The syndiospecific polymerization of styrene in the presence of fluorine‐containing half‐sandwich metallocenes

The syndiospecific polymerization of styrene was investigated with the fluorine‐containing half‐sandwich complexes η⁵‐pentamethylcyclopentadienyl titanium bis(trifluoroacetate) dimer, η⁵‐octahydrofluorenyl titanium tristrifluoro‐acetate, η⁵‐octahydrofluorenyl titanium dimethoxymonotrifluoroacetate, and η⁵‐octahydrofluorenyl titanium tris(pentafluorobenzoate) in comparison to known chloride and methoxide complexes in the presence of relatively low amounts of methylalumoxane and triisobutylaluminum. After the selection of effective reaction conditions for a solvent‐free polymerization, the following orders of decreasing polymerization activity of the titanium complexes can be observed: for pentamethylcyclopentadienyl compounds, Cp*Ti(OMe)₃ > [Cp*Ti(OCOCF₃)₂]₂O ≈ Cp*TiCl₃, and for octahydrofluorenyl compounds, [656]Ti(OMe)₃ > [656]Ti(OCOC₆F₅)₃ > [656]Ti(OCH₃)₂(OCOCF₃) > [656]Ti (OCOCF₃)₃. The [656]Ti complexes, showing the highest polymerization conversions at 70 °C and in comparison with the Cp* Ti compounds, turned out to be highly efficient catalysts for the syndiospecific styrene polymerization. The fluorine‐containing Cp* and [656]Ti complexes lead to much higher molecular weights than the chloride and methoxide compounds because of a reduction in chain‐limiting transfer reactions. The introduction of only one fluorine‐containing ligand into the coordination sphere of the metal compound is obviously sufficient for a significant increase in molecular weight. The active polymerization sites of the [656]Ti complexes with methylalumoxane and triisobutylaluminum are extremely stable during storage at room temperature in regard to their polymerization activity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2428–2439, 2000     

Mao based catalysts for syndiotactic polystyrene (sPS)

Several non-metallocene (Ti, Zr) and substituted mono-Cp titanium metallocenes have been tested in the presence of methylalumoxane (MAO) as catalyst for syndiospecific polymerization of styrene. Effect of substitutions on the titanium and Cp ligand, molar ratio of Al/Ti, TMA and temperature on activity, Mwt. and % sPS were studied. CpTi(OiPr)₃ gives a less active catalyst than Cp*Ti(OiPr)₃ and the resulting sPS is less stereoregular and of lower molecular weight.     

Stereospecific styrene polymerization and ethylene–styrene copolymerization with titanocenes containing a pendant amine donor

A series of monocyclopentadienyl titanium complexes containing a pendant amine donor on a Cp group ( A = CpTiCl₃, B = Cp^NTiCl₃, C = Cp^NTiCl₂TEMPO, for Cp = C₅H₅, Cp^N = C₅H₄CH₂CH₂N(CH₃)₂, and TEMPO = 2,2,6,6‐tetramethylpiperidine‐N‐oxyl) are investigated for styrene homopolymerization and ethylene–styrene (ES) copolymerization. When activated by methylaluminoxane at 70 °C, complexes with the amine group ( B and C ) are active for styrene homopolymerization and afford syndiotactic polystyrene (sPS). The copolymerizations of ethylene and styrene with B and C yield high‐molecular weight ES copolymer, whereas complex A yields mixtures of sPS and polyethylene, revealing the critical role that the pendant amine has on the polymerization behavior of the complexes. Fractionation, NMR, and DSC analyses of the ES copolymers generated from B and C suggest that they contain sPS. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1579–1585, 2010     

Syndiospecific polymerization of styrene with embedded metallocene catalysts

Syndiotactic polystyrene (sPS) is a highly crystalline polymer with high melting point (270°C). The syndiospecific polymerization of styrene to sPS with metallocene catalysts is characterized by significant phase changes that lead to global gelation. Since sPS does not dissolve in styrene or solvents such as toluene and n-heptane, sPS precipitates out immediately from the liquid phase with the start of polymerization. The polymer crystallites aggregate to primary particles and they develop to a gel. The gelation is not due to cross-linking polymerization but due to strong molecular interactions between the polymer and monomer molecules. In this work, homogeneous Cp*Ti(OMe)₃ catalyst is heterogenized or embedded into sPS prepolymer particles. The embedded catalyst has been tested in a laboratory scale diluent slurry process to illustrate the feasibility of slurry phase polymerization for the synthesis of sPS particles.     

End‐functionalization of syndiotactic polystyrene by vinylsilane inducing selective chain transfer reactions

Structurally well‐defined end‐functionalized syndiotactic polystyrene (sPS) can be prepared by conducting a simultaneous selective chain transfer reaction during the syndiospecific polymerization of styrene in the presence of vinylsilanes. The production of vinylsilane end‐capped sPS involves a unique selective chain transfer pathway via the incorporation of a terminal vinylsilane unit at the polymer chain end by 2,1‐insertion. This unusual insertion pattern situates the bulky silyl functional group at a closer β‐position from the active catalyst center, thus deactivating the propagating chain by a steric jam between the vinylsilane end group and the active catalyst. Subsequently, chain releasing by hydrogen addition (in the presence of H₂) or by β‐elimination (in the absence of H₂) can take place, which leads to the production of end‐functionalized sPS with precise controls of stereoregularity and of the location of functionality. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1690–1698, 2010     

Synthesis and crystallization behavior study of syndiotactic polystyrene‐g‐isotactic polypropylene (sPS‐g‐iPP) graft copolymers

Based on coordination polymerization mechanism only, novel stereoregular graft copolymers with syndiotactic polystyrene main chain and isotactic polypropylene side chain (sPS‐g‐iPP) were synthesized via two steps of catalytic reactions. First, a chain transfer reaction was initiated by a chain transfer complex composed of a styrene derivative, 1,2‐bis(4‐vinylphenyl)ethane, and hydrogen in propylene polymerization mediated by rac‐Me₂Si[2‐Me‐4‐Ph(Ind)]₂ZrCl₂ and MAO, which gave iPP macromonomer bearing a terminal styryl group (iPP‐t‐St). Then the iPP‐t‐St macromonomers of varied molecular mass were engaged in syndiospecific styrene polymerization over a typical mono‐titanocene catalyst (CpTiCl₃/MAO) under different conditions to produce sPS‐g‐iPP graft copolymers of varied structure. With an effective purification process, well‐defined sPS‐g‐iPP copolymers were obtained, which were then subjected to differential scanning calorimetry (DSC) and polarized optical micrograph (POM) studies. The graft copolymers were generally found with dual melting and crystallization temperatures, which were ascribable respectively to the sPS backbone and iPP graft. However, it was revealed that the two segments displayed largely different melting and crystallization behaviors than sPS homopolymer and the precursory iPP‐t‐St macromonomer. Consequently, the graft copolymer exhibited much distinctive crystalline morphologies when compared with their individual components. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Syndiospecific polymerization of styrene with Cp*TiCl((OCH(R)CH2)2NAr)/MMAO

A series of titanium complexes Cp*TiCl((OCH(R)CH₂)₂NAr) (Cp* = C₅Me₅, R = H, Ar = Phenyl ( 2a) ; R = H, Ar = 2,6‐dimethylphenyl ( 2b ); R = Me, Ar = Phenyl ( 2c )) was prepared by the reaction of corresponding N,N‐diethoxylaniline derivatives, with Cp*TiCl₃ in the presence of excessive triethylamine. All the titanium complexes display higher catalytic activities towards the syndiospecific polymerization of styrene in the presence of modified methylaluminoxane (MMAO) as a cocatalyst, and produce higher molecular weight polystyrenes with higher syndiotacticity and melting temperature than their mother complex Cp*TiCl₃. The catalyst activities and polymer yields as well as polymer properties are considerably affected by the steric and electronic effect of the tridentate ligands. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1562–1568, 2005     

Synthesis of Syndiotactic Polystyrene/Atactic Polypropene Block Copolymer in the presnece of Half-sandwich Titanocene Catalysts

Some highly active η5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp*Ti(Obz)3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polymerization and propene atactic polymerization. Styrene could be copolymerized with propene when the propene was prepolymerized for a period, to which styrene and tri-isobutylaluminum (TIBA) were then added. The titled block copolymer together with the related homopolymers was obtained. The copolymerization porducts can be divided into the homopolymers and the copolymer by successive solvent extraction with boiling butanone, heptane and tetrahydrofuran (THF), and each fraction was characterized by 13C NMR, DSC and WAXD. It was found that aPS and aPP were soluble in boiling butanone and heptane respectively. The block copolymer (sPS-b-aPP) composed of syndiotactic polystyrene segment was soluble in boiling THF and the residue was chiefly sPS.     

Novel Complex Catalyst of η3‐(Pentamethylcyclopentadienyl)dimethylaluminum/Titanium(IV) Butoxide (Cp*AlMe2/Ti(OBu)4) for Syndiotactic Polystyrene

A novel metallocene catalyst was prepared from the reaction of (η³‐pentamethylcyclopentadienyl)dimethylaluminum (Cp*AlMe₂) and titanium(IV) n‐butoxide Ti(OBu)₄. The resulting titanocene Cp*Ti(OBu)₃ was combined with methylaluminoxane (MAO)/tri‐iso‐butylaluminum (TIBA) to carry out the syndiotactic polymerization of styrene. The resulting syndiotactic polystyrene (sPS) possesses high syndiotacticity according to ¹³C NMR. Catalytic activity and the molecular weight of the resulting sPSs were discussed in terms of reaction temperature, concentration of MAO, amounts of scavenger TIBA added, and the hydrogen pressure applied during polymerization.     

单茂钛催化剂的苯乙烯间规聚合和乙烯聚合的比较

考察三甲基铝（ＴＭＡ） 部分水解法制备固体改性甲基铝氧烷（ｍ ＭＡＯ） 时,反应物Ｈ２Ｏ 和ＴＭＡ 的摩尔比对ｍ ＭＡＯ 的产量及ｍ ＭＡＯ 中ＴＭＡ 含量的影响;以五甲基茂基三苄氧基钛［Ｃｐ ＊ Ｔｉ（ＯＢｚ）３］／ｍ ＭＡＯ 组成的均相催化体系,分别考察ｍ ＭＡＯ 的用量［ 即Ａｌ／Ｔｉ 摩尔比］ 及ｍ ＭＡＯ 中ＴＭＡ 含量对苯乙烯间规聚合和乙烯聚合的影响．通过分析Ｃｐ ＊ Ｔｉ（ＯＢｚ）３／ｍ ＭＡＯ 催化体系钛氧化态的分布,发现Ｔｉ（ Ⅲ） 活性中心有利于合成间规聚苯乙烯;而Ｔｉ（ Ⅳ） 活性中心有利于合成聚乙烯．苯乙烯间规聚合时,外加三异丁基铝（ＴＩＢＡ） ,将提高催化活性,同时可节省ＭＡＯ 用量．     

Influence of the catalyst on monomer insertion in the syndiospecific copolymerization of styrene and para‐methylstyrene

The effect of the kind of transition‐metal catalyst on the extent of comonomer insertion in the syndiospecific complex‐coordinative copolymerization of styrene and para‐methylstyrene has been investigated. The results for the influence of the polymerization conditions have shown that there is no real difference between solution copolymerization in toluene and solvent‐free styrene copolymerization in bulk, with respect to the reactivity ratio for para‐methylstyrene (r₂), under comparable conditions in the presence of methylaluminoxane and triisobutylaluminum and at low polymerization conversions. All the investigated catalysts lead to a preferred incorporation of para‐methylstyrene into the polymer chain in comparison with styrene and over the whole range of monomer compositions. The increasing capability of the different catalysts to provide copolymers with enhanced para‐methylstyrene concentrations can be summarized by the increasing r₂ values for the copolymerization in bulk as follows: η⁵‐pentamethylcyclopentadienyl titanium trichloride < η⁵‐octahydrofluorenyl titanium trimethoxide < η⁵‐octahydrofluorenyl titanium tristrifluoroacetate < η⁵‐cyclopentadienyl titanium(N,N‐dicyclohexylamido)dichloride < η⁵‐cyclopentadienyl titanium trichloride. For a correlation between the catalyst structure and the comonomer insertion, the catalysts can be described by electronic effects (electrostatic charge of the transition‐metal atom) and steric effects (minimum structural cone angle). The results show that the steric properties of the transition‐metal complexes have the most important effect on the insertion of para‐methylstyrene into the copolymer. If the minimum structural cone angle of the ligand of the transition‐metal catalyst decreases, the incorporation of the comonomer para‐methylstyrene increases significantly. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2061–2067, 2005     

The influence of phenylsilane on the syndiotactic polymerization of styrene with η5‐pentamethylcyclopentadienyl titanium trifluoride

The syndiotactic polystyrene polymerization activity of a fluorinated half‐sandwich complex, η⁵‐pentamethylcyclopentadienyl titanium trifluoride (Cp*TiF₃), in the presence of relatively low amounts of methylalumoxane (MAO; MAO/Cp*TiF₃ molar ratio = 200/1) and triisobutylaluminum, is significantly increased by the addition of phenylsilane in molar ratios to Cp*TiF₃ ranging from about 300/1 to 600/1, if the phenylsilane is added to the monomer. Lower amounts of phenylsilane, such as a 100/1 molar ratio to Cp*TiF₃, lead to a reduced polymerization activity in comparison with styrene without phenylsilane. A prereaction of phenylsilane with the catalyst mixture shows a behavior that is strongly dependent on the storage time of the composition and the temperature. A storage time of about 16 h is sufficient to reduce the polymerization conversion to about half of the original value. The results are discussed on the basis of a chain‐transfer reaction with phenylsilane and several catalyst complexes of different stabilities and activities, including an alkylation product of phenylsilane. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3476–3485, 2000     

Titanium‐mediated living radical styrene polymerizations. V. Cp2TiCl‐catalyzed initiation by epoxide radical ring opening: Effect of solvents and additives

The effects of solvents, additives, ligands, and solvent in situ drying agents as well as catalyst and initiator concentrations have been investigated in the Cp₂TiCl‐catalyzed radical polymerization of styrene initiated by epoxide radical ring opening. On the basis of the solubilization of Cp₂Ti(III)Cl and the polydispersity of the resulting polymer, the solvents rank as follows: dioxane ≥ tetrahydrofuran > diethylene glycol dimethyl ether > methoxybenzene > diphenyl ether ≥ bulk > toluene ? pyridine > dimethylformamide > 1‐methyl‐2‐pyrrolidinone > dimethylacetamide > ethylene carbonate, acetonitrile, and trioxane. Alkoxide additives such as aluminum triisopropoxide and titanium(IV) isopropoxide are involved in alkoxide ligand exchange with the epoxide‐derived titanium alkoxide and lead to broad molecular weight distributions, whereas similarly to strongly coordinating solvents, ligands such as bipyridyl block the titanium active site and prevent the polymerization. By contrast, softer ligands such as triphenylphosphine improve the polymerization in less polar solvents such as toluene. Although mixed hydrides such as lithium tri‐tert‐butoxyaluminum hydride, sodium borohydride, and lithium aluminum hydride react with bis(cyclopentadienyl)titanium dichloride to form mixed titanium hydride species ineffective in polymerization control, simple hydrides such as lithium hydride, sodium hydride, and especially calcium hydride are particularly effective as in situ trace water scavengers in this polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2015–2026, 2006     

In situ‐generated Ru(III)‐mediated ATRP from the polymeric Ru(III) complex in the absence of activator generation agents

Past research has examined the atom transfer radical polymerization (ATRP) with high oxidation state metal complexes and without the need for any additives such as reducing agent or free radical initiator. To extend this research, half‐metallocene ruthenium(III) (Ru(III)) catalysts were used for the polymerization of methyl methacrylate (MMA) for the first time. These catalysts were generated in situ simply by mixing phosphorus‐containing ligand and pentamethylcyclopentadienyl (Cp*) Ru(III) polymer ((Cp*RuCl₂)_n). The complexes in their higher oxidation state such as Cp*RuCl₂(PPh₃) were air‐stable, highly active, and removable catalysts for the ATRPs of MMA with both precision control of molecular weight and narrow polydispersity index. The addition of ppm amount of metal catalyst contributed to the formation of very well‐defined homopolymers and copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Oxidation of Stereo‐regular Poly(styrene‐co‐4‐methylstyrene) by Cobalt(II) Acetate Tetrahydrate/Sodium Bromide Catalyst

Chemical modification on the stereo‐regular poly(styrene‐co‐4‐methylstyrene) (sPS‐PMS) was attempted in this study. Metallocene copolymerization of styrene (St) and 4‐methylstyrene (MSt) was performed by using η⁵‐pentamethylcyclopentadienyl‐titanium(IV)tributoxide (Cp*Ti(OBu)₃)/methylaluminoxane (MAO)/tri‐iso‐butylaluminum (TIBA) catalyst in the bulk state. Cobalt(II) catalyst was then applied to oxidize the benzylic methyl group on the MSt units of the resulting sPS‐PMS copolymer. Both aldehyde and carboxylic acid in the oxidized products were resolved by the FTIR and ¹H NMR. The oxidized sPS‐PMSs exhibit a low and a high‐temperature T_g and T_m corresponding to the transitions in the amorphous and the crystalline regions. Hydrogen‐bond and polar interactions between the aldehyde and carboxylic acids tend to interrupt the regular chain packing of the oxidized sPS‐PMS, resulting in the lowering of T_m with oxidation level. The oxidized sPS‐PMS showed better adhesion to glass fiber than pure sPS‐PMS copolymer as evaluated from the respective SEM fractured micrographs.     

Syndiospecific polymerization of styrene in the presence of cyclic olefins: A new approach for molecular weight,molecular weight distribution,and stereoregularity controls for syndiotactic polystyrene

A new approach for facilitating microstructural controls for syndiotactic polystyrene (sPS), in which, styrene polymerization is conducted in the presence of cyclic olefins and hydrogen, is proposed. Detailed structural analyses revealed that cyclic olefins are not incorporated into the polystyrene main chain; instead, they are capable of interrupting the chain propagation processes by binding onto the active catalyst to form a cyclic‐olefin‐coordinated active site. Thus, in the presence of hydrogen, chain transfer by hydrogen addition occurs selectively, which leads to the generation of drastically lower molecular weight sPS with a narrower range of molecular weight distribution. Chain end structural analyses of the resulting polymers revealed that styrene polymerization under theses conditions involves a selective chain transfer pathway for providing styrene polymers with uniform chain end structures. A unique method for inducing a selective chain transfer reaction by using non‐incorporated cyclic olefins to regulate the chain reaction mechanism is demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

新型茂钛催化剂的分子设计与苯乙烯间规聚合

合成了CpTiCl₃/MAO、Cp^*TiCl₃/MAO、Cp^*Ti(OCH₂CH＝CH₂)₃/MAO和cp^*Ti(OMe)₃/MAO四种均相催化体系.结果发现,[Cp^*Ti(OCH₂CH＝CH₂)₃]/甲基铝氧烷(MAO)催化体系热稳定性较高,在333～363K下进行苯乙烯问规聚合具有最高的催化活性;聚合反应产物用沸丁酮抽提8h,不溶部分间规聚苯乙烯(sPS)占总聚合产物重量的98%以上,sPS的分子量Mv达到4.15×10⁵～2.46×10⁵范围,熔融温度高达543K.     

Efficient introduction of aromatic vinyl group by incorporation of divinylbiphenyl,p‐divinylbenzene in syndiospecific styrene polymerization using aryloxo‐modified half‐titanocene catalysts

An efficient introduction of aromatic vinyl group into syndiotactic polystyrene has been achieved by incorporation of 3,3′‐divinylbiphenyl, p‐divinylbenzene (DVB) in syndiospecific styrene polymerization using aryloxo‐modified half‐titanocenes, Cp′TiCl₂(O‐2,6‐ⁱPr₂C₆H₃) (Cp′ = ^tBuC₅H₄, 1,2,4‐Me₃C₅H₂), in the presence of MAO. The resultant polymers possessed high molecular weights with uniform molecular weight distributions, and the DVB contents could be varied by the initial feed molar ratios (6–23 mol %) without decrease in the M_n values. The syndiotactic stereo‐regularity and presence of the vinyl groups were confirmed by NMR spectra. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1902–1907     

Syndiospecific polymerization of styrene with BzCpTiCl3 and methylaluminoxane as cocatalysts

Benzyl cyclopentadienyl titanium trichloride (BzCpTiCl₃) was synthesized from benzyl bromide, cyclopentadienyl lithium, and titanium tetrachloride and used in combination with methylaluminoxane (MAO) for the syndiospecific polymerization of styrene. Kinetic measurements of the polymerization were carried out at different temperatures. The polymerization with BzCpTiCl₃/MAO differs from the polymerization with cyclopentadienyl titanium trichloride in its behavior toward the Al/Ti ratio. In addition, high activities are observed at high Al/Ti ratios. By analyzing the polymerization runs and the physical properties of the polymers with differential scanning calorimetry, ¹³C NMR spectroscopy, wide‐angle X‐ray scattering measurements, and gel permeation chromatography, we found that the phenyl ring coordinates to the titanium atom during polymerization. Other known substitutions of the cyclopentadienyl ring (V. Scholz, Dissertation, University of Hamburg, 1998) in principle influence the polymerization activity. The physical properties of the polymers produced by the catalysts already known are nearly identical. BzCpTiCl₃ is the first catalyst that leads to polystyrene obviously different from the polystyrene produced by other highly active catalysts. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2805–2812, 2001     

Control of molecular weight in polymerization of vinyl chloride with Cp*Ti(OPh)3/MAO catalyst

Polymerization of vinyl chloride (VC) with titanium complexes containing Ti‐OPh bond in combination with methylaluminoxane (MAO) catalysts was investigated. Among the titanium complexes examined, Cp*Ti(OPh)₃/MAO catalyst (Cp*; pentamethylcyclopentadienyl, Ph; C₆H₅) gave the highest activity for the polymerization of VC, but the polymerization rate was slow. From the kinetic study on the polymerization of VC with Cp*Ti(OPh)₃/MAO catalyst, the relationship between the M_n of the polymer and the polymer yields gave a straight line, and the line passed through the origin. The M_w/M_n values of the polymer gradually decrease as a function of polymer yields, but the M_w/M_n values were somewhat broad. This may be explained by a slow initiation in the polymerization of VC with Cp*Ti(OPh)₃/MAO catalyst. The results obtained in this study demonstrate that the molecular weight control of the polymers is possible in the polymerization of VC with the Cp*Ti(OPh)₃/MAO catalyst. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3872–3876, 2007