YU Fu-Jiang, CHEN Jian-Jun, HE Xiao-Jin, CHEN Shu-Ming, LI Wei, LI Chuan-Qing, LI Hong-Bo. SELECTIVE CATALYTIC HYDROGENATION OF SBS BLOCK COPOLYMER WITH METALLOCENE CATALYST ACCELERATED BY METHYL BENZOATE. [J]. Acta Polymerica Sinica (11):1306-1312(2010)
DOI:
YU Fu-Jiang, CHEN Jian-Jun, HE Xiao-Jin, CHEN Shu-Ming, LI Wei, LI Chuan-Qing, LI Hong-Bo. SELECTIVE CATALYTIC HYDROGENATION OF SBS BLOCK COPOLYMER WITH METALLOCENE CATALYST ACCELERATED BY METHYL BENZOATE. [J]. Acta Polymerica Sinica (11):1306-1312(2010) DOI: 10.3724/SP.J.1105.2010.09436.
SELECTIVE CATALYTIC HYDROGENATION OF SBS BLOCK COPOLYMER WITH METALLOCENE CATALYST ACCELERATED BY METHYL BENZOATE
以苯甲酸甲酯为促进剂,用茂金属催化剂制备了活性丁苯嵌段共聚物(SBS)的选择性催化加氢产物,讨论了苯甲酸甲酯、SBS的数均分子量等因素在几种实验条件下对产物加氢度的影响.结果表明,每百克干胶使用0.15~0.3 mmol Ti 催化条件下,苯甲酸甲酯在特定添加方式下能较大程度地提高茂金属催化剂的活性.在不加入苯甲酸甲酯的情况下,Mn=6.5104和Mn=5.5104两种SBS基础胶加氢反应180 min时加氢度均<97.0%;加入酯以后,反应60~120 min时,基础胶的加氢度98%;与已报道的研究结果相比,将加氢反应时间缩短了60~120 min.在每百克干胶使用0.15~0.3 mmolTi催化条件下,数均分子量的大小也对SBS基础胶的加氢度有影响,反应30 min时,Mn=5.5104的加氢度97%,Mn=6.5104的加氢度<90%;随着反应时间的延长,这种差距在逐渐缩小;反应180 min时,两者已无明显差距,此时两种基础胶的加氢度都98%.对影响的加氢度的机理进行了解释.
Abstract
The selective catalytic hydrogenation of living styrene-butadiene copolymer (SBS) prepared in the presence of metallocene catalyst modified by methyl benzoate was studied.The effects of factors
such as number-average molecular weight (Mn) of SBS
on the hydrogenation degree of the copolymers under different experimental conditions were discussed.The results show that when the ratio of Ti to 100 g dry copolymer is in the range of 0.15~0.3 mmol
adding methyl benzoate in a special mode can significantly improve the activity of titanocene catalyst.The hydrogenation degree of both SBS basic copolymers with Mn of 6.5104 and 5.5104 respectively are <97.0% after reaction for 180 min in the case of using metallocene catalyst not modified by methyl benzoate.On the other hand
the hydrogenation degree of the same SBS samples is 98.0% after reaction for 60~120 min under the condition of using the modified metallocene catalyst.In contrast with the similar researches reported before
our experiments could shorten the hydrogenation time by 60~120 min.When the ratio of Ti to 100g dry copolymer falls in the range of 015~0.3 mmol
the hydrogenation degree of the SBS basic copolymer is affected by magnitude of the Mn.For 30 min after the reaction
the hydrogenation degree of SBS copolymer with Mn of 5.5104 is 97.0% whereas that of the copolymer with Mn of 6.5104 is <90.0%.The disparity in hydrogenation degree between the two SBS copolymers is gradually diminished as the hydrogenation process proceeds and becomes unobvious after reaction for 180 min.In such a case the hydrogenation degree of both SBS basic copolymers are 98%.The effect of every influential factor on the hydrogenation degree of the SBS copolymers is elucidated in terms of the hydrogenation mechanism.
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