• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for manufacturing 1,3-glycols is disclosed. The process comprises reacting an epoxide with synthesis gas in an acidic medium in the presence of rhodium and a phosphine.
    公开号:SU1634133A3
    申请号:SU874203222
    申请日:1987-08-19
    公开日:1991-03-07
    发明作者:Алан Марфи Марк；Ли Смит Брэд；Агуило Адольфо
    申请人:Хехст Силаниз Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    All catalysts and solvents are weighed in a nitrogen atmosphere and quickly loaded into a cold autoclave, which is then rinsed twice with nitrogen and twice with synthesis gas. The autoclave is then pressurized with synthesis gas until the desired pressure is reached and heated, with slow stirring, to the reaction temperature over a period of time from 0.5 h to 4.0 h. Then, ethylene oxide is introduced into the autoclave or from a high pressure vessel for injection. or from the Puska spray pump, and from this point on, rapid mixing is started, and the pressure in the reactor is increased to its final desired value using synthesis gas to control the pressure. During the process, constant pressures are automatically maintained in the reactor by supplying synthesis gas (as required) from a reservoir (for synthesis gas) to a high volume of known volume. Syngas absorption is monitored by periodically measuring the pressure in the synthesis gas reservoir. Usually, operations are stopped when the absorption of synthesis gas decreases to almost zero by slowing down the speed of movement, stopping the supply of synthesis gas, cooling the reactor as quickly as possible, usually during a period of 30 to 60 minutes.
    Some quantities of ethylene oxide are introduced into the reactor, which is heated and pressurized by means of a Ruska spray pump or high pressure vessel for injection. Using the latter method, ethylene oxide is introduced into a high pressure vessel for injection by condensation of ethylene oxide vapors, directed from a cylinder to an injection vessel, which is cooled to dry ice temperature. After the ethylene oxide has been introduced into the pressure vessel for injection, this vessel is separated from the portable device, weighed, then connected to an autoclave. The syngas pressure is used to force the introduction of ethylene oxide into the autoclave from the injection vessel.
    When using a Ruska pump to inject ethylene oxide, liquid ethylene oxide is supplied through pipes from
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    stainless steel into the Ruska spray pump, which then injects ethylene oxide into the autoclave unit.
    Since liquid ethylene oxide is retained in the pipes, fittings, and valves supplying the autoclave, it is necessary to introduce ethylene oxide in a quantity slightly higher than the theoretical amount and then calibrate the system for that amount of ethylene oxide. which actually reaches the autoclave. Calibration operations are carried out by entering into the reactor 100 g of water and I, 3 g of sulfuric acid and heating it to 100 ° C. Then ethylene oxide is introduced into the injection vessel or Ruska pump and introduced by injection into the reactor, which is heated for 2 hours in order to hydrolyze the ethylene oxide to ethylene glycol. The resulting ethylene glycol: water was analyzed for ethylene glycol using gas chromatography. In a typical process cycle, 12.0 g of ethylene oxide is introduced into the high pressure vessel and ethylene glycol is obtained in a reactor in an amount equivalent to 10.0 g of ethylene oxide. Ethylene oxide is calculated from the amount of ethylene glycol and the measured values of ethylene oxide are plotted. from the input amount of ethylene oxide. Such curves are generally linear over the entire range of 5–15 g of ethylene oxide and show efficiency in this transfer operation of 75–35% ethylene oxide. The results of this calibration test are used to calculate ethylene oxide in catalytic carbonylation processes.
    The products used in the implementation of these examples are ClRhCl (C0) 2 x X P (C6H () j and P (p-C4. H9) C supplied by Strem Chemicals and stored and transported in an azset atmosphere. Compound Rh (CO) 2Acac either supplied by Englahard or obtained from RliClj-3H O, acetylacetone and dimethylformamide and then recrystallized from hexane to give a green-red product in the form of needle crystals. Ethylene oxide (99.7%) supplies Macheson and is stored in chilled water. The Nl / CO mixture is supplied by Iveco. Tetraglyme and sulfolane used in the data example ah, obtained from Aldrich; n-butanol from Burdick and Jackson. Toluene and tetrahydrofuran, obtained from Aldrich, are beaten from metallic sodium under a nitrogen atmosphere.
    Reaction products are classified into four categories. The precursors of XDD include a total of 1,3-propanediol (1,3 - RDO), 3-hydroxypropion-; aldehyde (NRA) and 2-hydroxyethyl-1,3-dioxane (NED). Products Predecessors of RDO, along with 1,3-RDO, include NDA and NED, since they can be hydrolyzed and / or hydrogenated to 1,3-RDO. Et-OH precursors include total acetaldehyde and ethanol. Precursors of Proton include total acrolein, propionaldehyde and propanol. Others include all unspecified products that do not fall into any of the listed categories. In the examples where the yields are indicated, the latter are calculated by the measured number of moles of product divided by the calculated number of moles of EO (using the EO calibration operation), which was introduced into the reactor. In some cases, due to experimental error in the injection procedure of ethylene oxide and the calibration procedure associated with it, the sum of the analyzed products obtained from ethylene oxide is slightly higher than the calculated amount of ethylene oxide introduced into the reactor. In these examples, the effectiveness of the preparation of the product (which is taken per 100% EO) is given.
    Example 1. 30 g of tetraglime, 0.50 g (0.0019 mol) .Rh (CO) zAcac, 1.1 g (0.0039 mol) tricyclogogenyl phosphine and 0.1 g of hydroquinone are introduced into a 300 cm autoclave according to the common standard procedure. The mixture is heated to 100 ° C under a pressure of 1000 psi (7 MPa) 2: 1 gas, then the pressure in the reactor is increased to 1400 psi (9.8 MPa) and 3.9 g (9.7 wt.%) Are injected from the Ruska pump. .%) ethylene oxide. H2 / CO absorption (2: 1 ratio) begins after 25 minutes, and then this pressure is maintained at approximately 1400 psi (9.8 MPa) by entering Hj / CO (2: 1) as required. Reactions
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    ceased after 4.6 hours (the adsorption of the gas does not completely cease), and the product is removed and analyzed by gas chromatography. The product does not contain free 1,3-propanediol, but contains small amounts of HPA (0.0016 mol) and NED (0.0002 mol) .- The main products are non-jQ vertically ethylene oxide
    (0.0895 mol), acrolein (0.01774 mol), ethylene glycol (0.01112 mol) and 2-methylpentanol (0.0097 mol). A smaller amount of ace15 aldehyde, propanol and 2-methylpentane was found, along with a number of other by-products in small quantities. Ethylene oxide is carbonylated to products C, by using Rh /
    20 phosphine catalyst in the absence of acid promoters. Small amounts of precursor molecules are obtained and significant amounts of products C, which are formed as a result of the reaction of EO with CO and H. In addition, significant amounts of Cg products are obtained (which could be formed as a result of the aldehyde coupling reaction
    Sd),
    Example2. 30 g of tetraglyme, 0.53 g (0.0020 mol) of Rh (CO) iAcac ,, 0.54 g (0.0019 mol) of tricyclohexylphosphine, 1.0 g of 57% HJ, 5.0 g ( 5.15 wt.%) And 0.1 g of hydroquinone are introduced into the autoclave and heated to I 20.degree. C. under a pressure of 1500 psi.
    (10.5 MPa) H2 / CO (2: 1). From the Ruska spray pump, injection of ethylene oxide (8.9 g) (9.13 wt.%) Is introduced and eatem is fed at the request of H, Ј / CO (2: 1), maintaining a pressure of 1500 psi (10.5 MPa). ). The process stops after 116 minutes The product obtained contains 0.057 mol 1,3-RDO, 0.014 mol NDA and 0.012 mol NED for the total yield of the Precursor RDO (47.4%). The major by-products include ethanol (0.045 mol), acetaldehyde (0.019 mol), propanal (0.009 mol), propanol (0.004 mol), 2-methylpentanal (0.006 mol) and 2-methylpentanol (0.005 mol). Traces of ethylene glycol and unidentified products were also found. An acid promoter (HJ) is used to increase the activity and selectivity of the action of the rhodium phosphine catalyst for the carbonylation of ethylene oxide.
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    Lena to 1,3-propanediol at relatively low pressures.
    Prima rz. 30 g of tetraglkma, 0.54 g (0.0024 mol) of trichloride native hydrate, 0.53 g (0.021 mol of tricyclohexylphosphine, 0.20 g of a concentrated aqueous solution of HC1 5.11 g (5.28 wt.%) Hjp and O, I1 g of hydroquinone is introduced into the autoclave. The mixture is heated to 120 ° C under a pressure of 1000 psi (7 MPa) of H2 / CO gas and 9.4 g (9.72% by weight) of ethylene oxide are injection injected. from the injection tank using (2: 1), and the final pressure is adjusted to 2500 psi (17.5 MPa). The absorption of gata begins after about 50 minutes, and the test is completed after 3 hours when the absorption of gas almost stops. 0.1506 mol 1 , 3-RDO and 0.006 mol of HPA, the total yield of this product is 73.4%. The main by-products include ethanol (0.053 mol), propanol (0.017 mol), ethylene glycol (0.013 mol) and ethylene oxide (0.003 mol). Since the yield is of the EO products is 114.5%, then the efficiency of ethylene oxide is recalculated. The predecessors of the RDO are formed with an efficiency of 64.9% and a rate of 0.626 mol / l / h. 1,3-Prolanediol can be obtained with rather high efficiency from a catalyst precursor that does not contain acetylacetate ligand (hydrochloric acid promoter is used).
    Example4. 80 g of tetraglyme, 0.51 g (0.0020 mol) of Rh (CO) 2 Acac, 0.41 g (0.0026 mol) of triisobutylphosphine, 0.14 g of phosphoric acid, 5.11 g (5.11 wt%) .%) H20 and 0.1 g of hydroquinone are introduced into the autoclave. The mixture is heated to 120 ° C under a pressure of 1000 psi (7 MPa) of H2 / CO gas (1: 1), 10.0 g (10.38 wt.%) Of ethylene oxide is injected into the injection tank, and the pressure rises. up to 2500 psi (17.5 MPa). The absorption of synthesis gas begins after 40 minutes, and the test is completed after 3.6 hours, when the absorption signals of the gas are practically stopped. Analysis of the product shows the presence of 0.166 mol 1.3 - RDO. The main by-products include ethanol (0.0144 mol), acetaldehyde (0.0053 mol), ethylene glycol
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    thirty
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    (0.012 mol), propanal. (0.006 mol) and propanol (0, 01 1 mol). The yield of 1,3-propanediol is 74.3% at a formation rate of 0.567 mol / l / h. 1,3-Propanediol can be obtained with high efficiency by using trialkylphosphine other than tricyclohexylphosphine.
    Example 5. 30 g of tetraglime, 0.52 g (0.0020 mol) of Rh (CO). Ј Acac, 0.54. g (0.0020 mol) of dicyclohexylphenylphosphine, 0.14 g of phosphoric acid, 5.1 g (5.29 wt.%) of H20 and 0.1 g of hydroquinone are introduced into the autoclave and heated to 110 ° C under a pressure of 1000 psi (7 MPa) H2 / CO gas (2: 1). Injection ethylene oxide (10.1 g) (10.48 wt.%) Was injected from the injection vessel and the pressure was increased to 2500 psi (17.5 MPa). Absorption of the gas begins after about 1 hour, and the test is completed after 6.5 hours. Analysis of the product reveals the presence of 0.115 mol of 1,3-propanediol, 0.040 mol of acetaldehyde, 0.027 mol of ethanol and even smaller amounts of acrolein, propanal, propanol and ethylene glycol. The yield of 1,3-propanediol (as calculated) is 50%, the formation rate of this product is 0.22 mol / l / h. 1,3-Propanediol can be obtained by using a phosphine-mediated rhodium catalyst, which includes an aryl substituent.
    Example 80 g of tetraglyme, 0.51 g (0.0020 mol) of Rli (C0) 2Acac, 0.53 g (0.0019 mol) of tricyclohexylphosphine, 0.13 g of phosphoric acid, 5.0 g (5.13 wt.% ) H20 and O, 1 g of hydroquinone is introduced into the autoclave and heated to 110 ° C under a pressure of 1000 psi (7 MPa) of H2 / CO gas (2: 1). Ethylene oxide (10.2 g) (0.57 wt.%) Was injected from the injection vessel and the pressure was increased to 2500 psi (17.5 MPa). Gas absorption is stopped after 60 minutes, and the test is completed after 4.0 hours. The product contains 0.1905 mol of 1,3-propane diol, 0.0235 mol of ethanol, 0.0154 mol of propanol, 0.0125 mol of ethylene glycol and 0.0039 mol ethylene oxide. Since the yield of the molecules formed from EO is 110%, the efficiencies of ethylene oxide are recalculated and it has been shown that 1,3-propanediol is formed with an efficiency of 77.5% and
    0.595 mol / l / h The 1,3-propanediol can be obtained with relatively high efficiency and speed when using a rhodium-phosphine catalyst promoted with water and phosphoric acid.
    Example. 30 g of tetraglyme, 0.52 g (0.0020 mol) of Ph (CO) 2Acac, 0.53 g (0.0019 mol) of tricyclohexylphosphine, 0.13 g of phosphoric acid, 1.05 g (1.020 ma.A ) and 0.10 g of hydroquinone are introduced into the autoclave and heated to 110 ° C under a pressure of lOOOpsi (7 MPa) of K2 / CO gas (2: 1). From the injection vessel, ethylene oxide (10.0 g) is injected ( 12.63 wt.%) And the pressure drops to 2500 psi (17.5 MPa). Absorption of gas begins after about 90 minutes, and the test is completed after 5.5 hours. The product contains 0.1931 mol of 1,3-propanediol, 0.0172 mol of ethanol, 0.0191 mol of propanol and 0.0029 mol of oxide ethylene. 1, 3-11 propane diol is obtained with a total yield of 85% and a rate of 0.438 mol / l / h. The efficiency of the formation of 1,3-propane diol is slightly increased when the amount of water is reduced relative to the values used in the previous examples.
    Try on 80 g of tetraglyme, 0.52 g (0.0020 mol) of Rh (CO) 2Acac, 0.54 g (0.0019 mol) of tricyclohexylphosphine, 0.14 g of phosphoric acid and 0.10 g of hydroquinone are introduced into the autoclave . The code is not inserted. The mixture is heated to 110 ° C under a pressure of 1000 psi (7 MPa) of H2 / CO gas (2: 1). An ethylene injection mixture of 10.0 g (20.95 wt.%) Is injected from the injection vessel, and the pressure rises to 2500 psi (17.5 MPa). Gas absorption begins in about 160 minutes, and the test is completed in 6, 5 hours. The analysis of the product shows the presence of 0.1993 mol of 1,3-propanediol, 0.0166 mol of ethanol, 0.0046 mol of acetaldehyde and 0.0092 mol of proganol. The yield of 1,3-propanediol is 87%; its formation rate is 0.377 mol / l / h. 1,3- Propanediol can be obtained in high yield in the absence of a water promoter, with induction periods somewhat longer in the absence of water.
    Example9. 80 g of tetraglyme, 0.51 g (0.0020 mol) of Rh (CO) 2 Acac, 0.54 g (0.0019 mol) of tricyclohexylphosphine, 0.13 g of phosphoric acid and 1.05 g (1.13 mA% MO is injected into the autoclave and dobanlchpt hydroquinone. The mixture is heated to 110 ° C under a pressure of 1000 psi (0.7 MPa) of H2 / GO gas (2: 1) and injection of ethylene oxide (10.1 g) (10.93 wt.%) from the injection vessel, and the pressure rises to 2500 psi (17.5 MPa). The gas starts to drop after 90 minutes and the run is stopped after 6.5 hours. The product analysis rolls the presence of 0.2172 mol of 1,3-propanediol, 0.0196 mol of ethanol, 0.01333 mol of panola and traces of acetaldehyde and ethylene oxide. In view of the fact that the yield of molecules formed from ethylene oxide is 113%, the effectiveness of ethylene oxide is recalculated. 1,3-Promandiol is obtained with an efficiency of 35% and a rate of 0.41 mol / l / h. The absence of a hydroquinone promoter (which is included in many examples) does not significantly affect the yield or formation rate of 1,3-propanediol.
    Example 10. 80 g of Ucon 50-HB-100 polyglycolic ether, 0.52 g (0.0020 mol) of Rh (CO) 2 Acac, 0.53 g (0.0019 mol) of tricyclohexylphosphine, O, 13 g of phosphonic acid, 5.1 g (5.29 wt.%) Fi, 0 and 0.1 g of hydroquinone are introduced into the aytoklav and heated to 110 ° C under a pressure of 1000 psi (7 MPa) H2 / CO gas (2 :one). Ethylene oxide (10.0 g) was injected from the injection vessel and increased to 2500 psi (17.5 MPa). Absorption of gas begins after about 20 mi and the test is completed after 3.0 hours. Analysis of the product shows the presence of 0.1775 mol of 1,3-propanediol, 0.0243 mol of propanol, 0.0269 mol of ethanol, 0.0125 mol of acetaldehyde, 0, 0102 mol of acrolein and traces of ethylene oxide and ethylene glycol. Since the yield of molecules formed from ethylene oxide is 112%, they recalculate the effectiveness of ethylene oxide. 1,3-Propandiol is obtained with an efficiency of 70.2% and a rate of 0.717 mol / l / h. 1,3-Propanediol can be obtained with high efficiencies in a complex polyglycol ether solvent other than tetraglyme.
    Example 11. 80 g of tetrahydrofuran, 0.52 g (0.0020 mol) of Rh (CO) 2 Acac, 0.54 g (0.0019 mol)
    tricyclohexylphosphine, 0.13 g of phosphoric acid, 5.1 g (5.29 May L) and 0.10 g of hydroquinone are introduced into the autoclave and heated at 110 ° C under a pressure of 1000 psi (7 MPa) H2 / CO gas (2 :one). From the injection vessel, injection of ethylene oxide (10.0 g) (10.37 wt.%) And the pressure increased to 2500 psi (17.5 MPa). Absorption of gas begins after about 40 minutes and the test is completed after 3.5 hours. Analysis of the product shows the presence of 0.2053 mol of 1,3-propanediol, 0.0166 mol of ethanol, 0.01114 mol of propanol and 0.0026 mol of acrolein. Since the yield of ethylene oxide-derived molecules is 106%, the efficiencies of ethylene oxide are recalculated .1,3-Propandiol is obtained with an efficiency of 35.3% and a rate. 0.739 mol / l / h 1,3-Propanediol can be obtained with high efficiency in a monoester solvent, rather than by decomposition of the solvent.
     Example 12: 80 g of tetraglyme, 0.51 g (0.0020 mol) of Rh (CO) 2 Acac, 0.54 g (0.0019 mol) of tricyclohexylphosphine, 0.14 g of phosphoic acid, 5.11 g (5.0 wt.%)% 0 and 0.11 g of hydroquinone are loaded into an autoclave and heated to 110 C at a pressure of 1000 psi (7 MPa) at a H2 / CO ratio of 2: 1. Propylene oxide (15.8 g) (15.45 wt.%) Is loaded into a sparger and then introduced into an autoclave. Do not attempt to calibrate the loss of propylene oxide during the administration procedure. Absorption of gas begins after 2.5 hours, and the experiment ends after 7.5 hours before stopping the gas absorption. Remove the liquid product (101.7 g) and analyze chromatography and mass spectrometrically. The product contains 7.8 wt.% Unconverted propylene oxide, 5.5 wt.% 1,3-butanediol and 0.5 wt.% I, 2-propylene glycol. Noticeable amount of other product not detected. 1,3-bougandiol can be obtained by carbonylation of propylene oxide in a selective manner.
    Example 13. In accordance with the general procedure, 30 g of tetraglyme, 0.52 g (0.0020 mol) of Rh (CO) a Acac, 0.328 g (0.0019 mol) of triisopropylphosphine, 0.14 g of phosphoric acid, 5 , 1 g (4.9 wt.%) And O, 1 g of hydroquinone is loaded into the autoclave and
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    are heated to 110 ° C at a pressure of 1000 psi (7 MPa) at a ratio H2 / CO 2: 1. Ethylene oxide (10.1 g) (10.37 wt.%) Was introduced from the sparger and the pressure was increased to 2500 psi (7.5 MPa). Gas absorption begins and the experiment ends after 5.5 hours. The product analysis shows the yield of I, 3-propanediol to 65.2 mol%.
    Example 14. In accordance with the general procedure, 80 g of tetraglyme, 0.52 g (0.0020 mol) of Rh (CO) 2Acac, 0.398 g (0.0024 mol) of diisopropylphenylphosphine, 0.14 g of phosphoric acid, 5 , 1 g (4.9 wt.%) HgO and 0.1-g hydroquinone are loaded into an autoclave and heated to 110 C at a pressure of 1000 psi (7 atm) at a H2 / CO ratio of 2: 1. Ethylene oxide was introduced from a sparger (10.1 g) (0.37 wt.%) And the pressure was increased to 2500 psi (17.5 MPa). The gas absorption starts and the experiment ends after 6.5 hours. The analysis of the product shows the yield of 1,3-propane diol 50.0 mol%.
    Example 15. In accordance with the general procedure, 80 g of tetraglyme, 0.51 g (0.0020 mol) of Rh (CO) 2 Acac, 0.55 g (0.0020 mol) of tricyclohexylphosphine and 0.025 mol of p-toluenesulfonic acid are loaded into an autoclave and heated to 110 ° C at a pressure of 1000 psi (7 atm) at a ratio of H2 / CO 2: 1. Ethylene oxide (10.2 g) (10.57 wt.%) Was introduced from the sparger and the pressure was increased to 2500 psi (17.5 MPa). Absorption of the gas began after 10 minutes and the reaction was completed after 2 hours. Analysis of the product indicated a yield of 1,3-propane diol 64.7% by weight.
    The proposed method allows to simplify the process due to the possibility of using water in the composition of the reaction mass (anhydrous solvents are used in the known method), reducing catalyst amounts (the catalyst: ethylene glycol ratio 1: 1, in the proposed 1: 100) is used in the known method. Decreasing the amount of catalyst increases the productivity of the process.
    权利要求:
    Claims (6)
    [1]
    1. A method of producing 1,3-propanediol or I, 3-butanediol by contacting ethylene oxide or propylene oxide with carbon monoxide and hydrogen in a liquid-phase solution of an inert solvent in the presence of a catalyst based on a metal compound and a tertiary monophosphine at elevated temperature and pressure, characterized by that, in order to simplify the process and increase its productivity, the contacting is carried out at a concentration of 9-15 wt.% of ethylene oxide or propylene oxide in the reaction medium at a molar ratio of tii: CO 2: in ETS catalyst a catalyst consisting of a mixture of tertiary monophosphine of formula
    / Rl
    P-RI H
    (
    where R (, R and RJ are independently
    from each other, selected from the group consisting of aliphatic and aromatic groups containing 3.4 or 6 carbon atoms, and a rhodium compound, such as RhCl j or Rh (CO) 2 Acac, the molar concentration of the rhodium compound in the reaction medium being 0.002- : 0.0024 mol, the molar ratio of the rhodium to monophosphin compound is 1-1.3: 1 and the process
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    0
    lead in the presence of acid at a molar ratio of acid to monophosphine 2.3: 1 - 1: 1.7 at a temperature of 110–120 ° С, under a pressure of 7–17.5 MPa for 2–7.5 h with obtaining 0.06-0.65 mol of 1,3-propanediol or 1,3-butanediol.
    [2]
    2. The method according to claim 1, about t l and h and Yu and with the fact that the process is conducted in the presence of 1-6 wt.% Water by weight of the reaction medium,
    [3]
    3. Method pop. 1, of which it is different from the fact that HJ, HC1, p-toluene sulfonic acid or phosphoric acid are used as the acid.
    [4]
    4. Method as claimed in claim 1, characterized in that tetraslim, tetrahydrofuran or a mixture of glycolic polyethers of ethylene and propylene glycols are used as inert solvent.
    [5]
    5. The method of claim 1, which uses tricyclohexylphosphine, triisopropylphosphine, triisobutylphosphine, diisopropylphenylphosphine or dicyclohexylphenylphosphine as tertiary monophosphine.
    [6]
    6. The method according to claim 1, about tl and h and Yu and with the use of ethylene oxide, tetraglyme is taken as an inert solvent and the process is carried out at a temperature of 110-120 ° C and a pressure of 7-17.5 MPa.
    类似技术:
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    同族专利:
    公开号 | 公开日
    PT85558A|1987-09-01|
    FI873604A0|1987-08-20|
    HUT48190A|1989-05-29|
    AU7687887A|1988-02-25|
    NO168030C|1992-01-08|
    EP0257967A2|1988-03-02|
    CA1279657C|1991-01-29|
    NO873496D0|1987-08-19|
    EP0257967A3|1989-09-06|
    CN87105645A|1988-07-27|
    PL267402A1|1988-07-21|
    FI873604A|1988-02-21|
    NO873496L|1988-02-22|
    AT89540T|1993-06-15|
    KR880002788A|1988-05-11|
    DD264423A5|1989-02-01|
    ZA875926B|1988-02-15|
    DE3785896T2|1993-11-11|
    PT85558B|1989-12-29|
    DK431287D0|1987-08-19|
    JPS6351342A|1988-03-04|
    DE3785896D1|1993-06-24|
    IL83573D0|1988-01-31|
    YU154887A|1988-10-31|
    AU604045B2|1990-12-06|
    EP0257967B1|1993-05-19|
    DK431287A|1988-02-21|
    NZ221464A|1989-07-27|
    BR8704298A|1988-04-12|
    NO168030B|1991-09-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3463819A|1965-10-21|1969-08-26|Shell Oil Co|Glycol production|
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    JP6157592B2|2012-04-25|2017-07-05|ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ|Process for preparing diketonato-rhodium-carbonyl complexes|
    CN108017510B|2016-11-03|2021-02-02|万华化学集团股份有限公司|Preparation method of hydroxyl pivalic aldehyde and application of hydroxyl pivalic aldehyde in preparation of neopentyl glycol|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US89807286A| true| 1986-08-20|1986-08-20|
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