CN113399000B - 一种催化剂及其制备方法、催化剂组合物,及环氧化合物制备直链醇的方法 - Google Patents
一种催化剂及其制备方法、催化剂组合物,及环氧化合物制备直链醇的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 239000004593 Epoxy Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical compound C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 230000035484 reaction time Effects 0.000 claims description 7
- 150000003003 phosphines Chemical class 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000543 intermediate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000007142 ring opening reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 description 4
- HTXWKZDRDRFVHN-UHFFFAOYSA-N 2-methyloxiran-2-ol Chemical compound CC1(O)CO1 HTXWKZDRDRFVHN-UHFFFAOYSA-N 0.000 description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- OJOZHRCRUJKPIJ-UHFFFAOYSA-N magnesium;2,2,2-trifluoroacetic acid Chemical compound [Mg].OC(=O)C(F)(F)F OJOZHRCRUJKPIJ-UHFFFAOYSA-N 0.000 description 3
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FVCDMHWSPLRYAB-UHFFFAOYSA-N 2-ethenyl-2-methyloxirane Chemical compound C=CC1(C)CO1 FVCDMHWSPLRYAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WDIIYWASEVHBBT-UHFFFAOYSA-N di(propan-2-yl)phosphane Chemical compound CC(C)PC(C)C WDIIYWASEVHBBT-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 1
- VFRSADQPWYCXDG-LEUCUCNGSA-N ethyl (2s,5s)-5-methylpyrrolidine-2-carboxylate;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCOC(=O)[C@@H]1CC[C@H](C)N1 VFRSADQPWYCXDG-LEUCUCNGSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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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
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- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
Description
技术领域
本发明涉及催化剂及有机合成领域,具体涉及催化环氧化合物制备直链醇的催化剂及制备直链醇的方法。
背景技术
环氧化合物最主要的应用是通过开环反应制备醇,这些醇通常应用于聚氨酯及各种香料酯。在一些聚酯应用中,由于产品需要有高强度的特性,因此需要聚合物具有较低的支化度来增强结晶性能;从而需要高线性度的醇来充当单体,对于不对称环氧化合物的开环通常很难控制其开环方向,得到高选择性的直连醇。
专利CN110922478A利用KOH为催化剂通过微波加热的方法得到线性醇,但此方法得到的线性产率不高、且难以工业化生产,因此目前急需一中可应用于大规模生产的且具有高线性选择性的催化剂。
发明内容
为克服现有技术中存在的上述缺陷,本发明的目的是提供一种用于催化环氧化合物开环制备直链醇的催化剂及催化剂组合物,具有高反应活性和直链选择性。
本发明的另一目的是提供一种环氧化合物制备直链醇的方法,工艺步骤简单高效。
为解决以上技术问题,本发明提供以下技术方案:
一种用于催化环氧化合物制备直链醇的催化剂,其结构式为其中R1、R2为H、芳基或C1-C8的烷基;R2与R1相同或不同,优选的为C1-C4的烷基、苯基,进一步优选R1、R2相互独立的选自甲基、乙基、丙基、异丙基、丁基、异丁基、苯基。
一种制备本发明所述催化剂的方法,包括以下步骤:
(2)中间体与ZnCl2反应生成所述催化剂。
反应方程式示意如下:
本发明所述步骤(1)中,二取代基膦的加入量为二乙烯基硅烷摩尔量的2.0-6.0倍,优选为2.5倍-3.5倍。
本发明所述偶氮类催化剂选自偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈中的一种或多种,优选为偶氮二异丁腈。
本发明所述偶氮类催化剂的加入量为二乙烯基硅烷摩尔量的0.01-0.2倍,优选为0.05-0.1倍。
本发明所述步骤(1)的反应温度为60-140℃,优选的为90-120℃;反应时间为0.5h-5h,优选的为1h-2.5h。
本发明所述步骤(2)中,ZnCl2的加入量为二乙烯基硅烷摩尔量的1.0-3.0倍,优选为1.2-1.8倍。
本发明所述步骤(2)优选在溶剂存在下进行,所述溶剂为四氢呋喃、甲苯、氯仿中的一种或多种,优选为四氢呋喃。
本发明所述步骤(2)的反应温度为室温;反应时间为1.0-10h,优选1.5-3.0h。
一种用于催化环氧化合物制备直链醇的催化剂组合物,包含本发明所述催化剂、三氟乙酸盐和NaBH4。
本发明所述三氟乙酸盐包括三氟乙酸钠、三氟乙酸钾、三氟乙酸镁中的一种或多种。
本发明所述催化剂组合物中,本发明所述催化剂:NaBH4:三氟乙酸盐的摩尔比=1:(125-200):(50-100)。
一种环氧化合物制备直链醇的方法,包括以下步骤:环氧化合物与催化剂组合物加入到溶剂中,升温至反应温度,反应一定时间得到直链醇。
本发明所述的环氧化合物为C3-C10的烷基环氧烷、2-苯基环氧丙烷、2-羟基环氧丙烷、2-乙烯基环氧丙烷中的一种。
本发明所述的制备直链醇的方法中,所述反应温度为50-100℃,优选65-85℃。
本发明所述的制备直链醇的方法中,所述反应时间为1.0-3.0小时,优选1.0-2.0小时。
本发明所述的制备直链醇的方法中,所述催化剂组合物的用量,以本发明所述催化剂计算,为环氧化合物摩尔量的0.1%-0.5%。
本发明的配体,其原理是利用三氟乙酸盐的酸性开环后金属离子与氧形成配位键,由于三氟乙酸根较大空间位阻倾向于产生取代基较小的方向开环,开环后由于电子效应氢转移至β碳形成直链醛,催化剂在H给体NaBH4的存在下脱去两个Cl键与H结合,H与直链醛的O产生氢键连接,SiH2键中的H脱除产生Si=Zn双键从而使与直链醛产生H键的H脱除生成直链醇。
使用该组合催化剂得到直链醇,大大降低了设备投资,催化活性高、支链选择性好,与金属有较强的鳌合能力,反应活性高、适用于工业化大规模生产。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步详细说明。
本发明实施例和对比例中使用的试剂原料来源如下:
取代膦、偶氮二异丁腈、环氧丙烷、2-羟基环氧丙烷、2-苯基环氧丙烷购自百灵威试剂公司;甲苯、二氯甲烷、硼氢化钠、四氢呋喃、ZnCl2、二烯基硅烷购自上海国药试剂有限公司。
本发明实施例和对比例中使用的测试方法如下:
产物结构由元素分析仪器测定,仪器为德国Elementar公司Vario EL cube分析仪。
色谱分析为Agilent 7890B气相色谱仪:安捷伦DB-5色谱柱,进样口温度:220℃;检测器温度:250℃;H2流量:40/min;空气流量:360ml/min。柱箱升温程序为:初始温度20℃,升温速率为20℃/min,保持4min;100-250℃,升温速率15℃/min,保持10min。
以下结合具体实施例,对本发明作进一步说明。应理解,以下实施例仅用于说明本发明而非用于限定本发明的范围。
实施例1
(1)催化剂的制备
将二乙烯基硅烷(841.9g,10mol),二甲基膦(1551.25g,25mol)、偶氮二异丁腈(164.21g,1mol)混合至反应釜中,加热至90℃,反应1h;随后降温至室温,加入5L四氢呋喃,ZnCl2(1635.6g,12mol)搅拌1.5h,得到目标催化剂,结构式如下:
元素分析:C:27.82;H:6.72;P:17.96;Si:8.16。1HNMR(500MHz,Chloroform-d):δ7.24(m,1H),4.46(dh,2H),2.14(dddd,4H),1.81(s,12H),1.21(dddd,4H)。
(2)环氧丙烷制备丙醇
将环氧丙烷(580.8g,10mol)、催化剂(3.456g,0.01mol)、NaBH4(75.66g2mol)、三氟乙酸钠(68g,0.5mol)溶于二氯甲烷中,升温至60℃,反应1.5h,得到产物,经气相分析数据得丙醇的选择性为98.97%。
实施例2
(1)催化剂的制备
元素分析:C:56.65;H:5.26;P:10.46;Si:4.75。
1H NMR(500MHz,Chloroform-d):δ7.63(ddt,8H),7.38(tt,4H),7.26–7.18(m,4H),6.92–6.76(m,3H),3.10(dq,4H),1.44(dddd,4H)。
(2)2-羟基环氧丙烷制备乙二醇
将2-羟基环氧丙烷(600.5g,10mol)、催化剂(29.69g,0.05mol)、NaBH4(283.73g,7.5mol)、三氟乙酸镁(686.6g,5mol)溶于二氯甲烷中,升温至80℃,反应1.0h,得到产物,经气相分析数据得乙二醇的收率为99.12%。
实施例3
(1)催化剂的制备
元素分析:C:42.03;H:8.63;P:13.50;Si:6.11。
1H NMR(500MHz,Chloroform-d)δ3.41(m,2H),2.82(m,1H),2.72(dp,4H),2.40(td,2H),2.31(td,2H),1.29(d,24H),1.26–1.12(m,4H)。
(2)2-苯基环氧丙烷制备苯乙醇
将2-苯基环氧丙烷(1201.5g,10mol)、催化剂(11.74g,0.025mol)、NaBH4(118.03g,3.12mol)、三氟乙酸镁(256.8g,1.87mol)溶于甲苯中,升温至85℃,反应2.0h,得到产物,经气相分析数据得苯乙醇的收率为98.86%。
对比例1
环氧丙烷制备丙醇:将环氧丙烷(580.8g,10mol)、实施例1催化剂(3.456g,0.01mol)、NaBH4(378.3g 10mol)溶于二氯甲烷中,升温至60℃,反应1.5h,经气相分析数据得产物未反应。
对比例2
将环氧丙烷(580.8g,10mol)、实施例1催化剂(3.456g,0.01mol)、三氟乙酸钠(68g,0.5mol)溶于二氯甲烷中,升温至60℃,反应1.5h,得到产物,经气相分析数据得丙醛的收率为80.13%。
对比例3
将环氧丙烷(5.81g,0.1mol)、KOH(8.4g,0.15mol)溶于二氯甲烷中,微波至120℃,反应1.5h,得到产物,经气相分析数据得丙醇的收率为83.2%。
Claims (15)
2.根据权利要求1所述的催化剂组合物,其特征在于,R1、R2为C1-C4的烷基、苯基。
4.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(1)中,二取代基膦的加入量为二乙烯基硅烷摩尔量的2.0-6.0倍。
5.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(1)中,二取代基膦的加入量为二乙烯基硅烷摩尔量的2.5倍-3.5倍。
6.根据权利要求3所述的催化剂组合物,其特征在于,所述偶氮类催化剂选自偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈中的一种或多种;所述偶氮类催化剂的加入量为二乙烯基硅烷摩尔量的0.01-0.2倍。
7.根据权利要求6所述的催化剂组合物,其特征在于,所述偶氮类催化剂的加入量为二乙烯基硅烷摩尔量的0.05-0.1倍。
8.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(1)的反应温度为60-140℃;反应时间为0.5h-5h。
9.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(1)的反应温度为90-120℃;反应时间为1h-2.5h。
10.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(2)中,ZnCl2的加入量为二乙烯基硅烷摩尔量的1.0-3.0倍。
11.根据权利要求3所述的催化剂组合物,其特征在于,所述步骤(2)中,ZnCl2的加入量为二乙烯基硅烷摩尔量的1.2-1.8倍。
13.一种环氧化合物制备直链醇的方法,包括以下步骤:环氧化合物与权利要求1所述的催化剂组合物加入到溶剂中,升温至反应温度,反应一定时间得到直链醇。
14.根据权利要求13所述的方法,其特征在于,反应温度为50-100℃;反应时间为1.0-3.0小时。
15.根据权利要求13所述的方法,其特征在于,反应温度为65-85℃;反应时间为1.0-2.0小时。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4994592A (en) * | 1987-07-23 | 1991-02-19 | Shell Oil Company | Polymerization process |
US5614641A (en) * | 1992-07-02 | 1997-03-25 | Elf Aquitaine | Process for enantioselective hydrogenation of the oxo C═O double bond |
JP2013180991A (ja) * | 2012-03-02 | 2013-09-12 | Kyoto Univ | ビスホスフィン化合物、及びビスホスフィン化合物を配位子とする遷移金属触媒、並びにこれらの製造方法 |
CN105289742A (zh) * | 2015-11-11 | 2016-02-03 | 天津科技大学 | 用于乙烯选择性齐聚的催化剂、新型配体及其制备方法 |
CN110947423A (zh) * | 2019-12-13 | 2020-04-03 | 中国科学院过程工程研究所 | 一种用于合成丙二醇醚的催化剂及制备方法 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4994592A (en) * | 1987-07-23 | 1991-02-19 | Shell Oil Company | Polymerization process |
US5614641A (en) * | 1992-07-02 | 1997-03-25 | Elf Aquitaine | Process for enantioselective hydrogenation of the oxo C═O double bond |
JP2013180991A (ja) * | 2012-03-02 | 2013-09-12 | Kyoto Univ | ビスホスフィン化合物、及びビスホスフィン化合物を配位子とする遷移金属触媒、並びにこれらの製造方法 |
CN105289742A (zh) * | 2015-11-11 | 2016-02-03 | 天津科技大学 | 用于乙烯选择性齐聚的催化剂、新型配体及其制备方法 |
CN110947423A (zh) * | 2019-12-13 | 2020-04-03 | 中国科学院过程工程研究所 | 一种用于合成丙二醇醚的催化剂及制备方法 |
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