Synthesis and characterization of poly(ester-sulfone)s

Aliphatic and aromatic-aliphatic poly(ester-sulfone)s were synthesized by the transesterifications of diphenyl adipate and diphenyl phthalates (ortho, meta, para) with two sulfonecontaining diols, 1,3-bis (3-hydroxypropylsulfonyl) propane (Diol-333) and 1,4-bis(3-hydroxypropylsulfonyl) butane (Diol-343). Based on DSC and WAXD studies, the aliphatic homopoly(ester-sulfone)s are semicrystalline at room temperature and liquid crystalline at elevated temperature, while their copolymers with alkanediols are liquid crystalline. The liquid crystalline phase formation in aliphatic poly(ester-sulfone)s is attributed to the strong dipole-dipole interactions between sulfone groups. The aromatic-aliphatic poly(estersulfone)s from diphenyl phthalate (ortho) and isophthalate (meta) are amorphous. They are soluble in trifluoroacetic acid and m-cresol at room temperature, and DMF, DMAC, and DMSO at elevated temperature. The aromatic-aliphatic poly(ester-sulfone)s from diphenyl terephthalate are semicrystalline and are soluble only in trifluoroacetic acid. For a given diol, the glass transition temperatures of aromatic-aliphatic poly(ester-sulfone)s increase from phthalate to isophthalate to terephthalate. This is because the flexibility of the benzene ring in the polymer backbone decreases from ortho to meta to para substitution. As a comparison, polyesters without sulfone groups were synthesized from two alkanediols, 1,9-nonanediol and 1,10-decanediol, and the diphenyl esters. The poly(ester-sulfone)s have glass transition temperatures 60–80°C higher than the corresponding polyesters without sulfone groups, due to the strong dipolar interactions between sulfone groups. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(urethane-sulfone)s

Eight poly(urethane-sulfone)s were synthesized from two sulfone-containing diols, 1,3-bis(3-hydroxypropylsulfonyl)propane (Diol-333) and 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343), and three diisocyanates, 1,6-hexamethylene diisocyanate (HMDI), 4,4′-diphenylmethane diisocyanate (MDI), and tolylene diisocyanate (TDI, 2,4- 80%; 2,6-20%). As a comparison, eight polyurethanes were also synthesized from two alkanediols, 1,9-nonanediol and 1,10-decanediol, and three diisocyanates. Diol-333 and Diol-343 were prepared by the addition of 1,3-propanedithiol or 1,4-butanedithiol to allyl alcohol and subsequent oxidation of the resulting sulfide-containing diols. The homopoly(urethanesulfone)s from HMDI and MDI are semicrystalline, and are soluble in m-cresol and hot DMF, DMAC, and DMSO. The copoly(urethane-sulfone)s from a 1/1 molar ratio mixture of Diol-333 and Diol-343 with HMDI or MDI have lower crystallinity and better solubility than the corresponding homopoly(urethane-sulfone)s. The poly(urethane-sulfone)s from TDI are amorphous, and are readily soluble in m-cresol, DMF, DMAC, and DMSO at room temperature. Differential scanning calorimetry data showed that poly(urethane-sulfone)s have higher glass transition temperatures and melting points than the corresponding polyurethanes without sulfone groups. The rise in glass transition temperature is 20–25°C while the rise in melting temperature is 46–71°C. © 1994 John Wiley & Sons, Inc.     

Synthesis and dielectric analysis of aliphatic poly(carbonate-sulfone)s based on 1,4-bis(3-hydroxypropylsulfonyl) butane

High molecular weight aliphatic poly(carbonate-sulfone) homopolymer (PC-343) and random copolymer (PC-343-10) were synthesized from 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343) and a 1/1 molar mixture of Diol-343 and 1,10-decanediol, respectively. As a comparison, an aliphatic polycarbonate homopolymer (PC-10) was prepared from 1,10-decanediol. While PC-10 exhibited a single melting peak during its DSC heating scan, both PC-343 and PC-343-10 exhibited multiple reproducible first-order transitions during DSC heating scans. Both PC-343 and PC-343-10 showed broad reflections in their WAXD diagrams; the crystalline order of PC-343 is higher than that of PC-343-10. Based on the DSC and WAXD results and our discovery on the liquid crystalline behavior of aliphatic poly(carbonate-sulfone)s from 1,3-bis(hydroxypropylsulfonyl)propane, we suggest PC-343 and PC-343-10 are liquid crystalline and the liquid crystalline phase formation is directed by the dipole–dipole interactions between sulfone groups. Films were obtained from these polymers by compression molding and dielectric analyses were conducted on them. One glass transition related dielectric relaxation was observed in PC-343-10. One glass transition related dielectric relaxation and one sub-glass transition related dielectric relaxation were observed in PC-343. The glass transition temperature increases with the increase of sulfone content in the polymers. A dramatic rise in dielectric constant with temperature was observed in PC-343 and PC-343-10 at low frequencies, which is probably due to the sulfone dipole interaction with the electrical field. © 1994 John Wiley & Sons, Inc.     

Dipole–dipole interaction directed liquid crystalline polymers. I. Aliphatic poly(carbonate-sulfone)s based on 1,3-bis(3-hydroxypropylsulfonyl)propane

Aliphatic poly(carbonate-sulfone) homo- and copolymers were prepared from 1,3-bis(3-hydroxypropylsulfonyl)propane (Diol-333) and various alkanediols. The copolymers are random in nature since they were prepared by melt copolymerization. Both the homopolymer and the copolymers exhibited multiple reproducible first-order transitions during differential scanning calorimetry (DSC) heating scans, but most of them exhibited only single exotherm during cooling scans. Typical schlieren textures were observed when these polymers were cooled from their isotropic melts. The copolymers have wide-angle x-ray diffraction (WAXD) patterns almost identical to that of the homopolymer except in the low-angle spacing, indicating their packing in the crystalline domain in similar. DSC, cross-polarized optical microscopy, and WAXD revealed that these polymers were smectic liquid crystalline at room temperature. Since aliphatic poly(carbonate-sulfone)s are flexible linear polymers with no rigid rod components, the liquid crystalline phase formation is probably directed by the dipole–dipole interactions between sulfone groups in adjacent chains. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of thermally stable poly(ether-azomethine)s derived from 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane

A new dialdehyde 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane (BBMPC) was synthesized starting from cyclopentanone and O-cresol to give 1,1-bis(4-hydroxy-3-methyl phenyl)cyclopentane (BHMPC); followed by reaction with 4-fluorobenzaldehyde in N, N-dimethyl formamide (DMF), containing anhydrous potassium carbonate. New series of poly(ether-azomethine)s were synthesized from (BBMPC) with different diamines such as 4,4′- diamino diphenyl ether (ODA); 4,4′-diaminodiphenyl methane (MDA); 4-aminophenyl sulfone (SDA); p-phenylene diamines (p-PDA), etc. in N, N’- dimethyl acetamide (DMAc) with 5 wt% LiCl by the solution polycondensation method. Inherent viscosities of these polymers were in the range 0.20 to 0.38 dL/g indicating formation of moderate molecular weights. These polymers exhibited good solubility in various polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), DMAc, DMF, etc. However some polymers showed partial solubility in DMF and DMAc. X-Ray diffraction pattern of polymers showed amorphous nature. Thermal stability was assessed by 10% weight loss temperature and the degradation temperature of the resultant polymers falls in the ranges from 444-501°C in nitrogen. The glass transition temperature was in the range of 155-205°C. The structure-property correlation among these polyazomethines were studied; in view of their potential applications as high performance polymers.     

Synthesis and properties of new crystalline poly(arylene ether nitriles)

Crystalline poly(arylene ether nitrile) could be prepared by the polycondensation of 2,6-dihalobenzonitrile with resorcinol at 200°C in N-methylpyrrolidone in the presence of sodium carbonate. A reaction temperature of at least 200°C was necessary to attain high molecular weight polymer. Spectral data indicated that the polymer had the structure of a poly(meta-phenylene ether) with pendent nitrile groups on every other phenylene unit. Despite this structure, the crystallinity and the crystallization rate of the polymer were greater than those of the corresponding polymer with a para-linked structure. The glass transition temperature and the melting temperature of the polymer were almost the same as those of poly(etheretherketone) (PEEK^TM). A series of other new poly(arylene ether nitriles) were also examined. The polymers derived from 4,4′-biphenol, dihydroxytetra-phenylmethane, dihydroxydiphenylsulfone, and 1,5-isoquinolinediol had high glass transition temperatures. The poly(arylene ether nitriles) exhibited excellent tensile strength compared with the corresponding ketone- or sulfone-containing polymers. Comparing the three different kinds of polymers containing the same bisphenol units, the order of glass transition temperature was found to be sulfone- > nitrile- > ketone-containing polymers, while the order of tensile strength was nitrile- > ketone- > sulfone-containing polymers. The excellent mechanical properties are attributable to dipole-dipole interactions of nitrile groups. © 1993 John Wiley & Sons, Inc.     

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.     

Synthesis and Properties of Aromatic Poly(Ether Sulfone)s and Poly(Etherketone)s Containing Naphthalene or Quinoline Units,and Methyl-Substituted Biphenyl-4,4′-Diols

Abstract

A series of poly(ether sulfone)s and poly(ether ketone)s were synthesized from combinations of 1,5- and 2,6-bis(4-fluorosulfonyl)naphthalene, 2,6-bis(4-fluorobenzoyl)naphthalene, and 2,6-bis(4-fluorobenzoyl)quinoline with 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol. The polycondensations proceeded quantitatively in diphenylsulfone in the presence of anhydrous potassium carbonate to afford polymers with inherent viscosities between 0.40 and 1.28 dL/g measured in N-methyl-2-pyrrolidone or concentrated sulfuric acid. The tetramethyl- and hexamethyl-substituted aromatic polyethers exhibited good thermal stability, did not decompose below 330°C in both air and nitrogen atmospheres, and had higher glass transition temperatures than the corresponding unsubstituted polymers. The methylsubstituted poly(ether sulfone)s and poly(ether ketone)s showed good solubility in such common organic solvents as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetrahydrofuran, chloroform, and 1,4-dioxane.     

Preparation of dibenzofuran-type amorphous polyetherketone by novel etherification reaction

4-Fluorobenzophenone reacted with potassium carbonate in the presence of silica catalyst in diphenyl sulfone solvent to yield 4,4′-dibenzoyldiphenyl ether. This new etherification reaction was extended to three difluoro aromatic ketones. 4,4′-Bis(4-fluorobenzoyl)diphenyl ether ( I ) reacted with potassium carbonate to yield a crystalline poly(oxy-1,4-phenylene-carbonyl-1,4-phenylene) (PEK) and 4,4′-bis{4-[4-(4-fluorobenzoyl)phenoxy]benzoyl}benzene ( II ) gave a crystalline poly(oxy-1,4-phenylene-carbonyl-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene-carbonyl-1,4-phenylene)(PEKEKEKK). 2,8-Bis(4-fluorobenzoyl)dibenzofuran ( III ) or 2,8-bis(4-chlorobenzoyl)dibenzofuran ( IV ) reacted with potassium carbonate to yield a poly(oxy-1,4-phenylene-carbonyl-2,8-dibenzofuran-carbonyl-1,4-phenylene) (PEKBK). The PEKBK was a noval amorphous polymer with the glass transition temperature of 222°C and it showed excellent thermal stability [T. Tanabe and I. Fukawa, Jpn. Pat., Kokai 64–74223 (1989)]. Several amorphous dibenzofuran type polyetherketone copolymers were prepared by coplycondensation of III with 4,4′-difluorobenzophenone ( V ) or 1,4-bis(4-fluorobenzoyl)benzene ( VI ) [T. Tanabe and I. Fukawa, Jpn. Pat., Kokai 1153722 (1989)]. © 1992 John Wiley & Sons, Inc.     

Synthesis of sulfone-containing monomers and polymers using cationic cyclopentadienyliron complexes

The synthesis of sulfone-containing monomers with pendent cationic cyclopentadienyliron (CpFe⁺) moieties has been accomplished via nucleophilic aromatic substitution of dichloroarene complexes with a number aliphatic dithiols. These complexes were further oxidized using m-CPBA to give the sulfone-based monomers. Polymerization of the sulfone-based monomers with O-containing nucleophiles produced the sulfone-based polymers. Direct nucleophilic aromatic substitution of dichloroarene complexes with dinucleophiles allowed for the formation of organoiron sulfide-based polymers. Oxidation of these polymers led to the formation of sulfone polymers with the pendent iron moieties. The organometallic monomers and polymers were found to be more soluble in polar solvents in comparison to their organic analogues.     

Fluorinated poly(ether sulfone)s

New fluorinated poly(ether sulfone)s were prepared from bisphenols and α,ωbis(4-fluorophenylsulfonyl)perfluoroalkanes. The fluorinated sulfone monomers were synthesized by reaction of 4-fluorobenzenethiol salts with perfluoroalkylene diiodides, followed by oxidation. Sodium carbonate mediated polymerization gave high molecular weight polymers in excellent yield. The polymers are generally soluble in chlorinated hydrocarbons and some dipolar solvents, are amorphous with T_g's in the range of 120–160°C and are stable to 400°C. They form clear, colorless films by solution casting. Cast films have dielectric constants and dissipation factors somewhat below those of typical poly(ether sulfone)s, and show good permeability and selectivity for O₂/N₂ gas separations.     

Synthesis,curing and properties of poly(phthalazione ether sulfone ketone) copolymers crosslinked by click chemistry

Functionalized poly(phthalazinone ether sulfone ketone) was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu(Ⅰ) catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly(phthalazinone ether sulfone ketone) system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu(Ⅰ) catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly(ether sulfone)(PES) main chain except for the azido methyl poly(phthalazinone ether sulfone ketone) and 4,4'-bis(2-propynyloxy) biphenyl( AMPPESK-BP) system.     

Synthesis of aromatic polyethers by Scholl reaction. II. On the polymerizability of 4,4′-bis(phenoxy)diphenyl sulfones and of 4,4′-bis(phenythiol)diphenyl sulfone

4,4′-Bis(phenoxy)diphenyl sulfone ( 1 ), 4,4′-bis(phenylthio)diphenyl sulfone ( 2 ), and 1 substituted with various electron-donating groups in the phenoxy units were synthesized and polymerized under oxidative reaction conditions. The presence of methyl, tert-butyl, and methoxy groups as substituents on the phenoxy groups of 1 increases both the yield and the solubility of the resulting polymers. The structure-reactivity relationship of the monomers and of the growing species were discussed based on a radical-cation mechanism of polymerization. Monomers of high nucleophilicity and resonance stabilized radical-cation growing species are crucial to achieve polymers of high molecular weight. The structure of the polymers and in several cases of their chain ends were determined by ¹H-NMR spectroscopy. The mechanism of termination and the side reactions occuring during this polymerization process were discussed based on the structure of the resulting polymers.     

Synthesis of aromatic polyethers by scholl reaction. VIII. On the polymerizability of 1,5-bis(phenoxy)pentanes and 1,5-bis(phenylthio)pentane

The synthesis and the oxidative polymerization of 1,5-bis(phenoxy)pentane, 1,5-bis(phenoxy)pentane substituted with various electron-donating groups, and 1,5-bis(phenylthio)pentane is described. The polymers derived from methyl substituted 1,5-bis(phenoxy)pentane monomers contain diphenyl methane, 1,2-diphenylethane, and benzyl chloride structural units. The mechanism for the generation of these structural units is presented. It consists of the proton transfer reactions from the cation-radical propagating species and subsequent reactions of the resulting benzyl radicals. The polymerizability of monomers with 1,5-pentanedioxy group is lower than that of the monomers with diphenyl sulfone group. This dissimilarity was attributed to the difference between both the reactivity and the concentration of the cation-radical propagating species resulted from these two classes of monomers.     

Synthesis and properties of phosphorus polyesters with systematically altered phosphorus environment

Monomers with phosphorus-containing substituents were incorporated into aromatic-aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic-aliphatic diols. Starting from 10-(2,5-bis(2-hydroxyethoxy)phenyl)-9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO-HQ-GE), the chemical structure of the phosphorus monomers was systematically varied resulting in new polymers with diphenyl phosphine oxide substituents and bridged phosphine oxide units. The polymers were prepared by transesterification polycondensation in the melt in lab-scale as well as in a 2.4 l-autoclave. The properties of the polyesters were determined and compared to the DOPO-based polyester with respect to the achieved molar mass and polydispersity, solid state structure, glass transition temperature, thermal stability and combustion behavior.It was found that the different phosphorus substituents lead to different glass transition temperatures. The polymers containing bridged phosphorus structural units showed higher glass transition temperatures T_g and resulted in higher char yields after thermal decomposition. Both phosphine oxide structures showed only one-step decomposition with a shoulder at the end of the step. In contrast, two separate steps were observed in the polyesters with DOPO-substituents. The results indicated that the phosphorus polyesters under discussion are suitable to adjust the flame retarding mechanism.     

Synthesis,characterization, and thermal properties of novel arylene sulfone ether polyimides and polyamides

A new aromatic sulfone ether diamine was synthesized by nucleophilic aromatic substitution reaction of 5‐amino‐1‐naphthol with bis(4‐chlorophenyl) sulfone in the presence of potassium carbonate in a polar aprotic solvent. Polycondensation reactions of the obtained diamine with pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic anhydride (6FDA) resulted in preparation of thermally stable poly(sulfone ether imide)s. Poly(sulfone ether amide)s also were prepared by reaction of the diamine with terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC). The prepared monomer and polymers were characterized by conventional methods. Physical and mechanical properties of polymers, including thermal stability, thermal behavior, solution viscosity, solubility behavior, and modulus, also were studied. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1487–1492, 2000     

含蒽醌结构聚芳醚砜的合成及表征

以4,4'-二氟二苯砜,4,4'-联苯二酚及1,5-二氯蒽醌为原料,采用亲核缩聚方法将具有良好热稳定性的蒽醌生色团分子以共价键方式引入到聚芳醚砜体系中,制备出了蒽醌含量分别为10%、20%及30%的热分解温度在500℃以上的新型耐高温有机高分子染料.该系列聚合物具有较高的分子量和良好的溶解性.利用红外光谱(FTIR)、核磁共振(1H-NMR)等表征方法确定了聚合物的结构;利用紫外-可见光谱测试(UV-Vis)初步研究了聚合物的光谱学特性;利用差示扫描量热测试(DSC)和热失重分析测试(TGA)研究了聚合物的热性能.     

Li⁺ selective podand-type fluoroionophore based on a diphenyl sulfoxide derivative bearing two pyrene groups

New podand-type fluoroionophores having two pyrene moieties: 2,2′-bis(1-pyrenylacetyloxy)diphenyl sulfide (3), 2,2′-bis(1-pyrenylacetyloxy)diphenyl sulfoxide (4), and 2,2′-bis(1-pyrenylacetyloxy)diphenyl sulfone (5), have been synthesized by connecting two 1-pyrenecarbonylmethyl groups with the two hydroxy groups of 2,2′-dihydroxydiphenyl sulfide, sulfoxide, and sulfone, respectively. Their complexation behavior toward alkali metal ions was examined by fluorescence spectroscopy. Among these fluoroionophores, compound 4, having a sulfinyl group, showed high selectivity toward Li?.     

Poly(diarylsilmethylene)s,I. Synthesis and characterization

Poly(diarylsilmethylene)s with phenyl or tolyl substituents on Si atoms were synthesized by ring-opening polymerization of corresponding 1,1,3,3-tetraaryl-1,3-disilacyclobutanes, and were characterized by means of DSC, x-ray diffraction and melt viscosity measurements. Three preparative routes including catalytic and noncatalytic polymerization methods were examined to see differences in properties of the resulting polymers. The polymers thus obtained were crystalline and soluble in limited solvents such as diphenyl sulfone at tem-peratures above 250°C. Poly(diphenylsilmethylene) exhibited a melting temperature of about 350°C, whereas those of polymers with tolyl groups were observed in a temperature range between 310 and 330°C. The melt viscosity of the poly(diarylsilmethylene)s was measured to obtain insight into the molecular weights of the polymers, and the results indicated that the molecular weights are modifiable by varying the monomer-to-catalyst ratio when solution polymerization is employed. The DSC and x-ray studies were also carried out with focusing on the melting and crystallization behavior of these polymers. © 1995 John Wiley & Sons, Inc.     

Synthesis and structure–property relationships of poly(sulfone)s for anion exchange membranes

Membranes based on cationic polymers that conduct anions are important for enabling alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. Anion exchange membranes with poly(arylene ether sulfone) backbones are demonstrated by two routes: chloromethylation of commercially available poly(sulfone)s or radical bromination of benzylmethyl moieties in poly(sulfone)s containing tetramethylbisphenol A monomer residues. Polymers with tethered trimethylbenzyl ammonium moieties resulted from conversion of the halomethyl groups by quaternization with trimethyl amine. The water uptake of the chloromethylated polymers was dependent on the type of poly(sulfone) backbone for a given IEC. Bisphenol A-based Udel® poly(sulfone) membranes swelled in water to a large extent while membranes from biphenol-based Radel® poly(sulfone), a stiffer backbone than Udel, only showed moderate water uptake. The water uptake of cationic poly(sulfone)s was further reduced by synthesizing tetramethylbisphenol A and 4,4′-biphenol-containing poly(sulfone) copolymers where the ionic groups were clustered on the tetramethylbisphenol A residues. The conductivity of all samples scaled with the bulk water uptake. The hydration number of the membranes could be increased by casting membranes from the ionic form polymers versus converting the halomethyl form cast polymers to ionic form in the solid state. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1790–1798, 2013