CN112892602B - 一种含膦多孔有机聚合物负载型催化剂及其制备方法和应用 - Google Patents
一种含膦多孔有机聚合物负载型催化剂及其制备方法和应用 Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 32
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 14
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- -1 tri (3-vinyl benzene) phosphine Chemical compound 0.000 claims description 13
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052703 rhodium Inorganic materials 0.000 claims description 5
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- MDKPNSFXRWKCOH-UHFFFAOYSA-N tris(3-ethenylphenyl)phosphane Chemical compound C=Cc1cccc(c1)P(c1cccc(C=C)c1)c1cccc(C=C)c1 MDKPNSFXRWKCOH-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
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- IETKMTGYQIVLRF-UHFFFAOYSA-N carbon monoxide;rhodium;triphenylphosphane Chemical compound [Rh].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IETKMTGYQIVLRF-UHFFFAOYSA-N 0.000 claims description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 abstract description 26
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 19
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 16
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- 239000007983 Tris buffer Substances 0.000 description 9
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
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- 229910052741 iridium Inorganic materials 0.000 description 3
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- 239000000178 monomer Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000008300 phosphoramidites Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- UOYOTHRZSRWQNP-UHFFFAOYSA-N (2-ethenylphenyl)-diphenylphosphane Chemical compound C=CC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UOYOTHRZSRWQNP-UHFFFAOYSA-N 0.000 description 1
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- GEKRISJWBAIIAA-UHFFFAOYSA-N 5-methylhexanal Chemical compound CC(C)CCCC=O GEKRISJWBAIIAA-UHFFFAOYSA-N 0.000 description 1
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- SKWRXFAMSFJQRS-UHFFFAOYSA-N carbon monoxide;cobalt Chemical compound [Co].[O+]#[C-].[O+]#[C-] SKWRXFAMSFJQRS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UVEWQKMPXAHFST-SDNWHVSQSA-N chembl1256376 Chemical group C=1C=CC=CC=1/C=N/C1=CC=CC=C1 UVEWQKMPXAHFST-SDNWHVSQSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
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Abstract
本发明公开了一种多级孔结构含膦多孔有机聚合物负载型催化剂及其在1‑辛烯生产中的应用,所述多相催化剂中以金属Rh、Ru、Ir的一种或多种作为活性组分,以多级孔结构含膦多孔有机聚合物作为载体,含膦有机聚合物由单齿有机磷配体自聚而成。此类配位键型多相催化剂适用于固定床,浆态床,鼓泡床和滴流床等反应器中。本发明提供的多相催化剂在1‑辛烯氢甲酰化制备壬醛生产中具有很好的表现,能够生产高正异比的壬醛,正异比可达10以上,该多相催化剂稳定性好,催化剂与反应物、产品的分离简单而且高效。
Description
技术领域
本发明属于多相催化及精细化工领域,具体涉及一种含膦多孔有机聚合物负载型催化剂及其制备方法和其在1-辛烯氢甲酰化生产壬醛反应中的应用。
背景技术
近年来,原子经济反应成为绿色化学研究的热点之一。烯烃氢甲酰化反应属于典型的原子经济反应,是指烯烃与CO和H2在催化剂的作用下生成醛的反应,原料分子中的原子100%转化成产物,废物零排放。
烯烃氢甲酰化反应的产品是比烯烃多一个碳原子的醛,其中正构醛因其较大的后续加工潜能而成为大多数氢甲酰化反应的目标产物,因此,正构醛和异构醛的比例(称为正异比)是衡量催化剂催化性能的一个重要指标。为了提高醛的正异比,工业氢甲酰化反应中普遍采用具有较高的反应活性和正构醛选择性的端烯烃为原料。
辛烯氢甲酰化反应是研究的较为广泛的一个均相催化反应,其产品正、异壬醛在常温下均为无色液体,具有强烈的香气。正壬醛是具有较高附加值的化学品,主要用作调制香料、精油及食用香精。异壬醛的重要性不及正壬醛,但也可用于调制香精及食用香精。壬醛的生产方法主要为壬醇脱水或壬酸还原。目前,工业生产壬醛的技术路线大多采用壬醇脱水法。该方法生产成本高,耗能大,且产物正异比较低,有很大局限性。
专利CN1319580A叙述了具有较大空间位阻的多种二齿亚磷酸酯配体,这些配体与Rh和Co等配位均相催化剂的高碳烯烃的氢甲酰化反应,具有较高醛正异比的选择性。但是均相催化剂不易回收且配体合成较为困难。
专利CN108794527A报道了一种将亚磷酸脂与二苯基膦连接在N-苄叉苯胺骨架上的双膦配体,此配体与Rh络合物配位催化1-戊烯氢甲酰化具有较高的直链醛选择性,但是反应为均相反应,催化剂不易回收且配体合成较为困难。
专利CN109942750A中利用乙烯基化双齿亚磷酰胺配体和三(4-乙烯基苯)基膦自聚,而后浸渍乙酰丙酮羰基佬,形成负载型催化剂,用于在己烯的氢甲酰化反应中,正庚醛和异庚醛摩尔比大于40,且催化剂可回收循环利用,但是乙烯基化双齿亚磷酰胺配体合成难度大、产率低,不利于放大生产,没有工业应用前景。
发明内容
为了解决上述问题,本发明的目的在于提供一种易于合成且具有高选择性含膦有机聚合物负载型催化剂及其在壬醛生产中的应用。
本发明的技术方案为:
一种含膦有机聚合物负载型催化剂,以金属Rh、Co或Ir中的一种、两种、三种作为活性组分,以含膦有机聚合物为载体,催化剂中金属担载量为0.01~10wt%,含膦有机聚合物由含有烯烃基的单齿有机膦配体自聚而成。
所述的烯烃基优选为乙烯基,所述的含有烯烃基的单齿有机膦配体为含乙烯基的三苯基膦配体。
所述的有机聚合物载体具有多级孔结构,比表面积为100~3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1~5.0cm3/g,孔径分布在0.2~50.0nm。
所述的多相催化剂是将多齿有机膦配体和单齿有机膦配体混合后,采用溶剂热聚合法,经自由基引发剂引发有机膦配体中的烯烃基发生聚合反应,生成具有多级孔结构含膦有机聚合物作为载体,活性组分的前驱体与载体在有机溶剂中搅拌,活性组分与含膦有机聚合物载体中裸露的P形成多重配位键,蒸去挥发性溶剂后,得到配位键型的多相催化剂。
多相催化剂的制备方法为:
a)在273~473K,惰性气体气氛下,在有机溶剂中,加入单齿有机膦配体、添加或不添加交联剂、再加入自由基引发剂,混合后,将混合物搅拌0.1~100小时,优选的搅拌时间范围为0.1~50小时;
b)将步骤a)制得的混合溶液转移至合成高压釜中,273~473K,惰性气体气氛下,采用溶剂热聚合法,静置1~100小时进行聚合反应,得到一种含膦有机聚合物;
c)将步骤b)得到的聚合物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有裸露P的有机聚合物,即所述多相催化剂的载体;
d)在273~473K,惰性气体气氛下,在含有活性组分前驱体的溶剂中,加入步骤c)得到的有机聚合物载体,搅拌0.1~100小时,优选搅拌时间范围0.1~50小时,之后,真空抽除有机溶剂,得到多相催化剂。
步骤a)中所述的有机溶剂为苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上;所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯、二甲氧基甲烷、二碘甲烷、多聚甲醛或1,3,5-三乙炔基苯中的一种或两种以上;所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。
步骤a)中所述的单齿有机膦配体,在交联剂添加的情况下,单齿有机膦配体与交联剂的摩尔比为0.01:1~10:1,单齿有机膦配体与自由基引发剂的摩尔比为300:1~10:1,聚合成有机聚合物前,单齿有机膦配体在有机溶剂中的浓度范围为0.01-1000g/L。
步骤d)中所述的溶剂为水、苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上,所述的活性组分为Rh、Co、Ir中的一种、两种或三种,其中Rh的前驱体为Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3;Co的前驱体为Co(CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2;Ir的前驱体为Ir(CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4。催化剂中金属担载量范围为0.1~0.3wt%。
惰性气体为氮气、氩气、氦气中的一种或二种以上。
一种多相催化剂在壬醛生产中的应用,反应过程为将制备得到的催化剂装入反应器中,通入反应混合气,混合气的主要组分为H2和CO,H2+CO的体积含量为20~70%,剩余组成为惰性气体,H2/CO体积比为0.5~5.0,原料辛烯纯度为20~98%,反应温度323~573K,反应压力0.1~10.0MPa,气体空速100~20000h-1,液时空速0.01~10.0h-1条件下进行氢甲酰化反应,所述的反应器为固定床,浆态床,滴流床或鼓泡床反应器。
本发明的反应原理:
本发明将典型的单齿膦配体比如三苯基膦的芳环上引入乙烯基(Vinyl)基团,即一种含有乙烯基的单齿有机膦配体(Vinyltriphenylphosphine)作为聚合单体,在高压釜中利用溶剂热聚合法,聚合形成具有高表面积和多级孔道结构的有机聚合物,由于该有机聚合物骨架中具有大量暴露含有孤对电子的P,可作为催化剂载体与活性过渡金属离子空轨道形成多重配位键,进而形成催化活性位。在该催化剂中,有机膦聚合物同时具备载体和配体的双重功能,活性金属组分高分散于该载体中,与高浓度裸露P形成多重配位键。活性金属组分以单原子形式高分散于有机膦聚合物载体中,大大提高了金属的利用效率。且活性组分不易流失,催化剂寿命长,骨架中的膦配体具有显著的立体效应,制备出来的催化剂可显著提高产物的立体选择性。
本发明所提供的催化剂有机聚合物载体骨架中含有P,有机聚合物兼具配体和载体的双重功能;活性金属组分能够以单原子或离子的方式分散在这种大表面积多级孔结构有机聚合物载体中,大大提高了金属利用效率。载体有机膦聚合物骨架中的单膦配体结构单元使聚合物具有较高P浓度,容易与活性金属组分形成二重或多重金属-P配位键,该配位键具有较强的化学键合能力,使得活性组分不易流失。
本发明的有益效果为:
本发明所述的多相催化剂骨架中含有单齿有机膦配体结构单元,其中聚合物的表面上存在较高裸露的P,活性金属原子或离子与聚合物上的裸露P形成多重配位键,活性组分不易流失,催化剂的活性组分为Rh、Co或Ir,此类催化剂具有较高的立体选择性,聚合物具有高比表面积多级孔结构,具备载体和配体的双重功能,活性金属组分可能以单原子形式高分散于有机膦聚合物载体孔道中或表面上,提高了金属组分的利用效率。
此类配位键型多相催化剂适用于固定床,浆态床,鼓泡床和滴流床等反应工艺,本发明所提供的辛烯氢甲酰化反应生产壬醛的方法,能够显著提高烯烃的转化率和正构醛的选择性,可以解决烯烃氢甲酰化反应多相化过程中长期存在的稳定性和选择性差,以及金属组分流失严重等问题。同时这种辛烯氢甲酰化反应生产的壬醛具有较高的正异比,降低了辛烯氢甲酰化工业生产的成本,催化剂稳定性好,反应物和产品与催化剂的分离简单而且高效,为辛烯氢甲酰化生产壬醛提供了新的工业化技术。
附图说明
图1中,A图为典型的烯烃基功能化的单膦配体,B图为三(3-乙烯基苯)基膦结构示意图。
图2是三(3-乙烯基苯)基膦聚合技术路线示意图。
图3是具有对高碳烯烃较高选择性的典型的单齿有机膦配体及交联剂的示意图,其中,L1-L13为单齿有机膦配体,L14-L16为交联剂。
图4为三(3-乙烯基苯)基膦配体的1H谱。
图5为三(3-乙烯基苯)基膦配体的13C谱。
图6为三(3-乙烯基苯)基膦配体的31P谱。
图7为N2氛围下实施例1合成的催化剂热重曲线。
具体实施方式
下述实施例对本发明进行更好的说明,但不限制本发明所要保护的范围。
实施例1
在298K和惰性气体保护氛围下,将10.0克三(3-乙烯基苯)基膦加入300mL四氢呋喃中,向上述溶液中加入1.0克自由基引发剂偶氮二异丁腈,搅拌2小时。将搅拌好的溶液移至高压釜中,于393K和惰性气体保护氛围下利用溶剂热聚合法进行聚合24h。待上述聚合后的溶液冷却至室温,室温条件真空抽走溶剂,即得到由三(3-乙烯基苯)基膦有机单体自聚的有机膦聚合物载体。图2为三(3-乙烯基苯)基膦聚合技术路线示意图。称取6.28毫克乙酰丙酮二羰基铑溶于100.0ml四氢呋喃溶剂中,加入1.0克由三(3-乙烯基苯)基膦自聚得到的有机聚合物载体,将此混合物在298K和惰性气体保护氛围下搅拌24小时,然后在室温条件下真空抽走溶剂,即获得应用于辛烯氢甲酰化的多相催化剂。
实施例2
在实施例2中,除了称取0.1克自由基引发剂偶氮二异丁腈替代1.0克自由基引发剂偶氮二异丁腈外,其余的催化剂合成过程与实施例1相同。
实施例3
在实施例3中,除了用50.0ml四氢呋喃溶剂替代100.0ml四氢呋喃溶剂外,其余的催化剂合成过程与实施例1相同。
实施例4
在实施例4中,除了用100.0ml二氯甲烷溶剂替代100.0ml四氢呋喃溶剂外,其余的催化剂合成过程与实施例1相同。
实施例5
在实施例5中,除了用373K聚合温度替代393K聚合温度外,其余的催化剂合成过程与实施例1相同。
实施例6
在实施例6中,除了用12h聚合时间替代24h聚合时间外,其余的催化剂合成过程与实施例1相同。
实施例7
在实施例7中,除了再加入10.0克L20作为交联剂外,其余的催化剂合成过程与实施例1相同。
实施例8
在实施例8中,除了再加入1.0克苯乙烯作为交联剂外,其余的催化剂合成过程与实施例1相同。
实施例9
在实施例9中,称取3.14毫克乙酰丙酮二羰基铑溶于10.0ml四氢呋喃溶剂外,其余的催化剂合成过程与实施例1相同
实施例10
在实施例10中,称取28.2毫克乙酰丙酮二羰基钴替代乙酰丙酮二羰基铑溶于10.0ml四氢呋喃溶剂外,其余的催化剂合成过程与实施例1相同。
实施例11
在实施例11中,称取4.1毫克乙酰丙酮二羰基铱替代乙酰丙酮二羰基铑溶于10.0ml四氢呋喃溶剂外,其余的催化剂合成过程与实施例1相同。
实施例12
在实施例12中,将实施例1中的三(3-乙烯基苯)基膦替换为三(4-乙烯基苯)基膦,其余条件同实施例1。
将上述制备的催化剂0.5g装入到固定床反应器中,两端装入石英砂。通入反应混合气(H2:CO=1:1)与液体原料1-辛烯,在393K,1.0MPa,反应混合气空速2000h-1条件下进行氢甲酰化反应。
反应经收集罐收集。所获得产物采用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用正丁醇作内标。经水吸收后反应尾气采用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析。反应结果列于表1。
表1实施例1-12中合成的催化剂比表面积和辛烯反应数据
*实验条件为120℃,1MPa,配气(CO:H2=1:1)空速2000h-1,TOF计算时认为所有的金属均是活性位点。**表示反应温度为230℃,实施例9的活性组分为Co,实施例10的活性组分为Ir。实施例12的聚合物载体为三(4-乙烯基苯)基膦单体自聚成的聚合物。实施例10、11、12为对比例。
结果表明,具有间位乙烯基的三苯基膦聚合物,负载乙酰丙酮二羰基铑后制得的催化剂,对辛烯氢甲酰化生产壬醛反应的活性,产物正异比选择性优于对比例中催化剂,具有较好的应用前景。
Claims (10)
1.一种含膦多孔有机聚合物负载型催化剂,其特征在于:
所述催化剂以金属Rh、Ru的一种或二种作为活性组分,以三(3-乙烯基苯)基膦自聚的聚合物为载体:
催化剂中金属担载量范围为0.1-0.5wt%;
所述的负载型催化剂是将单齿有机膦配溶解后,采用溶剂热聚合法,经三(3-乙烯基苯)基膦自聚的聚合物作为载体,活性组分的前驱体与载体在有机溶剂中搅拌,活性组分与含膦多孔有机聚合物载体中裸露的P形成多重配位键,蒸去挥发性溶剂后,得到配位键型的多相催化剂。
2.按照权利要求1所述的负载型催化剂,其特征在于:所述的多孔有机聚合物载体具有多级孔结构,比表面积为100-1000m2/g,同时含有大孔、中孔和微孔,孔容为0.1-5.0cm3/g,孔径分布在0.2-50.0nm。
3.一种权利要求1-2任一所述的负载型催化剂的制备方法,其特征在于:所述的负载型催化剂是将单齿有机膦配溶解后,采用溶剂热聚合法,经三(3-乙烯基苯)基膦自聚的聚合物作为载体,活性组分的前驱体与载体在有机溶剂中搅拌,活性组分与含膦多孔有机聚合物载体中裸露的P形成多重配位键,蒸去挥发性溶剂后,得到配位键型的多相催化剂。
4.按照权利要求3所述的负载型催化剂的制备方法,其特征在于:
a)在273-473 K,惰性气体气氛下,在有机溶剂中,加入三(3-乙烯基苯)基膦、添加或不添加交联剂、再加入自由基引发剂,混合后,将混合物搅拌0.1-100小时;
b)将步骤a)制得的混合溶液转移至合成高压釜中,273-473K,惰性气体气氛下,采用溶剂热聚合法,静置1-100小时进行聚合反应,得到一种含膦多孔有机聚合物;
c)将步骤b)得到的聚合物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有裸露P的有机聚合物,即所述多相催化剂的载体;
d)在273-473K,惰性气体气氛下,在含有活性组分前驱体的溶剂中,加入步骤c)得到的有机聚合物载体,搅拌0.1-100小时,之后,真空抽除有机溶剂,得到多相催化剂。
5.按照权利要求3所述的负载型催化剂的制备方法,其特征在于:
a)在298-323 K,惰性气体气氛下,在有机溶剂中,加入三(3-乙烯基苯)基膦、添加或不添加交联剂、再加入自由基引发剂,混合后,将混合物搅拌0.1-10小时;
b)将步骤a)制得的混合溶液转移至合成高压釜中, 353-423 K,惰性气体气氛下,采用溶剂热聚合法,静置5-48小时进行聚合反应,得到一种含膦多孔有机聚合物;
c)将步骤b)得到的聚合物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有裸露P的有机聚合物,即所述多相催化剂的载体;
d)在298-323K,惰性气体气氛下,在含有活性组分前驱体的溶剂中,加入步骤c)得到的有机聚合物载体,搅拌5-48小时之后,真空抽除有机溶剂,得到多相催化剂。
6.按照权利要求4所述的制备方法,其特征在于:步骤a)中所述的有机溶剂为苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上;所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯、二甲氧基甲烷、二碘甲烷、多聚甲醛或1,3,5-三乙炔基苯中的一种或两种以上;所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。
7.按照权利要求4所述的制备方法,其特征在于:步骤a)中所述的单齿有机膦配体在交联剂添加的情况下,单齿有机膦配体与交联剂的摩尔比为0.01:1-10:1,单齿有机膦配体与自由基引发剂的摩尔比为300:1-10:1,聚合成有机聚合物前,单齿有机膦配体在有机溶剂中的浓度范围为0.01-1000g/L。
8.按照权利要求4所述的制备方法,其特征在于:步骤a)中所述的单齿有机膦配体在交联剂添加的情况下,单齿有机膦配体与交联剂的摩尔比为0.1:1-1:1,单齿有机膦配体与自由基引发剂的摩尔比为150:1-50:1,聚合成有机聚合物前,单齿有机膦配体在有机溶剂中的浓度范围为5-100g/L。
9.按照权利要求5所述的制备方法,其特征在于:步骤d)中所述的溶剂为水、苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上,所述的活性组分为Rh,其中Rh的前驱体为Rh(CH3COO)2、RhH(CO)(PPh3)3 、Rh(CO)2(acac)、RhCl3。
10.按照权利要求9所述的制备方法,其特征在于:催化剂中金属担载量范围为0.1-0.3wt%。
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