Photoinduced Controlled Radical Polymerization

Well‐controlled radical polymerization of methyl methacrylate can be achieved by in situ photochemical generation of copper (I) complex from air‐stable copper (II) species without using any reducing agent at room temperature. The living character of this polymerization was confirmed by both the linear tendency of molecular weight evolution with conversion and a chain extension experiment.

     

CIDNP.-Investigation of Photoinduced Polymerization

The photochemistry and some initiator characteristics of the polymerization initiators ω,ω-dimethoxy-ω-phenyl-acetophenone ( A ), ω,ω-diethoxy-acetophenone ( B ) and ω,ω-diisopropoxy-acetophenone ( C ) have been studied by ¹H- and ¹³C-chemically-induced nuclear polarization (CIDNP.) experiments. The primary reaction of initiator A is a Norrish-type I cleavage, while for B and C Norrish-type I and Norrish-type II cleavages are of comparable importance. Three different recombination products could be detected for initiator A which correspond to the three canonical resonance forms of the substituted benzyl radical. In a number of polymerization experiments the competition between reactions among initiator radicals and reactions of initiator radicals with the monomer acrylic acid methyl ester was studied at low concentrations of the monomer. These experiments give insight into the first steps of the polymerization process. The positive sign of the α-hydrogen hyperfine couplings of the dimethoxy-methyl- and the diisoproproxymethyl-radicals could be established, in agreement with the deviation of these radicals from planarity. A slow square-wave light-modulation technique has been employed in ¹³C-FT.-experiments to measure absolute CIDNP.-intensities.     

Synthesis of Ethyl 7-Methoxy-4-Oxocinnoline-3-Carboxylate

The synthesis of ethyl 7-methoxy-4-oxocinnoline-3-carboxylate from 4-methoxy-2-aminoacetophenone is described.     

4-甲氧基-3-[3-(吗啉-4-基)丙氧基]苯甲腈的合成研究

以3-羟基-4-甲氧基苯甲醛为原料,在甲酸、甲酸钠、盐酸羟胺作用下,将醛基转化为氰基,在含有碳酸钾的DMF中,所得化合物与N-(3-氯丙基)吗啉反应得目标化合物,总收率为87.5%。产物结构由1HNMR表征。本方法具有操作简单、易于纯化、收率高等特点,为工业化生产提供实验基础。     

Radiation-Induced Solid-state Polymerization in Some Methacrylates

This paper presents a comparison of some of our results on the polymerization of methacrylic acid, octadecyl methacrylate, zinc methacrylate, and barium methacrylate monohydrate in the solid state. Polymerization was initiated by cobalt-60 γ rays, both in-source and post-irradiation polymerization techniques being used. Electron spin resonance studies showed that the polymerization proceeded by a free radical mechanism in all cases. The initial radicals formed by irradiation at low temperatures added a first monomer unit about 100° below the temperature of long-chain polymerization. Some radical decay occurred in the early stages of polymerization. The rate of polymerization increased rapidly, approaching the melting point or other phase change in the monomer.     

Solid-state photodimerization of cholest-4-en-3-one

Crystalline cholest-4-en-3-one undergoes solid-state dimerization by UV radiation to give two ring A - ring A connected dimers. No dimerization occurs in solution. The first dimer, characterized by a cyclobutane ring, is formed by connection of C-2 and C-3 of a moiety with C-5' and C-6' of another moiety, respectively. The latter dimer has a six-membered ketal ring formed by connection of C-2 with C-5' and of O, linked to C-3, with C-3'. The structures have been determined by spectroscopic means. X-ray analysis of title compound evidences the proximity of the axial H-2 of a molecule to the C-4' of a molecule in the upper layer. The transfer of the hydrogen and the connection between C-2 and C-5' might be the driving force of dimerization.     

反应型受阻胺-4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP)熔融本体光聚合反应动力学研究

合成了反应型受阻胺4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP),用FTIR、¹H-NMR和元素分析对其结构和组成进行了综合表征.以AATP为聚合单体,利用光-DSC技术研究了AATP熔融本体光聚合反应动力学.结果表明:AATP光聚合的诱导时间随引发剂浓度和辐照光强增加而缩短,光聚合速率随温度的升高而减小;在聚合初期,AATP光聚合速率分别与引发剂浓度和辐照光强的平方根呈较好的线性增长关系.并用稳态和非稳态相结合的光-DSC方法测定了AATP光聚合过程的动力学参数:链增长速率常数k_p=2.22-7.96×10²L/mol·s、链终止速率常数k_t=0.08-2.67×10⁴L/mol·s、表观活化能为E_p-E_t/2=-7.70-13.36kJ/mol、指前因子A_p/A_t^0.5=0.076-0.333(L/mol·s)0.5,k_p和k_t在聚合初期均随单体转化率的提高而增大,但kt增加的幅度远大于k_p.     

4-Methoxy-3-methylgoniothalamin from marine-derived fungi of the genus Penicillium

The new styrylpyrone derivative, viz. 4-methoxy-3-methylgoniothalamin (1), and the known compound sulochrin were isolated from the marine-derived fungi Penicillium glabrum and P. implicatum. The structure of compound 1 was determined by X-ray diffraction, 2D NMR spectroscopy, and high-resolution mass spectrometry. It was shown for the first time that sulochrin increases expression of the protein Hsp70.     

New Technology for Solid-state Polymerization of Polymers: Polyethylene terephthalate–Solid-state Polyaddition

This article introduces the new M&G technology for Solid state polyaddition (SSPA) of polyethylene terephthalate (PET). The new SSPA is characterized by the following: (1) It is based on a novel chemical process, SSPA. (2) It is suitable for high-performance polyesters. (3) It enables separate control of many different key properties of the polyester (molecular weight, rheology, crystallinity, etc.). This intrinsic flexibility has already been exploited to produce tailor-made polyesters suitable for most important applications in packaging and related fields. It is also a powerful tool for the upgrading of recycled PET. The SSPA reaction has a much faster kinetic than the standard solid-state upgrading process so that accordingly the intrinsic viscosity (I.V.) built up in the solid state is much faster than that of solid-state polycondensation. This raises the possibility of solid-state upgrading at lower temperatures, where standard solid-state polycondensation reactions are barely noticeable. The accelerating reactions used in this process could be utilized to de-bottleneck the existing production plants in order to attain greater productivity, more flexibility, lower costs and higher quality. © 1997 John Wiley & Sons, Ltd.     

A Concise Route to 3-Hydroxy-4-Methoxy-5-Methylbenzaldehyde Derivative

3-Hydroxy-4-methoxy-5-methylbenzaldehyde derivative (1c) has been synthesized in 7 steps from 2,3-dihydroxytoluene (4). An isopropyl derivative has been used to protect a phenol during this transformation. The overall yield of 1c was 37%.     

A Single Crystal Study of a Solid-state Polymerization Reaction

Halogenoacetates are known to undergo a solid-state elimination reaction to metal halide and poly(hydroxyacetic acid), polyglycolide. Earlier studies have shown that the reaction takes place exclusively in the solid-state without the occurrence of liquid intermediates. Single crystals of sodium chloroacetate and silver chloroacetate were reacted and studied with X-ray diffractometry, scanning electron microscopy and thermomicroscopy. The results show that the reaction leads from single crystals to a composite of polyglycolide and metal halide. Neither the salt nor the polymer exhibit a preferred crystallographic orientation, therefore it must be concluded that the crystal lattice is not preserved during the reaction.This revised version was published online in November 2005 with corrections to the Cover Date.     

Photoinduced Acrylate Polymerization: Unexpected Reduction in Chain Branching

The branching stemming from midchain radical formation in n‐butyl acrylate polymerization is investigated via melt‐state ¹³C NMR measurements. The dependence of the degree of branching (DB) on the monomer conversion of the system is examined for photoinduced polymerizations, revealing a steady increase in branching with conversion. For polymerization at moderate light intensities, an increase in branching from 0.03% to 0.37% is observed for polymerizations at 60 °C, which is fivefold below the level of branching observed in thermally initiated poly­merizations under otherwise identical reaction conditions. The reason for this overall reduction in branching remains momentarily unclear; yet, a strong dependence of branching on light intensity is observed. While polymerization under a 1 W LED lamp results at almost full monomer conversion in branching degrees of 0.22%, polymerization under a 400 W lamp yields 1.81% of chain branches.

     

Photosensitized Solid-state Polymerization of Diacetylenes in Nanoporous TiO2 Structures

In situ topochemical polymerization of two diacetylene monomers within nanoporous TiO₂ thin films was carried out under visible light irradiation. One of the monomers used contains a carboxylic acid group, which could help to link the monomer onto the TiO₂ surface covalently. UV-Vis absorption and Raman studies showed that both monomers were successfully photopolymerized. These results suggest that the covalent linkage of the diacetylene to the nanoparticle through the carboxylic acid group is not needed. Since photopolymerization of diacetylene is typically induced by excitation of the monomer at λ< 300 nm, the observed red shift of the photopolymerization wavelength is attributed to the photosensitization effect of TiO₂. The morphological study of the polydiacetylene/TiO₂ nanocomposite revealed that the diacetylene monomers were polymerized in the vicinity of the TiO₂ nanoparticles. This is attributed to the fact that the electron-transfer process occurs at the interface of nanocrystalline TiO₂ (nc-TiO₂) and the diacetylene monomer and the polymerization is expected to be initiated near the nc-TiO₂ surface. Photopolymerization of the carboxylated diacetylene monomer with other oxides nanoparticles, such as ZnO and SiO₂ was also investigated.     

Reactions of 4-Methoxy-3-quinolinyl and 1,4-Dihydro-4-oxo-3-quino-linyl Sulfides Aiming at the Synthesis of 4-Chloro-3-Quinolinyl Sulfides

The preparation of 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 or 1,4-dihydro-4-oxo-3-(alkylthio)quinolines 4 by acid catalysed hydrolysis of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 4-methoxy-3-(alkylthio)-quinolines 2 is described. The reactions of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 with phosphoryl chloride in DMF afforded 4-chloro-3′-alkylthio-3,4′-diquinolinyl sulfides 5 . Treatment of the title compounds 1 or 3 with boiling phosphoryl chloride systems:leads to 4-chloro-3-(alkylthio)quinolines 6 and thioquinanthrene but those of alkoxy- or oxo-quinolines 2 or 4 lead to 4-chloro-3-(alkylthio)quinolines 6 . The reactions of N-methyl-4(1H)-quinolinones 3n and 4n with phosphoryl chloride directed to 4-chloro-3-(alkylthio)quinolines 6 were studied as well.     

The Solid-state Polymerization of Styryl Monomers: A Structural Perspective

Abstract

Styryl monomers p-acetamidostyrene 1, p-benzamidostyrene 2 and p-vinylbenzoic acid 3 polymerize upon heating, or under γ- or UV-irradiation. The crystal structures of 1–3 (including two polymorphs of 3) contain short contacts (≈ 4.2 Å) between ?CH?CH₂ groups. Monomer single crystals subjected to heat or irradiation did not diffract X-rays and did not exhibit birefringence. NMR spectra of the polymerized product (at high degrees of conversion) were consistent with the formation of atactic polymer.