CN101811982B - 2,3-diisopropyl-2.3-dicyano-diethyl succinate compound, preparation method and application thereof - Google Patents
2,3-diisopropyl-2.3-dicyano-diethyl succinate compound, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of 2,3-diisopropyl succinate and ester compound thereof, which comprises the steps of: carrying out an oxidative coupling reaction of a 3-methyl-2-cyano butyrate compound for preparing a 2,3-diisopropyl-2.3-dicyano-diethyl succinate compound; carrying out a hydrolysis reaction and a decarboxylation reaction for preparing the 2,3-diisopropyl succinate; and further esterifying for preparing the 2,3-diisopropyl diethyl succinate compound. An intermediate of the 2,3-diisopropyl-2.3-dicyano-diethyl succinate compound and the preparation method thereof are beneficial to commercially producing 2,3-diisopropyl succinic ester which is an internal electron donor compound used capable of being used for preparing a Ziegler-Natta polypropylene catalyst. The invention can be used for the technical field of petrochemical polypropylene.
Description
Technical field
The present invention relates to organic compound and preparation method thereof, be specifically related to 2,3-di-isopropyl-2,3-dicyano succinate compound and preparation method thereof and as the application of intermediate in preparation 2,3-di-isopropyl succsinic acid.
Background technology
Seek desirable electron donor compound is the focus of Novel polypropylene catalyst research always.Existing document CN1313869A discloses 2,3-dialkyl succinic acid ester compound as one of catalyst component, is used for the preparation of the solid catalyst of olefinic polymerization.Wherein, 2,3-di-isopropyl succinate is a kind of particularly preferred internal electron donor compound.This series succinate is the internal electron donor of Ziegler-Natta catalyst, has improved the controllability of catalyzer to relative molecular mass distribution, degree of isotacticity and the oligomer of olefin polymer.Adopt this catalyzer, can improve the resistance to impact shock of product, can keep modulus in flexure again simultaneously; Perhaps when improving modulus in flexure (the bending amount of touching is higher than 2100MPa), keep again shock strength; Even can accomplish that the two improves simultaneously.It is reported (contemporary petrochemical complex, 2003,11 (10), 4-11), have rigidity and the impact property of balance with this impact copolymer of doing the novel propylene polymerizing catalyst production of electron donor with succinate, higher by 20%～30% than the old trade mark.
The CN1313869A document also discloses 2,3-dialkyl succinic acid ester synthesis method, comprises esterification, alkylation, reduction, oxidative coupling and S
N2 couplings, and their combination (referring to the Table A in this patent documentation).But this patent documentation does not specify the synthetic method of 2,3-di-isopropyl succinate (referring to the Table A in this patent documentation and the embodiment sequence number in the table 1: 10～11,19～21).
Those skilled in the art think that the described oxidative coupling of CN1313869A document or esterification process suit to prepare 2,3-di-isopropyl succinate.Take 2-alkyl acetic ester as raw material, prepare 2,3-dialkyl succinic acid ester by the existing literature method oxidative coupling method of quoting, wherein embodiment 18 has illustrated that Valeric acid ethylester is at lithium diisopropylamine and TiCl
4The lower oxidative coupling of effect obtains 2,3-dipropyl ethyl succinate.But synthetic 2, the 3-dialkyl group succinate method of prior art is difficulty comparatively.Mostly need to use the lithium diisopropylamine (LDA) by the preparation of hazardous product n-Butyl Lithium, and temperature requirement is-70 ℃, under so harsh condition, should not realizes industrialization.The CN1313869A document discloses 2,3-dicyclohexyl ethyl succinate embodiment 22, the esterification that it can be by 2,3-phenylbenzene succsinic acid and the reaction that phenyl is reduced into cyclohexyl prepared.Although by 2, the 3-dialkyl succinic acid can prepare 2 by the esterification process of prior art, 3-dialkyl succinic acid ester, but the CN1313869A document does not disclose the concrete preparation method (referring to the Table A in this patent documentation) of 2,3-di-isopropyl succsinic acid and ester thereof.
Summary of the invention
The present invention 2,3-di-isopropyl-2,3-dicyano succinate compound and preparation method thereof, and with this compound as intermediate, opened up one new 2, the synthetic method of 3-di-isopropyl succinic diester compounds avoids using the cold operation under the lithium diisopropylamine (LDA) of hazardous product n-Butyl Lithium preparation and-70 ℃, so that 2,3-di-isopropyl succinic diester realizes industrialization easily as the internal electron donor of polypropylene catalyst.
The technical problem to be solved in the present invention is: provide a kind of 2,3-di-isopropyl-2,3-dicyano succinate compound and preparation method thereof, so that this compounds is used for suitability for industrialized production 2,3-di-isopropyl succsinic acid, this is conducive to commercially produce 2,3-di-isopropyl succinate, and is used for the preparation of Ziegler-Natta polypropylene catalyst as the internal electron donor compound.
The present invention is a kind of to have 2 of general formula (I), 3-di-isopropyl-2, and 3-dicyano succinate compound:
Wherein, the R group is selected from the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl.Preferred R group is C
1～C
8Alkyl, with methyl, ethyl, propyl group, butyl or isobutyl-for better.Preferably be selected from following compounds: 2,3-di-isopropyl-2,3-dicyano dimethyl succinate or 2,3-di-isopropyl-2,3-dicyano diethyl succinate.
The present invention 2,3-di-isopropyl-2, and the preparation method of 3-dicyano fourth two ester compounds may further comprise the steps:
Take the 3-methyl of general structure (II)-ethyl cyanacetic ester compound as raw material, at alcoholic solution
In react with pure potassium compound, after generation sylvite also concentrates and solid occurs, be mixed with reaction solution with aprotic solvent as solvent, after oxygenant is dissolved in aprotic solvent, join in the described reaction solution, the dimerization linked reaction occurs, generate 2,3-di-isopropyl-2,3-dicyano succinate compound, described pure potassium compound are selected from a kind of in following: potassium methylate, potassium ethylate, potassium propylate, butanols potassium, isobutyl potassium alcoholate or potassium tert.-butoxide; Particular methanol potassium, potassium ethylate or potassium tert.-butoxide are take potassium ethylate as best.Described alcoholic solution is selected from the solution of methyl alcohol, ethanol, propyl alcohol, Virahol or the trimethyl carbinol, the solution of particular methanol, ethanol or the trimethyl carbinol, take ethanolic soln as best, the consumption of alcohol is that every gram general formula is 1～50 milliliter of alcohol of raw material need of (II), be preferably every gram general formula and be 10～40 milliliters of alcohol of raw material need of (II), the best is that every gram general formula need 15～25 milliliters of alcohol for the raw material of (II).Described aprotic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO) or acetonitrile, preferred tetrahydrofuran (THF) or acetonitrile are take acetonitrile as good.Described oxygenant is selected from halogen or transiting metal oxidation attitude compound, and preferred halogen is take iodine as best.Wherein, the amount of used tetrahydrofuran (THF) or acetonitrile is that every gram general formula is 1～50 milliliter of tetrahydrofuran (THF) of compound need or the acetonitrile of (II), and the compound that preferred every gram general formula is (II) formula needs 10～40 milliliters of tetrahydrofuran (THF)s or acetonitrile.The tetrahydrofuran (THF) of described sylvite or acetonitrile solution react under the effect of oxygenant iodine, and its temperature of reaction is that room temperature to reaction solution refluxes, and its reaction pressure is normal pressure to 20 normal atmosphere, preferred normal pressure.The consumption of iodine is that the compound of general formula (II) and the mol ratio of iodine are 1: 0.4～0.6, preferred 1: 0.5～0.6.The raw material of general formula (II) and the mol ratio of pure potassium compound are 1: 0.8～1.2, preferably 1: 1～1.2; Take 1: 1 as best.Temperature of reaction is-10 ℃～45 ℃, preferred-5 ℃～40 ℃, and take room temperature as good.
Wherein, the R group is selected from the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl.Preferred R group is C
1～C
8Alkyl, with methyl, ethyl, propyl group, butyl or isobutyl-for better, take methyl or ethyl as optimum.
Step for preparation (II) formula compound, can be undertaken (referring to A.C.Cope by prior art, Org.React.1957,9,107), be cyanoacetate compound under the effect of sodium alkoxide with bromo propane generation nucleophilic reaction, generate general formula and be the 3-methyl of (II) formula-ethyl cyanacetic ester compounds.Wherein, 3-methyl-2-cyano butyric acid methyl esters and 3-methyl-2-cyano butyric acid ethyl ester is made by industrial raw material methyl-cyanacetate and cyan-acetic ester and bromo propane reaction respectively.
2,3-di-isopropyl succinic compound synthetic route is as shown in the formula expression:
The present invention is a kind of 2, the preparation method of 3-di-isopropyl succsinic acid; May further comprise the steps:
Take general structure as 2 of (I) formula, 3-di-isopropyl-2,3-dicyano succinate compound is raw material;
Described 2,3-di-isopropyl-2,3-dicyano succinate compound, under acidic conditions or alkaline condition, hydrolysis reaction all occurs in 2 cyano group and 2 ester groups; Decarboxylic reaction has occured again in the ester group of above-mentioned general formula (I) after hydrolysis obtains carboxyl, or cyan-hydrolysis decarboxylic reaction occured again after becoming carboxyl, generates 2,3-di-isopropyl succsinic acid;
Wherein the restriction of acidic hydrolysis and decarboxylic reaction scheme is:
Described general structure is the compound of (I) formula, under 60%～90% sulfuric acid condition, under room temperature to 100 ℃ temperature, described hydrolysis and decarboxylic reaction occurs, and generates 2,3-di-isopropyl succsinic acid.
Further preferred:
Described general structure is the compound of (I) formula, under the condition of 62%～70% sulfuric acid, under 150 ℃～170 ℃ temperature, described hydrolysis and decarboxylic reaction occurs, and generates 2,3-di-isopropyl succsinic acid.
For the preferred technical scheme of above-mentioned fundamental sum, especially for following preferred group:
In general structure (I), (II): the R group is selected from C
1～C
8Alkyl.
Further preferred, in general structure (I), (II): R group represent methylidene, ethyl, propyl group, butyl or isobutyl-.
Particularly preferably, in general structure (I), (II):
The R group is selected from a kind of in following: methyl, ethyl;
The i.e. first methyl of the 3-from the compound of general structure (II)-2-cyano butyric acid methyl esters or 3-methyl-2-cyano butyric acid ethyl ester, prepare one of the midbody compound 2 of general structure (I), 3-di-isopropyl-2,3-dicyano dimethyl succinate or 2,3-di-isopropyl-2,3-dicyano diethyl succinate is prepared 2,3-di-isopropyl succinic compound again.
For the preparation method of 2,3-di-isopropyl succinate compounds, be above-mentioned 2, on the preparation method basis of 3-di-isopropyl succsinic acid, increased esterif iotacation step, prepare 2,3-di-isopropyl succinate compounds from 2,3-di-isopropyl succsinic acid.
2,3-di-isopropyl succsinic acid, with the alcohol reaction, perhaps reacts preparation 2,3-di-isopropyl succinic diester by the esterif iotacation step of prior art with haloalkane or sulfuric acid diester under alkaline condition under acidic conditions;
By 2,3-di-isopropyl succsinic acid by the esterification process of prior art (referring to CN1313869A and " Vogel ' s Textbook of Practical Organic Chemistry ", 5Ed, 1989,695-706.) can prepare 2,3-di-isopropyl succinic diester.For example, under acidic conditions, with the alcohol reaction, perhaps under alkaline condition, react preparation 2,3-di-isopropyl succinic diester with haloalkane or sulfuric acid diester.
The compound of particularly preferred general structure (I) is through being hydrolyzed into 2, behind the 3-di-isopropyl succsinic acid, esterification process by prior art is prepared: 2,3-di-isopropyl Succinic acid dimethylester, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl succsinic acid di-n-propyl ester, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl succsinic acid diisoamyl ester, 2,3-di-isopropyl succsinic acid two dissident's esters, 2,3-di-isopropyl succsinic acid two (2-methyl hexyl) ester.
For above-mentioned 2, the preparation method of 3-di-isopropyl succinic diester compounds, esterif iotacation step is preferred: under the sulphuric acid catalysis condition, adopt describedly 2,3-di-isopropyl succsinic acid and alcohol reaction generate 2,3-di-isopropyl succinic diester compounds.
The invention has the beneficial effects as follows:
Of the present invention 2,3-di-isopropyl-2,3-dicyano succinate compound and its preparation method and application, make this compound as intermediate, opened up one new 2, the synthetic method of 3-di-isopropyl succinic diester compounds, avoid using lithium diisopropylamine (LDA) and the cold operation under-70 ℃ of the preparation of hazardous product n-Butyl Lithium, so that 2,3-di-isopropyl succinic diester realizes industrialization easily as the internal electron donor of polypropylene catalyst, make this Novel polypropylene catalyzer can be on a large scale for the production of the high-performance polymer commodity, thereby can improve polyacrylic production technology level.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1:
Preparation 2,3-di-isopropyl-2,3-dicyano diethyl succinate
Under nitrogen protection, the 0.75g potassium metal is added in the sublimed dehydrated alcohol of 40ml the preparation potassium ethylate.The potassium ethylate drop for preparing is added in 3g 3-methyl-2-cyano butyric acid ethyl ester.Stirring reaction 1h at room temperature.The sylvite desolventizing for preparing is got white solid, add the tetrahydrofuran (THF) of 30ml purifying, then be added in the tetrahydrofuran solution of the 90ml that has dissolved 2.46g iodine, at room temperature stirring reaction 4h.Then desolventizing gets the mixture of sorrel thickness oily liquids and solid.Add 75ml ether and 20ml water washing, keep organic layer, with the NaHCO of 20ml 10%
3Wash at twice organic phase, then wash with water until organic phase is neutral.Spend the night with the anhydrous magnesium sulfate drying organic phase.Filter, desolventizing gets red liquid, separates to get colourless transparent liquid with the chromatography column that is filled with silica gel.
The spectral data of product:
High resolution electrospray ionization mass spectrum (ESI): 331.1625 with molecular formula C
15H
25NO
4The quasi-molecular ions total mass number of compound M+Na (theoretical value 331.1634) is consistent.
The Low Resolution Mass Spectra instrument is analyzed MS (EI, m/z): 308 (M
+), 309 (M+1), 293 (M-15), 263 (M-45), 235 (M-73).
IR(cm
-1)：2974.5，2939.1，2878.4，2250.7，2026.6，1744.3，1713.5，1467.2，1393.3，1371.1，1269.1，1191.9。
1H?NMR(CDCl
3/TMS，300MHZ)(δppm)：1.10～1.170(m，12H，2CH(CH
3)
2)，1.246&1.3692(2t，6H，2CH
2CH
3)，2.547～2.732(m，2H，2CH(CH
3)
2)，4.156～4.402(m，4H，2CH
2CH
3).
Embodiment 2:
Preparation 2,3-di-isopropyl-2,3-dicyano diethyl succinate
Press the working method of embodiment 1, substitute tetrahydrofuran solvent with acetonitrile, get product, its mass spectrum and infrared analysis collection of illustrative plates and 2,3-di-isopropyl-2,3-dicyano diethyl succinate compound structure is consistent.
Embodiment 3:
Preparation 2,3-di-isopropyl succsinic acid
The vitriol oil of 10ml (95%～98%) slowly is added drop-wise in the 5ml water cool to room temperature preparation sulphuric acid soln.Then join and fill 0.22g 2, in the there-necked flask of 3-di-isopropyl-2-dicyano diethyl succinate, the heated and stirred reaction, temperature of reaction is made as 160 ℃, reaction 16h.React complete rear cooling, then add the dilution of 30ml water, cooling adds the anhydrous diethyl ether extracted organic phase, and desolventizing gets the mixture of white solid and oily liquids.KOH dissolving with 10ml 10% is heated to 50 ℃ of stirring reaction 45min until reaction solution is transparence.Use the extracted with diethyl ether organic phase, with concentrated hydrochloric acid acidifying water, the adularescent precipitation generates, and filtration drying gets product 2,3-di-isopropyl succsinic acid.
The spectral data of product:
The Low Resolution Mass Spectra instrument is analyzed MS (EI, m/z): 185 (M-17)
+, 160 (M-42)
+
IR(cm
-1)：2968，2940，2884，2698，1703，1468，1439，1392，1377，1278，1247，1217，1179，1133，946，756。
Embodiment 4:
Preparation 2,3-di-isopropyl ethyl succinate
Add 1g 2 in 100ml single port flask, 3-di-isopropyl succsinic acid is used the 60ml anhydrous alcohol solution.Drip again the vitriol oil of 0.5ml.Start stirring, reaction is 24 hours under reflux state.
Reaction is cooled to room temperature after finishing, and removes unnecessary ethanol, gets light yellow thick liquid, with the anhydrous diethyl ether dissolving, uses NaHCO
3Solution washing.Keep organic phase, then wash with water to organic phase and be neutral, get organic layer, spend the night with anhydrous magnesium sulfate drying.Filter sal epsom, slough solvent ether, get crude product.With crude product KOH solution washing, then use extracted with diethyl ether, spend the night with the dried over mgso organic phase, the filtration drying agent, desolventizing obtains target compound 2 at last, 3-di-isopropyl ethyl succinate.
The spectral data of product:
The Low Resolution Mass Spectra instrument is analyzed MS (EI, m/z): 216 (M-42)
+, 213 (M-45)
+
IR(cm
-1)：2965，2934，2876，1732，1465，13912，1374，1264，1227，1241，1179，1159，1116，1030，926。
Claims (10)
1. one kind has 2 of logical formula I, 3-di-isopropyl-2, and 3-dicyano succinate compound is characterized in that:
Wherein, the R group is selected from the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl.
2. according to claim 12,3-di-isopropyl-2,3-dicyano succinate compound is characterized in that: wherein the R group is selected from C
1～C
8Alkyl.
3. according to claim 22,3-di-isopropyl-2,3-dicyano fourth two ester compounds is characterized in that: wherein the R group is methyl, ethyl, n-propyl, normal-butyl or isobutyl-.
4. according to claim 12,3-di-isopropyl-2,3-dicyano fourth two ester compounds, it is characterized in that: be selected from following compounds: 2,3-di-isopropyl-2,3-dicyano dimethyl succinate or 2,3-di-isopropyl-2,3-dicyano diethyl succinate.
5. one of claim 1～4 is described 2,3-di-isopropyl-2, and the preparation method of 3-dicyano fourth two ester compounds is characterized in that, may further comprise the steps:
Take the 3-methyl of general structure (II)-ethyl cyanacetic ester compound as raw material, at alcoholic solution
In react with pure potassium compound, after generation sylvite also concentrates and solid occurs, be mixed with reaction solution with aprotic solvent as solvent, after oxygenant is dissolved in aprotic solvent, join in the described reaction solution, the dimerization linked reaction occurs, generate 2,3-di-isopropyl-2,3-dicyano succinate compound, described pure potassium compound are selected from a kind of in following: potassium methylate, potassium ethylate, n-propyl alcohol potassium, propyl carbinol potassium, isobutyl potassium alcoholate or potassium tert.-butoxide; Described alcoholic solution is selected from the solution of methyl alcohol, ethanol, n-propyl alcohol, Virahol or the trimethyl carbinol; Described aprotic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO) or acetonitrile; Described oxygenant is selected from the iodine in the halogen; The raw material of logical formula II and the mol ratio of pure potassium compound are 1:0.8～1.2; Temperature of reaction is-10 ℃～45 ℃.
6. according to claim 52,3-di-isopropyl-2, the preparation method of 3-dicyano fourth two ester compounds is characterized in that described aprotic solvent is tetrahydrofuran (THF) or acetonitrile; Oxygenant is the iodine in the halogen; The alcohol potassium compound is potassium methylate, potassium ethylate or potassium tert.-butoxide, and alcoholic solution is methyl alcohol, ethanol or t-butanol solution; The raw material of logical formula II and the mol ratio of pure potassium compound are 1:1～1.2; Temperature of reaction is-5 ℃～40 ℃.
7. according to claim 62,3-di-isopropyl-2, the preparation method of 3-dicyano fourth two ester compounds is characterized in that described aprotic solvent is or acetonitrile; Oxygenant is iodine; The alcohol potassium compound is potassium ethylate, and alcoholic solution is ethanolic soln; The raw material of logical formula II and the mol ratio of pure potassium compound are 1:1; Temperature of reaction is room temperature.
One kind described 2 with one of claim 1～4,3-di-isopropyl-2,3-dicyano succinate compound is intermediate, preparation 2, the method of 3-di-isopropyl succsinic acid is characterized in that: with 2 of logical formula I, 3-di-isopropyl-2,3-dicyano succinate compound is reactant, under the condition of 60%～90% sulfuric acid, under 90 ℃～180 ℃ temperature, hydrolysis and decarboxylic reaction occur, generate 2,3-di-isopropyl succsinic acid.
One kind described 2 with one of claim 1～4,3-di-isopropyl-2,3-dicyano succinate compound is intermediate, the method for preparation 2,3-di-isopropyl succinate is characterized in that:
(1) with 2 of logical formula I, 3-di-isopropyl-2,3-dicyano succinate compound is reactant, under the condition of 60%～90% sulfuric acid, under 90 ℃～180 ℃ temperature, hydrolysis and decarboxylic reaction occurs, and generates 2,3-di-isopropyl succsinic acid;
(2) with above-mentioned obtain 2,3-di-isopropyl succsinic acid under acidic conditions with the alcohol reaction, preparation 2,3-di-isopropyl succinic diester, described alcohol is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
One kind described 2 with one of claim 1～4,3-di-isopropyl-2,3-dicyano succinate compound is intermediate, preparation 2, the method of 3-di-isopropyl succinate is characterized in that: (1) is to lead to 2 of formula I, 3-di-isopropyl-2,3-dicyano succinate compound is reactant, under the condition of 60%～90% sulfuric acid, under 90 ℃～180 ℃ temperature, hydrolysis and decarboxylic reaction occur, generate 2,3-di-isopropyl succsinic acid;
(2) with above-mentioned obtain 2,3-di-isopropyl succsinic acid under alkaline condition with haloalkane or the reaction of sulfuric acid diester, preparation 2,3-di-isopropyl succinic diester; Described haloalkane is selected from methyl halide, halo ethane, halo n-propane, halo isopropyl alkane, halo normal butane or halo Trimethylmethane, and described sulfuric acid diester is selected from methyl-sulfate, ethyl sulfate or dibutyl sulfate.
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| CN103145553B (en) * | 2013-03-06 | 2016-06-01 | 大连理工大学 | Synthesis and application of 2,3-hydrocarbyl substituted succinic acid diesters |
| US9790291B2 (en) * | 2013-03-14 | 2017-10-17 | Formosa Plastics Corporation, Usa | Non-phthalate compounds as electron donors for polyolefin catalysts |
| CN106608935B (en) * | 2015-10-27 | 2019-07-19 | 中国石油化工股份有限公司 | Catalytic component, catalyst and its application for olefinic polymerization |
| CN109890852B (en) * | 2016-11-18 | 2020-10-20 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN111185241B (en) * | 2020-03-09 | 2022-08-02 | 邯郸学院 | Metal catalyst and preparation method and application thereof |
| CN113149823B (en) * | 2021-03-29 | 2023-12-08 | 上海青平药业有限公司 | 2-R 1 Process for preparing valeric acid |
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| CN1313869A (en) * | 1999-04-15 | 2001-09-19 | 巴塞尔技术有限公司 | Components and catalysts for the polymerization of olefins |
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