Polymerization via zwitterion. 20. Alternating copolymerizations of 2-phenyl-1,3,2-dioxaphospholane with p-and o-formylbenzoic acids

Summary Spontaneous alternating copolymerizations of 2-phenyl-1,3,2-dioxaphospholane (M_N) with p- and with o-formylbenzoic acids (M_E) were examined. The copolymerizations took place without catalysts affording the copolymer 3 via zwitterion 6. The copolymerizations involve the oxidation of the phosphorus monomer and the reduction of formylbenzoic acid. The scheme of the copolymerizations was presented. The yields of copolymers were quite different between these two copolymerizations. With ortho acid, the copolymer yield was low due to producing phthalide 4.     

Polymerization via zwitterion. 24. Copolymerization of a cyclic acyl phosphonite with aromatic aldehydes

Summary Spontaneous copolymerizations of 2-phenyl-4-oxo-5, 6-benzo-1,3,2-dioxaphosphorinane, a new cyclic acyl phosphonite, (M_N) with p- and o-substituted aromatic aldehydes (M_E) gave 1∶2 (M_N ∶ M_E) alternating copolymers. This copolymerization took place without added catalyst affording copolymers via zwitterion . The intermediate of spiro acyloxyphosphorane was detected in situ by 31p NMR. The formation of a stabilized intermediate was taken as an important factor to control the 1∶2 composition. The scheme of the copolymerization involving a zwitterion was presented. For the comparison with the above system, copolymerizations of ethylene phenyl phosphonite with aromatic aldehydes were also examined.     

Alternating copolymerization of 5-oxazolones with electrophilic monomers via zwitterion intermediates

Summary 5-Oxazolone (1a) and 4-methyl-5-oxazolone (1b) were found to serve as a nucleophilic monomer (M_N) toward electrophilic monomers (M_E) like acrylamide (AM) and 2-hydroxyethyl acrylate (HEA). Copolymerizations between these M_N and M_E monomers took place without added initiator at room temperature and at110 °C to give solid polymers having alternating structures of 3 and 4. The molecular weight of these alternating copolymers is not high. The copolymerization mechanism is explained in terms of zwitterionic intermediates involving a proton-transfer step.     

Polymerization via zwitterions. 22. Alternating copolymerization of 2-acryloxypropionic acid with cyclic phosphorus compounds

Summary Alternating copolymerization of 2-acryloxypropionic acid (APA) as a new M_N with two M_N monomers of phosphorus containing ethylene phenyl phosphonite (EPO) and ethylene phenyl phosphite (EPI) have been disclosed. Copolymerizations took place without added catalyst to produce 11 alternating copolymers of APA-EPO and of APA-EPI. The structures of the copolymers were determined by IR and NMR spectroscopy, elemental analyses, as well as the identification of the alkaline hydrolysis products. The copolymerizations were explained in terms of a mechanism of zwitterion intermediates involving a hydrogen transfer process.     

Synthesis and characterization of poly(terphenylenevinylene) derivative with electron withdrawing CN group and an electron donating alkoxy group

New poly(terphenylenevinylene) derivative with an alkoxy group and an electron withdrawing cyano group, poly(1,4-phenylene-2′-methoxy-5′-ethylhexyl-1′,4′-phenylene-1″,4″-phenylene-α-cyanovinylene), was synthesized via the Suzuki coupling reaction. The polymer was completely soluble in common organic solvent and showed good thermal stability up to 380 °C. The presence of the electron withdrawing cyano group lowered LUMO energy level and the presence of the electron donating alkoxy group increased HOMO energy level of the polymer relative to those of poly(terphenylenevinylene). Light emitting diodes (LEDs) with the configuration ITO/PTPCNV/Al and ITO/PPV/PTPCNV/Al were fabricated. ITO/PTPCNV/Al device showed turn on voltage of 5 V (0.005 mA), however, ITO/PPV/PTPCNV/Al exhibited turn on voltage of 2.5 V (0.003 mA). The maximum brightness of the ITO/PPV/PTPCNV/Al device is about 5200 cd/m² at 8 V with a maximum efficiency of 1.243 lm/W. The EL spectrum of the ITO/PPV/PTPCNV/Al device, which was consistent with PL spectrum of PTPCNV, had a maximum peak at 491 nm with a shoulder peak at around 520 nm.     

Polymerization via zwitterion 27. No-catalyst copolymerization of 2-phenyl-1,3,2-dioxaphospholane with β-hydroxyalkyl acrylates and methacrylates

Summary This paper describes No-Catalyst Copolymerizations between ethylene phenylphosphonite (EPO) as M_N and four -hydroxyalkyl acrylates and methacrylates as M_E. In all combinations polyphosphinate type copolymers were obtained above 130 °C without added catalyst. The first step of reaction was a proton-transfer step to yield a transient phosphonium-alkoxide zwitterion 5 and generated a phosphorane intermediate like 6. The subsequent reactions of 6 were rather complicated. It was possible to conceive several zwitterions to lead to polymer units. The liberation of ethylene oxide and/or propylene oxide was observed as a side reaction during polymerization.Dedicated to the 60th birthday of Professor C. I. Simionescu     

Polymerization of cyclic monomers 9. Synthesis and radical polymerization of spirocyclic 2-vinylcyclopropanes

Summary 6,6-Diethyl- (1a) and 6-methyl-6-propyl-5,7-dioxa-4,8-dioxo-1-vinylspiro[2.5]octane (1b) were synthesized by the acetalization of 2-vinylcyclopropane-1,1-dicarboxylic acid with 2- or 3-pentanone. The new monomers were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy. The radical polymerization of the monomers 1a and 1b, in addition of 6,6-methyl-5,7-dioxa-4,8-dioxo-1-vinylspiro[2.5]octane (1c) and (exo/endo)-7-ethoxycarbonyl-2-oxo-7-vinyl-bicyclo[4.1.0]heptane (1d), was carried out in bulk with 2,2`-azoisobutyronitrile (AIBN) as the initiator. The polymer yield with 1d was only low. The polymerization of the monomers 1a and 1c resulted in cross-linked polymers, whereas in case of the polymerization of monomer 1b soluble polymers in a high yield were obtained. Received: 17 February 1999/Revised version: 7 July 1999/Accepted: 7 July 1999     

Polymerization of cyclic monomers6. Synthesis and radical polymerization of asymmetric disubstituted 2-vinylcyclopropanes

Summary Asymmetric disubstituted 1-phenoxy-2-vinylcyclopropanes 1 were synthesized either by the esterification of the corresponding 1-alkoxycarbonyl-2-vinylcyclopropane-1-carboxylic acid with phenol or by the reaction of asymmetric malonates with trans-1,4-dibromo-2-butene. The structure of the new vinylcyclopropanes was confirmed by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The radical polymerization of the asymmetric substituted 2-vinylcyclopropanes in bulk with 2,2'-azoisobutyronitrile (AIBN) results in transparent polymers. The glass transition temperature of the formed polymers varries between 41 und 61°C. Received: 14 November 1997/Accepted: 20 November 1997     

Reactions of unsaturated fatty alcohols. XIII. copolymers of unsaturated fatty vinyl ethers and cyclic monomers

Conjugated linseed, conjugated soybean, and nonconjugated linseed vinyl ethers were copolymerized with various cyclic comonomers. The comonomers used were dihydroabietyl, cyclohexyl, 5-norbornene-2-methyl, di- and tetra-hydrodicyclopentadienyl vinyl ethers, and cyclo-and methylcyclo-pentadiene. All copolymers containing a cyclic comonomer gave baked films that are distinctly superior to unmodified drying oils or vinyl ether homopolymers in hardness and alkali resistance. Several of these copolymers air-dried overnight to moderately hard, wrinkle-free films. The improvement in hardness and alkali resistance may be caused by the steric effects of the cyclic comonomers. These hold the fatty side chains apart thus increasing the proportion of intermolecular to intramolecular crosslinking. Presented in part at the spring meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.     

Electroinitiated emulsion polymerisation of vinyl monomers. III. Homopolymerisation and copolymerisation with vinyl acetate

Of the monomers studied, vinyl acetate and vinyl n-caproate are the only ones capable of electroinitiated homopolymerisation in aqueous acidic emulsion. Water solubility does not appear to be the overriding consideration. Activity of the radical would seem to be most important. Copolymerisation with monomers not undergoing homopolymerisation in this system produces good yields of copolymers low in vinyl acetate concentration.     

Poly(vinyl chloroformate) and derivatives: 2. Copolymerization of vinyl chloroformate and of phenyl vinyl carbonate with vinyl monomers

Vinyl chloroformate and phenyl vinyl carbonate have been copolymerized with vinyl acetate in methylene chloride at 35°C, using dicyclohexylperoxydicarbonate as initiator. The copolymerization parameters obtained show that vinyl chloroformate and vinyl acetate have nearly the same reactivity whereas phenyl vinyl carbonate is slightly less reactive than vinyl acetate.     

The plasma polymerization of vinyl monomers. I. The design,construction, and operation of an inductively coupled plasma generator and preliminary studies with nine monomers

An apparatus was constructed which would allow vinyl-type monomers (and others) to polymerize at ambient temperatures in the presence of an inductively coupled RF field. The details of the construction of the system are reported along with preliminary results obtained from nine monomers: styrene, methylvinyldichlorosilane, vinyl acetate, acrylonitrile, vinyl fluoride, 1,1-difluoroethylene, vinyl chloride, ethylene, and 1,3-butadiene.     

Organotin polymers XIV. Synthesis and copolymerization reactions of p-acryloyloxy-tri-n-butyltin benzoate with some vinyl monomers

p-Acryloyloxy-tri-n-butyltin benzoate (ABTB) was prepared by the reaction of p-hydroxy-tri-n-butyltin benzoate and acrylic acid in the presence of dicyclohexylcarbodiimide. The monomer reactivity ratios for the copolymerizations of ABTB (M₁) with methyl acrylate (M₂), ethyl acrylate (M₂), n-butyl acrylate (M₂), methyl methacrylate (M₂), styrene (M₂) and acrylonitrile (M₂) have been found to be r₁ = 0.080, r₂ = 1.046; r₁ = 0.039, r₂ = 1.585; r₁ = 0.019, r₂ = 2.076; r₁ = 0.150, r₂ = 1.710; r₁ = 0.113, r₂ = 1.339 and r₁ = 0.007, r₂ = 2.853, respectively. The Q and e values for the prepared organotin monomer were calculated. Copolymerization reactions were carried out in solution at 70°C using 1 mol-% azobisisobutyronitrile. The structure of the ABTB monomer and the prepared copolymers was investigated by IR and ¹H-NMR spectroscopy.     

低聚合度、低醇解度聚乙烯醇的合成与性能研究——I.低聚合度聚醋酸乙烯酯的合成

以甲醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,采用自由基聚合方法合成了低聚合度聚醋酸乙烯酯,并对其结构进行了表征。讨论了聚合时间、引发剂用量、物料配比、聚合温度等因素对聚合率的影响,获得了相对较佳的工艺参数。     

Graft copolymerization of vinyl monomers with modified cotton. II. Grafting of acrylonitrile and methyl methacrylate on acetylated cotton

Ce(IV)-induced polymerization of acrylonitrile and methyl methacrylate with acetylated cotton having different acetyl contents was investigated. The extent of interaction between the cotton and monomer is dependent upon the acetyl content of the former as well as on the reaction conditions. Increasing the acetyl content caused a significant decrease in the graft yield. Increasing the acrylonitrile concentration was accompanied by a substantial increase in the graft yields. The same effect was found with the initiator up to a certain concentration, but beyond it there was a reversal. The rate of grafting increased by rising the temperature and follow the order 60° > 40° > 30°C. The Ce(IV) consumption during grafting is greater than that consumed during oxidation. The consumption of Ce(IV) by the cellulosic materials was favorably influenced by the concentrations of monomer and initiator, time, and temperature. Rates of grafting and Ce(IV) consumption during oxidation of acetylated cottons having different acetyl contents strongly support the postulated mechanism of grafting using the Ce(IV)–cellulose redox system. Ce(IV) oxidation had practically no effect on the acetyl groups (expressed as per cent combined acetic acid) of the modified cotton.     

Permeability of solutes through cellophanes grafted with vinyl monomers. I. Diffusion of potassium chloride,urea, and uric acid

The diffusive permeability of potassium chloride, urea, and uric acid through cellophanes grafted with acrylamide, acrylic acid, styrene, and N-vinyl-2-pyrrolidone by γ-ray irradiation was studied. The diffusive permeability coefficients of the permeants through the grafted cellophanes were increased with increase in hydration of the grafted membranes, except for the permeation of potassium chloride through cellophanes grafted with acrylic acid. The permeation of potassium chloride, urea, and uric acid through the various grafted cellophanes is explained by the free volume concept of homogeneously water-swollen membranes. However, the behavior of the permeation of potassium chloride through cellophane grafted with acrylic acid deviated from that of nonionic membranes because of the contribution of the electrical interaction between electrolyte and charge of the membrane.