Poly[tris(diorganophosphinato)alanes]

Poly[tris(diorganophosphinato)alanes], [Al(OPRR′O)₃]_n, were synthesized in which the organic moieties (R,R′) contained from one to eighteen carbon atoms. Polymeric properties depended upon the organic moieties; polymers were fusible, tractable, and flexible when the organic moieties contained six or more carbon atoms. Soluble polymers were prepared by using mixtures of symmetrical and unsymmetrical phosphinates. One polymer, poly{bis[n-butyl(benzyl)phosphinato]di-n-octylphosphinatoalane}, exhibited a degree of polymerization greater than 1000 and an exceptionally high intrinsic viscosity of 37 dl/g. The properties of the different polymers are discussed, and feasible structures are proposed.     

Preparation and properties of poly(phosphonatoalanes)

Two general types of poly(phosphonatoalanes), [? Al(X)O? P(O)(R)O? ]_n (X = Cl or F, R = alkyl or aryl) and [? Al(OP(O)R₂)O? P(O)(R′)O? ]_n, were prepared and studied. Poly[chloro(phosphonato)alanes] are influsible and have low molecular weights (n = 4–11). Polyfluoro(phosphonato)alanes are fusible and also have low molecular weights, but under certain conditions grow to higher polymers (n = 30–45). Poly[phosphinato(phosphonato)alanes] are fusible and are prepared with high molecular weights (n = 83–340).     

Polybis(phosphinato)fluoroalanes

A new class of coordination polymers, polybis(phosphinato)fluoroalanes, [Al(F) (OPRR′O)_2n], where R,R′ are alkyl, phenyl, or benzyl, was prepared and studied. The properties of these polymers are influenced by the phosphinate (R) substituents; polymers having n-alkyl groups with more than five carbons are flexible and exhibit unusual hydrolytic stability. A polymer was obtained with a degree of polymerization of 104 by incorporating a 2:1 ratio of benzyl(n-heptyl) and di-n-octyl phosphinate groups. The properties of the flexible materials are consistent with linear rather than highly crosslinked or network systems. Feasible structures are proposed for the polymers.     

Bis(difluoroaluminum)organophosphonates and difluoroaluminumdiorganophosphinates

Oligomers and polymers of the general types [RR′P(O)OA1F₂]_n, I, and [F₂AlOP(R)(O)OAlF₂]_n, II, were prepared by the addition of phosphonic or phosphinic acids and hydrogen fluoride to etherated alanes. The hydrocarbon moieties (R,R′) on the phosphonic and phosphinic acids were important determinants of physical and chemical properties. When the alkyl moieties contained six or more carbon atoms type I oligomers were partially crystalline, soluble in tetrahydrofuran, and fused below 415°C. Type II polymers were soluble in tetrahydrofuran when n-octyl or larger alkyl moieties were used, but these polymers tended to be amorphous and liberated solvated tetrahydrofuran below 225°C. Data are presented in support of inter-monomer fluorine bridge bonding; that is, Al? F? Al bonds.     

Influence of alkoxy tail length and unbalanced mesogenic core on phase behavior of mesogen‐jacketed liquid crystalline polymers

When the flexible terminal substituent changes from butoxy to hexyloxy or longer, smectic C (S_C) liquid crystalline phase was firstly reported to develop from a kind of mesogen‐jacketed liquid crystalline polymer (MJLCP) whose mesogenic side groups are unbalancedly bonded to the main chain without spacers. A series of MJLCPs, poly[4,4′‐bis(4‐alkoxyphenyl)‐2‐vinylbiphenyl(carboxide)] (nC2Vp, n is the number of the carbons in the alkoxy groups, n = 2, 4, 6, 8, 10, and 12) were designed and synthesized successfully via free radical polymerization. The molecular weights of the polymers were characterized with gel permeation chromatography, and the liquid crystalline properties were investigated by differential scanning calorimetry, polarized light microscopy experiments, and 1D, 2D wide‐angle X‐ray diffraction. Comparing with the butoxy analog, the polymer with unbalanced mesogenic core and shorter flexible substituents (n = 2, 4) keeps the same smectic A (S_A) phase, but other polymers with longer terminal flexible substituents (n = 6, 8, 10, and 12) can develop into a well‐defined S_C phase instead of S_A phase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 505–514, 2009     

NEW CYCLIC AND POLYMERIC PHOSPHAZENES DERIVED FROM N-SILYLPHOSPHORANIMINES

Silicon-nitrogen-phosphorus compounds of the type Me ₃ SiN═PR(R′)X(X= Cl, Br, OCH₂CF ₃ , OPh), known as N-silylphosphoranimines,are useful precursors to both cyclic and polymeric phosphazenes.Depending on the leaving group (X), thermolysis reactions afford either cyclic trimers, [N═PR(R′)] ₃ (when X = Cl, Br), or linear polymers,[N═PR(R′)]_n (when X = OCH ₂ CF ₃ or OPh). Treatment of the P-trifluoroethoxy and P-phenoxy derivatives, Me ₃ SiN═PR(R′)X (X = OCH ₂ CF ₃ , OPh), with alcohols at lower temperature usually results in the formation of cyclic phosphazene trimers via silyl ether elimination. Recently, we have applied these synthetic methods to the preparation of some new phosphazene systems including a series of 4-aryl-functionalized trimers and polymers and a variety of non-geminal, mixed-substituent cyclic trimers. Representative examples of the synthesis, structural characterization, and reactivity of these new phosphazenes and their Si─N─P precursors are reported here.     

Living cationic isomerization polymerization of β-pinene. III. Synthesis of end-functionalized polymers and graft copolymers

α-End-functionalized polymers and macromonomers of β-pinene were synthesized by living cationic isomerization polymerization in CH₂Cl₂ at −40°C initiated with the HCl adducts [ 1; CH₃CH(OCH₂CH₂X)Cl; X = chloride ( 1a ), acetate ( 1b ), and methacrylate ( 1c )] of vinyl ethers carrying pendant substituents X that serve as terminal functionalities. In conjunction with TiCl₃(OiPr) and nBu₄NCl, these functionalized initiators led to living β-pinene polymerization where the carbon–chlorine bond of 1 was activated by TiCl₃(OiPr). Similarly, end-functionalized poly(p-methylstyrene)-block-poly(β-pinene) were also obtained. ¹H-NMR analysis showed that the polymers possess controlled molecular weights (DP _n = [M]₀/[ 1 ]₀) and number-average end functionalities close to unity. The end-functionalized methacrylate-capped macromonomers form 1c were radically copolymerized with methyl methacrylate (MMA) to give graft copolymers carrying poly(β-pinene) or poly(p-methylstyrene)-block-poly(β-pinene) as graft chains attached to a PMMA backbone. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1423–1430, 1997     

Perhalophenyl complexes of palladium(II) containing keto-stabilized phosphorus ylides of the type Ph2P(CH2)nPPh2CHC(O)R

From suitable perhalophenyl derivatives of palladium(II), viz.: Pd(C₆F₅)₂-(SC₄H₈)₂, [Pd(μ-X′) (C₆X₅)₂]₂(NBu₄)₂, [Pd(μ-Cl)(C₆X₅)(SC₄H₈)]₂ (X = F, Cl, X′ = Cl, Br), new complexes of various types have been prepared, viz.: trans-Pd(C₆F₅)₂(Y)₂, Pd(C₆X₅)₂(Y), PdCl(C₆X₅)(Y) (X = F, Cl). The neutral ligand Y is a keto-stabilized phosphorus ylide of the type Ph₂P(CH₂)_nPPh₂CHC(O)R (n = 1, R = CH₃, C₆H₅; n = 2, R = C₆H₅) acting in a terminal monodentate P-donor or a bidentate chelate P,C-donor mode. The reaction of PdCl(C₆F₅)(Y) complexes with HCl leads to the corresponding PdCl₂(C₆F₅)(YH) complexes in which the phosphonium cation [YH]⁺ behaves as monodentate P-donor at its phosphinic end.IR and ³¹P NMR spectroscopy were used to decide the coordination mode of the ligands and, in some cases, to reveal the presence of two isomers.     

Synthesis of comb‐type polycarbosilanes via nucleophilic substitution reactions on the main‐chain silicon atoms

A series of comb‐type polycarbosilanes of the type [Si(CH₃)(OR)CH₂]_n {where R = (CH₂)_mR′, R′ = ? O‐p‐biphenyl? X [X = H (m = 3, 6, 8, or 11) or CN (m = 11)], and R′ = (CF₂)₇CF₃ (m = 4)} were prepared from poly(chloromethylsilylenemethylene) by reactions with the respective hydroxy‐terminated side chains in the presence of triethylamine. The product side‐chain polymers were typically greater than 90% substituted and, for R′ = ? O‐p‐biphenyl? X derivatives, they exhibited phase transitions between 27 and 150 °C involving both crystalline and liquid‐crystalline phases. The introduction of the polar p‐CN substituent to the biphenyl mesogen resulted in a substantial increase in both the isotropization temperature and the liquid‐crystalline phase range with respect to the corresponding unsubstituted biphenyl derivative. For R = (CH₂)₁₁? O‐biphenyl side chains, an analogous side‐chain liquid‐crystalline (SCLC) polysiloxane derivative of the type [Si(CH₃)(O(CH₂)₁₁? O‐biphenyl)O]_n was prepared by means of a catalytic dehydrogenation reaction. In contrast to the polycarbosilane bearing the same side chain, this polymer did not exhibit any liquid‐crystalline phases but melted directly from a crystalline phase to an isotropic liquid at 94 °C. Similar behavior was observed for the polycarbosilane with a fluorocarbon chain, for which a single transition from a crystalline phase to an isotropic liquid was observed at ?0.7 °C. The molecular structures of these polymers were characterized by means of gel permeation chromatography and high‐resolution NMR studies, and the crystalline and liquid‐crystalline phases of the SCLC polymers were identified by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 984–997, 2003     

Synthesis of Styrenic‐Terminated Methacrylate Macromonomers by Nitroanion‐Initiated Living Anionic Polymerization

N‐Isopropyl‐4‐vinylbenzylamine (PVBA) was synthesized and used as an initiator for the polymerization of methacrylates to synthesize macromonomers with terminal styrenic moieties. LiPVBA initiated a living polymerization and block copolymerization of methyl methacrylate, 2‐(N,N‐dimethylamino)ethyl methacrylate and tert‐butyl methacrylate and produced polymers having well‐controlled molecular weights and very low polydispersities (M̄_w/M̄_n < 1.1) in quantitative yield. ¹H NMR analysis revealed that the polymers contained terminal 4‐vinylbenzyl groups. The macromonomers were reactive in the copolymerization with styrene.     

INORGANIC RINGS WITH GALLIUM ORGANYLS AND IMINODIPHOSPHINECHALCHOGENIDES

The organometallic complexes of general formula [Me ₂ Ga{(XPR ₂ ) (YPR′ ₂ )N}] (R, R′ = Ph, X, Y = O, (1); R, R′ = Ph, X, Y = S (2); R, R′ = Ph, X = O, Y = S (3); R = Me, R′ = Ph, X = O, Y = S (4)) were obtained by alkane eliminations from Me ₃ Ga and the free acidic ligands, LH, in toluene solutions. Complexes 1– 4 seem to be potential precursors to cationic gallium species.     

Quantum-Chemical Estimation of the Stability and Reactivity of Diphosphonium Salts

For a series of diphosphonium salts containing two positively charged covalently bonded phosphorus atoms, X_{/sub> n} Y_3-n P⁺P⁺X _n Y_3-n (X = alkyl substituent, Y = amino group, n = 0-3), the stability, reactivity, and P-P bond strength were evaluated by various physicochemical methods. The P-P bond energy is appreciably influenced by both steric factors and donor properties of the substituents. The calculations confirmed that transformations of diphosphonium salts can involve cleavage of both P-P and P-N (or P-C) bonds.     

Constitution moléculaire d' α,ω-difluoro-μ-oxo-poly(méthylphosphanoxy diméthylsilanes): Mise en evidence d'une forte tendance à l'alternance régulière des centres siliciés et phosphorés à l'equilibre

The purpose of this study was to gain a closer knowledge of the molecular constitution of the linear fluorine-terminated oxygen-bridged methylphosphanoxy/dimethylsilane polymers, for example, to find evidence for preferential sorting (or, on the contrary, for random scattering) of the substituents and building units. The title polymers were prepared by reaction of MeP(O)F₂ with cyclic dimethylsiloxanes (Me₂SiO)_n (n = 3 or 4). An equilibrium is reached in the redistribution of fluorine vs. bridging oxygen atoms among the phosphorus and silicon-based centers, and among the resulting building units, after about 2 months at 120°C. The excellent resolution of the ¹H-NMR spectra (Fig. 2), even at 60 MHz, allowed identification of seventeen different fragments (Table II). Nineteen equilibrated samples of varied overall compositions (R = F/(Si + P); R′ = P/(Si + P)) have been analyzed (Table IV), and their molecular constitution is described by a set of four basic constants. The fundamental features which govern the structure of these polymers are as follows. (a) The regular (Si-O-P) alternation of the two different centers, which is thermodynamically favored, as shown by the linkage constant K₀ = [Si-O-Si][P-O-P]/[Si-O-P]² ? 10⁴, which describes the sorting of the silicon and phosphorus atoms on the bridging oxygens, and which deviates by four orders of magnitude from its random value of 0.25. (b) A somewhat surprising lack of preferential distribution of fluorine and oxygen between the two centers (K_I = [MeP(O)F₂][Me₂SiO_1/2]₂/[Me₂SiF₂]-[MeP(O)(O_1/2)₂]) differs little from (a), which contrasts with the preferential affinity of fluorine for silicon and oxygen for phosphorus (K_I ? 10⁷) that was found when F atoms and OCH₃ groups were exchanged between the same centers. (c) The sorting of the fluorine atoms and oxygen bridges on each center, to give neso molecules and the terminal and medium building units, resulting in a slight preference for the formation of the terminal units, as expressed by      

Polarity and steric effect of di-lateral substitution on the mesophase behaviour of some azo/ester compounds

Eight homologous series of 2-(or 3-)substituted phenyl 4?-(4″-alkoxy (2?-, or 3″-substituted phenylazo) benzoates (In_XY) were prepared in which the suffix ‘X’ refers to the lateral substituent X attached to the terminal benzene ring that carries the alkoxy group, and the suffix ‘Y’ refers to the substituent attached to the other terminal phenyl group. Within each homologous series, the length of the terminal alkoxy group varies from 8 to 16 carbons, while the lateral polar substituents, X and Y, alternatively varies between CH₃ and F. The mesophase behaviour was investigated by differential scanning calorimetry and identified by polarised optical microscopy. The results were discussed in terms of the polarity and steric effects of the two lateral substituents. Comparative correlations were made to investigate the effect of the second lateral substituent on the mesophase behaviour of the previously investigated mono-laterally substituted analogues. UV–vis spectroscopic study revealed that the compounds I8_XY exhibited two absorption bands: low intense bands at 254–263 and a broad band at 364–376 nm. These bands are attributed to the π–π? transition of the phenyl rings and the whole mesogenic portion.     

含氧亚甲基中心桥键席夫碱型液晶化合物的合成及介晶性

报道了两个系列含氧亚甲基中心桥键席夫碱型棒状液晶化合物的合成, 其结构通式为: XC₆H₄N＝CHC₆H₃(Y)OCH₂C₆H₄COOC₁₆H₃₃, Y＝H, OCH₃; X＝OC_nH_2n＋1 (n＝1～12, 14, 16), Me, F, Cl, Br. 通过热台偏光显微镜和DSC对其介晶性进行了研究. 结果显示分子中末端烷氧基链长的变化和苯环侧向取代基Y对这些液晶化合物的介晶性有重要影响.     

End-Functionalized polymers by living cationic polymerization. IV. Poly(vinyl ethers) with acidic or basic terminal groups by functional initiator method

Carboxylic acid or primary amine-terminated poly(isobutyl vinyl ethers) were synthesized by living cationic polymerizations with functionalized initiators (CH₃CHIO? CH₂CH₂ ? X; X: that are the adducts of the corresponding vinyl ethers (CH₂ ? CH ? OCH₂CH₂? X) with hydrogen iodide. In the presence of iodine, these initiators induced living cationic polymerization of isobutyl vinyl ether to give polymers with the α-end group of X originating from the initiators. The polymer molecular weights were regulated by the monomer to initiator feed ratio and the molecular weight distributions were very narrow (M _w/M _n ≤ 1.15). Subsequent deprotection of the terminal group X led to polymers with a terminal carboxylic acid or primary amine. ¹H- and ¹³C-NMR analyses showed that the end functionalities of these polymers were all close to unity.     

Synthesis and characterization of 4‐arm star side‐chain liquid crystalline polymers containing azobenzene with different terminal substituents via ATRP

4‐Arm star side‐chain liquid crystalline (LC) polymers containing azobenzene with different terminal substituents were synthesized by atom transfer radical polymerization (ATRP). Tetrafunctional initiator prepared by the esterification between pentaerythritol and 2‐bromoisobutyryl bromide was utilized to initiate the polymerization of 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl methacrylate (MMAzo) and 6‐[4‐(4‐ethoxyphenylazo)phenoxy]hexyl methacrylate (EMAzo), respectively. The 4‐arm star side‐chain LC polymer with p‐methoxyazobenzene moieties exhibits a smectic and a nematic phase, while that with p‐ethoxyazobenzene moieties shows only a nematic phase, which derives of different terminal substituents. The star polymers have similar LC behavior to the corresponding linear homopolymers, whereas transition temperatures decrease slightly. Both star polymers show photoresponsive isomerization under the irradiation with UV–vis light. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3342–3348, 2007     

Precise Synthesis of New Triblock Co- and Terpolymers by a Methodology Combining Living Anionic Polymers with a Specially Designed Linking Reaction

Five A-B-A′, A-C-A′, B-A-B′, C-A-C′, and C-B-C′ triblock terpolymers with block orders difficult to synthesize by sequential polymerization have been successfully synthesized by a new methodology combining living anionic polymers with a specially designed linking reaction using α-phenylacrylate as the reaction site. Here, A(A′), B(B′), and C(C′) represent groups of polymers (having chain-end anions with different nucleophilicities), which are only polymerizable from A(A′) to B(B′) to C(C′) via sequential polymerization. The corresponding polymers are polystyrene (A) and poly(α-methylstyrene) (A′), poly(2-vinylpyridine) (B) and poly(4-vinylpyridine) (B′) and polymers from methacrylate type monomers like poly(methyl methacrylate) (C), poly(tert-butyl methacrylate) (C′), poly(2-hydroxyethyl methacrylate) (C′), poly(2,3-dihydroxypropyl methacrylate) (C′), and poly(ferrocenylmethyl methacrylate) (C′). Furthermore, three synthetically difficult B-A-B, C-A-C, and C-B-C triblock copolymers with molecular asymmetry in both side blocks have also been synthesized by the developed methodology. All of the polymers thus synthesized are quite new triblock terpolymers and copolymers with well-defined structures, i.e., precisely controlled molecular weights, compositions and narrow molecular weight distributions (M_w/M_n ≤ 1.05).     

Synthesis and chiroptical properties of L‐valine‐containing poly(phenylacetylene)s with (a)chiral pendant terminal groups

Poly(phenylacetylene)s containing L ‐valine residues (P 1 ) with (a)chiral pendant terminal groups R^(*) [?(HC?C{C₆H₄CONHCH[CH(CH₃)₂]COO? R^(*)})_n?]; R^(*) = 1‐octyl (P 1 o), (1S,2R,5S)‐(+)‐menthyl [P 1 (+)], (1R,2S,5R)‐(?)‐menthyl [P 1 (?)] are designed and synthesized. The polymers are prepared by organorhodium catalysts in high yields (yield up to 88%) with high molecular weights (M_w up to ?6.4 × 10⁵). Their structures and properties are characterized by NMR, IR, TGA, UV, and circular dichroism analyses. All the polymers are thermally fairly stable (T_d ≥ 320 °C). The chiral moieties induce the poly(phenylacetylene) chains to helically rotate in a preferred direction. The chirality of the pendant terminal groups affects little the helicity of the polymers but their bulkiness stabilizes the helical conformation against solvent perturbation. The backbone conjugation and chain helicity of the polymers can be modulated continuously and reversibly by acid. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2117–2129, 2006     

Linear polymers of some vinyl monomers containing a terminal acetylenic group

The synthesis and polymerization of representative acrylic-type esters containing a terminal acetylene group, CH₂?C(R)COO(CHR′)_m? C?CH, where R and R′ are H and CH₃ and m = 1 or 2, by anionic initiation to linear polymers are described. In contrast, crosslinked polymers were formed when radical and cationic initiators were used. Crosslinked polymers were also obtained with organolithium compounds but not with sodium naphthalene and sodium benzalaniline; this observation is discussed and compared to the behavior of the acetylenic acrylic esters which do not contain a terminal acetylenic hydrogen. The unpolymerized acetylenic bonds in the resulting linear polymers were shown to be present by infrared spectroscopic methods and by the following post-reactions of these bonds: (1) the heat- and radical-initiated crosslinking of the polymers through the acetylenic bonds; (2) the post-bromination of the acetylenic bonds; and (3) the reaction of decaborane with the acetylenic bonds. The anionic copolymerization of acrylonitrile and styrene with these acetylenic monomers were performed and compared to the copolymerizations with 1-acryloxy-2-butyne and 1-methacryloxy-2-butyne. Dibromination of the linear polymers affords self-extinguishing polymers, while decaboronation yields soluble polymers which do not soften up to 300°C. The linear polymers may be classified as “self-reactive” polymers which yield thermosetting polymers.