Development of an Advanced Process for Manufacturing Polyacetal Resin

Abstract

An advanced process for manufacturing polyacetal resin has been developed. First, a new technology for the production of highly concentrated aqueous formaldehyde was developed by oxidizing methylal. Whereas the oxidation of methanol yields 1 mol water per mole formaldehyde, methylal oxidation produces only 1 mol water for every 3 mol formaldehyde. Thus, the output from methylal oxidation is more than 70% formaldehyde, compared with 55% from methanol oxidation. Second, a new extraction distillation process for formaldehyde purification was developed in order to get highly purified formaldehyde directly from formalin. By using highly purified formaldehyde, an end-capped polymer was obtained in the presence of acetic anhydride as a chain transfer or end-capping agent during polymerization. Third, the relatively high formaldehyde concentration enhances the formation of trioxane. Purified trioxane is copolymerized with ethylene oxide in the presence of an end-capping agent to get an end-capped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated, and a new initiation mechanism was proposed. Fourth, the world's first acetal block copolymer was commercialized by the polymerization of formaldehyde in the presence of a lubricant functional polymer having an active hydrogen atom. This acetal block copolymer exhibits super lubrication properties.     

New Polymers Derived from Poly(Methylphenylphosphazene)

Abstract

The sequential treatment of [Me(Ph)PN]_n with n-BuLi and electrophiles such as substituted chlorosilanes, aldehydes and ketones, and carbon dioxide results in new functionalized polyphosphazenes. Graft copolymers have also been prepared by using the anionic polymer intermediate to initiate anionic addition polymerization of styrene, CH₂=C(Ph)H, and ring opening polymerization of hexamethylcyclotrisiloxane, [Me₂SiO]₃.     

A novel scheme of heterogeneous polymerization of ethylene

The heterogeneous polymerization of ethylene initiated by radiation in tert-butyl alcohol was studied. The polymerization was carried out in a 100-ml reactor at 25–100°C and pressures of 200–300 kg/cm² in the presence of 50 ml of tert-butyl alcohol containing 7 wt-% water. The amounts of polymerized monomer, the average molecular weight of polymer formed, and the molecular weight distribution of polymer were measured at various stages of reaction and at various temperatures. The molecular weight distribution was found to be very much dependent on the reaction time and temperature. For the polymer formed at 50–60°C in the very early stages of reaction, the molecular weight distribution is unimodal, and in the intermediate stage a shoulder appears at a molecular weight higher than the first peak which increases as the polymerization proceeds; eventually a bimodal curve is formed. The bimodal distribution curves were analyzed to determine the fractions and average molecular weights of the each peak. On the basis of these data for the molecular weight distribution and kinetic behavior, a new scheme for the heterogeneous polymerization is proposed which indicates that the polymerization proceeds via propagating radicals in two different physical states, namely, loose and rigid states.     

Cationic Grafting of Vinyl Polymers onto a Carbon Whisker,Initiated by Acylium Perchlorate Groups Introduced onto the Surface

Abstract

The cationic graft polymerization of vinyl monomers onto a carbon whisker, vapor-grown carbon fiber, initiated by acylium perchlorate groups introduced onto the surface, was investigated. The introduction of acylium perchlorate groups onto a carbon whisker was achieved by the treatment of a carbon whisker having acyl chloride groups, which were introduced by the reaction of surface carboxyl groups with thionyl chloride, with silver perchlorate in nitrobenzene. It was found that the cationic polymerization of vinyl monomers, such as styrene, indene, N-vinyl-2-pyrrolidone, and n-butyl vinyl ether, is initiated by acylium perchlorate groups on a carbon whisker. In the polymerization, the corresponding vinyl polymers were grafted onto a carbon-whisker surface based on the propagation of polymer from the surface: the percentage of grafting of polystyrene and polyindene reached 42.5 and 100.3%, respectively. The percentage of polystyrene grafting decreased with increasing polymerization temperature because of preferential chain transfer reactions at higher temperatures. Polymer-grafted carbon whisker gave a stable colloidal dispersion in a good solvent for grafted polymer.     

Anionic Polymerization of Z,Z-2,4Hexadienedinitrile

Abstract

Z,Z-2,4-Hexadienedinitrile, synthesized by the oxidative cleavage of o-phenylenediamine, was found to undergo anionic polymerization with n-BuLi in DMF at room temperature or below. The polymerization behavior appears to be similar to that of acrylonitrile polymerization using n-BuLi as initiator. Infrared and NMR analysis of the polymer indicate the presence of both 1,4 and 1,2 linkages, with the latter predominating.     

Ionic Polymerization under an Electric Field as a Relaxational Method for the Investigation of Kinetics. I. On Results of the Change in Space Distribution of Ions

Abstract

Investigations were made which show that the change in the dynamics of polymerization and in molecular weight of the polymer under an electric field is connected with the redistribution of the ions growing macromolecules and counterions. Analysis of the equations obtained showed that the field can either increase or decrease the rate of the process. The effect's trend and magnitude depend on the ratio of the mobilities of macroions and counterions, degree of dissociation of active centers, and the ratio of rate constants of free ions and ion pairs. An analysis of literature data relevant to polymerization under an electric field was made.     

Structure of cholesteric gels and their electrically induced light scattering and colour changes

Abstract

Networks with a helical structure containing large amounts of low mass liquid crystal molecules (gels) were produced by photopolymerization of a nematic diacrylate in the presence of low mass cholesteric mixtures. Prior to polymerization the systems selectively reflected a band of circularly polarized light. Upon polymerization, the gels obtained gave rise to two reflection peaks which were subsequently associated with polymer rich and polymer poor phases. At high network concentrations (>40 per cent w/w) one of the peaks did not appear, indicating that the behaviour of the molecules which were not chemically attached to the network was totally dominated by the network. From the gap required for the suppression of the rotation of the director, it was estimated that the molecules, which were not crosslinked, were confined in layers thinner than 85 nm. The gels were very transparent and did not give rise to excess light scattering as compared with the monomeric state. Upon application of an electric field, colour changes as well as light scattering were induced. These efffects were found to be highly dependent on the state of the polarization of the light as well as the kind of field applied. The response times were very short and they depended strongly on the structure of the network.     

Effect of oxygen on the γ-radiation-induced polymerization of ethylene

The effects of oxygen on the γ-radiation-induced polymerization of ethylene were studied at a temperature of 30°C.; the pressure was 400 kg./cm.², the dose rate was 1.9 × 10⁵ rad/hr.; and oxygen content was from 1–2000 ppm. The main product was solid polymer, and no liquid product was found. The gaseous products were hydrogen, acetylene, higher hydrocarbons, carbon dioxide, aldehydes, and acids. Several kinds of carbonyls similar to those formed in γ-ray oxidized polyethylene were observed in the polymer. The polymer yield and the degree of polymerization decreased markedly with increasing oxygen content, while the amount of carbonyls in the polymer increased. The number of moles of polymer chain and the amounts of hydrogen and acetylene were found to be almost independent of the oxygen content. The polymerization of pure ethylene was not affected by carbon dioxide and formic acid. On addition of acetaldehyde, the polymer yield and the degree of polymerization decreased markedly, while the number of moles of polymer chain increased. In the polymerization of ethylene containing oxygen, both the rate of oxygen consumption and the carbonyl content of the polymer increased, while the inhibition period decreased by the addition of acetaldehyde. It was found that the degree of polymerization after the inhibition period is almost independent of the reaction time in the presence of acetaldehyde, while it increases with the time in the absence of acetaldehyde.     

Effect of Water and Oxygen on the Polymerization of Vinyl Acetate Initiated by Aluminum Alkyls,Bipyridyls, and Nitroxyl Radicals

Abstract

Effect of water and oxygen on the polymerization of vinyl acetate initiated by aluminum alkyls, bipyridyls and TEMPO is reported. Reactions with nearly complete exclusion of water and oxygen is very slow and provides a mixture of oligomers in a few hours. With small amounts of oxygen (0.01 to 0.05 mol %) and water (0.05 to 0.08 mol %), reactions were significantly accelerated, however, at higher concentrations of water and oxygen, the polymerization rates decreased and polydispersities were higher.     

Radical Photopolymerization of Vinyl Monomers

Abstract

Photopolymerization is the initiation by light of a chain polymerization process. In the more general sense, photopolymerization implies the increase of molecular weight caused by light. Photopolymerization is not only useful for the detection and identification of photochemically produced free radicals; since photopolymerization reactions can be started or stopped at will by the simple expedient of turning on or off light, a means is provided for studying the nonsteady-state kinetics of polymerization [1]. Photopolymerization also allows for the subtle control of molecular weight and molecular weight distribution by varying the intensity of light. Photopolymerization can be confined to local regions since the light can be spatially controlled. Photopolymerization can be carried out at very low temperatures. Hence, chain-transfer processes leading to branched macromolecules will be absent. Photopolymerization at low temperature yields the low-energy stereospecific polymeric species, namely the syndiotactic configuration of the polymer [2]. Certain monomers can only be polymerized at low temperature, i.e., they have low ceiling temperatures; the photopolymerization offers this possibility [3]. Because photopolymerization need not be carried out at elevated temperatures, it has applications to biochemistry. One important application of the method is in disk electrophoresis [4]. Photopolymerization played an important role in the early development of polymer chemistry. One of the first procedures for polymerizing vinyl monomers was to expose the monomer to sunlight. Blyth and Hoffman [5] reported the polymerization of styrene by this method in 1845.     

乙二醛存在时脲醛树脂的控制性聚合现象

考察了乙二醛存在时脲醛树脂的控制性聚合现象.聚合微球的粒径分散在1.0～14μm之间,但当乙二醛存在时粒径集中在6.5～9.0μm;控制乙二醛的用量和比例可以调整所得微球的大小、改善微球的形貌和均匀性.添加乙二醛或增加乙二醛的比例能大幅延长沉淀反应的诱导期(延长25%以上);红外分析以及XRD分析结果证明醛基总量或甲醛比例的增加都可减小聚合产物的结晶性特征;乙二醛的存在调整了脲醛树脂的成核过程或初级粒子的生长速度,推测乙二醛覆盖了聚合物的表面或表面活性位,限制了尿素甲醛的扩散反应过程.乙二醛存在时杂化过程所得氧化硅微球的粒径仅为杂化微球的20%,分析结果推测杂化微球中存在氧化硅的径向含量梯度,这种梯度是氧化硅纳米粒子的杂化和脲醛树脂的聚合速度差异造成的.     

Some Peculiarities of the Radical Polymerization of Methyl Methacrylate in the Presence of Low Molecular Weight Liquid Crystals

Abstract

Radical polymerization of methyl methacrylate (MMA) in the presence of propylbenzene, benzonitrile, their equimolar mixture, and a mixture of nematic liquid crystals (LC) was studied. Chain transfer reaction and unexpected dependence of the initial polymerization rate on LC concentration were revealed by means of UV spectrophotometry, viscometry, and dilatometry. The chain transfer reaction which occurred at the boundary of LC domains in the polymer matrix caused binding of some of the LC molecules to the macromolecules of PMMA. An increase in the initial rate of polymerization and a decrease of polydispersity were explained with formation of the LC phase because growth of the macroradicals continued not only in the homogeneous polymer phase but simultaneously also at the interfacial boundary between the polymer matrix and the LC phase. It is assumed that the LC molecules anchored to the PMMA matrix can affect the mobility of free LC molecules in the LC domains when an external electric field is applied to LC/polymer composite films.     

Polymerlzatlon of 1-Ethynyl-1-Cyclohexanol by Radiation,Electroinitiation, and Chemical Catalysts

Abstract

Solid-state polymerization of 1-ethynyl-1-cyclohexanol was carried out by irradiation in vacuum and in open air at 20°C. Radiation-induced polymerization was also done in a benzene solution. The products were mixtures of oligomers and polymers. IR, NMR, U V, and x-ray investigations showed the initial formation of trimer, oligomer, and polymer. The polymer fraction increased with an increase of conversion. Electro-initiated polymerization gave soluble and insoluble fractions. The soluble fraction was an ether. However, the results were not reproducible. No polymers were obtained with n-butyllithium and borontrifluoride etherate as chemical catalysts.     

Determination of Low-Molecular-Mass Aldehydes in Water Samples by Liquid Chromatography and Chemiluminescence Detection Using Continuous in situ Derivatization/Preconcentration with Dansylhydrazine

Abstract

A simple, expeditious, and sensitive method has been developed for the determination of low-molecular-mass aldehydes in water samples by liquid chromatography and peroxyoxalate–chemiluminescence detection. The method is based on continuous solid-phase extraction with in situ derivatization/preconcentration of the aldehydes using dansylhydrazine, which was first adsorbed on an RP–C₁₈ mini-column. For 10 mL of aqueous sample, the limits of detection (LOD) for C₁ to C₄ aldehydes were 20–30 ng L^?1, except for formaldehyde, which had an LOD of 400 ng L^?1. Application was illustrated by the determination of these aldehydes in water samples; the interday precision was always less than ca. 7%, and relative recoveries were more than 96%.     

RAFT Polymerization of Styrene in the Presence of 2‐Nonyl‐benzoimidazole‐1‐carbodithioic Acid Benzyl Ester

A novel dithiocarbamate, 2‐nonyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1a ), was synthesized and successfully used in RAFT polymerization of styrene in bulk with thermal initiation. The effect of molar ratio of styrene to RAFT agent on the polymerization was investigated. The linear relationship between ln([M]₀/[M]) and polymerization time indicated that the polymerization was first‐order with respect to monomer concentration. The molecular weights increased linearly with monomer conversion and were close to corresponding theoretical values. The molecular weight distributions (M _w /M _n ) kept very narrow (M _w /M _n <1.1) at a wide range of conversions of 14.2% to 73.3%. The obtained polymer had a strong ultraviolet absorption at 329 nm, which indicated that the 1a moiety remained at the end of polymer chain.     

Diazaisoindigo bithiophene and terthiophene copolymers for application in field‐effect transistors and solar cells

Two donor–acceptor conjugated polymers with azaisoindigo as acceptor units and bithiophene and terthiophene as donor units have been synthesized by Stille polymerization. These two polymers have been successfully applied in field‐effect transistors and polymer solar cells. By changing the donor component of the conjugated polymer backbone from bithiophene to terthiophene, the density of thiophene in the backbone is increased, manifesting as a decrease in both ionization potential and in electron affinity. Therefore, the charge transport in field‐effect transistors switches from ambipolar to predominantly hole transport behavior. PAIIDTT exhibits hole mobility up to 0.40 cm²/Vs and electron mobility of 0.02 cm²/Vs, whereas PAIIDTTT exhibits hole mobility of 0.62 cm²/Vs. Polymer solar cells were fabricated based on these two polymers as donors with PC₆₁BM and PC₇₁BM as acceptor where PAIIDTT shows a modest efficiency of 2.57% with a very low energy loss of 0.55 eV, while PAIIDTTT shows a higher efficiency of 6.16% with a higher energy loss of 0.74 eV. Our results suggest that azaisoindgo is a useful building block for the development of efficient polymer solar cells with further improvement possibility by tuning the alternative units on the polymer backbone. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2691–2699     

Enantioselective arylation of aldehydes catalyzed by a soluble optically active polybinaphthols ligand

A soluble chiral polymer ligand was synthesized by the polymerization of (R)-6,6′-dibutyl-3,3′-diformyl-2,2′-binaphthol (R-M-1) with 2,5-diaminopyridine (M-2) via a nucleophilic addition-elimination reaction. While arylboronic acids were used as the source of the transferable aryl group, the chiral polybinaphthols ligand in combination with Et₂Zn without Ti(OⁱPr)₄ exhibited higher enantioselectivity in asymmetric addition to aromatic aldehydes than alphatic aldehydes. When aromatic aldehydes with electron-withdrawing groups were chosen as substrates, the resulting diarylmethanols were produced in higher ee values than those with electron-donating groups as substrates. 2-Naphthaldehyde used as a substrate afforded product in 95% ee, which could be ascribed to the steric effect influence on this asymmetric arylation reaction. Moreover, the chiral polymer was easily recovered and reused, but exhibited a decrease of enantioselectivity in the third recycle.     

CYCLOPOLYMERIZATION OF DIPROPARGYL DERIVATIVES BY Cp2MoCl2-EtAlCl2 CATALYST SYSTEM

ABSTRACT

A Cp₂MoCl₂-EtAlCl₂ catalyst system was used for the cyclopolymerization of various dipropargyl derivatives having different functionalities. These catalyst systems were found to be very effective for the polymerization of some dipropargyl monomers to give a relatively high yield of polymer. The polymerization behaviors were strongly dependent on the functionalities of dipropargyl monomers. The polymerization of such dipropargyl monomers as 1,6-heptadiyne, diphenyldipropargyl methane, diethyldipropargyl malonate, etc. proceeded well to give a quantitative yield, whereas this catalyst system was found to be less effective for the polymerization of dipropargyl monomers having perfluoroalkyl groups and quaternary ammonium salts. The polymer structure of the resulting polymers was characterized by various instrumental methods such as NMR, IR, and UV-visible spectroscopies to have a conjugated polyene backbone system with cyclic recurring units. The portion of 5- and 6-membered rings of the present conjugated cyclopolymer were also discussed.     

Fabrication and performance of microencapsulated phase change materials with hybrid shell by in situ polymerization in Pickering emulsion

Microencapsulated phase change materials (MePCMs) using melamine–formaldehyde resin/SiO₂ as shell were investigated in this paper. Organically modified SiO₂ particles were employed to stabilize Pickering emulsion, and in situ polymerization of melamine and formaldehyde was carried out to form hybrid shell. The performances of resultant MePCMs with hybrid shell were investigated comparatively with the MePCMs with polymer shell. SiO₂ particles raise the microencapsulation efficiency by improving the stability of emulsion and providing a precipitation site for melamine–formaldehyde resin. Also, the mechanical strength, thermal reliability, and anti‐osmosis performance of MePCMs were improved significantly by SiO₂ particles in the shell. Our study shows that Pickering emulsion is a simple and robust template for MePCMs with polymer‐inorganic hybrid shell. Copyright © 2015 John Wiley & Sons, Ltd.     

The Mannich reaction in the synthesis of N,S-containing heterocycles 6. New approaches to the synthesis of pyrimido[4,3-b][1,3,5]thiadiazine derivatives

Aminomethylation of 2,6-diamino-4-aryl-4H-thiopyran-3,5-dicarbonitriles in the Mannich reaction with p-toluidine and formaldehyde unexpectedly gave pyrimido[4,3-b][1,3,5]thiadiazine derivatives. The same compounds were obtained in an independent way involving a multicomponent cascade condensation of aromatic aldehydes, cyanothioacetamide, p-toluidine, and formaldehyde. For Part 5, see Izv. Akad. Nauk, Ser. Khim., 2007, 1384 [Russ. Chem. Bull., Int. Ed., 2007, 56, 1437]. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1420–1422, July, 2007.