共查询到20条相似文献,搜索用时 31 毫秒
1.
Friedrich G. Sernetz Rolf Mülhaupt 《Journal of polymer science. Part A, Polymer chemistry》1997,35(13):2549-2560
Ethene was co- and terpolymerized with 1-octene and styrene using the methylalumoxane (MAO) activated halfsandwich metallocene Me2Si(Me4Cp)(N-t.-butyl)TiCl2(Cp = cyclopentadienyl, Me = methyl) as catalyst. At temperatures of 40 and 60°C styrene concentration was varied in order to investigate the influence of the comonomers. Despite decreasing the overall activity with respect to ethene/1-octene copolymerization, polymerization activity was found to exibit a relative maximum with increasing styrene concentration. An explanation is given taking two different comonomer effects into account. Low styrene concentration promoted higher 1-octene incorporation compared to ethene/1-octene copolymerization but significantly lowered the molecular weight of the terpolymers. With constant ethene and 1-octene concentration it was possible to produce ethene/1-octene/styrene terpolymers with styrene content varying from 0 to 25 mol % and 1-octene content varying from 8 to 21 mol %. All terpolymers were amorphous. With constant ethene content it was found possible to vary their glass transition temperature with 1-octene/styrene molar ratio incorporated in the terpolymer. 13C-NMR spectroscopic microstructure analysis showed that no styrene/1-octene sequences were found in the terpolymer backbone. Furthermore terpolymerizations were conducted successfully incorporating norbornene, 1,5-hexadiene and propene as monomers in terpolymertization with ethene and styrene. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2549–2560, 1997 相似文献
2.
The copolymerization of propene and norbornene with the isospecific metallocene catalyst dimethylsilylenebis(η5-inden-1-yl)zirconium dichloride/methylaluminoxane ((CH3)2Si[Ind]2ZrCl2/MAO) was investigated. Because of the surprisingly high reactivity of the cyclic olefin copolymers with a norbornene content of 11 mol-% up to 98 mol-% were synthesized. The resulting copolymers are amorphous. The glass transition temperatures studied by differential scanning calorimetry measurements increase with rising norbornene content in the copolymer. High glass transition temperatures of Tg > 240°C were found for the copolymers with the highest content of norbornene. 相似文献
3.
Kiyoshi Endo Hiroharu Nagahama Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1979,17(11):3647-3653
A study of the monomer isomerization polymerization of 2-, 3-, and 4-octenes has been made with TiCl3–(C2H5)3Al catalyst at 80°C in comparison with the ordinary polymerization of 1-octene. It was found that all these octenes underwent monomer-isomerization polymerization to give high-molecular-weight homopolymer consisting exclusively of the 1-octene unit. The addition of an isomerization catalyst such as nickel acetylacetonate accelerated this polymerization. The rates of polymerization were found to decrease in the following order: 1-octene > 2-octene > 3-octene > 4-octene. These results indicate that the isomerization proceeded by a stepwise double-bond migration. It was also found that the monomer-isomerization copolymerization of 2-octene and 2-butene occurred under similar conditions and produced copolymers of both 1-olefin units. 相似文献
4.
Hui Yao Shi-jing Xiao Institute of Chemistry Chinese Academy of Sciences Beijing China 《高分子科学》2000,(2):169-176
(CpCH_2CH_2CH = CH_2)_2MCl_2(M=Zr, Hf)/MAO and Cp_2ZrCl_2/MAO (Cp=cyclopentadienyl; MAO=methylaluminoxane) catalyst systems have been compared for ethylene copolymerization to investigate the influence of theligand and transition metal on the polymerization activity and copolymer properties. For both CH_2CH_2CH=CH_2 substitutedcatalysts the catalytic activity decreased with increasing propene concentration in the feed. The activity of the hafnocenecatalyst was 6~8 times lower than that of the analogous zirconocene catalyst, ~(13)C NMR analysis showed that the copolymerobtained using the unsubstituted catalyst Cp_2ZrCl_2 has greater incorporatien of propene than those produced byCH_2CH_2CH=CH_2 substituted Zr and Hf catalysts. The melting point, crystallinity and the viscosity-average molecularweight of the copolymer decreased with an increase of propenc concentration in the feed. Both CH_2CH_2CH= CH_2 substitutedZr and Hf catalysts exhibit little or no difference in the melting point and crystallinity of the produced copolymers. However,there are significant differences between the two zirconocene catalysts. The copolymer produced by Cp_2ZrCl_2 catalyst havemuch lower T_m and X_c than those obtained with the (CpCH_2CH_2CH=CH_2)_2ZrCl_2 catalyst. The density and molecular weightof the copolymer decreased in the order: (CpCH_2CH_2CH=CH_2)_2HfCl_2>(CpCH_2CH_2CH=CH_2)_2ZrCl_2>Cp_2ZrCl_2. The kineticbehavior of copolymerizaton with Hf catalyst was found to be different from that with Zr catalyst. 相似文献
5.
Characterization and Catalytic Activity of Ni2+ -X and -Y Zeolites. II. Reducibility of Ni2+ by Low Olefines and the Dimerization Activity of the Ni2+ -Zeolites The reducibility of Ni2+ in X and Y zeolites by hydrogen, but-1-ene, propene, and ethene is compared. The degree of reduction was determined after isothermal reduction and reoxidation by the TPR method. At 673 K on X zeolites the reducibility decreases in the order: H2 > but-1-ene, propene > ethene. On Y zeolites an inversion takes place: but-1-ene, propene > H2, ethene. The mechanism of reduction by olefins should be determined by an intermediate splitting off of a hydride ion as a reducing species. Such a mechanism explains the higher degree of reduction in the more acid Y zeolites. Assuming low valent nickel as an active center in ethen dimerization the induction period results from the reduction of Ni2+ ions. 相似文献
6.
Pentamethylcyclopentadienyltitanium tribenzyloxide, Cp*Ti(OBz)3, was used as the catalyst precursor for polymerizations of propene and styrene. The titanocene catalyst affords atactic polypropene and syndiotactic polystyrene with high activities in the presence of methylalumimoxane (MAO). Block copolymerization of propene and styrene was carried out in the presence of Cp*Ti(OBz)3/MAO catalyst system by the means of external addition of triisobutylaluminum (TIBA) and sequential monomer feed. The copolymerization product is mainly a mixture of atactic polypropene(aPP) and syndiotactic polystyrene(sPS) homopolymers and aPP-b-sPS block copolymers, which can be separated into fractions with successive extraction with boiling methylethyl ketone(MEK), heptane, tetrahydrofuran(THF), and chloroform. Studies on thermal properties showed that rubbery phases and crystalline regions both appear in the block copolymer at the room temperature and that aPP-b-sPS block copolymer has better toughness than sPS. 相似文献
7.
Hoang The Ban Toshiya Uozumi Kazuo Soga 《Journal of polymer science. Part A, Polymer chemistry》1998,36(13):2269-2274
Both the rac- and meso-dinuclear ansa-zirconocene catalysts (μ-C12H8{[SiPh(Ind)2]ZrCl2}2) were prepared by a coupling reaction between 2 equiv of diindenylphenylchlorosilane (rac- and meso-isomers) and 1 equiv of p-dilithiobiphenyl in diethyl ether at −80°C, followed by a successive reaction with ZrCl4 · 2THF in THF at −78°C. Polymerizations of ethene and propene were conducted in a 1 dm3 high-pressure glass reactor equipped with a mechanical stirrer at 60, 80, 100, 120, and 150°C using methylalumoxane (MAO) as cocatalyst and toluene or decahydronaphthalene as the solvent. Copolymerization of ethene and 1-octene was also checked in brief. For ethene polymerization, the meso-catalyst was found to be more active, which displayed an extremely high activity to give linear polyethene with a high molecular weight and a narrow molar mass distribution (MMD). The apparent activity increased monotonously with rising polymerization temperature from 60°C up to 150°C, indicating that the active species are stable even at a high temperature. On the other hand, both the rac- and meso-catalysts showed very poor activities for propene polymerization. However, copolymerization of ethene and 1-octene proceeded at a high speed. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2269–2274, 1998 相似文献
8.
采用MgCl2负载TiCl4及1,3-二氯-2-丙醇给电子体(XROH),与三乙基铝助催化剂组成的催化剂体系,合成了1-己烯共聚率高且宽分子量分布的乙烯/1-己烯共聚物。 讨论了催化体系的组成、配比和聚合条件对乙烯/1-己烯共聚合行为,共聚物结构、分子量及分子量分布的影响。 结果表明,n(Ti)∶n(Mg)=10∶1,n(XROH)∶n(MgCl2)=2.6∶1,n(Al)∶n(Ti)=100∶1,乙烯压力0.45 MPa,聚合温度80 ℃,聚合时间2 h,共聚单体(1-hexene)浓度0.25 mol/L时,催化效率达23.2 kg/g cat。 采用13C NMR、X-ray、SEM、WAXD、DSC、GPC等测试技术对催化剂、共聚物的结构进行了表征。 结果表明,在Zieglar-Natta(Z-N)催化体系中,给电子体多卤代醇与TiCl4结合,载体MgCl2的晶体结构发生了变化。 结晶度降低,有利于催化剂负载量的提高(ω(Ti)=4.8%)和催化效率增大。 催化体系产生了多种活性中心,使聚烯烃分子量分布变宽(15~20)。 多卤代醇还可增强1-己烯与乙烯的共聚能力,在共聚物中1-己烯的摩尔分数达5.1%。 相似文献
9.
Stephan Jüngling Rolf Mülhaupt Udo Stehling Hans-Herbert Brintzinger David Fischer Franz Langhauser 《Macromolecular Symposia》1995,97(1):205-216
Propene polymerization of methylalumoxane (MAO) activated rac-Me2Si(Benz[e]Indenyl)2ZrCl2 ( BI ) and rac-Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2 ( MBI ) was studied to investigate the influence of the ligand substitution pattern and the role of dormant sites. Poly(propene) end group composition as well as regio- and stereoirregularities were examined by means of 1H- and 13C-NMR spectroscopy. Dormant sites, resulting from 2, 1-propene insertion, were reactivated either by β-hydrogen transfer to propene, yielding 2-butenyl end groups, or by 1, 2-insertion of propene, yielding regioirregularities. Propene polymerization in the presence of hydrogen gave n-butyl end groups and less regioirregularities as expected for hydrogenolysis of such dormant sites. Methyl substitution in 2-position of the benz[e]indenyl ligand suppressed β-hydrogen transfer to propene, and increased molecular weight with increasing propene concentration. Also, activation energy increased from 30 kJ/mol ( BI /MAO) to 59 kJ/mol ( MBI /MAO). For both catalysts activity depended on propene concentration. The order of reaction relative to propene was 1.7. 相似文献
10.
《Journal of organometallic chemistry》2011,696(26):4315-4320
Permethylated cyclopentadienyl dinuclear constrained geometry titanium catalyst, [μ-(C6H4)2-2,2′]{(η5-C5Me3)[1-Me2Si(η1-N-tBu)](TiCl2)}2 (BPTi2) linked by a biphenylene bridge was synthesized and tested in ethylene and ethylene/1-octene polymerizations upon activation by TIBA (triisobutylaluminum)/[Ph3C][B(C6F5)4]. When compared with the corresponding highly active, mononuclear analogs, Me2Si(η5-2-PhC5Me3)(η1-N-tBu)TiCl2 (PhTi1) and Me2Si(η5-C5Me4)(η1-N-tBu)TiCl2 (MeTi1), BPTi2 exhibits significantly increased molecular weight of polymer (>two-fold), as well as high level of activity and 1-octene incorporations in ethylene and ethylene/1-octene polymerizations. Although the lower activity was observed at high 1-octene feeds, the combined effects of rigidity and electronic conjugation induced by the biphenylene bridge might be responsible for the observed polymerization properties of BPTi2. 相似文献
11.
Min Hyung Lee Myung Hwan Park Woo Young Sung Seong Kyun Kim AuJiRu Son Youngkyu Do 《Journal of organometallic chemistry》2012,696(26):4315-4320
Permethylated cyclopentadienyl dinuclear constrained geometry titanium catalyst, [μ-(C6H4)2-2,2′]{(η5-C5Me3)[1-Me2Si(η1-N-tBu)](TiCl2)}2 (BPTi2) linked by a biphenylene bridge was synthesized and tested in ethylene and ethylene/1-octene polymerizations upon activation by TIBA (triisobutylaluminum)/[Ph3C][B(C6F5)4]. When compared with the corresponding highly active, mononuclear analogs, Me2Si(η5-2-PhC5Me3)(η1-N-tBu)TiCl2 (PhTi1) and Me2Si(η5-C5Me4)(η1-N-tBu)TiCl2 (MeTi1), BPTi2 exhibits significantly increased molecular weight of polymer (>two-fold), as well as high level of activity and 1-octene incorporations in ethylene and ethylene/1-octene polymerizations. Although the lower activity was observed at high 1-octene feeds, the combined effects of rigidity and electronic conjugation induced by the biphenylene bridge might be responsible for the observed polymerization properties of BPTi2. 相似文献
12.
Titanium complexes were prepared by the reaction of 2,2′-thiobis(6-tert-butyl-4-methylphenol) (TBP) with TiCl4 or Ti(OPri)4. These complexes in combination with methyalumoxane as cocatalyst are highly active towards ethylene and propene, giving polymers having high molecular weights. The polymerization activities for ethylene and propene are comparable to those of Cp2ZrCl2-MAO catalyst. Polypropylene obtained had extremely high molecular weight (Mw>6 million) and low regioregularity (30% of head-to-head and tail-to-tail linkages). Highly syndiotactic polystyrene was obtained with these catalysts with activity up to 27 kg polymer per g Ti and hour. Copolymerization of styrene with ethylene gave highly alternating copolymer with isotactic styrene units. These catalysts are also active toward both conjugated and nonconjugated dienes such as butadiene and 1,5-hexadiene. Polybutadiene had mainly cis-1,4-structure (98%). The structure of poly(1,5-hexadiene) is rather complicated, which is quite different from that prepared with heterogeneous TiCl3 catalysts. 相似文献
13.
K. E. Russell D. C. McFaddin B. K. Hunter R. D. Heyding 《Journal of Polymer Science.Polymer Physics》1996,34(14):2447-2458
The phase structure of random copolymers of ethylene and ethylene-d4 with 1-octadecene and other 1-alkenes has been investigated. CPMAS 13C NMR spectra show that a fraction of the central sections of C16H33 side chains in ethylene-d4 copolymers are in ordered environments at 298 K. They give rise to resonances from 32.9 ppm to 33.8 ppm, which show that they are in trans conformations; T1C values for this group of resonances range from 1 s to 7 s. The remaining side chains are in an amorphous environment, the internal methylenes having a chemical shift of 30.8 ppm and a T1C close to 0.4 s. A Raman band at 1062 cm−1 in the spectrum of an ethylene-d4-1-octadecene copolymer is consistent with partial crystallization of side chains. Some side-chain crystallization also occurs in a 1-tetradecene copolymer. X-ray diffraction studies suggest that smaller side chains do not crystallize to a significant extent at 298 K. © 1996 John Wiley & Sons, Inc. 相似文献
14.
The copolymerizations of ethylene with 1-hexene or 1-octene by using TiCl4 /MgCl2 /THF catalysts modified with different metal halide additives(ZnCl2, SiCl4, and the combined ZnCl2-SiCl4) were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnCl2-SiCl4 revealed the highest activities for both ethylene/1-hexene and ethylene/1-octene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C―O―C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiCl4 /MgCl2 /THF catalytic system leading to an increase in activities as well as comonomer insertion(as proven by13C-NMR). However, Lewis acidmodifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnCl2 and/or SiCl4 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of α-olefins insertion, regardless of the types of Lewis acids and comonomer. 相似文献
15.
Toshiya Uozumi Tatsuya Toneri Kazuo Soga Takeshi Shiono 《Macromolecular rapid communications》1997,18(1):9-15
Two kinds of SiO2-supported Cp*TiCl3 (Cp* = η5-1,2,3,4,5-pentamethylcyclopentadienyl) catalysts were prepared, using SiO2 modified with 3-aminopropyltrimethoxysilane (N SiO2) and the ordinary SiO2 as the carrier. The copolymerization of ethylene and 1-octene was conducted over them combined with methylaluminoxane (MAO) as cocatalyst. From a detailed analysis of the produced copolymers, it was found that the N SiO2 supported Cp*TiCl3 catalyst gives poly(ethylene-co-1-octene) with a higher content of 1-octene and a narrower molar mass distribution as well as a narrower chemical composition. 相似文献
16.
The relative OH reaction rates from the simulated atmospheric oxidation of 4-methyl-2-pentanone, trans-4-octene, and trans-2-heptene have been measured. Reactions were carried out at 297 ± 2 K in 100-liter FEP Teflon®-film bags. The OH radicals were produced from the photolysis of methyl nitrite. The measured rate constants (×1011 cm3 molecule?1 s?1) were as follows: 6.77 ± 0.50 for trans-4-octene, 1.40 ± 0.07 for 4-methyl-2-pentanone, and 6.70 ± 0.23 for trans-2-heptene using an absolute rate constant of 2.63 × 1011 cm3 molecule?1 s?1 for the reaction of OH with propene; the principal reference organic. © John Wiley & Sons, Inc. 相似文献
17.
H. Kothandaraman M. Saroja Devi 《Journal of polymer science. Part A, Polymer chemistry》1994,32(7):1283-1294
A number of TiCl4 catalysts supported on MgCl2 which was activated by the recrystallization method using different alcohols were prepared with ethyl benzoate or dibutyl phthalate as the internal electron donor. All the catalysts were characterized by BET, x-ray diffraction, and hydrolysis–GC analysis. Kinetics of polymerization of 1-octene was studied with three of the above catalysts (having different internal electron donors) activated by AlEt3. The rate of polymerization increased linearly with increasing temperature, and catalyst and monomer concentrations. From the Arrhenius plot, the overall activation energies of polymerization were determined and the dependence of rate on the AlEt3 concentration could be explained by the Langmuir-Hinshelwood mechanism. 13C-NMR was used to study the effect of internal electron donors on the % isotacticity of poly(1-octene). The catalytic activities of all the catalysts were compared in 1-octene polymerization. © 1994 John Wiley & Sons, Inc. 相似文献
18.
The polymerization of 1-octene initiated by methylalumoxane(MAO)-activated Ni(Ⅱ)-based-α-diimine complexes[(2,6-i-Pr)2C6H3-DAB(An)]NiBr2 was investigated.Using this catalyst,poly(1-octene)s with molecular weight between 100×103 and 400×103 and polydispersity(Mw/Mn) between 1.3 and 1.5 were synthesized successfully by varying reaction time at room temperature.The poly(1-octene)s were amorphous polymers and could be well soluble in tetrahydrofuran(THF).After fractional precipitation,poly(1-octene)s with narrow molecular weight distributions(Mw/Mn≤1.12) were obtained.Their weight-average molecular weights were measured by gel permeation chromatography(GPC) in conjunction with online model BI-MwA multiangle laser light scattering(MALLS),and their intrinsic viscosities were measured by Maron’s single-point method.The k and a values in Mark-Houwink equation[η]= KMαin THF at 40℃were 0.089 mL/g and 0.61 respectively. 相似文献
19.
The linear aliphatic olefins, such as 1-octene, 1-decene, 1-dodecene and 1-tetradecene, were effectively epoxidized with molecular oxygen catalyzed by the amino acid Schiffbase manganese complex (Sal-Phe-Mn). The products of the reaction was 1, 2-epoxy alkane 相似文献
20.
Mujie Yang Xiaojun Zhang Jianfu Li Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》1992,30(1):63-69
The study of rare earth coordination catalysts for polymerization of 1-octene has been successfully carried out for the first time. Some features and kinetic behavior of polymerization of 1-octene by Nd(naph)3–AIEt3 catalyst system in tetrachloro-methane are described. The overall polymerization activation energy Ea measured was 74.5 kJ/mol and the rate equation could be expressed as Rp = kp [Nd] [M] (kp = 3.21 × 10?3 L/mol s, at 50°C). The catalytic activity of various rare earth elements in Ln (naph)3 and ligands in NdL3 for the polymerization was compared. A 1-octene oligomer with double bonds was obtained. It is either a white or pale yellow waxy semi-solid. Its number-average molecular weight is about 103 and the molecular weight distribution is less than 2. 相似文献