Cationic polymerization of 3,6- dibromo-9(2,3-epoxypropyl) carbazole in the presence of allyl alcohol or acrylic acid

Polymerization of 3,6-dibromo-9-(2,3-epoxypropyl) carbazole with SnCl₄ in the presence of allyl alcohol or acrylic acid has been studied. This reaction has proved to be a convenient method of obtaining macromonomers containing allyl or acrylic functional groups. It was shown that both in the presence of allyl alcohol and acrylic acid polymerization proceeds by an activated monomer mechanism. Allyl alcohol and acrylic acid at the initial stage of reaction play the role of starting proton donor compound. However in contrast to allyl alcohol, acrylic acid is not totally consumed. Peculiarities of the mechanism of propagation are discussed.     

Novel carbazole phenoxy-based methacrylates to produce high-refractive index polymers

A novel, high-refractive index homopolymer was produced by incorporating carbazole and phenol into the methacrylate monomer structure. The reaction of phenol with 9-(2,3-epoxypropyl)-carbazole, followed by the reaction of the carbazole phenoxy-based intermediate with methacryloyl chloride or methacrylic anhydride, and recrystallization from methanol, produced a good yield of highly pure carbazole phenoxy functionalized methacrylate monomer. Subsequent free radical polymerization or UV photopolymerization of the functionalized methacrylate monomer, in addition to copolymerizations with methyl methacrylate, provided for high-refractive index materials well suited for lightweight optical applications. Unlike N-vinyl carbazole, the novel carbazole phenoxy-based methacrylate readily copolymerized with methyl methacrylate. Statistical copolymers of carbazole based methacrylates with methyl methacrylate were produced by free radical solution polymerization in DMAC or by photopolymerization in DMF. The carbazole phenoxy-based methacrylate monomer was characterized for molecular weight using gel permeation chromatography (GPC), for melting point and glass transition temperature using differential scanning calorimetry (DSC), for decomposition using thermal gravimetric analysis (TGA), and for chemical composition by one- and two-dimensional ¹H nuclear magnetic resonance (NMR) spectroscopy and by elemental analysis. The AIBN initiated carbazole phenoxy-based methacrylate polymerization was followed using in situ FTIR, which showed the reaction to be complete within 40 min in DMAC at 90 °C. Refractive indices of the carbazole based methacrylate homopolymers and copolymers ranged from 1.52 to 1.63. PhotoDSC was used to determine the heat of polymerization (ΔH_p) for the carbazole phenoxy-based methacrylate (ΔH_p=−39.4 kJ/mol). The carbazole phenoxy-based methacrylate homopolymer had a surprisingly high onset of decomposition temperature (T_onset=316 °C). ¹³C NMR spectroscopy experiments and molecular modeling were used to explore the configuration of the polymerized carbazole phenoxy-based methacrylate. The lack of head-to-head linkages due to steric considerations reasonably explains the high thermal stability observed for the carbazole phenoxy-based methacrylate polymer.     

Polymerization of carbazolyl-containing epoxides with triphenylcarbenium salts

Summary Polymerization of 9-(2,3-epoxypropyl) carbazole (EPC) and 1,2-epoxy-6-(9-carbazolyl)-4-oxahexane (ECOH) with triphenylcarbenium hexachloroantimonate and triphenylcarbenium tetrafluoroborate have been studied by the microcalorimetric technique. Triphenylcarbenium salts have turn out to be more efficient catalyst for the polymerization of carbazolyl-containing epoxides than Lewis acids, giving high yields at low initial concentration of the catalyst. Using comparatively restricted conditions of reaction ([triphenylcarbenium saltyda]_o0.02 mol/l t50° C) transition from the conventional active chain end mechanism to the activated monomer mechanism has been observed at a sufficiently high degree of conversion of monomer.     

Synthesis and cross-linking of bifunctional monomers containing carbazole moieties

New bifunctional carbazolyl-containing monomers were synthesized and their cationic photo-initiated polymerization investigated. The monomers containing two reactive groups such as epoxy, oxetanyl and vinyloxyethyl, were prepared from commercially available 9-(2,3-epoxypropyl)carbazole. The kinetics of UV curing of the monomers was monitored by real-time FT-IR technique. The type of functionality was found to have a considerable influence on the photo-curing rate, but has not an evident effect on the final reactive group conversion. The cross-linked systems were found to have low glass transition temperatures ranging from 7 to 10 °C. Electron photoemission spectroscopy revealed ionization potentials of 5.75–5.8 eV for the thin cross-linked layers of the monomers.     

Degradation of poly(vinyl chloride) in the presence of 9-(2,3-epoxypropane)carbazole studied by means of TGA/FTIR

Blends containing poly(vinyl chloride) and 9-(2,3-epoxypropane)carbazole in different weight ratios were subjected to investigations using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The effect of additive on the polymer degradation process was studied. It was found that 9-(2,3-epoxypropane)carbazole causes an increase in the onset temperature of hydrogen chloride emission by about 20–25°C. Finally, the mechanisms of stabilization were proposed. © 1995 John Wiley & Sons, Inc.     

Epoxy systems with improved water resistance,and the non-fickian behaviour of epoxy systems during water ageing

N,N-Bis (2, 3-epoxypropyl) aniline and 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl) aniline] containing bromo, chloro, trifluoromethyl or polyfluoroalkoxy substituents were synthesised and cured with aromatic diamines in order to investigate the effect of substituted halogen on water absorption. Significant improvements were achieved: thus use of 4,4′-methylenebis-[N, N-bis (2, 3-epoxypropyl)-3, 5-dichloroaniline] and 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl)-3-(trifluoromethyl) aniline] instead of 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl) aniline] reduced the water absorption by about a half. Departures from Fickian behaviour were observed during water immersion ageing at room temperature and were a general feature of the epoxy systems examined. Plots of water absorption against the Fickian parameter (√t/d) usually showed at least mild sigmoid character and were not independent of specimen thickness. Further, slow continued uptake of water occurred during long-term ageing, and evidence is provided that the associated network distortions are reversible.     

Immobilization of enzymes to porous-bead polymers and silica gels activated by graft polymerization of 2,3-epoxypropyl methacrylate

Three types of organic polymers and bead-shape silica gels were activated by graft polymerization of 2,3-epoxypropyl methacrylate; in some cases, epoxide groups on the support surface were modified to NH₂ groups. Eight active matrices so obtained were assessed as supports for immobilized enzymes using peroxidase, glucoamylase and urease. The immobilization yield of protein and specific activities of enzymes were better with supports containing NH₂ groups than with those containing epoxide spacer arms. Maximum enzyme immobilization and storage stabilities were obtained with silica-gel beads activated by graft polymerization of 2,3-epoxypropyl methacrylate. With all eight matrices tested, the immobilized enzymes showed good stability with not less than 82% of the original activity persisting after 28 days. The developed matrices have potential for use in process-scale biotechnological operations.     

Internal structure of porous glass coated with a polymer layer of poly (2,3-epoxypropyl methacrylate)

A change in the internal structure of porous glass due to the formation of a polymer layer of poly(2,3-epoxypropyl methacrylate) by polymerization on its surface was investigated. By using the methods of dynamic desorption of nitrogen and mercury porosimetry, the character of the polymer layer and its effect on the final porosity for various types of the original material were determined.     

Glass fiber-reinforced epoxy composites

Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethane

1 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane.

(TGDDM) and tetraglycidyl bis(o-toluidino)-methane

2 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane.

(TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.     

Influence of the chemical structure of dithiocarbamates with different R groups on the reversible addition‐fragmentation chain transfer polymerization

Four dithiocarbamates, carbazole‐9‐carbodithioic acid benzyl ester (R1), carbazole‐9‐carbodithioic acid naphthalen‐1‐ylmethyl ester (R2), 2‐(carbazole‐9‐carbothioylsulfanyl)‐2‐methyl‐propionic acid ethyl ester (R3), and (carbazole‐9‐carbothioylsulfanyl)‐phenyl‐acetic acid methyl ester (R4), were synthesized and used to the reversible addition‐fragmentation chain transfer (RAFT) polymerizations of styrene (St), methyl methacrylate (MMA), and methyl acrylate (MA), respectively. The influence of chemical structure of dithiocarbamates with different R groups on the RAFT polymerizations was investigated. The results showed that the four RAFT agents were effective RAFT agents for the polymerizations of styrene or MA, and that the polymerizations were well‐controlled with the characteristics of controlled/“living” polymerization. The polymerization rate of styrene with thermal initiation was markedly influenced by the chemical structures of the group R in dithiocarbamates, and decreased in the order of R3 > R2 > R4 > R1. For the polymerization of MA, the efficiency of RAFT agents was in the following order: R2–R3 > R1 > R4. However, they were not efficient enough to control the polymerization of MMA. The obtained polystyrene (PSt) with carbazole group labeled strongly absorbed UV light at 294 nm and emitted fluorescent light in N,N‐dimethyl formamide (DMF). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 982–988, 2007     

Mass spectral studies of some epoxy resin precursors

The mass spectra were determined of three epoxy resin precursors: N,N-bis-(2,3-epoxypropyl)-N′,N′-dimethyl-4,4′-diaminodiphenylenemethane (G2A); N,N′-bis-(2,3-epoxypropyl)-N,N′-dimethyl-4,4′-diaminodiphenylene methane (G2S); and N′,N′,N′,N′-tetrakis-(2,3-epoxypropyl)-4,4′-diaminodiphenylene methane (TGDDM); and of three related model compounds: N,N-dimethylaniline (DMA); N-methyl-N-glycidylaniline (MGA) and N,N-digrycidylaniline (DGA). The results helped to confirm the structure of the resin precursors and are intended to pave the way for subsequent thermal degradation studies of cured resin samples. Despite the similarity in chemical structure of the compounds studied there are quite large differences in the mass spectral results obtained.     

2,3-环氧丙基2,3,4,6-四-O-乙酰基-β-D-吡喃型葡萄糖苷的合成

用Fischer Helferich方法,对2,3 环氧丙基2,3,4,6 四 O 乙酰基 β D 吡喃型葡萄糖苷的合成方法进行了研究。以D 葡萄糖为原料,在碱性条件下乙酰化得到1,2,3,4,6 五 O 乙酰基 β D 葡萄糖。然后在SnCl4催化下与烯丙醇反应得到2,3,4,6 四 O 乙酰基 β D 吡喃型葡萄糖烯丙苷。再经间氯过氧苯甲酸氧化得到目标化合物2,3 环氧丙基2,3,4,6 四 O 乙酰基 β D 吡喃型葡萄糖苷。其路线要比文献报道的少一步,总收率可达40%。目标化合物的结构经IR、13CNMR、EIMS和元素分析得到了确证。     

Studies on the curing kinetics and thermal stability of the novel tetrafunctional epoxy resin N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline

A novel tetrafunctional epoxy resin, namely N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline, has been synthesized. The curing kinetics has been studied by differential scanning calorimetry (DSC) using various amine curing agents. Thermal stabilities of the cured products have been investigated by thermogravimetric (TG) analyses. The overall activation energies for the curing reactions are observed to be in the range 63.6–196.7 kJ·mol^–1. The cured products have good thermal stability.     

Bifunctional oligoetherols with carbazole ring

A new synthetic method for bifunctional oligoetherols with carbazole ring was presented. 9‐(2,3‐Epoxypropyl)carbazole was obtained from carbazole and epichlorohydrine. The epoxide ring opening occurred upon the consecutive reaction with ethylene glycol to give the semiproduct well soluble in ethylene oxide and propylene oxide and reactive toward these epoxides at temperatures above 60–90°C to form oligoetherols. Structure of these oligoetherols and their physical properties and application for synthesis of linear polyurethanes were studied in details. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SYNTHESIS,CHARACTERIZATION, AND THERMAL STABILITY OF HOMOPOLYMER AND COPOLYMER OF SOME 3-ARYL-2-HYDROXYPROPYL METHACRYLATES

Three new hydroxypropyl methacrylates having three different aryl rings were synthesized by addition of 2,3-epoxypropyl aromatic hydrocarbon to methacrylic acid. The monomers prepared are 3-phenyl-2-hydroxypropyl methacrylate, 3-tolyl-2-hydroxypropyl methacrylate, (THPMA), and 3-naphtyl-2-hydroxypropyl methacrylate. The homopolymers of these monomers and two different copolymers, [poly(THPMA-co-BMA)], were obtained from polymerization at 60°C in 1,4-dioxane solution using AIBN as initiator. All the monomers and the polymers were characterized by FT-IR and ¹H and ¹³C NMR techniques. Solubility parameters of the polymers and average molecular weight of poly(THPMA) were determined. Thermal stabilities of the polymers were given as comparing with each other by using TGA curves. Thermal degradation of poly(THPMA60%-co-BMA40%) was studied in detail.     

碘化钾催化合成2,3-环氧丙基三甲基氯化铵的研究

以环氧氯丙烷(EPIC)和三甲胺(TMA)为原料,碘化钾为催化剂,在乙醇介质中常温下合成了高活性醚化剂2,3-环氧丙基三甲基氯化铵(GTA)。采用正交实验法考察了反应温度、物料配比、催化剂用量和反应时间对产品收率的影响。GTA最佳合成工艺条件为:n(EPIC)∶n(TMA)∶n(KI)=1∶0.3∶0.02,反应温度20℃,总反应时间4 h,在此优化条件下收率可达87.1%。     

Radiation-induced grafting of sulfonates on polyethylene

Indirect methods for introducing sulfonate groups into polyethylene, using the preirradiation technique, were studied. One of the methods involved graft polymerization of 2,3-epoxypropyl acrylate into polyethylene followed by sulfonation of the epoxy ring with bisulfite. The hydroxy sulfonate thus obtained was unstable in an acid or base environment and hydrolyzed at the esteric bond. The second method involved hydrophylization of the polyethylene by forming a pregraft of polyacrylic acid or polyvinyl alcohol, followed by preirradiation grafting with sodium styrene sulfonate or, less successfully, with sodium vinyl sulfonate. The sulfonates thus obtained were resistant to acids and bases. The acid capacity, water absorption, and water permeability of the grafted films were determined.     

阳离子化改性腈纶废丝在正电钻井液中的应用研究

以腈纶废丝为原料,水解合成出部分水解聚丙烯腈钠,再以其为接枝底物,以2,3-环氧丙基三甲基氯化铵为阳离子化剂进行改性,合成出了阳离子化度为0.09~1.03 mmol／g的改性腈纶废丝产品。钻井液性能评价结果表明,所合成出的阳离子化度为0.2-0.5 mmol／g的改性腈纶废丝样品,在正电性钻井液中具有较好的抑制性和降滤失作用效果,能较好地保持正电性钻井液体系的电性和流变性特征。     

Reaction mechanism,kinetics and network structure of the DGEBA-DDS system

Different techniques were used to analyse the reaction mechanisms and kinetics of the system 2,2-[4-(2,3-epoxypropyl)phenyl]propane polycondensed with 4,4′-sulphonyl-dianiline in the temperature range 100?185°C. The results show the role of catalysts, of stoichiometry and of curing cycles in the reaction mechanisms and paths. Based on chemical balances of residual epoxy groups, and of hydroxy and ether groups formed, we have shown the effect of these functions on the thermal properties of the material.     

3-溴-9-(2-萘基)-9H-咔唑的合成

以咔唑为原料,通过乌尔曼反应合成了N-(2-萘基)咔唑,然后经溴化反应,合成空穴传输材料中间体3-溴-9-(2-萘基)-9H-咔唑,并对溴化条件进行了初步探索。结果表明,溴化的最佳反应条件为:25℃,24 h,n[N-(2-萘基)咔唑]∶n(四丁基三溴化铵)=1∶1.05,二氯乙烷100 mL。其结构经元素分析、1HNMR和MS确认。