglycidyl ether. The initiator system used was triethylaluminum/water/acetylacetone (1.0/0.5/1.0) in about 5 mol %. In the copolymerizations using methyl 3,4-epoxybutanoate as a comonomer, only small yields of polymer (in the range of 1 to 2%) were realized, while for methyl 4,5-epoxypentanoate the yields were generally in the range of 20 to 60%. Methyl 7,8-epoxyoctanoate copolymerized readily and gave yields of copolymers of 50 to 90%.     

Determination of the Relative Configurations in the Side Chains of the Antibiotics Hedamycin and Pluramycin A; Synthesis and NMR. Data of Suitable Model Compounds

Several diepoxyhexanoates and epoxyhexenoates were prepared by epoxidation of methyl 2-methyl-2,4-hexadienoate or by Darzens condensation. Their ¹ H- and ¹³C-NMR. spectra were measured and assigned. Comparison of these data with the spectra of the antibiotics hedamycin ( 1 ) and pluramycin A ( 2 ) allowed the determi-nation of the relative configurations in the side chains of these antibiotics. They were found to be (14R*,16S*,17R*,18S*) for hedamycin ( 1 ) and (14R*,16S*,17Z) for pluramycin A ( 2 ).     

Synthesen und chemische Reaktionen von ω,ω-Bis(alkylthio)chinonmethiden des 1,6-Methano[10]annulens

Syntheses and Chemical Reactions of ω,ω-Bis(alkylthio)quinonemethides of 1.6-Methano[10]annulenes The syntheses of the donor-acceptor-substituted compounds 3 – 5 , 9 starting from 2 , 7 , or 8 , furthermore, the syntheses of 12 , 15 – 21 are described. The detailed results of ¹H- and ¹³C-NMR-spectroscopic measurements are reported.     

Synthesis and characteristics of the poly(carboxybetaine)s and the corresponding cationic polymers

Two types of carboxybetaines and their corresponding cationic monomers and polymers are synthesized in this study. Comparing the chemical shifts of the methylene groups in the cationic monomers and carboxybetaines in both ¹H- and ¹³C-NMR spectra reveal that the respective methylene groups are clearly distinguished from their chemical shifts in ¹H- and ¹³C-NMR spectra. The solubilities, moisture regain properties, and solution properties of the poly(carboxybetaine)s and cationic polymers are investigated in relation to their molecular structures. Because the cationic polymers were ionized in an aqueous solution, the cationic polymers were more soluble than the poly(carboxybetaine). For the various functional groups of poly(carboxybetaine)s and cationic polymers, the order of tendency for moisture regain is  COO >  CONH . Results obtained from the reduced viscosity for cationic poly(TMMPAMS) are reversed from that for zwitterionic poly(DMAEAPL). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3527–3536, 1997     

Poly(alkylene oxide) ionomers. XIII. Copolymers of trioxane with the epoxide and 1,3-dioxolane of methyl 10-undecenoate

Cationic copolymerization of 1,3,5-trioxane with methyl 10,11-epoxyundecanoate or methyl 7,8-epoxyoctanoate and terpolymerization with 1,3-dioxolane was successfully carried out. Co-and terpolymerization of 1,3,5-trioxane with 4-(1-carbomethoxynonyl)-1,3-dioxolane was also achieved. Feed compositions of the functional comonomers were varied from 5 to 40 mol %; in all cases the isolated copolymers contained less than 5% of the functional mer units. The composition of the copolymers showed that the methyl ω-epoxyalkanoates were much less reactive than 1,3,5-trioxane. A similar trend was observed with the functional dioxolane monomer, although significantly shorter induction periods were observed in comparison with the epoxy/trioxane copolymerizations. The oxymethylene copolymers and terpolymers were characterized primarily by their infrared spectra; however, the thermal and base stabilities of selected copolymers were also determined.     

Darstellung und Charakterisierung von α,ω-Dihydroperchloroligosilanen

Preparation and Characterization of α,ω-Dihydroperchloro Silanes Synthesis for the new compounds H(SiCl₂)_nH, n = 3?7 and HSi₄Cl₅ were described, starting from the perphenylated cyclosilanes. The new compounds were characterized and ¹H- and ²⁹Si-NMR spectra are discussed.     

Stereoregularity of poly(α-methylvinyl alkyl ether)s determined by 1H- and 13C-NMR spectroscopy

α-Methylvinyl methyl ether, ethyl ether, and isobutyl ether were polymerized under various polymerization conditions and the structure of the polymers was determined by ¹H- and ¹³C-NMR spectroscopy. α-Methyl and β-methylene carbon spectra of poly(α-methylvinyl isobutyl ether) showed splitting and were analyzed by triad and tetrad sequences. β-Methylene carbon spectra of poly(α-methylvinyl ethyl ether) also showed splitting. When Eu(fod)₃ was added, α-methyl and methoxy proton spectra in benzene of poly(α-methylvinyl methyl ether) showed splitting assigned to triad tacticities. All the polymers obtained in polar solvents exhibited an increase in syndiotacticity. The polymerization mechanism is discussed.     

Durable and refreshable polymeric N‐halamine biocides containing 3‐(4′‐vinylbenzyl)‐5,5‐dimethylhydantoin

A novel vinyl‐hydantoin monomer, 3‐(4′‐vinylbenzyl)‐5,5‐dimethylhydantoin, was synthesized in a good yield and was fully characterized with Fourier transform infrared (FTIR) and ¹H NMR spectra. Its homopolymer and copolymers with several common acrylic and vinyl monomers, such as vinyl acetate, acrylonitrile, and methyl methacrylate, were readily prepared under mild conditions. The polymers were characterized with FTIR and ¹H NMR, and their thermal properties were analyzed with differential scanning calorimetry studies. The halogenated products of the corresponding copolymers exhibited potent antibacterial properties against Escherichia coli, and the antibacterial properties were durable and regenerable. The structure–property relationships of the polymers were further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3348–3355, 2001     

Infrared spectroscopic analysis of poly(methyl acrylate-co-styrene)

Methyl acrylate–styrene copolymers of different copolymer compositions were free-radically prepared. The relative intensities of the carbonyl frequencies of the methyl acrylate units at v 1730 cm^?1 were correlated with the copolymer composition. The positions and shapes of the carbonyl bands in the infrared absorption spectra of the copolymers-dissolved in chloroform, were shown to depend on the composition of the copolymers and upon the presence of different proportions of methyl acrylate centered triads. The results obtained by infrared spectroscopy were compared with those obtained by ¹³C-NMR. Infrared spectra may be used to yield information about both the copolymer composition and the triad sequence distribution.