一类含多氟烷基侧链的螺环化合物的合成及结构表征

A series of spiro compounds have been synthesized via several steps.The structure of these compounds wereconfirmed by ~1H NMR,~(13)C NMR,IR,MS spectra and X-ray diffraction analysis.The possible mechanism to formthese products was also proposed.     

Synthesis and characterization of new AB-type poly(etherimide)s containing bisphenol moieties

A series of new AB-type poly(etherimide)s having bisphenol-type moiety was prepared by the one-pot polyimidization using triphenylphosphite(TPP) in N-methyl-2-pyrrolidone(NMP)/pyridine solution at 150°C. Complete cyclodehydration was observed in the polymerizations as well as in model reactions. Polymers were obtained with inherent viscosities in the 0.27–0.49 dL/g range. The M_n and M_w/M_n of poly[4-(1,4-phenyleneoxy-1,4-phenylenehexafluoro-isopropylidene-1,4-phenylene)oxyphthalimide] (4d) with η_inh = 0.49 dL/g were 73,400 g/mol and 1.5, respectively. Most polymers could readily be dissolved in common organic solvents such as DMAc, NMP, and m-cresol. The polymer 4d was soluble even in chloroform. These polymers had glass transition temperatures between 205 and 235°C, and 5% weight loss temperatures in the range of 511–532°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3530–3536, 1999     

Synthesis and electronic properties of poly (E,E)-[6.2]-(2,5) thiophenophane-1,5-diene)

Cationic cyclopolymerization of (E, E)-[6.2]-(2,5) thiophenophane-1,5-diene ( 2 ) gave polymer 3 which has bridged thiophene rings pendant to the polymer backbone. The structural, thermal, and electronic properties of polymer 3 were compared to those of its benzene analogue ( 1 ) and its nonbridged analogue poly (2-vinylthiophene) ( 5 ). The onsets of thermal degradation for polymers 3 and 5 under helium were 425 and 382°C, respectively. Polymer 3 exhibited conductivity in the 10^?3?10^?4 S/cm range when exposed to iodine vapor, four orders of magnitude higher than for 5 treated in the same manner. Apparent energies of activation for conductivity in iodine saturated polymers 3 (0.57 eV) and 5 (0.61 eV) were calculated from conductivity temperature dependence measurements. Conductivity parameters for iodine saturated 3 show both a higher level of conductivity and weaker temperature dependence than for the corresponding cyclopolymer 1 which has benzene rather than thiophene moieties, suggesting that greater charge generation occurs in 3 , due to the lower oxidation potential of the thiophenophane repeat units. Differences in conductivity behavior for iodine saturated polymers 1, 3 , and 5 are discussed in terms of both charge generation and mobility. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units

Bis(4-oxybenzoic acid) tetrakis(phenoxy) cyclotriphosphazene (IUPAC name: 4-[4-(carboxyphenoxy)-2,4,6,6-tetraphenoxy-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-yl]oxy-benzoic acid) was synthesized and direct polycondensed with diphenylether or 1,4-diphenoxybenzene in Eaton's reagent at the temperature range of 80–120°C for 3 hours to give aromatic poly(ether ketone)s. Polycondensations at 120°C gave polymer of high molecular weight. Incorporation of cyclotriphosphazene groups in the aromatic poly(ether ketone) backbone greatly enhanced the solubility of these polymers in common organic polar solvents. Thermal stabilities by TGA for two polymer samples of polymer series ranged from 390 to 354°C in nitrogen at 10% weight loss and glass transition temperatures (T_g) ranged from 81.4 to 89.6°C by DSC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1227–1232, 1998     

Synthesis and characterization of soluble copoly(ether ketone)s containing double bonds

A series of copoly(ether ketone)s containing double bonds along the polymer chains were synthesized from the condensation polymerization of hydroquinone with 4,4′‐difluorobenzophenone and 4,5‐bis(4‐fluorobenzoyl)‐1‐methylcyclohexene in sulfolane containing anhydrous potassium carbonate. The presence of methylcyclohexene in the polymer chains resulted in an improvement in the solubility of poly(ether ketone)s in organic solvents such as chloroform, chlorobenzene, and sulfolane. As a result, the conditions for synthesizing these polymers were much milder than those for poly(ether ether ketone). The new copoly(ether ketone)s also showed good tensile properties and reasonable thermal stability. New polyethers containing pyrazine unites were obtained from the cyclization reaction of these copoly(ether ketone)s with hydrazine. The hydrazine cycloderivatives led to an increase in the glass‐transition temperatures and a decrease in solubility in organic solvents. © 2002 Government of Canada. Exclusive world‐wide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3449–3454, 2002     

Synthesis and characterization of poly(aryl ether)s containing the pyrimidine moiety

A series of new poly(aryl ether)s containing the pyrimidine moiety were prepared by a nucleophilic aromatic substitution polymerization reaction in an aprotic solvent (DMAc) in the presence of excess potassium carbonate. These polymers are high molecular weight, amorphous, and soluble in common solvents at room temperature. The polymers are easily cast from solution into flexible, colorless, and transparent films. They showed high glass transition temperatures ranging from 198 to 304°C by DSC analysis. The 5% weight losses by thermogravimetric analysis ranged from 478 to 580°C, indicating that these polymers are very thermostable in nitrogen and air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1107–1110, 1998     

Synthesis and characterization of new poly(arylene ether)s containing heterocyclic units. II.

A series of new poly(arylene ether)s, containing naphthalene, pyridine, and quinoline units have been prepared by solution condensation polymerization. The synthesis involves nucleophilic displacement of aromatic dihalides with aromatic potassium bisphenates in an anhydrous dipolar aprotic solvent at elevated temperatures. The polymers, having inherent viscosity from 0.24 to 1.32 dL/g, were obtained in quantitative yield, have excellent thermal stability as shown by 10% weight loss temperatures in nitrogen and air (above 450 and 430°C, respectively) and high glass transition temperatures (in the range of 150–220°C). The introduction of quinoline moieties in the polymer backbone positively influences the thermal properties, such as high T_g/T_m ratios. © 1995 John Wiley & Sons, Inc.     

Crystal structure of poly(p-benzamide)

Redetermination of the crystal structure of poly(p-benzamide) was made by using newly collected intensity data. The molecular conformation is TCTC, where the internal rotation angles about the N? C bond of the amide group and about the virtual bond of N-phenyl-C are T (trans) and C (cis) conformations, respectively. Two molecular chains pass through a rectangular unit cell with dimension, a = 7.75 Å, b = 5.30 Å, c (fiber axis) = 12.87 Å, and the space group, P2₁2₁2₁-D. The reflection observed at the spacing of 010 may be attributed to the reflection due to another crystal polymorph or the diffuse scattering due to disorder. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(vinylcyclohexane) derivatives

Six nearly monodisperse substituted poly(styrene) homopolymers, poly(styrene) (PS), poly(2-methylstyrene) (P2MS), poly(3-methylstyrene) (P3MS), poly(4-methylstyrene) (P4MS), poly(tertiary-butylstyrene) (PtBS), and poly(α-methylstyrene) (FαMS) were anionically polymerized and subsequently saturated using heterogeneous hydrogenation techniques to poly(vinylcyclohexane) (PVCH), poly(2-methylvinylcyclohexane) (P2MVCH), poly(3-methylvinylcyclohexane) (P3MVCH), poly(4-methylvinylcyclohexane) (P4MVCH), and poly(tertiary-butylvinylcyclohexane) (PtBVCH), respectively. In each case, except PαMS, the materials were saturated to > 99% conversion with no chain degradation. PS hydrogenations required the addition of small amounts of tetrahydrofuran to the reaction solvent cyclohexane to enhance miscibility and eliminate large-scale chain degradation. Density gradient and differential scanning calorimetry (DSC) measurements were used to characterize the density and glass transition temperature, T_g, of the unsaturated and saturated polymers. Saturation reduces the density by 3% to 11% and changes T_g substantially. The greatest variation in T_g is obtained with the 3-methyl substituted species where a 63°C increase is observed, while the highest measured T_g is 186°C for P2MVCH. Small-angle neutron scattering (SANS) experiments on binary mixtures of hydrogenous and deuterium labeled PVCH derivatives provided a determination of bulk chain statistics. The statistical segment length is relatively insensitive to vinylcyclohexane ring substitution, except with P3MVCH where a 20% greater value is obtained. ©1995 John Wiley & Sons, Inc.     

Synthesis and characterization of four-armed poly(1,3-dioxepane) tetraol

A new four-armed poly(1,3-dioxepane) tetraol was prepared by cationic ring-opening polymerization of 1,3-dioxepane (DOP) in the presence of 6,6-bis(5-hydroxyl-2-oxapentyl)-4,8-dioxaundecanediol-1,11 (THA) with triflic acid(I) as initiator. The structure of the poly(DOP) tetraol obtained was characterized by ¹H and ¹³C NMR spectra. The molecular weights of the obtained tetraols were controlled by the mole ratio of DOP consumed to initial THA, and it was found that each macromolecule contains only one THA unit on the average. GPC studies showed that the cyclic oligomers in the products were negligible. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2347–2353, 1999     

Synthesis and thermal characterization of poly(1,3-phenyl octanoate)

Poly(1,3-phenyl octanoate) (polyHPOA) was prepared by melt and solution polycondensation methods from 8-(3-hydroxyphenyl)octanoic acid (HPOA), a novel monomer useful as a chain disruptor in liquid crystalline copolyesters. The melt polycondensation technique gave a polyester of higher inherent viscosity (0.80 dL/g in p-chlorophenol) than that (0.75 and 0.56 dL/g, respectively, for the Ogata method and thionyl chloride/pyridine method in the same solvent) of solution techniques. The solubility of the polyesters was limited to strongly acidic and polar solvents. The polyester was characterized by elemental analysis, IR spectroscopy, WAXD, TGA, isothermal TGA and DTA. x-ray diffraction pattern of the polyesters indicated that it is amorphous in nature. TGA of the polyesters gave a thermal stability of 470°C in nitrogen atmosphere at 50% decomposition. The available thermal data suggest that the polyester undergoes thermal decomposition by a pyrolytic cleavage involving the ester linkage with the formation of ketene and phenol ended groups as intermediates. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of novel poly(amide-imide)s containing hexafluoroisopropylidene linkage

A series of novel soluble poly(amide-imide)s were prepared from the diimide-dicarboxylic acid, 2,2-bis[N-(4-carboxyphenyl)-phthalimidyl]hexafluoropropane, with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone containing CaCl₂ using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 0.78–1.63 dL g⁻¹. The polymers were amorphous and readily soluble in aprotic polar solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide as well as in less polar solvents such as pyridine and γ-butyrolactone, and also in tetrahydrofuran. The polymer films had tensile strength of 84–129 MPa, an elongation at break range of 6–22%, and a tensile modulus range of 2.0–2.7 GPa. The glass transition temperatures of the polymers were determined by DSC method and they were in the range of 240–282°C. These polymers were fairly stable up to a temperature around or above 400°C, and lose 10% weight in the range of 450–514°C and 440–506°C in nitrogen and air, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2629–2635, 1999     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units. II

A new monomer di(4‐carboxyphenoxy) tetrakis(4‐fluorophenoxy)cyclotriphosphazene 1 was synthesized in a two‐step reaction sequence. The direct polycondensation of 1 and/or 4,4′‐dicarboxydiphenylether with aromatic ethers was carried out in P₂O₅/methanesulfonic acid (Eaton's reagent) at 120 °C for 3 h to give two series of aromatic poly(ether ketone)s containing cyclotriphosphazene units. The effect of the introduction of the cyclotriphosphazene group on the solubility and thermal properties of these polymers was discussed with relation to the cyclotriphosphazene contents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2300–2305, 2000     

Synthesis and characterization of poly(ethylene glycol) methyl ether endcapped poly(ethylene terephthalate)

Linear and branched poly(ethylene terephthalate) (PET) copolymers with polyethylene glycol) (PEG) methyl ether (700 or 2000 g/mol) end groups were synthesized using conventional melt polymerization. DSC analysis demonstrated that low levels of PEG end groups accelerated PET crystallization. The incorporated PEG end groups also decreased the crystallization temperature of PET dramatically, and copolymers with a high content of PEG (>17.6 wt%) were able to crystallize at room temperature. Rheological analysis demonstrated that the presence of PEG end groups effectively decreased the melt viscosities and facilitated melt processing. XPS and ATR-FTIR revealed that the PEG end groups tended to aggregate on the surface, and the surface of compression molded films containing 34.0 wt% PEG were PEG rich (85 wt% PEG). PEG end-capped PET (34.0 wt% PEG) and PET films were immersed into a fibrinogen solution (0.7 mg/mL BSA) for 72 h to investigate the propensity for protein adhesion. XPS demonstrated that the concentration of nitrogen (1.05%) on the surface of PEG endcapped PET film was statistically lower than PET (7.67%). SEM analysis was consistent with XPS results, and revealed the presence of adsorbed protein on the surface of PET films.     

Synthesis and photochromic properties of spiro (benzindoline-naphthoxazines)

A new photochromic compound belonging to the class of spiro(indoline-naphthoxazines) was synthesized. Nitration of this compound was carried out and the structures of two photochromic nitro-substituted products were determined. The photochromic properties of the products were studied in solvents of different polarity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 732–736, April, 1995.     

Synthesis, characterization and spectroscopic investigation of pyrazinoporphyrazine network polymer-supported metal (II)-based catalysts

Chloranil through condensation reaction with vicinal diamine such as diaminomaleonitrile produced heterocyclic monomer, p-benzoquinonebis[2,3-b; 2′,3′-b′]pyrazine-5,6-dinitrile. The tetranitrile monomer was cyclo-tetramerised using lithium/pentanol and acetic acid affording the corresponding tetra p-benzoquinone bis[2,3-b; 2′,3′-b′]pyrazinoporphyrazine)]-based network polymer (2H-Pz). The tetranitril monomer was cyclo-tetramerised using metal salt and quinoline affording the corresponding porphyrazinato-metal II-based network polymers (M-Pz), M = Co, Ni or Cu. Elemental analytical results, IR and NMR spectral data of the prepared molecules are consistent with their assigned formulations. Molecular masses and metal contents of the synthesized polymers proved to be of high molecular masses which confirm the efficiency of tetramerization polymerization and complexation reactions. The prepared pyrazinoporphyrazines were used as efficient catalysts for the oxidation of thiophenol and benzylthiol to their disulfides in the presence of air atmosphere. The results of oxidation of thiophenol and benzylthiol show that after 15 min the maximum yield of the corresponding disulfides reached 95%, 91%, respectively.     

Synthesis and properties of poly(dipropargyl sulfoxide)

The preparation and cyclopolymerization of dipropargyl sulfoxide were studied. The polymerization of dipropargyl sulfoxide was carried out by various transition metal catalysts. WCl₆–EtAlCl₂, MoCl₅, and PdCl₂ catalyst systems were very effective. The resulting poly(dipropargyl sulfoxide) structures were characterized by NMR (¹H and ¹³C), IR, and elemental analysis to have conjugated polyene units. Poly(dipropargyl sulfoxide) prepared by PdCl₂ was mostly soluble in organic solvents such as DMF and DMSO. Thermal and oxidative properties of poly(dipropargyl sulfoxide) were also studied. The electrical conductivity of iodine-doped poly(dipropargyl sulfoxide) was 5.2 × 10^?2 Ω^?1 cm^?1. Comparisons of poly(dipropargyl sulfoxide) properties with other similar polymers from dipropargyl sulfur derivatives such as dipropargyl sulfide and dipropargyl sulfone were also carried out. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of thianthrene-containing poly(benzoxazole)s

New thioether- and thianthrene-containing poly(benzoxazole)s (PBOs) were synthesized from 4,4′-thiobis[3-chlorobenzoic acid] and thianthrene-2,7- and -2,8-dicarbonyl chlorides with commercially available bis-o-aminophenols. Polymers were prepared via solution polycondensation in poly(phosphoric acid) at 90–200°C. Transparent PBO films were cast directly from polymerization mixtures or m-cresol. The films were flexible and tough. Non-fluorinated PBOs were soluble only in strong acids and AlCl₃/NO₂R systems by forming complexes with the benzoxazole heterocycle Glass transition temperatures ranged from 298–450°C, and thermogravimetric analysis showed good thermal stabilities in both air and nitrogen atmospheres. © 1995 John Wiley & Sons, Inc.     

Thermal characterization of poly(lactide-co-glycolide) microspheres containing bupivacaine base polymorphs

Solid-state chemistry of bupivacaine base, obtained by precipitation from bupivacaine hydrochloride solutions with ammonia, was investigated. Two bupivacaine base polymorphs (Form I: T _m=105.6±0.0°C; Form II: T _m=97.6±0.2°C) were isolated depending on the precipitation conditions and characterised by thermal analysis and FTIR spectroscopy. No weight loss was evidenced by TG confirming that no solvate formation had occurred. Biodegradable poly(lactide-co-glycolides) microspheres containing bupivacaine base were prepared by spray-drying. In the microspheres bupivacaine base was present as the metastable low melting crystal form independently of the bupivacaine base / poly(lactide-co-glycolides) ratio.     

Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction

High‐molecular‐weight poly(phthalazinone)s with very high glass‐transition temperatures (T_g's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers ( 7a–e ) were synthesized from 2‐(4‐chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited T_g's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4‐flurophenyl) sulfone demonstrated the highest T_g of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4′‐isopropylidenediphenol and 4,4′‐(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly‐(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481–2490, 2003