CN113880881B - 一种刚性有机膦配体的合成及其在乙烯齐聚中的应用 - Google Patents
一种刚性有机膦配体的合成及其在乙烯齐聚中的应用 Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000005977 Ethylene Substances 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 45
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 27
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- KKQDIUNZFJXUNS-UHFFFAOYSA-L chromium(2+) oxolane dichloride Chemical compound [Cl-].[Cl-].[Cr++].C1CCOC1.C1CCOC1 KKQDIUNZFJXUNS-UHFFFAOYSA-L 0.000 claims description 2
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims description 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 30
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- 239000000047 product Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
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- 239000006227 byproduct Substances 0.000 abstract description 4
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
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- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
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- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
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- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
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Abstract
本发明属于乙烯四聚反应技术领域，具体涉及一种刚性有机膦配体的合成及其在乙烯齐聚中的应用。所述刚性有机膦配体结构式如下：；上述刚性有机膦配体作为乙烯四聚催化剂的配体，在催化过程中能有效构成双金属中心提高1‑辛烯的选择性，同时可有效抑制聚乙烯副产物的生成。该催化剂催化乙烯齐聚时，具有催化剂活性高、产物中1‑辛烯选择性高、聚乙烯副产物少等优点。
Description
技术领域
本发明属于乙烯四聚反应技术领域，具体涉及一种刚性有机膦配体的合成及其在乙烯齐聚中的应用。
背景技术
1-辛烯作为一种重要的有机单体，在合成高聚物、高性能润滑油和洗涤剂方面有着广阔的应用，目前尽管1-辛烯的价值是众所周知的，但本领域目前并未像乙烯三聚生产1-己烯一样以高选择性生产1-辛烯。传统的1-辛烯生产方法是乙烯齐聚法，乙烯齐聚技术按照Schulz-Flory分布，不仅得到1-辛烯产品，同时还有其他α-烯烃及少量固体高聚物，而且目的产物1-辛烯的选择性很低，由于在工艺末端需连续精馏才能要得到纯净的1-辛烯，需消耗大量的能量。乙烯选择性齐聚是与非选择性齐聚相反的一种制备α烯烃的工艺，该类工艺选择性地生成一到两种α烯烃，目前乙烯二聚制备1-丁烯、三聚制备1-己烯均已实现工业化。在乙烯选择性四聚方面，已有大量的专利。如中石化申请的专利CN102040624B、CN102451759B、CN103100420A、CN105268480B、CN105498840B、CN105562095B、CN105562101B、CN105562102B、CN105562103B、CN105566037B、CN107282128B；中石油的CN103285926 A、迈瑞尔公司的CN110801864 A；Sasol公司的US10539517、US10538088、US11629533、US11993396等均公开使用铬化合物/配体/助剂催化剂体系进行乙烯选择性齐聚，产物中1-辛烯选择性可大于70％。从上述分析可知，乙烯四聚制备1-辛烯技术的关键在于选择合适的配体提供合适的给电子能力和空间构型，从而有利于1-辛烯的合成。但是当前的主流技术是使用SASOL公司披露的PNP(bis(diarylphosphino)-amine)或者类似衍生物作为配体(US7511183)与有机铬以及MAO形成乙烯四聚催化剂体系，且大量专利已披露了各种配体的合成技术。现有技术绝大部分发明均是基于Sasol公司(US10539517)发明的PNP型配体进行的部分改进，没有非常大的创新点。且PNP型配体极易吸水失活，且实验过程中会形成较多聚合物，不利于长周期运行。
发明内容
本发明目的在于提供一种刚性有机膦配体的合成方法及其在乙烯四聚中的应用，本发明要求保护的上述刚性有机膦配体作为乙烯四聚催化剂的配体，在催化过程中能有效构成双金属中心提高1-辛烯的选择性，同时可有效抑制聚乙烯副产的生成。该催化剂催化乙烯齐聚时，具有催化剂活性高、产物中1-辛烯选择性高、聚乙烯副产物少等优点。
为实现上述目的，本发明采用如下技术方案：
所述刚性有机膦配体，结构式如下：
所述刚性有机膦配体的合成方法分为两步，其中步骤(1)：通过正丁基锂夺取芴上的活泼氢与多聚甲醛发生亲核反应，接着与二苯基氯化磷(PPh2Cl)
反应获得单齿膦配体；步骤(2)：单齿膦配体以进一步在正丁基锂的作用下与PPh2Cl反应获得刚性双齿膦化合物。
进一步地，所述刚性有机膦配体在乙烯四聚催化剂中的应用，其中该乙烯四聚催化剂还包括过渡金属化合物以及烷基铝助催化剂。
所述烷基铝助催化剂为甲基铝氧烷、三乙基铝、三甲基铝中的一种；
所述过渡金属化合物选自铬化合物、钼化合物、铁化合物、钛化合物、锆化合物和镍化合物中的至少一种，优选为乙酰丙酮铬、异辛酸铬、三(四氢呋喃)三氯化铬或二(四氢呋喃)二氯化铬中的至少一种；
所述烷基铝助催化剂与催化剂中金属的摩尔比100:1～1000:1；
所述刚性有机膦配体与催化剂中金属的摩尔比0.01:1～100:1；优选为0.1:1～10:1；
所述刚性有机膦配体进行烯齐聚反应，优选在有机溶剂，更优选在烷烃溶剂中进行乙烯齐聚反应；
在所述乙烯齐聚反应中，反应温度为0-200℃，优选为30-100℃；乙烯压力为0.1-20.0MPa，优选为0.5-6.0MPa；反应时间0.5～4h；
所述刚性有机膦配体存在下进行乙烯三聚和/或四聚反应，优选在有机溶剂、更优选在烷烃中进行乙烯三聚和/或四聚反应；
所述刚性有机膦配体在乙烯四聚中的应用，具体方法包括以下步骤：
(1)反应前先将反应釜釜体和内衬置于烘箱中120℃烘干过夜，连接到评价体系，密封，抽真空条件下加热至100℃恒温1h(尾气阀关闭)，除去残留的水、氧和含氧杂质。然后温度设置为反应温度，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气已被置换干净。然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯。
(2)打开尾气阀，在搅拌条件下使用注射器依次注入环己烷溶剂和一定量助催化剂，待温度稳定至反应温度后，用注射器注入过渡金属化合物和刚性有机膦配体，关闭尾气阀，调节减压阀，待压力升至预定压力值后开始计时，并记录质量流量计数据，加入烷基铝助剂，反应一定时间后关闭乙烯气体，记录质量流量计数据，反应停止，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。
(3)开启反应釜后，尽快称量液体和固体总重，在注射器中塞入适量石英棉，取1～2ml液体样品过滤后转移至样品瓶，放至GC-MS上分析产物组分和比例。将剩余样品过滤，滤纸提前称量并记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所有聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得纯质量。通过MS可以标定液体产物组成。结合液体和固体总重，固体质量和GC结果可计算各组分选择性，结合催化剂使用量可计算催化剂活性。
本发明的显著优点在于：
(1)首次使用刚性有机配体作为四聚催化剂的配体与金属中心构成催化剂体系用于乙烯选择性齐聚反应；
(2)产物中1-辛烯选择性高；
(3)产物中聚乙烯含量极少。
附图说明
图1目标产物有机膦配体的核磁氢谱(1H NMR)。
具体实施方式
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。
实施例刚性有机膦配体的合成：
1)在6mL的无水乙醚溶剂中，加0.5013g的芴配成溶液，然后在0℃下加入0.2127g的正丁基锂(n-BuLi)，最后将所得的混合物搅拌30min后，再加入5mL含有0.6641g的PPh2Cl的Et2O溶液得到悬浮液。将所得悬浮液搅拌20h后，再将黄色的悬浮液在真空下干燥，并将获得的固体在0℃下用甲醇洗涤，并真空干燥，得到0.95g，产率为90％的黄色粉末，其为芴结构的单齿膦配体。
2)在0℃下，向6mL的THF中加入0.3920g芴结构的单齿膦配体配成溶液，然后加入0.0801g的正丁基锂，将混合物搅拌30min后，然后再加5mL含有0.2758g PPh2Cl的THF溶液，并且搅拌18h，然后再真空下干燥。将所得的橘红色油在0℃下用甲醇洗涤，并在真空下干燥，得到0.52g，0.97mmol的芴结构的双齿膦配体，其产率为86％，形状为黄色粉末，最后通过THF/己烷重结晶获得橙色晶体。
应用例
乙烯齐聚反应在300mL高压反应釜中进行。反应前先将反应釜釜体置于烘箱中120℃烘干过夜，连接到评价体系，密封，抽真空条件下加热至100℃恒温1h(尾气阀关闭)，除去残留的水、氧和含氧杂质。然后将温度设置为反应温度，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气已被置换干净。然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯。打开尾气阀，在搅拌条件下使用注射器依次注入90mL环己烷溶剂、一定量甲基铝氧烷(甲基铝氧烷为1.5mol/L的甲苯溶液)和一定量的刚性有机膦配体溶液，待温度稳定至设定温度后，将过渡金属溶液注入反应釜中,随后再用10mL的环己烷洗注射器，确保全部催化剂组分已注入到反应器中。搅拌3～5min后，关闭尾气阀，调节减压阀，待压力升至设定压力后开始计时，反应一定时间后关闭乙烯气体，记录质量流量计数据，反应停止，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。开启反应釜后，尽快称量液体和固体总重，在注射器中塞入适量石英棉，取1～2ml液体样品过滤后转移至样品瓶，放至GC-MS上分析产物组分和比例。将剩余样品过滤，滤纸提前称量并记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所有聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得纯质量。通过MS可以标定液体产物组成。结合液体和固体总重，固体质量和GC结果可计算各组分选择性，结合催化剂使用量可计算催化剂活性。应用例1～4和对比例中相关反应条件汇总于表1。
表1实施例反应条件汇总表
表2本发明实施例和对比例乙烯齐聚活性和产物分布。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (5)
1.一种刚性有机膦配体在乙烯四聚催化剂中的应用，其特征在于：所述乙烯四聚催化剂还包括过渡金属化合物以及助催化剂；所述助催化剂为甲基铝氧烷；所述过渡金属化合物为乙酰丙酮铬、异辛酸铬、三(四氢呋喃)三氯化铬或二(四氢呋喃)二氯化铬中的至少一种；
所述刚性有机膦配体结构式如下：
式（1） 。
2.根据权利要求1所述的刚性有机膦配体在乙烯四聚催化剂中的应用，其特征在于：所述助催化剂与乙烯四聚催化剂中金属的摩尔比100:1~1000:1。
3.根据权利要求1所述的刚性有机膦配体在乙烯四聚催化剂中的应用，其特征在于：所述刚性有机膦配体与乙烯四聚催化剂中金属的摩尔比0.01:1~100:1。
4.根据权利要求1所述的刚性有机膦配体在乙烯四聚催化剂中的应用，其特征在于：所述刚性有机膦配体进行乙烯齐聚反应，选择在烷烃溶剂中进行乙烯齐聚反应。
5.根据权利要求4所述的刚性有机膦配体在乙烯四聚催化剂中的应用，其特征在于：在乙烯齐聚反应中，反应温度为0-200℃，乙烯压力为0 .1-20 .0MPa，反应时间0.5~4h。
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