A HIGHLY ACTIVE NEODYMIUM CHLORIDE ISOPROPANOL COMPLEX/MODIFIED METHYLALUMINOXANE CATALYST FOR PREPARING POLYISOPRENE WITH HIGH CIS-1,4 STEREOSPECIFICITY AND NARROW MOLECULAR WEIGHT DISTRIBUTION

Neodymium chloride isopropanol complex （NdCl3.3＇prOH） activated by modified methylaluminoxane （MMAO） was examined in isoprene polymerization in hexane, with regards to Nd compounds, aluminum （Al） compounds, [Al]/[Nd] ratio, polymerization temperature and time. NdCl3＇3iprOH exhibited high activity producing polymers feasting high cis-l,4 stereospecificity （〉 96%）, very high molecular weight （Mn 〉 1.0 × 10^6） and fairly narrow molecular weight distribution （MWD, Mw/Mn 〈 2.0） simultaneously. In comparison, neodymium isopropoxide also showed high activity providing polymers with narrow MWD （Mw/Mn = 2.07）, but somewhat low cis-1,4 content （ca. 92%）, while neodymium chloride had no activity under present polymerization conditions. The Al compounds affected the polymer yield in the order of Al（i-Bu）3 〉 MMAO 〉 Al（i-Bu）2H. MMAO as cocatalyst afforded polyisoprene with high Mn over 1.0 × 10^6, whereas as stronger chain transfer agent than MMAO, AI（i-Bu）3 and AI（i-Bu）EH yielded polymers with low Mn （1.0 × 10^5-8.0 × 10^5）. NdCl3·3＇PrOH/MMAO catalyst showed a fairly good catalytic activity even at relatively low [Al]/[Nd] ratio of 30, and the produced polymer remained high cis-1,4 content of 95.8% along with high Mn over 1.0× 10^6 even at elevated temperatures up to 70℃. The polymerization rate is of the first order with respect to the concentration of isoprene. The mechanism of active species formation was discussed preliminarily.

低温预制钛系催化剂合成cis-1,4-聚异戊二烯

采用Ziegler-Natta配位聚合制备了高顺式聚异戊二烯,主要考察了非均相催化体系四氯化钛-三异丁基铝二组分催化剂的预制方法以及催化剂预制条件对异戊二烯体系聚合规律的影响。讨论了催化剂配比、预制催化剂温度和陈化温度对催化剂活性及聚合物的凝胶含量、特征黏度、微观结构含量等方面的影响。同时讨论了催化剂用量、聚合温度和聚合时间对聚合活性及聚合物的凝胶含量、特征黏度、微观含量等方面的影响。研究结果表明,合成高cis-1,4-聚异戊二烯的最佳实验条件为:Al/Ti摩尔比1.0,催化剂预制温度-40℃,陈化2 h,Ti/Ip摩尔比6×10-3,聚合温度50℃,聚合时间5 h。所得聚合物最高转化率为87.1%,cis-1,4结构含量为91.76%。

Phase Structure and Crystallization Behavior of Polyethylene in Its Blends with cis-1,4-Butadiene Rubber

Phase structure and crystallization behavior of polyethylene （PE） in its blends with cis-1,4-butadiene rubber （BR） at different blend ratios and sample preparation conditions were studied. The PE is finely dispersed in the BR matrix. For samples hot pressed at 145 ℃, circular PE microdomains with randomly oriented PE lamellar aggregates were produced. The domain size and number increase with increasing PE content. When the PE content is over 10 wt%, most of the PE domains impinged each other. The separated PE domains are connected by PE stripes with parallel arranged lamellar aggregates. For samples hot pressed at 140 ℃, elongated PE microdomains with oriented PE lamellar aggregates were obtained due to the shear flow. The crystallization of PE in the blends depends on the phase structure. Confined crystallization of PE occurs in small microdomains at relatively low temperature. With the increase of domain size, the crystallization ability of PE increases while the confined crystallization decreases.

Effects of Binding Energy of Bioinspired Sacrificial Bond on Mechanical Performance of cis-1,4-Polyisoprene with Dual-crosslink

Although bioinspired sacrificial bonds have been demonstrated to be efficient in improving the mechanical properties of polymer materials, the effect of binding energy of a specific dynamic bond on the ultimate mechanical performance of a polymer network with dual-crosslink remains unclear. In this contribution, diamine and sulfur curing package are introduced simultaneously into a sulfonated cis-1,4-polyisoprene to create dually-crosslinked cis-1,4-polyisoprene network with sulfonate-aminium ionic bonds as the sacrificial bonds. Three diamines （primary, secondary and tertiary） with the same spacer between the two nitrogen atoms are used to create the ionic bonds with different binding energies. Although the binding energy of ionic bond does not affect the glass transition temperature of cis-1,4-polyisoprene （IR）, it exerts definite influences on strain-induced crystallization and mechanical performance. The capabilities of diamine in dissipating energy, promoting strain-induced crystallization and enhancing the mechanical performance are in the same order of secondary diamine 〉 primary diamine 〉 tertiary diamine. The variations in mechanical performances are correlated to the binding energy of the ionic bond, which is determined by pKa values.

Yttrium-catalyzed cis-1,4-Selective Polymerization of 2-(4-Halophenyl)-1,3-butadienes and Their Copolymerization with Isoprene

Polymerization of 2-(4-halophenyl)-1,3-butadiene(2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex(1) activated by [Ph_3 C][B(C_(6) F_(5))_(4)] and Ali Bu3 shows high cis-1,4-selectivity(>98%) for the polymerization of 2-XPB(2-XPB = 2-FPB, 2-Cl PB and 2-Br PB) to afford halogenated plastic poly(dienes) with glass transition temperatures of30–55 ℃. Moreover, the copolymerization of 2-XPB with isoprene(IP) has also been achieved by this catalyst, and the insertion ratios of 2-XPB can be facilely tuned in a full range of 0%–100% simply by changing the 2-XPB-to-IP ratio. Quantitative hydrogenation of cis-1,4-poly(2-XPB) results in perfect alternating ethylene-halostyrene copolymers, and an alternating copolymer of 4-vinylbenzoic acid with ethylene is obtained by a consecutive reaction of ethylene-4-bromostyrene copolymer with ^(n)Bu Li, CO_(2) and HCl.

Neodymium Organic Sulfonate Complexes: Tunable Electronegativity/Steric Hindrance and Application in Controlled Cis-1,4-polymerization of Butadiene

Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stereoselectivity better than those of traditional metallocene and Ziegler-Natta catalysts in diene polymerization. In this work, a series of neodymium organic sulfonate complexes,Nd(CF_3SO_3)_3·x H_2O·y L(x, y: the coordination number; L refers to an organic electron donating ligand, such as acetylacetone(acac), isooctyl alcohol(IAOH), tributyl phosphate(TBP), etc.), have been synthesized to form the cationic active species in the presence of alkylaluminum such as Al(i-Bu)_3, AlEt_3, and Al(i-Bu)_2H, which display high activities and distinguishing cis-1,4 selectivities(up to99.9%) for the polymerization of butadiene. The microstructures, yield, molecular weight, and molecular weight distribution of the resulting polymer are well controlled by adjusting electronegativity/steric hindrance of the complexes. In addition, the kinetics, active species, and the possible process of polymerization are also discussed in this article.

Molecular Dynamics Simulation of the Glass Transition Temperature of Fullerene Filled Cis-1,4-polybutadiene Nanocomposites

In this work, the effect of the fullerene（C_（60）） weight fraction and PB-C_（60） interaction on the glass transition temperature（T_g） of polymer chains has been systemically investigated by adopting the united atom model of cis-1,4-poly（butadiene）（cis-PB）. Various chain dynamics properties, such as atom translational mobility, bond/segment reorientation dynamics, torsional dynamics, conformational transition rate and dynamic heterogeneity of the cis-PB chains, are analyzed in detail. It is found that T_g could be affected by the C_（60） weight fraction due to its inhibition effect on the mobility of the cis-PB chains. However, T_g is different, which depends on different dynamics scales. Among the chain dynamics properties, T_g is the lowest from atom translational mobility, while it is the highest from the dynamic heterogeneity. In addition, T_g can be more clearly distinguished from the dynamic heterogeneity; however, the conformational transition rate seems to be not very sensitive to the C_（60） weight fraction compared with others. For pure cis-PB chains, T_g and the activation energy in this work can be compared with those of other polymers. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The activation energy below T_g is lower than that above T_g. This work can help to understand the effect of the C_（60） on the dynamic properties and glass transition temperature of the cis-PB chains from different scales.

芳烃试剂对稀土催化异戊二烯聚合的影响

在实验室通过在稀土催化剂配制时引入芳烃试剂的方法 ,考察了芳烃对稀土催化双烯烃聚合的影响。与作为聚合溶剂组分的芳烃导致催化活性降低的作用不同 ,在稀土催化剂配制时引入芳烃可提高催化活性 ,并在一定程度上可降低聚合产物相对分子质量。

CHEMICAL STRUCTURE DEPENDENCE OF THE INTERNAL ENERGY CONTRIBUTION IN RUBBER ELASTICITY

Conformational elasticity theory recently developed has been used to explore the internal energy contribution to the elastic force f(e)/f as a function of strain for poly(cis-1,4-isoprene) and poly(trans-1,4-isoprene). Calculated f(e)/f values are in good agreement with those obtained experimentally. Results show that behavior of f(e)/f is mainly contributed by chemical structure, or intramolecular interaction, supporting the experimental observations, and that the internal energy contribution is strain dependent.

Polymerization of 1,3-Butadiene Catalyzed by Cobalt(Ⅱ) and Nickel(Ⅱ) Complexes Bearing Pyridine-2-imidate Ligands

Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.

Water-Promoted Kinetic Separation of trans- and cis-Limonene Oxides

The efficient hydrolytic kinetic separation of trans/cis-（R）-（＋）-limonene oxides was realized in a 1 ： 1 mixed solvent of water and 1,4-dioxane without additional catalyst. Optically pure trans-（R）-（＋）-limonene oxide was recovered in high yield （77%）.