Synthesis and characterization of poly(cyclohexane 2,2-dipropargyl-1,3-propylene ketal) containing double spiro structure

The Polymerization was carried out by MoCl₅ and WCl₆ associated with various organo-metallic cocatalysts. MoCl₅-based catalysts were found to be more effective. Polymerization of monomer containing a spiro structure proceeded rapidly to reach 80% yield within 2 h at 30°C. Polymerization of monomer led to a soluble, purple colored polymer with number average molecular weight (M_n) of 50000. Elemental analysis, ¹H-NMR, ¹³C-NMR, IR, and UV-visible spectra of the resulting polymer indicated that the polymer contains alternating double and single bonds along the polymer backbone and a cyclic recurring unit with a double spiro structure. In addition, the polymer had good oxidative and thermal stability and good solubility in common organic solvents. © 1995 John wiley & Sons, Inc.     

Polymerization of α-Hydroxyacetylenes by Transition Metal Catalysts

Abstract

α-Hydroxyacetylenes (2-propyn-1-ol, DL-3-butyn-2-ol, 1-octyn-3-ol, 2-phenyl-3-butyn-2-ol) with a hydroxy functional group were polymerized by various Mo- and W-based catalysts. In general, the catalytic activities of Mo-based catalysts were greater than those of W-based catalysts for these polymerizations. In the polymerization of 2-propyn-l-ol, MoCl₅ alone and the MoCl₅-EtAlCl₂ catalyst system gave a quantitative yield of polymer. In the polymerization of 2-propyn-l-ol and its homologues by Mo-based catalysts, the polymer yield decreased as the bulkiness of the substituent increased. On the other hand, the polymer yield increased as the bulkiness of the substituent increased in WCl₆-EtAlCl₂-catalyzed polymerization. Polymers with a bulkier substituent showed better solubility in organic solvents than those without a substituent [e.g., poly (2-propyn-l-ol)]. The structures of the resulting polymers were characterized by various instrumental methods such as ¹H- and ¹³C-NMR, IR, and UV-visible spectroscopies. Thermogravimetric analyses and thermal transitions of the resulting polymers were also studied.     

二茂铁四唑和二茂铁甲醛缩3-取代丙二醇衍生物的合成

以甲酰基二茂铁6为原料, 通过与NH₄OH•HCl的缩合反应得到二茂铁肟7, 再经脱水剂脱水得到二茂铁腈8, 最后在(n-C₄H₉)₃SnCl的作用下与NaN₃反应生成新化合物二茂铁四唑(9). 以甲酰基二茂铁为原料, 在对甲苯磺酸(PTSA)的催化作用下与原甲酸三甲酯反应生成二甲基二茂铁缩醛(10), 然后与(R)-(－)-3-氯-1,2-丙二醇反应得到新的二茂铁缩醛衍生物12, 12再与NaN₃发生取代反应得到新的二茂铁缩醛衍生物13. 而新的二茂铁缩醛衍生物15的合成则是先由(R)-(－)-3-氯-1,2-丙二醇与CH₃OH在NaOH的作用下生成(R)-(－)-1-甲氧基-2,3-丙二醇(14), 再由14与二甲基二茂铁缩醛(10)反应得到的. 所合成的新化合物都用MS, ¹H NMR和IR谱确证了它们的结构.     

SYNTHESIS AND PROPERTIES OF POLY(1,6-HEPTADIYNE) HAVING A BULKY AND RIGID t-BUTYLBENZOYL GROUP

The polymerization of 4,4-bis(t-butylbenzoylmethyl)-1,6-hepta-diyne (BTBH) was carried out by group 5,6-transition metal catalysts. MoCl₅- as well as WCl₆-based catalysts were effective for the cyclopolymerization of BTBH. The polymer structure was analyzed to have conjugated backbone and recurring 5-membered ring by various spectroscopes. The polymer showed good solubility in common organic solvents. The polymer had good thermal stability and mechanical property. The oxygen permeability coefficient (PO₂) and permselectivity of oxygen to nitrogen (PO₂/PN₂) of poly(BTBH) with bulky and rigid t-butyl benzoyl group were 23.2 barrer and 4.63, respectively.     

Synthesis and Properties of Poly(Phenyl Propargyl Ether) and Its Homologues

Abstract

Various para-substituted phenyl propargyl ethers (substitutent = H, OMe, and CN) were synthesized and polymerized by transition metal catalyst systems including MoCl₅, WC1₆, and PdCl₂. The catalytic activity of MoCl₅-based catalysts was greater than that of WCl₆-based catalysts for the present polymerization. The polymer yield increased in the following order: H > OMe > CN, according to substitutents. The [poly-(pheny] propargyl ether) [poly(PPE)] and poly(methoxy phenyl propargyl ether) [poly(OMe-PPE)] obtained are completely soluble in various organic solvents such as chloroform, methylene chloride, THF, and 1,4-dioxane. However, poly(cyanophenyl propargyl ether) [poly(CN-PPE)] is partially soluble in various organic solvents such as those mentioned above. The electrical conductivities of the undoped and iodine-doped polymers and found to be about 10^?13 and 10^?4-10^?5 S/cm, respectively. The solubilities, thermal properties, and morphologies of the resulting polymers were also studied.     

Synthesis and properties of poly(1‐naphthylacetylene) and poly(9‐anthrylacetylene)

Polymerizations of 1‐naphthylacetylene (1‐NA) and 9‐anthrylacetylene (9‐AA) by various transition metal catalysts were studied, and properties of the polymers were clarified. 1‐NA polymerized with WCl₆‐based catalysts to offer dark purple polymers in good yield. Especially, a binary catalyst composed of WCl₆ and Ph₃Bi gave a polymer with high molecular weight (M_w = 140×10³) and sufficient solubility in common solvents. The use of Mo and Rh catalysts, in contrast, resulted in the formation of insoluble red poly(1‐NA)s. 9‐AA gave insoluble polymers by both WCl₆‐ and MoCl₅‐based catalysts in moderate to good yields. Copolymerization of 9‐AA with 1‐NA by WCl₆–Ph₃Bi provided a soluble copolymer which exhibited the largest third‐order nonlinear optical susceptibilities (χ⁽³⁾(−3ω; ω, ω, ω) = 40×10⁻¹²) among all the substituted polyacetylenes synthesized so far. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 277–282, 1999     

Polymerization of 1-chloro-2-β-naphthylacetylene by Mo catalysts and polymer properties

1-Chloro-2-β-naphthylacetylene (ClβNA) polymerized in good yields in the presence of MoCl₅-based catalysts. The highest weight-average molecular weight of poly(ClβNA) reached about 3 × 10⁵. The polymer was a yellow solid (absorption cutoff in CHCl₃ 450 nm). It was soluble in toluene, chloroform, etc., and provided a tough film by the solvent casting method. The polymer retained its weight up to 300°C in air; it was thermally less stable than poly(1-chloro-2-phenylacetylene) but more stable than poly(β-naphthylacetylene). The oxygen permeability coefficient (P_O2) of this polymer was 19 barrers (25°C), which is fairly small for a substituted polyacetylene. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] having high oxygen permselectivity

Cyclopolymerization of 4,4-bis(pivaloxymethyl)-1,6-heptadiyne containing a bulky ester group was examined by group 5,6-transition metal catalysts. Both of the MoCl₅-based and WCl₆-based catalysts were effective for the cyclopolymerization. The obtained polymer was characterized to have planar backbone and recurring cyclic ring structure by various spectroscopy. The poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] was soluble in common organic solvents to easily cast the free standing film. The polymer film had good mechanical property and high oxygen permselectivity to nitrogen. The oxygen permeability coefficient (PO₂) and permselectivity of oxygen to nitrogen (PO₂/PN₂) of poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] were 19.7 barrer and 5.71, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4135–4139, 1999     

Synthesis and Properties of Poly(1,6-Heptadiyne) Derivatives Containing Hydroxy Functional Group

Abstract

1,6-Heptadiyne derivatives containing hydroxy and aromatic substituents, 4-hydroxy-4-phenyl-l,6-heptadiyne (HPHD), 4-hydroxy-4-(4′-methylphenyl)-l,6-heptadiyne (HMHD), and 4-hydroxy-4-(4′-methoxy-phenyl)-l,6-heptadiyne (HMOHD), were prepared and polymerized by various transition metal catalyst systems. A molybdenum complex was found to be the most effective catalyst for the cyclopolymerization of 4-hydroxy-l,6-heptadiyne derivatives. Polymerization of 4-hydroxy-l,6-heptadiyne derivatives by MoCl₅-based catalysts gave soluble and highly colored polymers. HMOHD containing the methoxy functional group showed the highest reactivity in cyclopolymerization. The structures of the resulting polymers were elucidated with IR, ¹H- and ¹³C-NMR, and UV-visible spectroscopies. The present polymers were thermally and oxidatively more stable and had higher number-average molecular weights (M_n) of 2 × 10⁴ to 3 ×10⁴ than the corresponding 4-hydroxy-1,6-heptadiyne derivatives containing aliphatic substituents.     

Synthesis and properties of poly(phenylacetylenes) having o-silylmethyl groups

Novel phenylacetylene (PA) monomers, which have o-silylmethyl groups of different bulkinesses, i.e., o-Me₃SiCH₂PA, o-Et₃SiCH₂PA, and o-t-BuMe₂Si-CH₂PA, polymerized with W and Mo catalysts in high yields. The MoCl₅-Ph₄Sn catalyst achieved the highest weight-average molecular weights (M _w 7 × 10⁵ ? 12 × 10⁵), and the M _w increased as the ortho-substitutent became bulkier (e.g., M_w of o-t-BuMe₂SiCH₂PA: 12 × 10⁵). These monomers polymerized in a living fashion by the MoOCl₄-n-Bu₄Sn-EtOH catalyst. The resulting polymers were soluble in common solvents such as toluene and chloroform. In the UV-visible spectra, a tendency was observed that absorption maxima shifted to longer wavelengths as the substituents became bulkier. Membranes of the polymers were fairly permeable to gases (e.g., oxygen permeability coefficients 30-80 barrers). Though o-(Me₃Si)₂CHPA also polymerized with W and Mo catalysts, the product polymer was partly insoluble in any solvent. © 1995 John Wiley & Sons, Inc.     

Cyclopolymerization of dipropargyl isopropylidene malonate and characterization of the product

The polymerization of dipropargyl isopropylidene malonate (DPIPM) was polymerized by WCl₆ and MoCl₅ associated with various organometallic cocatalysts. MoCl₅ was found to be the most effective catalyst and Ph₄Sn was observed to have a high cocatalyst activity. Structure and physical properties of poly(DPIPM) were investigated. The spectral data indicated that poly(DPIPM) contains alternating double and single bonds along the polymer backbone and a cyclic recurring unit. The poly(DPIPM) was partially soluble in common organic solvents. The M?_n values of the polymer from soluble fraction were in the range of 5100–8000 relative to polystyrene standards by GPC. In addition, poly(DPIPM) possesses good stability to air oxidition. When poly(DPIPM) is exposed to iodine vapor, the electrical conductivity was increased from 4.5 × 10^?11 to 7 × 10^?2 S/cm. © 1993 John Wiley & Sons, Inc.     

Polymerization of [o-n-(perfluorohexyl)phenyl]acetylene and polymer properties

Synthesis, properties, and membrane-separation functions of a novel fluorine-containing poly(phenylacetylene) were examined. The monomer used was [o-n-(perfluorohexyl)phe-nyl]acetylene, which has a rigid rod-like ortho-substituent. Polymers, whose intrinsic vis-cosities ([η]) were ca. 0.4–2.2 dL/g, were obtained in high yields with various W and Mo catalysts. The MoCl₅–Ph₃Sb catalyst achieved the highest [η] of 2.25 dL/g corresponding to an M_w over one million. The polymer was a brown solid soluble only in F -containing solvents such as m-(CF₃)₂C₆H₄. The oxygen permeability coefficient of the polymer mem-brane was 90 barrers, which is the second highest among those of ortho-substituted poly(phenylacetylenes). In the pervaporation of an ethanol–water mixture, the poly-mer membrane showed ethanol permselectivity [α(EtOH/H₂O) = 1.7]. © 1995 John Wiley & Sons, Inc.     

Monohydrazido(2-)-complexes of molybdenum and tungsten (IV), (V) and (VI)

Summary Reaction of MoCl₅ or WCl₆ with 1-methyl-1-phenylhydrazine or 1, 1-diphenylhydrazine hydrochloride results in the formation of M^VI species [MCl₄(NNRR)]. These react with tertiary phosphines PR₃ to form M^V species [MCl₃(NNRR)(PR₃) _n ] (n=1 or 2).[MoCl₃(NNMePh)(PMe₃)₂] can be reduced in the presence of PMe₃ to the Mo^IV speciescis-mer-[MoCl₂(NNMePh)(PMe₃)₃].     

Chain transfer reaction in the polymerization of substituted acetylenes. II. Chain transfer reaction to trimethylvinylsilane in the polymerization of disubstituted acetylenes by MoCl5–n-Bu4Sn

The effect of various olefins as chain transfer agents was studied in the polymerization of 1-chloro-1-octyne, 1-chloro-2-phenylacetylene, 2-octyne, etc., catalyzed by MoCl₅–n-Bu₄Sn (1 : 1). Si-containing olefins, especially trimethylvinylsilane, greatly lowered the polymer molecular weight in the polymerization of the Cl-containing acetylenes, e.g., the M _n of poly(1-chloro-1-octyne) was 4.2 × 10⁵ without an olefin, whereas it decreased to 3.4 × 10⁴, i.e., below 1/10 in the presence of trimethylvinylsilane (1/2 equiv to monomer). In contrast, the molecular weight of poly(2-octyne) did not decrease that much, even with trimethylvinylsilane. The Cl-containing polyacetylenes obtained in the presence of trimethylvinylsilane as chain transfer agent possessed the trimethylsilyl group. Thus, the present study enables control of the molecular weight of substituted polyacetylenes by chain transfer, and further verifies the metal carbene mechanism for the polymerization of substituted acetylenes. © 1993 John Wiley & Sons, Inc.     

Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis

Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s by polymerization of the corresponding diphenylacetylenes using MoCl₅- and WCl₄-based catalytic systems have been developed. MoCl₅ induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph₄Sn and ArSnⁿBu₃ to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights (number-average molar mass (M_n)=30,000–3,200,000) in good yields (up to 98 %). On the other hand, WCl₄ induces ring expansion polymerization of diphenylacetylenes in the presence of Ph₄Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights (M_n=20,000–250,000) in moderate to good yields (up to 90 %). Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods using WCl₆-Ph₄Sn and TaCl₅-ⁿBu₄Sn systems.     

Polymerization of 1-methoxy-1-ethynylcyclohexane by transition metal catalysts

The polymerization of 1-methoxy-1-ethynylcyclohexane (MEC) was carried out by various transition metal catalysts. The catalysts MoCl₅, MoCl₄, and WCl₆ gave a relatively low yield of polymer (≤ 16%). The catalytic activity of Mo-based chloride catalyst was greater than that of W-based chloride catalyst. However, catalyst tungsten carbene complex (I) gave a larger molar mass and higher yield in the presence of a Lewis acid such as AlCl₃ than in the absence of a Lewis acid. The activity of the tungsten carbene complex was obviously affected by Lewis acidity. The catalyst PdCl₂ was a very effective catalyst for the present polymerization and gave polymers in a high yield. The structure of the resulting poly(MEC) was identified by various instrumental methods as a conjugated polyene structure having an α-methoxycyclohexyl substituent. The poly(MEC)s were mostly light-brown powders and completely soluble in various organic solvents such as tetrahydrofuran (THF), chloroform (CHCl₃), ethylacetate, n-butylacetate, dimethylformamide, benzene, xylene, dimethylacetamide, 1,4-dioxane, pyridine, and 1-methyl-2-pyrrolidinone. Thermogravimetric analysis showed that the polymer started to lose mass at 125°C and that maximum decomposition occurred at 418°C. The x-ray diffraction diagram shows that poly(MEC) has an amorphous structure. © 1997 John Wiley & Sons, Inc.     

Crowned polyacetylene. I. Synthesis and characterization of poly(4′-ethynylbenzo-15-crown-5)

4′-Ethynylbenzo-15-crown-5 ( EB15C5 ) polymerized with high yields in the presence of (bicyclo[2.2.1] hepta-2,5-diene) rhodium(I) chloride dimer and triethylamine as a cocatalyst in chloroform at 30°C. Common catalysts for the polymerization of substituted acetylenes, WCl₆ and MoCl₅, did not produce any polymer from EB15C5 . The structure of the main chain for poly(4′-ethynylbenzo-15-crown-5) ( PEB15C5 ) was determined to be predomi-nantly cis form, based upon the relatively sharp signals attributed to the main chain atoms that was observed in the ¹H and ¹³C NMR spectra. The cation-binding properties of PEB15C5 are very similar to that of poly(4′-vinylbenzo-15-crown-5), and the selectivity is in the order of K⁺> Rb⁺ ? Cs⁺ ? Na⁺, Li⁺. The electrical conductivity of PEB15C5 increased from 1.3 × 10^?10 to 1.3 × 10^?6 S. cm^?1, when the polymer was doped with iodine. © 1995 John Wiley & Sons, Inc.     

N(SCl)2 ⊕[MoCl5(NSCl)]⊖, ein Chlorthionitrenokomplex von Molybdän(VI)

N(SCl)₂^⊕ [MoCl₅(NSCl)]^?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl₃(N₃S₂) by the reaction of MoCl₄ or MoCl₅ with (NSCl)₃ in CH₂Cl₂. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)₂^⊕[MoCl₅(NSCl)]^? crystallizes in the monoclinic space group P2₁/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl₅(NSCl)]^? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh₄[MoCl₅(NSCl)] are reported.     

Cyclopolymerization of dipropargylfluorene by transition‐metal catalysts

A fluorene‐containing spiro‐type conjugated polymer, poly(dipropargylfluorene), was synthesized via the cyclopolymerization of dipropargylfluorene by Mo‐ and W‐based transition‐metal catalysts. The polymerization of dipropargylfluorene proceeded well by MoCl₅ catalyst itself to give a quantitative yield of polymer. The Mo‐based catalysts are more effective than those of W‐based catalysts. The structure of poly(dipropargylfluorene) was characterized by various instrumental methods (NMR, IR, and UV–visible spectroscopies) to have the conjugated polymer backbone carrying fluorene moieties. Analysis of the ¹³C NMR spectrum revealed that the polymer structure consists of only six‐membered rings. The resulting poly(dipropargylfluorene)s were brown or black powder and soluble in aromatics and halogenated hydrocarbons such as benzene, chlorobenzene, tetrahydrofuran, chloroform, and methylene chloride. Thermal and morphological properties of the polymer are also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4101–4109, 2001     

Polymerization of N-carbazolylacetylene by various transition metal catalysts and polymer properties

N-Carbazolylacetylene (CzA) was polymerized in the presence of various transition metal catalysts including WCl₆, MoCl₅, [Rh(NBD)Cl]₂, and Fe(acac)₃ to give polymers in good yields. The polymers produced with W catalysts were dark purple solids and soluble in organic solvents such as toluene, chloroform, etc. The highest weight-average molecular weight of poly(CzA) reached about 4 × 10⁴. In the UV–visible spectrum in CHCl₃, poly(CzA) exhibited an absorption maximum around 550 nm (ε_max = 4.0 × 10³ M⁻¹ cm⁻¹) and the cutoff wavelength was 740 nm, showing a large red shift compared with that of poly(phenylacetylene) [poly(PA)]. Poly(CzA) began to lose weight in TGA under air at 310°C, being thermally more stable than poly(PA) and poly[3-(N-carbazolyl)-1-propyne]. Poly(CzA) showed a third-order susceptibility of 18 × 10⁻¹² esu, which was 2 orders larger than that of poly(PA). © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2489–2492, 1998