Syndiospecific polymerization of styrene with multi-nuclear titanium complexes

Two multi-nuclear titanium complexes [Ti(eta(5)-Cp-*) Cl(mu-O)](3) ( 1) and [(eta(5)-(CpTiCl)-Ti-*)(mu-O)(2)(eta(5)-(CpTi)-Ti-*)(2)(mu-O)(mu-O)(2)](2)Ti (Cp-* = C5Me5) ( 2) have been investigated as the precatalysts for syndiospecific polymerization of styrene. In the presence of modified methylaluminoxane ( MMAO) as a cocatalyst, complexes 1 and 2 display much higher catalytic activities towards styrene polymerization, and produce the higher molecular weight polystyrenes with higher syndiotacticities and melting temperatures ( T-m) than the mother complex (CpTiCl3)-Ti-* does when the polymerization temperature is above 70 degrees C and the Al/Ti molar ratio is in the low range especially.

Influence of montmorillonite on syndiotactic polymerization behavior of styrene

The influence of montmorillonite (MMT) on the syndiotactic polymerization behavior of styrene was studied. To avoid the hydrophilic surface of the MMT coming into contact with the catalyst, which could poison it, SAN was introduced between the MMT and Cp*Ti (OCH3)(3). MMT was introduced into the catalytic system as a supporter for the Ti catalyst (supported catalytic system) or just dispersed in the polymerization solvent directly (in situ polymerization system). The polymerization results showed that surface modification of MMT dramatically affected the catalytic activity as well as the syndiotacticity of the polymers. This is mainly explained by the insulator SAN preventing the formation of the inactive/little active species Si-O-Ti and other atactic active species resulting from the reaction of the -OH on the MMT layer surface with Cp*Ti(OCH3)(3).

Rare earth metal bis(alkyl) complexes bearing amino phosphine ligands: Synthesis and catalytic activity toward ethylene polymerization

Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)(2) (HL1) and Lu(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h generated mono(alkyl) complex (L-1)(2)Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)(2) (HL2) with Lu(CH2SiMe3)(3)(THF)(2) afforded (L-2)(2)Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L-2)(3)Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)(2) (HL3) swiftly reacted with Ln(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L(3)Ln(CH2SiMC3)(2)(THF)(n) (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and [Ph3C][B(C6F5)(4)], was able to catalyze the polymerization of ethylene to afford linear polyethylene.

Preparation of poly(4-vinylpyridine)/silica hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

Poly(4 - vinylpyridine)/silica( PVP/SiO2) organic - inorganic nanoscale hybrid was prepared using sol - gel method, in which PVP was used as an organic component and TEOS as a SiO2 precusor, This hybrid was used as CpTiCl3 support. The XPS and IR measurements showed that two kinds of catalytic active site were formed through analyzing the interaction mode between support and CpTiCl3. The results of styrene polymerization showed that syndiotactic was the highest at 50 degreesC. The catalytic activity was 1.09 x 10(6) g PS/ (mol Ti . h) at 70 degreesC when n(Al)/n(Ti) = 1500. GPC results showed a bimodal molecular weight distribution.

新型单茂钛苯乙烯间规聚合催化剂的研究

本论文合成、表征了一系列改性单茂钦配合物，研究了这些配合物催化苯乙烯间规聚合反应行为。主要工作和结论如下：1．合成、表征了一系列双酚（胺）氧基五甲基单茂钦氯化物。在改性甲基铝氧烷（MMAO）的活化下，这些配合物可高效地催化苯乙烯间规聚合，在较高的聚合温度时（70-90℃），催化活性接近或超过五甲基氯化单茂钦的活性，在较低的铝钦比时（500／1），催化活性远远高于五甲基氯化单茂钦的活性。2．合成、表征了一系列新型单乙醇苯胺五甲基单茂钦氯化物。在MMAO的活化下，这类配合物是苯乙烯间规聚合的高效催化剂，催化活性高于母体配合物五甲基单茂钦氯化物，在较高的聚合温度和较低的铝钦比时，体现出优异的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。3．合成、表征了一系列新型双乙醇苯胺五甲基单茂钦氯化物。在MMAO的活化下，可以高效催化苯乙烯间规聚合，催化活性高于母体配合物五甲基单茂钦和相应的单乙醇苯胺配合物，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。4．合成、表征了一系列新型含曼尼希碱类配体的五甲基单茂钦氯化物。在MMAO的活化下，可高效催化苯乙烯间规聚合，催化活性远远高于母体配合物五甲基单茂钦氯化物，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。这类配合物的催化活性随着配体的空间位阻的增大而逐渐升高。5．合成、表征了一种新型的多核单茂钦配合物。在MMAO的活化下，这类钦配合物可催化苯乙烯间规聚合，在优化条件下，催化活性可以达到五甲基氯化单茂钦活性的三倍，尤其在较高的聚合温度和较低的铝钦比时，更加体现出优于母体配合物的催化性能。随着中心金属原子个数的增多，催化所需的MMAO的用量逐渐减少。

Investigations of the origin of stereocontrol in syndiospecific Ziegler-Natta polymerizations

In order to expand our understanding of the mechanism of stereocontrol in syndiospecific α-olefin polymerization, a family of Cs-symmetric, ansa-group 3 metallocenes was targeted as polymerization catalysts. The syntheses of new ansa-yttrocene and scandocene derivatives that employ the doubly [SiMe₂]- bridged ligand array (1,2-SiMe₂)₂{C₅H-3,5-(CHMe₂)₂} (where R = t- butyl, tBuThp; where R = i-propyl, iPrThp) are described. The structures of tBuThpY(µ-Cl)₂K(THF)₂, tBuThpSc(µ-Cl)₂K(Et₂O)₂, tBuThpYCH(SiMe₃)₂, Y₂{µ₂-(tBuThp)₂}(µ₂-H)₂, and tBuThpSc(µ-CH₃)₂ have been examined by single crystal X-ray diffraction methods. Ansa-yttrocenes and scandocenes that incorporate the singly [CPh₂]-bridged ligand array (CPh₂)(C₅H₄)(C₁₃H₈)(where C₅H₄ = Cp, cyclopentadienyl; where C₁₃H₈ = Flu, fluourenyl) have also been prepared. Select meallocene alkyl complexes are active single component catalysts for homopolymerization of propylene and 1-pentene. The scandocene tetramethylaluminate complexes generate polymers with the highes molecular weights of the series. Under all conditions examined atactic polymer microstructures are observed, suggesting a chain-end mechanism for stereocontrol.

A series of ansa-tantalocenes have been prepared as models for Ziegler-Natta polymerization catalysts. A singly bridged ansa-tantalocene trimethyl complex, Me₂Si(η⁵-C₅H₄)₂TaMe₃, has been prepared and used for the synthesis of a tantalocene ethylene-methyl complex. Addition of propylene to this ethylene-methyl adduct results in olefin exchange to give a mixture of endo and exo propylene isomers. Doubly-silylene bridged ansa-tantalocene complexes have been prepared with the tBuThp ligand; a tantalocene trimethyl complex and a tantalocene methylidene-methyl complex have been synthesized and characterized by X-ray diffraction. Thermolysis of the methylidene-methyl complex affords the corresponding ethylene-hydride complex. Addition of either propylene or styrene to this ethylene-hydride compound results in olefin exchange. In both cases, only one product isomer is observed. Studies of olefin exchange with ansa-tantalocene olefin-hydride and olefin-methyl complexes have provided information about the important steric influences for olefin coordination in Ziegler-Natta polymerization.

New titanium complexes with two beta-enaminoketonato chelate ligands: Syntheses, structures, and olefin polymerization activities

New titanium complexes with two nonsymmetric bidentate beta-enaminoketonato (N,O) ligands (4a-e), [(Ph)NC(R-2)C(H)C(R-1)O](2)TiCl2, have been synthesized. X-ray crystal structure reveals that complex 4a has a C-2-symmetric conformation with a distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-e are active catalysts for ethylene polymerization at room temperature, producing high molecular weight polyethylenes bearing linear structures. The 4a,b/MMAO catalyst systems exhibit the characteristics of a quasi-living polymerization of ethylene, producing polyethylenes with narrow molecular weight distributions. Moreover, the 4a-d/MMAO catalyst systems are also capable of promoting the quasi-living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight alternating copolymers with narrow molecular weight distributions. The quasi-living nature of the catalysts allows the synthesis of new A-B polyethylene-block-poly(ethylene-conorbornene) diblock copolymer.

A profluorescent azaphenalene nitroxide for nitroxide-mediated polymerization

A novel nitroxide-mediated polymerization (NMP) control agent; 1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl (TMAO), was used in the free-radical polymerization of styrene. The conversion of styrene during NMP was studied using FT-Raman spectroscopy and the effectiveness of TMAO as a NMP control agent was assessed by GPC analysis. Fidelity of the TMAO-alkoxyamine end-group on the synthesized polymers was confirmed by GPC, UV-Vis and fluorescence spectroscopic analyses. Comparison to the well known NMP control agent, TEMPO was made. TMAO showed control of molecular weight approaching that of TEMPO. Attempts to improve the properties of TMAO as an NMP control agent by synthesizing an analogue with bulkier substituents around the nitroxide did not generate the target molecule but demonstrated some of the interesting chemistry of the azaphenalene ring system

Living characteristics of the free-radical ring-closing polymerization of diallyldimethylammonium chloride

In this communication we provide the most recent results on RAFT-mediated ring-closing polymerization of diallyldimethylammonium chloride (DADMAC). The polymerization was carried out in aqueous solution employing 2,2′-azobis(2-methylpropionamidine)-dihydrochloride as the free radical initiator and trithiocarbonate RAFT agent (2-{[(dodecylsulfanyl)carbonothioyl sulfanyl]}propanoic acid, DoPAT) as the controlling RAFT agent. The results show that – while the system is not as completely controlled as previously described – it is nevertheless possible to mediate the polymerization of DADMAC and impart some living characteristics onto the system. The initial study on the RAFT-mediated polymerization of DADMAC may have overestimated the degree of livingness within this reaction. However, it is possible – at low conversions – for some living characteristics to be observed, as the evolution of molecular weight with conversion is linear. In addition, polymers with a reasonably narrow polydispersity can be isolated.

Crowded Diphosphinomethane Ligands in Catalysis: [(R2PCH2PR′2-κ2P)-NiR″]+ Cations for Ethylene Polymerization without Activators

The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR′2 is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-η3-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)2]+[B(3,5-(CF3)2C6H3)4]−, while the complex [(dtbpm κ2P)Ni(η3-CH(CH2Ph)Ph]+[B(3,5-(CF3)2C6H3)4]−is obtained from protonation of the Ni(0) olefin complex (dtbpm-κ2P)N(η2-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic η3-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the η3-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R′ on the phosphine ligand has been examined, and a clear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial η3 to η3 haptotropic shift processes of the[(R2PCH2PR′2)Ni] fragment and the η3−η1 change of the coordination mode of the benzyl group required for polymerization in those cations.