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1.
Poly-[3′,4′-dimethoxyacrylophenone], poly-4′-phenylacrylophenone, poly-2′-acrylonaphthone and copolymers of acrylophenone monomers with styrene and methyl methacrylate were prepared. Quantum yields of main chain scission in chlorobenzene by 313 nm radiation were 103 times lower for all homopolymers and copolymers studied than for polyacrylophenone. The emission spectra of the polymers, copolymers and model compounds were taken for films at 77 K. The 3′,4′-dimethoxyacrylophenone, 4′-phenylacrylophenone and 2′-acrylonaphthone structural units exhibited poorly resolved emission spectra in homopolymer, copolymer and model compound. No difference in the emission spectra of films and dispersed homopolymer or copolymer in a poly(methyl methacrylate) matrix was observed. The decay of the emission of all homopolymers and copolymers under study was exponential, the life-time exceeding 0.20 sec.  相似文献   

2.
Copolymerization of vinyl cyclohexane (monomer-1) with styrene was investigated in the presence of the stereospecific complex catalyst TiCl3 + Al(iso-C4H9)3. Monomer reactivity ratios were r1 = 0·177 ± 0·051 and r2 = 2·117 ± 0·370. The monomer unit distributions in the copolymers were estimated by comparison of the i.r.-spectra of copolymers and the isotactic homopolymers using absorption bands at 565 and 1084 cm?1 which correspond to the vibrations of styrene blocks containing ? 5 styrene units and the band at 985 cm?1 characterizing polystyrene crystallinity. The data indicate the tendency towards alternation in the copolymerization. Analysis of the experimental and literature data led to the conclusion that distribution of the units in copolymers of vinyl cyclohexane with α-olefins is determined by the nature of the α-olefin. The following activity series is proposed for α-olefins in their copolymerization with vinyl cyclohexane in the presence of catalytic systems based on titanium salts and organo-aluminium compounds: propylene >; 4-methylpentene-1 >; styrene >; 3-methylbutene-1 ~ vinyl cyclohexane.  相似文献   

3.
Novel trisubstituted ethylenes, ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO2C3H7 (where R is 2-C6H5CH2O, 3-C6H5CH2O, 4-C6H5CH2O, 4-CH3COO, 3-CH3CO, 4-CH3CONH, 2-CN, 3-CN, 4-CN, 4-(CH3)2N, 4-(C2H5)2N) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (2.7–8.6% wt.), which then decomposed in the 500–800°C range.  相似文献   

4.
The photodegradation of films (2 × 10?4 cm thick) of poly(vinyl-acetophenone) [poly(4-acetylstyrene)] exposed to 254 nm radiation under high vacuum at 25 ± 1°C was studied. The principal gaseous product was H2, but CH4, C2H6, and smaller amounts of acetaldehyde and CO were also formed. The photochemistry more closely resembles that of other substituted styrene polymers than that occuring on the long wave (λ > 300 nm) irradiation of the polymer in that the principal initial processes involve fissions of bonds in the β-position to the phenyl chromophores. Studies of a deuterated analogue (D3 acetyl) indicate that H-abstractions occur from the polymer and also that fission of C? H bonds in the acetyl group does not occur. The polymer undergoes rapid cross linking. Mechanisms of the various primary and secondary processes are discussed.  相似文献   

5.
Novel trisubstituted ethylenes, ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C4H9 (where R is 2-C6H5CH2O, 3-C6H5CH2O, 4-C6H5CH2O, 4-CH3COO, 3-CH3CO, 4-CH3CO, 4-CH3CONH, 2-CN, 3-CN, 4-CN, 4-(CH3)2N, 4-(C2H5)2N) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-C6H5CH2O (6.39) > 2-C6H5CH2O (2.06) > 3-CH3CO (1.86) > 3-C6H5CH2O (1.78) > 4-CH3COO (1.58) > 3-CN (1.47) > 4-CN (1.21) > 4-(C2H5)2N (1.19) > 4-(CH3)2N (1.18) > 2-CN (1.04) > 4-CH3CO (0.71) > 4-CH3CONH (0.63). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.6–9.5% wt), which then decomposed in the 500–800°C range.  相似文献   

6.
The reaction of ethylenimine with anhydrides of monocarboxylic acids (RCO)2O gives theβ-acylaminoethyl esters of the acids RCONHCH2CH2OCOR, hitherto unknown (only an ester with R=Me known). When R=C6H5 dibenzoylaminoethyl benzoate (C6H5CO)2· · NCH2CH2OCOC6H5 is also formed. The IR spectra of the compounds prepared are studied.  相似文献   

7.
Radiation induced crosslink formation, main chain scission and product formation for polyethyl acrylate (PEA), poly-ß-chloroethyl acrylate (PCIEA) and copolymers of the two components were investigated. Partially deuterated polymers were used to identify the positions of reaction. Radiolysis of PEA induces degradation of the ethyl ester group. The primary step is either hydrogen abstraction from the α-position of the ethyl group or removal of larger fragments (ethyl, ethoxy, methyl radicals) giving rise to the formation of the following volatile products: H2 (G=0·46), CO (G=0·7), CO2 (G=0·12), C2H6 (G=0·22), C2H4 (G=0·07), CH4 (G=0·08), CH3CHO (G=0·15), C2H5OH (G=0·18). The results obtained for partially deutrated polymers show that degradation of the ethyl ester group precedes crosslinking (Gci=0·32) as well as main chain scission (Gsc=0·14). The G-value for crosslinking increases with increasing content of ß-chloro-ethyl acrylate in the copolymer. Gct for pure PCIEA is found to be 2·2.  相似文献   

8.
Electrophilic trisubstituted ethylene monomers, some ring‐substituted 2‐phenyl‐1,1‐dicyanoethylenes, RC6H4CH?C(CN)2 (where R is 3‐C6H5O, 4‐C6H5O, 3‐C6H5CH2O, 4‐C6H5CH2O, 4‐CH3CO2, 4‐CH3CONH, 4‐(C2H5)2N) were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, 1H‐ and 13C‐NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C‐NMR, GPC, DSC, and TGA. High T g of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 190–700°C range.  相似文献   

9.
The syntheses and properties of the titanium(III) complexes Cp2Tir · R′CN (R = C6H5, o-, m-, p-CH3C6H4, CH2C6H5, C6F5, Cl; R′ = CH3, t-C4H9, C6H5, o-CH3C6H4, 2,6-(CH3)2C6H3) are described. In the complexes the nitrogen atom of the cyanide ligands is coordinated to the metal. The thermal stabilities of the complexes depend markedly on R and R′; on heating they undergo a novel reaction in which two cyanide ligands are coupled by formation of a CC bond, while the metal is oxidized to titanium(IV).  相似文献   

10.
Inclusion compounds (intercalates) of fluorinated graphite matrix with butanone (C2FxBrz·yCH3COC2H5, x = 0.49, 0.69, 0.87, 0.92, z ≈ 0.01) were prepared by guest substitution from acetonitrile to butanone. The kinetics of the thermal decomposition (the 1st stage of filling → the 2nd stage of filling) was studied under isothermal conditions at 294–313 K. The relationship of the host matrices structure with inclusion compounds’ thermal properties and kinetic parameters is discussed.  相似文献   

11.

Electrophilic trisubstituted ethylene monomers, ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC6H4CH?C(CN)CON(CH3)2 (where R is 4‐(CH3)2N, 4‐CH3CO2, 4‐CH3CONH, 2‐CN, 3‐CN, 4‐CN, 4‐(C2H5)2N) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, 1H‐ and 13C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C NMR, GPC, DSC, and TGA. High Tg of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.  相似文献   

12.
The highly insoluble organic-inorganic hybrid ionic compounds N,N??-methylenedipyridinium tetrachloroplatinate(II) [(C5H5N)2CH2] · [PtCl4] and N,N??-methylenedipyridinium hexachloroplatinate(IV) [(C5H5N)2CH2] · [PtCl6] were obtained by the treatment of N,N??-methylenedipyridinium dichloride monohydrate [(C5H5N)2CH2]Cl2 · H2O with K2[PtCl4] or (NH4)2[PtCl6], respectively, in an aqueous solution. Both complexes were isolated, purified, characterised by elemental analysis, and their molecular structures were confirmed by powder X-ray diffraction. The crystal structure of both compounds consists of separated discrete dications [(C5H5N)2CH2]2+ and anions [PtCl n ]2? (n = 4 or 6). As anticipated, the dications formed a butterfly shape consisting of two pyridine rings bound to the methylene group via their N atoms, while the Pt centre had a square planar geometry in [(C5H5N)2CH2] · [PtCl4] and an octahedral coordination in [(C5H5N)2CH2] · [PtCl6]. Interestingly, both crystal structures are stabilised by intermolecular C-H??Cl non-standard hydrogen bonds, ??-?? ring interactions between two pyridine rings of adjacent dications, and also by Cl-?? interactions.  相似文献   

13.
The copolymerization of styrene and 1-hexene with the TiCl4-Al(C6H13)3 · Mg(C6H13)2 catalytic system has been investigated. The microstructure of polymer chains, molecular-mass characteristics, and thermophysical properties of the resulting copolymers have been studied. These copolymers contain 15 to 65 mol % styrene and mostly consist of isotactic polystyrene and poly(1-hexene) blocks.  相似文献   

14.
The crystal structures of N-o-hydroxybenzimido-meso-tetraphenylporphyrinatozinc(II) toluene solvate [Zn(N-NCO(o-OH)C6H4-tpp)·C6H5CH3; 4·C6H5CH3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatonickel(II) chloroform solvate [Ni(N-NCO(o-OH)C6H4-tpp)·0.6CHCl3; 5·0.6 CHCl3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatocopper(II) toluene solvate [Cu(N-NCO(o-OH)C6H4-tpp)·C6H5CH3; 6·C6H5CH3] and N-o-oxido-benzimido-meso-tetraphenylporphyrinato(-κ4,N1,N2,N3,N5,κO2) manganese (III) methylene chloride·methanol solvate [Mn(N-NCO(o-O)C6H4-tpp)·CH2Cl2·MeOH; 8·CH2Cl2·MeOH] were established. The coordination sphere around Zn2+ ion in 4·C6H5CH3, (or Ni2+ ion in 5·0.6 CHCl3 or Cu2+ ion in 6·C6H5CH3) is a distorted square planar (DSP) whereas for Mn3+ in 8·CH2Cl2·MeOH, it is a distorted trigonal bipyramid (DTBP) with O(1), N(1) and N(3) lying in the equatorial plane for 8·CH2Cl2·MeOH. The g value of 8.27 measured from the parallel polarization of X-band EPR spectra at 293 K is consistent with the high-spin mononuclear manganese(III) (S = 2) in 8. The magnitude of axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) in 8 was determined approximately as 3.0 cm?1 by the paramagnetic susceptibility measurements and conventional EPR spectroscopy.  相似文献   

15.
A series of polyaryloxyphosphazene copolymers with the general formulas [NP(OC6H5)(OR)]n and [NP(OC6H4–4–OCH3)(OR)]n, where R = C6H4–4–CH3, C6H4–4–C2H5, C6H4–4–isoC3H7, C6H4–4–sec-C4H9, C6H4–4–tert–C4H9, C6H4–4–OCH3 or C6H4–4–OC4H9, have been prepared under anhydrous conditions. Copolymers as well as selected homopolymers were prepared by the reaction of polydichlorophosphazene with appropriate sodium aryloxides. Each of the polymers was characterized by elemental analysis, infrared spectroscopy, gel–permeation chromatography, and differential scanning calorimetry. Elemental analysis established the empirical formula for the polymers and showed that there were no residual P? Cl bonds left on the polymer backbone. Infrared spectroscopy indicated the presence of a phosphorus–nitrogen backbone with two aryloxy groups bonded to each phosphorus atom. The copolymers examined exhibited molecular weights of above 1 × 106. Polyaryloxyphosphazene copolymers were examined by differential scanning calorimetry and compared to several of the corresponding homopolymers. Glass transition temperatures ranged between ?34 and +44°C for the polymers. The Kelley-Bueche equation was used to predict the glass transition temperatures of the copolymers. Close agreement was found between calculated and experimental values for most of the systems examined.  相似文献   

16.
The reactions oi tributyltin ethoxide, Bu3SnOEt, with N,N-dialkylalkanolamines, HORNR2 (where R = ? CH2 · CH2? , ? CH2 · CH2 · CH2? and ? CH2 · MeCH? ; R = ? CH3 and ? C2H5) give Bu3SnORNR2. In reactions of Bu3SnOEt with N-methylethanolamine, HOCH2 · CH2NHMe, and various alkanolamines, HO · R · NH2, (where R = ? CH2 · CH2? ? CH2 · CH2 · CH2? , ? CHMe · CH2? ? CH2 · Me2C? and ? CH2 · CH · CH2 · Me) both the hydroxy as well as the amino groups show reactivity to form products of the type: Bu3SnOCH2 · CH2NHMe, Bu3SnOCH2 · CH2NMeSnBu3, Bu3SnO · R · NH2, Bu3SnO · R · NHSnBu3, and Bu3SnO · R · N(SnBu3)2, respectively. The reaction between Bu3SnOEt and o-aminophenol yields only Bu3SnO · C6H4NH2.  相似文献   

17.
Electrophilic trisubstituted ethylene monomers, ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RC6H4CH?C(CN) CO2CH3 (where R is 4-C2H5O, 4-C3H7O, 4-C4H9O, 3-C6H5O, and 3-CN), were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the propenoates were copolymerized with styrene (M1) in solution with radical initiation (AIBN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H- and 13C-NMR. The order of relative reactivity (1/r1 ) for the monomers is 3-CN (1.21) > 3-C6H5O (1.16) > 4-C2H5O (0.94) > 4-C3H7O (0.8305) > 4-C4H9O (0.616). The high T g's of the copolymers (> 130°C) in comparison with that of polystyrene indicate a substantial decrease in the chain mobility of the copolymers due to the high dipolar character of the trisubstituted monomer unit. Gravimetric analysis indicated that the copolymers decompose in the range 300–400°C.  相似文献   

18.
Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H2O) and semicarbazone (HL′·H2O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX2·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO3; HL = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0–3; Solv = H2O, CH3OH], CuX2·HL·nH2O [M = Ni, Cu; n = 0, 1], ML2·nH2O and ML′·nH2O [M = Co, Ni, Zn; HL′ = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0–3]. In the presence of amines (A = C5H5N, 2-CH3C5H4N, 3-CH3C5H4N, and 4-CH3C5H4N) these reactions yield the complexes Cu(A)LCl·CH3OH and M(A)LX·nH2O [M = Cu, Ni; X = Cl, NO3; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).  相似文献   

19.
On the refluxing ofM(II) oxalate (M=Mn, Co, Ni, Cu, Zn or Cd) and 2-ethanolamine in chloroform, the following complexes were obtained: MnC2O4·HOCH2CH2NH2·H2O, CoC2O4·2HOCH2CH2NH2, Ni2(C2O4)2·5HOCH2CH2NH2·3H2O, Cu2(C2O4)2·5HOCH2CH2NH2, Zn2(C2O4)2·5HOCH2CH2NH2·2H2O and Cd2(C2O4)2·HOCH2CH2NH2·2H2O. Following the reaction ofM(II) oxalate with 2-ethanolamine in the presence of ethanolammonium oxalate, a compound with the empirical formula ZnC2O4·HOCH2CH2NH2·2H2O1 was isolated. The complexes were identified by using elemental analysis, X-ray powder diffraction patterns, IR spectra, and thermogravimetric and differential thermal analysis. The IR spectra and X-ray powder diffraction patterns showed that the complexes obtained were not isostructural. Their thermal decompositions, in the temperature interval between 20 and about 900°C, also take place in different ways, mainly through the formation of different amine complexes. The DTA curves exhibit a number of thermal effects.  相似文献   

20.
Abstract

Electrophilic trisubstituted ethylenes, ring‐substituted ethyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC6H4CH?C(CN)CO2C2H5 (where R is 2‐CH3, 3‐CH3, 4‐CH3, 2‐OCH3, 3‐OCH3, and 4‐OCH3) were prepared and copolymerized with styrene (ST). The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C NMR. All the ethylenes were copolymerized with ST (M1) in solution with radical initiation (AIBN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C NMR. The order of relative reactivity (1/r 1) for the monomers is 3‐OCH3 (0.88)?>?4‐CH3 (0.71)?>?2‐OCH3 (0.68)?>?3‐CH3 (0.55)?>?2‐CH3 (0.47)?>?4‐OCH3 (0.40). Higher T g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the TSE structural unit. Gravimetric analysis indicated that the copolymers decompose in the 257–287°C range.  相似文献   

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