Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage mol...Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.展开更多
Styrene emulsion polymerization using an alkyl-9-BBN, synthesized by reacting 9-BBN（9-borabicyclo-[3.3.1]-nonane） and styrene, in an aqueous sodium dodecyl sulfate（SDS） solution was studied. Ultra-high-molecular-w...Styrene emulsion polymerization using an alkyl-9-BBN, synthesized by reacting 9-BBN（9-borabicyclo-[3.3.1]-nonane） and styrene, in an aqueous sodium dodecyl sulfate（SDS） solution was studied. Ultra-high-molecular-weight（〉 1.0 × 10~7） polystyrene was synthesized using a radical initiator formed through the aerobic oxidation of this alkyl-9-BBN in a high yield（〉 80%）. The kinetics of this emulsion polymerization of styrene with the alkyl-9-BBN was investigated. We confirmed that in the initial stage of the polymerization, the initial reaction rate followed first-order kinetics. The activation energy for this emulsion polymerization of styrene was approximately 56.2 kJ/mol.展开更多
We introduce a new method for separation/enrichment of the low-content cellular protein in high mo-lecular weight on the basis of molecular imprinting. The template protein, bacterial cloned immu-noglobulin binding pr...We introduce a new method for separation/enrichment of the low-content cellular protein in high mo-lecular weight on the basis of molecular imprinting. The template protein, bacterial cloned immu-noglobulin binding protein (BiP), was selectively assembled with assistant recognition polymer chains (ARPCs) from their library, which consists of numerous limited length polymer chains with randomly distributed recognition and immobilizing sites. The assemblies of proteins and ARPCs were adsorbed by porous polymeric beads and immobilized by cross-linking polymerization. After the template was removed, the synthesized imprinted polymer was used to adsorb authentic BiP from endoplasmic re-ticulum (ER) extract, and its proportional content was enriched 45 times. It is the first time that the low-content cellular natural protein, whose molecular weight reaches 78 kDa, is enriched by molecular imprinting.展开更多
Suppressing the chain transfer reactions during polymerization in late-transition metal-catalyzed olefin polymerization systems is the key to obtaining high molecular weight polyolefin materials. In this work, two eff...Suppressing the chain transfer reactions during polymerization in late-transition metal-catalyzed olefin polymerization systems is the key to obtaining high molecular weight polyolefin materials. In this work, two efficient strategies(“sandwich” and rotation-restricted strategies)to retard chain transfer reactions in ethylene(co)polymerization were employed for the iminopyridyl system. Herein, a family of iminopyridyl Ni(Ⅱ)and Pd(Ⅱ) complexes with a flexible backbone and rigid axial bulky aryl substituents were designed, synthesized and characterized. In ethylene polymerization, the iminopyridyl Ni(Ⅱ) and Pd(Ⅱ) catalysts using the two strategies exhibited reasonable activities and generated highly branched polyethylenes with high molecular weights, where catalysts with dibenzosuberyl substituents exhibited significantly higher activities and produced higher molecular weight polyethylene than catalysts with 8-arylnaphthalenyl substituent. A similar trend of activities and molecular weights was also found in the copolymerization of ethylene with MA using the Pd(Ⅱ) catalysts. Moreover, highly branched E-MA copolymers with moderate to high molecular weights and high incorporation ratios(up to 17.4 mol%) were generated with the two Pd(Ⅱ) catalysts. Most interestingly, as compared with the dibenzhydryl Ni(Ⅱ) and Pd(Ⅱ) catalysts, the catalysts using the two strategies exhibited a superior ability to retard the chain transfer reactions and generated polymers and copolymers with 1-2 orders of magnitude higher molecular weights during ethylene(co)polymerization.展开更多
An alternative cationic polymerization method is developed to produce high molecular weight polyisobutylene (HM-PIB) with molecular weights above 5×10^5g/mol. The method involves micelle formation via functionali...An alternative cationic polymerization method is developed to produce high molecular weight polyisobutylene (HM-PIB) with molecular weights above 5×10^5g/mol. The method involves micelle formation via functionalized low molecular weight polyisobutylene (LM-PIB) in non-polar solvent. One end of LM-PIB is modified with an imidazolium-containing ionic group, which together with the anion (eg. Al2Cl7) works as Lewis acid. While the monomer isobutylene dissolves readily in non-polar solvent, polymerization can occur only within the micelle, which affords stable HM-PIB particles. HM-PIB with a molecular weight (MW) close to 1 × 10^6 g/mol was produced successfully with the described method.展开更多
本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有...本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有明显提高。聚合活性最高可达7.8 kg PE/g催化剂·2小时,聚合物的重均分子量最高可达38.5×10^(5)。展开更多
文摘Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.
文摘Styrene emulsion polymerization using an alkyl-9-BBN, synthesized by reacting 9-BBN（9-borabicyclo-[3.3.1]-nonane） and styrene, in an aqueous sodium dodecyl sulfate（SDS） solution was studied. Ultra-high-molecular-weight（〉 1.0 × 10~7） polystyrene was synthesized using a radical initiator formed through the aerobic oxidation of this alkyl-9-BBN in a high yield（〉 80%）. The kinetics of this emulsion polymerization of styrene with the alkyl-9-BBN was investigated. We confirmed that in the initial stage of the polymerization, the initial reaction rate followed first-order kinetics. The activation energy for this emulsion polymerization of styrene was approximately 56.2 kJ/mol.
基金Supported by the National Natural Science Foundation of China (Grant No. 20674040)
文摘We introduce a new method for separation/enrichment of the low-content cellular protein in high mo-lecular weight on the basis of molecular imprinting. The template protein, bacterial cloned immu-noglobulin binding protein (BiP), was selectively assembled with assistant recognition polymer chains (ARPCs) from their library, which consists of numerous limited length polymer chains with randomly distributed recognition and immobilizing sites. The assemblies of proteins and ARPCs were adsorbed by porous polymeric beads and immobilized by cross-linking polymerization. After the template was removed, the synthesized imprinted polymer was used to adsorb authentic BiP from endoplasmic re-ticulum (ER) extract, and its proportional content was enriched 45 times. It is the first time that the low-content cellular natural protein, whose molecular weight reaches 78 kDa, is enriched by molecular imprinting.
基金Natural Science Foundation of Anhui Province(No.2108085Y06)Anhui Provincial Key Laboratory Open Project Foundation(No.LCECSC-01).
文摘Suppressing the chain transfer reactions during polymerization in late-transition metal-catalyzed olefin polymerization systems is the key to obtaining high molecular weight polyolefin materials. In this work, two efficient strategies(“sandwich” and rotation-restricted strategies)to retard chain transfer reactions in ethylene(co)polymerization were employed for the iminopyridyl system. Herein, a family of iminopyridyl Ni(Ⅱ)and Pd(Ⅱ) complexes with a flexible backbone and rigid axial bulky aryl substituents were designed, synthesized and characterized. In ethylene polymerization, the iminopyridyl Ni(Ⅱ) and Pd(Ⅱ) catalysts using the two strategies exhibited reasonable activities and generated highly branched polyethylenes with high molecular weights, where catalysts with dibenzosuberyl substituents exhibited significantly higher activities and produced higher molecular weight polyethylene than catalysts with 8-arylnaphthalenyl substituent. A similar trend of activities and molecular weights was also found in the copolymerization of ethylene with MA using the Pd(Ⅱ) catalysts. Moreover, highly branched E-MA copolymers with moderate to high molecular weights and high incorporation ratios(up to 17.4 mol%) were generated with the two Pd(Ⅱ) catalysts. Most interestingly, as compared with the dibenzhydryl Ni(Ⅱ) and Pd(Ⅱ) catalysts, the catalysts using the two strategies exhibited a superior ability to retard the chain transfer reactions and generated polymers and copolymers with 1-2 orders of magnitude higher molecular weights during ethylene(co)polymerization.
文摘An alternative cationic polymerization method is developed to produce high molecular weight polyisobutylene (HM-PIB) with molecular weights above 5×10^5g/mol. The method involves micelle formation via functionalized low molecular weight polyisobutylene (LM-PIB) in non-polar solvent. One end of LM-PIB is modified with an imidazolium-containing ionic group, which together with the anion (eg. Al2Cl7) works as Lewis acid. While the monomer isobutylene dissolves readily in non-polar solvent, polymerization can occur only within the micelle, which affords stable HM-PIB particles. HM-PIB with a molecular weight (MW) close to 1 × 10^6 g/mol was produced successfully with the described method.
文摘本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有明显提高。聚合活性最高可达7.8 kg PE/g催化剂·2小时,聚合物的重均分子量最高可达38.5×10^(5)。
