CN101885795A - 一种给电子体催化剂及制备和应用 - Google Patents
一种给电子体催化剂及制备和应用 Download PDFInfo
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- CN101885795A CN101885795A CN 201010231403 CN201010231403A CN101885795A CN 101885795 A CN101885795 A CN 101885795A CN 201010231403 CN201010231403 CN 201010231403 CN 201010231403 A CN201010231403 A CN 201010231403A CN 101885795 A CN101885795 A CN 101885795A
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- metal halide
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
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- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical class Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
本发明涉及一种给电子体催化剂及其制备和应用;主催化剂由载体、过渡金属卤化物、有机醇化合物、有机硅氧烷和有机硅胺组成;按摩尔比为1∶(0.01-20)∶(0.1-6)∶(0.01-5)∶(0.01-5);助催化剂为有机铝化合物;主催化剂中的过渡金属卤化物与助催化剂的摩尔比为1∶(30-500);本催化剂催化活性高,聚合物分子量高,聚合物分子量分布较宽;共聚单体的共聚性能好;适用于淤浆法、气相聚合工艺或组合聚合工艺;制备方法简单,对设备要求低,对环境污染小。
Description
技术领域
本发明涉及一种用于乙烯聚合或丙烯聚合或共聚合的催化剂及催化剂的制备和应用。
背景技术
烯烃聚合催化剂是聚烯烃聚合技术的核心,从烯烃聚合催化剂的发展来看,概括起来主要有两个方面:(1)开发能够制备特殊性能或性能更优异的聚烯烃树脂催化剂,如茂金属催化剂及非茂后过渡金属催化剂等;(2)对于通用聚烯烃树脂的生产而言,在进一步改善催化剂性能的基础上,简化催化剂制备工艺,降低催化剂成本,开发对环境友好的技术,以提高效益,增强竞争力。20世纪80年代以前,聚乙烯催化剂研究的重点是追求催化剂效率,经过近30年的努力,聚乙烯催化剂的催化效率呈数量级提高,从而简化了聚烯烃的生产工艺,降低了能耗和物耗。
然而,传统的Z-N催化剂催化乙烯/高级Alpha-烯烃共聚合时,高级Alpha-烯烃的***量小。Bialek[Bialk M,et al.Polymer,2000,41:7899],采用钒系催化剂MgCl2(THF)2/VCl4/Et2AlCl催化乙烯与1-辛烯共聚合,共聚物中1-辛烯的***量为0.47%,在相同聚合条件下,钛系催化剂MgCl2(THF)2/TiCl4/Et2AlCl的单体***量要比钒体系的低,为0.39%。
但是,负载型的Ziegler-Natta催化剂在工业上的应用已经成熟,因此,改进传统的Z-N催化剂,提高1-辛烯的共聚合能力,制备1-辛烯摩尔含量高的乙烯/1-辛烯共聚合物的研究具有一定的理论意义和重要的实际应用价值。我们(申请号:200910083230.8)发现传统的高效Ziegler-Natta催化剂用醇等改性后,催化剂可以有效催化乙烯与高级Alpha-烯烃共聚合,但是采用这种改性的高效Ziegler-Natta催化剂催化乙烯/空间阻碍大的烯烃共聚合时,共聚单体的共聚能力低。因此,本发明进一步改进传统高效Ziegler-Natta催化剂,在主催化剂的制备过程中加入有机硅胺,提高Alpha-烯烃的共聚合能力,具有重要的理论意义和重要的实际应用价值。
发明内容
本发明的目的在于提供一种催化活性高的用于乙烯聚合或乙烯与共聚单体共聚合的催化剂组分及其制备方法。
本发明所提供的乙烯聚合催化剂由主催化剂和助催化剂组成;其中,所述的主催化剂由载体、过渡金属卤化物、有机醇化合物、有机硅氧烷化合物和有机硅胺组成。载体、过渡金属卤化物、有机醇化合物、有机硅氧烷化合物和有机硅胺的用量关系为:载体、过渡金属卤化物、有机醇化合物、有机硅氧烷化合物和有机硅胺的摩尔比为1∶(0.01-20)∶(0.1-6)∶(0.01-5)∶(0.01-5);所述的助催化剂为有机铝化合物;主催化剂与助催化剂的用量关系为:主催化剂中的过渡金属卤化物与助催化剂的摩尔比为1∶(30-500)。
所述的载体是指无机氧化物载体、卤化物载体或聚合物载体。无机氧化物载体是SiO2或Al2O3,在负载前经300度-700度活化处理4小时;
其中,所述的卤化物载体为二卤化镁、二卤化镁的水或醇的络合物、二卤化镁分子式中其中一个或两个卤原子被羟基或卤羟氧基所置换的衍生物。具体的化合物如:二氯化镁、二溴化镁、二碘化镁、氯化甲氧基镁、氯化乙氧基镁、氯化丙氧基镁、氯化丁氧基镁、氯化苯氧基镁、乙氧基镁、异丙氧基镁、丁氧基镁、氯化异丙氧基镁、二丁基镁、氯化丁基镁等中的至少一种。其中,优选二氯化镁。
其中,所述的聚合物载体是环糊精、聚苯乙烯。
本发明的特征之一是在主催化剂制备过程中加入有机硅胺,所述的有机硅胺是选自通式为HN(R1)-SiR2R3R4的化合物中的一种或两种或两种以上的混合物,式中,R1,R2,R3或R4是碳原子数为1-20的烷基,碳原子数为3-20的环烷基或碳原子数为6-30芳基,R2,R3或R4可以相同,也可以不同。具体包括:三甲基硅基甲基胺、三甲基硅基特丁基胺、三甲基硅基异丁基胺、三甲基硅基正丁基胺、三甲氧基硅基甲基胺、三乙基硅基甲基胺、三乙氧基硅基乙基胺、二(三甲基硅)基胺、三苯基硅基甲基胺、三苯氧基硅基甲基胺、三环己基硅基甲基胺、三异丙基硅基甲基胺、三异氧丙基硅基甲氧基胺、二甲基苯基硅基甲基胺、二乙氧基苯基硅基甲基胺、二甲基乙氧基硅基甲基胺、二甲氧基乙氧基硅基甲基胺。在制备主催化剂的过程中加入有机硅胺与过渡金属卤化物反应,使过渡金属卤化物全部或部分生成如通式(1)的化合物。
MPzClx[N(R1)-SiR2R3R4]y
(通式1)
通式(1)中M表示Ti,Zr,V,Nd,Y,Sc或Sm等;R1,R2,R3或R4是碳原子数为1-20的烷基,碳原子数为3-20的环烷基或碳原子数为6-30的芳基,R2,R3或R4可以相同,也可以不同;P表示C5-C30的环戊二烯基、茚基或芴基或其衍生物;P为单茂配体时,x=2,y=1,Z=1;P为双茂或桥联茂配体时,x=1,y=1,Z=2;P不存在时,P不存在时,x=1,2或3,y=1,2,或3,x+y=4,Z=0。
所述的有机硅胺与载体的摩尔比优选0.001-5∶1。
本发明的特征之一是在主催化剂制备过程中加入过渡金属卤化物,所述的过渡金属卤化物选自通式为M(R1)4-mXm的化合物中的至少一种,式中,M是Ti,Zr,Hf,V,Nd,Y,Sc或Sm等;X是卤原子,选自Cl,Br,F;m为0到4的整数;R1选自C1~C20的脂肪烃基、C1~C20的脂肪烷氧基、C1~C20的环戊二烯基及其衍生物、C1~C20的芳香烃基、COR`或COOR`,R`是具有C1~C10的脂肪族基或具有C1~C10的芳香基。R1具体可选自:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、异丁基、叔丁基、异戊基、叔戊基、2-乙基己基、苯基、萘基、邻-甲基苯基、间-甲基苯基、对-甲基苯基、邻-磺酸基苯基、甲酰基、乙酰基或苯甲酰基等中的至少一种。所述的Ti,Zr,Hf,V,Nd,Y,Sc或Sm等过渡金属卤化物具体可选用四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、四乙氧基钛、一氯三乙氧基钛、二氯二乙氧基钛、三氯一乙氧基钛、钛酸正丁酯、钛酸异丙酯、甲氧基三氯化钛、二丁氧基二氯化钛、三丁氧基氯化钛、四苯氧基钛、一氯三苯氧基钛、二氯二苯氧基钛、三氯一苯氧基钛中的一种或几种的混合。其中,优选四氯化钛、环戊二烯三氯化钛、环戊二烯三氯化锆、五甲基环戊二烯三氯化钛、二环戊二烯二氯化钛、二戊二烯二氯化锆、桥联二茚基二氯化钛、桥联二芴基二氯化锆、CGC催化剂、水杨醛亚胺钛(锆)催化剂(F1)。过渡金属卤化物与载体的摩尔比优选0.01-20∶1。
本发明的特征之一是在主催化剂制备过程中加入有机硅氧烷化合物,所述的有机硅氧烷化合物是符合通式为RxSi(OR’)y,式中,R和R’为C1-C15的烷基,C3-C20的环烷基,或C6-C30的芳基;x是0,1,2,3;y是1,2,3,4;x+y=4。四个OR’基团可以相同也可以不同。有机硅氧化合物具体可选自:三乙氧基异丙氧基硅烷、二乙氧基异丙氧基叔丁氧基硅烷、三异丙氧基叔丁氧基硅烷、二异丙氧基二叔丁氧基硅烷、二乙氧基环己氧基叔丁氧基硅烷、二乙氧基苯氧基叔丁氧基硅烷、一乙氧基二异丙氧基叔丁氧基硅烷、乙氧基异丙氧基叔丁氧基环己氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷、四(2-乙基己氧基)硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、正丙基三乙氧基硅烷、正丙基三甲氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、环戊基三甲氧基硅烷、环戊基三乙氧基硅烷、2-甲基环戊基三甲氧基硅烷、2,3-二甲基环戊基三甲氧基硅烷、环己基三甲氧基硅烷、环己基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、叔丁基三乙氧基硅烷、正丁基三甲氧基硅烷、正丁基三乙氧基硅烷、异丁基三乙氧基硅烷、环己基三乙氧基硅烷、环己基三甲氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、一氯三甲氧基硅烷、一氯三乙氧基硅烷、乙基三异丙氧基硅烷、乙烯基三丁氧基硅烷、三甲基苯氧基硅烷、甲基三烯丙氧基硅烷、乙烯基三乙酸基硅烷、二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二丁基二甲氧基硅烷、二异丙基二甲氧基硅烷、二异丙基二乙氧基硅烷、叔丁基甲基二甲氧基硅烷、叔丁基甲基二乙氧基硅烷、叔戊基甲基二乙氧基硅烷、二环戊基二甲氧基硅烷、二环戊基二乙氧基硅烷、甲基环己基二甲氧基硅烷、甲基环戊基二乙氧基硅烷、甲基环戊基二甲氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、甲基苯基二乙氧基硅烷、甲基苯基二甲氧基硅烷、双邻甲苯基二甲氧基硅烷、双邻甲苯基二乙氧基硅烷、双间甲苯基二甲氧基硅烷、双间甲苯基二乙氧基硅烷、双对甲苯基二甲氧基硅烷、双对甲苯基二乙氧基硅烷、三甲基甲氧基硅烷、三甲基乙氧基硅烷、三环戊基甲氧基硅烷、三环戊基乙氧基硅烷、二环戊基甲基甲氧基硅烷和环戊基二甲基甲氧基硅烷等中的一种或几种。优选三乙氧基异丙氧基硅烷、二乙氧基异丙氧基叔丁氧基硅烷、三异丙氧基叔丁氧基硅烷、二异丙氧基二叔丁氧基硅烷、二乙氧基环己氧基叔丁氧基硅烷或一乙氧基二异丙氧基叔丁氧基硅烷或四乙氧基硅烷。
所述的有机硅氧化合物与载体的摩尔比优选0.01-5∶1。
本发明的特征之一是在主催化剂制备过程中加入有机醇化合物,所述的有机醇化合物选自碳原子数为1-15的直链醇、碳原子数为1-15的支链烷基醇、碳原子数为1-15的环烷基醇或碳原子数为1-15的异构醇的中的至少一种。具体包括:乙醇、乙二醇、丙醇、异丙醇、丁醇、异丁醇、1,3-丙二醇、丙三醇,己醇,2-甲基戊醇,2-乙基丁醇,正庚醇,2-乙基己醇,正辛醇,癸醇,山梨醇等;环烷醇,如环己醇,甲基环己醇;芳香醇,如卞醇,甲基卞醇,异丙基卞醇等。其中,优选脂肪醇,尤其优选乙醇、丁醇、2-乙基己醇或丙三醇中的至少一种。有机醇的加入对聚合物的氢调重要。所述的有机醇化合物与卤化镁的摩尔比优选0.5-6∶1。
以卤化物作载体时,在主催化剂的制备过程中可以加入有机环氧化合物作助溶剂,所述的有机环氧化合物选自碳原子数为2-8的脂肪族烯烃、碳原子数为2-8的二烯烃、碳原子数为2-8的卤代脂肪族烯烃、碳原子数为2-8的二烯烃的氧化物、碳原子数为2-8的缩水甘油醚或碳原子数为2-8的内醚中的至少一种。具体如:环氧乙烷、环氧丙烷、环氧丁烷、丁二烯氧化物、丁二烯双氧化物、环氧氯丙烷或甲基缩水甘油醚中的至少一种。其中,优选环氧丙烷或环氧氯丙烷中的至少一种。
所述的有机环氧化合物与卤化镁的摩尔比优选0.5-5∶1。
以卤化物作载体时,在主催化剂的制备过程中可以加入有机磷酸酯作助溶剂,所述的有机磷酸酯选自正磷酸的烃基酯或亚磷酸的烃基酯中的至少一种。具体如:正磷酸三甲酯、正磷酸三乙酯、正磷酸三丙酯、正磷酸三丁酯、正磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯或亚磷酸苯甲酯中的至少一种。其中,优选正磷酸三丁酯。
所述的有机磷酸酯与卤化镁的摩尔比优选0.5-5∶1。
以卤化物作载体时,卤化物先溶解,再以球形颗粒状态析出,在主催化剂的制备过程中加入饱和烷烃或环烷烃做助析出剂。在卤化物溶解后于50度-120度加入助析出剂,滴入四氯化钛后于-10度-30度加入助析出剂,升温至50度-80度加入助析出剂。所述助析出剂是C5-C20饱和烷烃或环烷烃,优选正己烷、正庚烷、辛烷、环己烷。有利于催化剂以颗粒形态析出。
本发明的助析出剂是饱和烷烃或环烷烃,优选正己烷,正庚烷或环己烷。本发明的特征之一在主催化剂的制备过程中助析出剂分多次加入的效果比一次加入好,优选3次,分别在载体卤化物完全溶解后加入,滴加TiCl4后加入,滴加TiCl4后升温至50度以上再加入。每次加入的助析出剂的量可以相同,也可以不相同。
在催化剂制备过程中助溶剂、助析出剂和溶剂不参与化学反应。
所述的助催化剂有机铝化合物选自通式为AlR5 nX3-n的化合物中一种或两种的混合,式中,R5为氢或碳原子数为1-20的烃基或烷氧基、X为卤素,n为0<n≤3的整数,具体可选自:三甲基铝、三乙基铝、三丙基铝、三异丁基铝、三正己基铝、三叔丁基铝、三辛基铝、一氯二乙基铝、二氯乙基铝、倍半乙基氯化铝等中的一种或两种的混合;甲基铝氧烷、乙基铝氧烷等。其中,优选三乙基铝或三异丁基铝或甲基铝氧烷中的一种或两种的混合。
作为本发明的优选技术方案,主催化剂与助催化剂的用量关系为:过渡金属卤化物与助催化剂的摩尔比为1∶30-500。
本发明所提供的烯烃聚合催化剂的制备方法,包括以下步骤:
1)将载体在10-150℃,分散于有机溶剂中,再加入有机醇化合物;
2)在-40-30℃下,向步骤1)中得到的溶液中加入过渡金属卤化物,滴加完毕后加入有机硅氧烷化合物和有机硅胺,并升温至40-110℃,反应0.5-24小时,在升温过程中,固体物逐渐析出并形成颗粒,反应结束后,采用甲苯或正己烷洗涤4-6次,过滤,除去未反应物,真空抽干,得到主催化剂组分。
3)将主催化剂和助催化剂按助催化剂与过渡金属卤化物的摩尔比为1∶30-500混合,得到烯烃聚合催化剂。
所述的有机溶剂选自甲苯、二甲苯、己烷、庚烷、辛烷或癸烷,或它们的混合溶剂,优选甲苯、己烷、庚烷或癸烷。
本发明所提供的乙烯聚合催化剂的用途为:可作为乙烯聚合或乙烯与α-烯烃的共聚合催化剂,其中,所述的α-烯烃优选丙烯,1-丁烯,1-己烯,1-辛烯,1-癸烯,3-甲基-1-丁烯,环戊烯,4-甲基-1-戊烯,1,3-丁二烯,异戊二烯,苯乙烯,甲基苯乙烯,降冰片烯,取代降冰片烯等。
本发明所提供的烯烃聚合催化剂具有以下有益效果:
本发明所提供的乙烯聚合催化剂的颗粒形态良好,呈球形;催化剂活性高,用于乙烯与α-烯烃共聚合时α-烯烃***率高;聚合物分子量高,聚合物分子量分布宽;适用于淤浆法、气相聚合工艺或组合聚合工艺;制备方法简单,对设备要求低,对环境污染小。
具体实施方式
实施例1
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入二氯化镁4g,环氧氯丙烷3.5ml,磷酸三丁酯5.5ml,甲苯75ml,己烷10ml,乙醇3.2ml,搅拌下升温至70℃,固体完全溶解形成均一的溶液后,恒温1h;而后降温至-25℃,滴加58ml四氯化钛,滴加完毕后加入0.5g三甲基硅基特丁基胺,3.5ml三乙氧基异丙氧基硅烷,反应1h后,依次于-10℃恒温1h,0℃恒温1h,20℃恒温1h,加入己烷5ml,升温至60℃恒温,加入己烷10ml,反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分10mg,脱水己烷200ml,AlEt3溶液0.6ml(2mmol/ml),升温至80℃后充入氢气至0.28MPa,充入乙烯至0.73MPa,加入1-己烯35mL,恒压恒温反应2h。
实施例2
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入二氯化镁4g,环氧氯丙烷7.5ml,磷酸三丁酯10.5ml,甲苯75ml,己烷8ml,乙醇6.2ml,搅拌下升温至60℃,固体完全溶解形成均一的溶液后,恒温1h;而后降温至-25℃,滴加40ml四氯化钛,滴加完毕后加入1.5g三乙基硅基异丁基胺,2g四乙氧基硅烷,反应1h后,升温至60℃恒温,己烷3ml,反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.2ml(2mmol/ml),升温至80℃后充入氢气至0.28MPa,充入乙烯至0.73MPa,加入1-辛烯40mL,恒压恒温反应2h。
实施例3
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入二氯化镁3g,环氧氯丙烷5ml,磷酸三丁酯10.5ml,甲苯75ml,乙醇5.2ml,己烷3ml,搅拌下升温至60℃,固体完全溶解形成均一的溶液后,恒温1h;而后降温至-25℃,滴加50ml四氯化钛,滴加完毕后加入2.5g三壬基硅基-2,6-二甲基苯胺,3g二乙氧基异丙氧基叔丁基硅烷,反应1h后,依次于-10℃恒温1h,0℃恒温1h,20℃恒温1h,升温至60℃恒温反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.17ml(2mmol/ml),升温至80℃后充入氢气至0.28MPa,充入乙烯至0.73MPa,加入4-甲基-1-戊烯30mL,恒压恒温反应2h。
实施例4
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO25g,甲苯75ml,降温至-25℃,滴加55ml四氯化钛,乙醇3.2ml,滴加完毕后加入1.8g二甲基环己基硅基环己胺,2ml四乙氧基硅烷,反应1h后,依次于-10℃恒温1h,0℃恒温1h,20℃恒温1h,升温至60℃恒温反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.17ml(2mmol/ml),升温至80℃后充入氢气至0.28MPa,充入乙烯至0.73MPa,加入3-甲基-1-丁烯40mL,恒压恒温反应2h。
实施例5
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入聚苯乙烯载体2g,正己烷75ml,降温至-25℃,滴加5g二氯二茂钛,滴加完毕后加入1g二甲基乙基硅基正丁基胺,0.5g四乙氧基硅烷,反应1h后,加入辛醇3.2ml,升温至80℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.5ml(2mmol/ml),升温至80℃后充入氢气至0.20MPa,充入乙烯至0.60MPa,加入异戊烯30mL,恒压恒温反应2h。
实施例6
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体2g,甲苯75ml,降温至-25℃,加入3g环戊二烯三氯化钛,再加入1.5g二甲基苯基硅基见甲基苯胺,加入辛醇3.2ml,反应1h后,加入0.5g四乙氧基硅烷,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液25ml(10%wt/v),升温至70℃后充入乙烯至0.45MPa,加入1-戊烯30mL,恒压恒温反应2h。
实施例7
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入环湖精载体2g,甲苯75ml,降温至-25℃,加入3g环戊二烯三氯化锆,再加入1.5g三甲基硅基特丁基胺,加入辛醇3.2ml,反应1h后,加入1.5g二乙氧基异丙基叔丁基硅烷,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液40ml(10%wt/v),升温至70℃后充入乙烯至0.45MPa,加入苯乙烯30mL,恒压恒温反应2h。
实施例8
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体5g,甲苯75ml,降温至-25℃,加入3g环戊二烯三氯化镱,再加入1.5g三甲基硅基特丁基胺,加入乙醇3.2ml,反应1h后,加入1.5g二乙氧基异丙基叔丁基硅烷,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液35ml(10%wt/v),升温至70℃后充入乙烯至0.25MPa,加入对甲基苯乙烯30mL,恒压恒温反应2h。
实施例9
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体3g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75ml,搅拌,加入3g乙基桥联二茚基二氯化钛,再加入1.5g三甲基硅基特丁基胺,加入乙醇3.2ml,反应1h后,加入2.5g二乙氧基异丙基叔丁基硅烷,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液15mL(10%wt/v),升温至70℃后充入乙烯0.45MPa,加入环戊烯40mL,恒压恒温反应2h。
实施例10
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体5g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75ml,搅拌,加入3g五甲基环戊二烯三氯化钛,再加入0.5g三甲基硅基特丁基胺,乙醇3.2ml,1.0g二乙氧基异丙氧基叔丁氧基硅烷,反应1h后,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液35ml(10%wt/v),升温至70℃后充入乙烯0.45MPa,加入环戊烯30mL,恒压恒温反应2h。
实施例11
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体3g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75mL,搅拌,加入3g CGC钛催化剂,再加入3.5g三苯基硅基特丁基胺,乙醇3.2ml,1.0g三乙氧基异丙氧基硅烷,反应1h后,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液25ml(10%wt/v),升温至70℃后充入乙烯0.45MPa,加入环戊烯30mL,恒压恒温反应2h。
实施例12
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO2载体3g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75ml,搅拌,加入3g水杨醛亚胺钛催化剂(F1),再加入1.0g三甲基硅基特丁基胺,乙醇3.2ml,反应1.5h后,加入1.0g三乙氧基异丙氧基硅烷,升温至60℃恒温反应4h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,MAO溶液20ml(10%wt/v),升温至70℃后充入乙烯0.45MPa,加入环戊烯25mL,恒压恒温反应2h。
实施例13
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入二氯化镁3g,环氧氯丙烷3.5ml,磷酸三丁酯5.5ml,甲苯75ml,己烷10ml,乙醇3.2ml,间甲基苯酚1g,搅拌下升温至70℃,固体完全溶解形成均一的溶液后,恒温1h;而后降温至-25℃,滴加40ml四氯化钛,滴加完毕后加入0.5g三甲基硅基特丁基胺,1g三乙氧基异丙氧基硅烷,己烷5ml,反应2h后,升温至60℃,加入己烷8ml,恒温反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.5ml(2mmol/ml),升温至85℃后充入氢气0.28MPa,充入乙烯0.45MPa,恒压恒温反应2h。
实施例14
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO23g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75ml,搅拌,加入2.5g四氯化钕,滴加完毕后加入0.5g三甲基硅基特丁基胺,乙醇3.2ml,2g四乙氧基硅烷,反应2h后,升温至60℃恒温反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.5ml(2mmol/ml),升温至85℃后充入乙烯压力至0.55MPa,加入异戊二烯30mL,恒压恒温反应2h。
实施例15
1)制备主催化剂:在经过氮气充分置换过的反应器中,依次加入SiO25g,甲苯75ml,降温至-25℃,加入2M苄基氯化镁(5mL),升温至50℃反应3h,室温用甲苯和正己烷洗至无氯离子,再加入甲苯75ml,搅拌,加入2.5g四氯化钒,滴加完毕后加入1.5g三甲基硅基特丁基胺,乙醇3.2ml,反应2h后,加入2g四乙氧基硅烷,升温至60℃恒温反应2h,停止搅拌,静置悬浮液,分层,抽除上层清液,甲苯洗涤两遍,己烷洗涤两遍,氮气吹干,得到流动性好、粒径分布窄的主催化剂组分;
2)乙烯共聚合:将0.5升不锈钢高压釜经氮气充分置换后,依次向釜中加入主催化剂组分20mg,脱水己烷200ml,AlEt3溶液1.5ml(2mmol/ml),升温至85℃后充入乙烯压力至0.55MPa,加入异戊二烯30mL,恒压恒温反应2h。
结果见表1。
表1
Claims (5)
1.一种给电子体催化剂,由主催化剂和助催化剂组成,其特征在于:所述的主催化剂由载体、过渡金属卤化物、有机醇化合物、有机硅氧烷化合物和有机硅胺组成;载体、过渡金属卤化物、有机醇化合物、有机硅氧烷化合物和有机硅胺的摩尔比为1∶(0.01-20)∶(0.1-6)∶(0.01-5)∶(0.01-5);助催化剂为有机铝化合物;主催化剂中的过渡金属卤化物与助催化剂的摩尔比为1∶(30-500);
所述的有机硅胺是选自通式为HN(R1)-SiR2R3R4的化合物中的一种或两种或两种以上的混合物,式中,R1,R2,R3或R4是碳原子数为1-20的烷基,碳原子数为3-20的环烷基或碳原子数为6-30芳基,R2,R3或R4相同或不同;
所述的助催化剂有机铝化合物选自通式为AlR5 nX3-n的化合物中一种或两种的混合,式中,R5为氢或碳原子数为1-20的烃基或烷氧基、X为卤素,n为0<n≤3的整数;
所述的载体是无机氧化物载体、卤化物载体或聚合物载体。
2.根据权利要求1所述的给电子体催化剂,其特征在于:所述的过渡金属卤化物选自通式为M(R1)4-mXm的化合物,式中,M是Ti,Zr,Hf,V,Nd,Y,Sc或Sm;X是卤原子,选自Cl,Br,F;m为0到4的整数;R1选自C1~C20的脂肪烃基、C1~C20的脂肪烷氧基、C1~C20的环戊二烯基及其衍生物、C1~C20的芳香烃基、COR`或COOR`,R`是具有C1~C10的脂肪族基或具有C1~C10的芳香基。
3.根据权利要求1所述的给电子体催化剂,其特征在于:所述的有机硅氧烷化合物是符合通式为Si(OR4)4的有机硅氧烷化合物中的一种或多种,式中,R4为碳原子数为1-15的烷基,四个R4可以相同或不同。
4.一种权利要求1所述的给电子体催化剂的制备方法,其特征在于:包括以下步骤:
1)将载体在10-150℃,分散于有机溶剂中,再加入有机醇化合物;
2)在-40-30℃下,向步骤1)中得到的溶液中加入过渡金属卤化物,滴加完毕后加入有机硅氧烷化合物和有机硅胺,并升温至40-110℃,反应0.5-24小时,在升温过程中,固体物逐渐析出并形成颗粒,反应结束后,采用甲苯或正己烷洗涤4-6次,过滤,真空抽干,得到主催化剂组分;
3)将主催化剂和助催化剂按助催化剂与过渡金属卤化物的摩尔比为(30-500)∶1混合,得到烯烃聚合催化剂。
5.一种权利要求1所述的给电子体催化剂应用,其特征在于:用于催化乙烯聚合的催化剂或催化乙烯与1-丁烯、1-己烯、1-辛烯、1-癸烯、3-甲基-1-丁烯、环戊烯、4-甲基-1-戊烯、1,3-丁二烯、异戊二烯、苯乙烯、甲基苯乙烯、降冰片烯或取代降冰片烯聚合。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102382217A (zh) * | 2011-08-30 | 2012-03-21 | 浙江大学 | 分子量可调的双峰或宽峰分布聚乙烯的制备方法 |
CN102464734A (zh) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | 烯烃聚合催化剂及其制备方法和烯烃聚合的方法 |
CN105985490A (zh) * | 2015-02-16 | 2016-10-05 | 中国石油天然气股份有限公司 | 耐热聚乙烯共聚物的制备方法及耐热聚乙烯共聚物、管材 |
CN114174356A (zh) * | 2019-07-31 | 2022-03-11 | 陶氏环球技术有限责任公司 | 用于产生高分子量聚乙烯的聚合催化剂 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969332A (en) * | 1973-08-21 | 1976-07-13 | Ethylene Plastique | Polymerization of ethylene |
JPS5792009A (en) * | 1980-11-29 | 1982-06-08 | Mitsubishi Petrochem Co Ltd | Solid catalytic component for polymerizing olefin |
US4395360A (en) * | 1980-04-22 | 1983-07-26 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
CN101845104A (zh) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | 烯烃聚合催化剂及其制备方法 |
-
2010
- 2010-07-14 CN CN2010102314039A patent/CN101885795B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969332A (en) * | 1973-08-21 | 1976-07-13 | Ethylene Plastique | Polymerization of ethylene |
US4395360A (en) * | 1980-04-22 | 1983-07-26 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
JPS5792009A (en) * | 1980-11-29 | 1982-06-08 | Mitsubishi Petrochem Co Ltd | Solid catalytic component for polymerizing olefin |
CN101845104A (zh) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | 烯烃聚合催化剂及其制备方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464734A (zh) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | 烯烃聚合催化剂及其制备方法和烯烃聚合的方法 |
CN102382217A (zh) * | 2011-08-30 | 2012-03-21 | 浙江大学 | 分子量可调的双峰或宽峰分布聚乙烯的制备方法 |
CN102382217B (zh) * | 2011-08-30 | 2013-05-08 | 浙江大学 | 分子量可调的双峰或宽峰分布聚乙烯的制备方法 |
CN105985490A (zh) * | 2015-02-16 | 2016-10-05 | 中国石油天然气股份有限公司 | 耐热聚乙烯共聚物的制备方法及耐热聚乙烯共聚物、管材 |
CN114174356A (zh) * | 2019-07-31 | 2022-03-11 | 陶氏环球技术有限责任公司 | 用于产生高分子量聚乙烯的聚合催化剂 |
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