CN102952010A - Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium preparation method - Google Patents
Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium preparation method Download PDFInfo
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Abstract
The present invention relates to a bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium preparation method, which comprises the following steps that: bicyclo[2.2.1]-hept-5-en-2,3-dicarboxylic acid disodium is subjected to a catalytic hydrogenation reaction to obtain the bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium, wherein a catalyst used in the catalytic hydrogenation reaction is 20-120 mesh aluminum-nickel alloy, a ratio of the bicyclo[2.2.1]-hept-5-en-2,3-dicarboxylic acid disodium to the catalyst is 0.02 mol:1.10-1.75 g, a reaction temperature is 15-40 DEG C, and reaction pressure is atmospheric pressure. The method has a high yield, wherein the yield is more than 98%.
Description
Technical field
The present invention relates to a kind of two ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium.
Background technology
Two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium is the important decentralized polypropylene nucleater that development in recent years is got up, the commercial disignation of Milliken company is HPN-68, is outstanding commercially produced product.This class nucleator Main Function is the isotropy that improves polyacrylic Tc and modified polypropene (PP) contraction, it is high to have nucleation efficient, the PP Tc is high, crystallization half-life is short, each advantage to the contraction same sex of forming polymer is the main raw material that exploitation has polypropylene (PP) composite nucleating agent of two ring structures.
Although disclosed in the prior art about two ring [2.2.1] heptane-2, all there are the not high problem of yield in the preparation method of 3-dicarboxylic acid disodium, these methods.Therefore, still need existing two ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium improves.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of two ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium.
Two ring [2.2.1] heptane-2 provided by the invention, the preparation method of 3-dicarboxylic acid disodium may further comprise the steps:
Two rings [2.2.1]-heptan-5-alkene-2,3-dicarboxylic acid disodium 4 carries out catalytic hydrogenation and obtains two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium 5;
Wherein, the catalyzer of described catalytic hydrogenation use is 20 ~ 120 order alumino nickels; In two rings [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid disodium 4 is 0.02mol:1.10g ~ 1.75g with the amount ratio of described catalyzer; The temperature of described reaction is 15 ~ 40 ℃; The pressure of described reaction is normal pressure.
Described 20 ~ 120 order alumino nickel catalyzer include but not limited to 20 ~ 40 order alumino nickel catalyzer, 40 ~ 80 order alumino nickel catalyzer and 80 ~ 120 order alumino nickel catalyzer.
Preferably, described catalyzer is 20 ~ 40 order alumino nickels; In two rings [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid disodium 4 is 0.02mol:1.10g with the amount ratio of described catalyzer; The temperature of described reaction is 20 ~ 35 ℃; The time of described reaction is 90 ~ 180min.
Preferably, the solvent of described catalytic hydrogenation is methyl alcohol, ethanol or Virahol.
The preparation process of described catalyzer is: according to the 1g alumel: the ratio of 20mL distilled water is mixed, and adds the solid sodium hydroxide of 1.6 times of alumel weight after mixing in batches; The adding speed of control sodium hydroxide is not overflowed reaction vessel with foam and is advisable, till overflowing without obvious hydrogen; Then reactant is placed 10min in room temperature, then in 70 ℃ of water-baths, be incubated 0.5h; The supernatant liquid that inclines respectively washs 3 times with distilled water and 95% ethanol successively with decantation.
Contain weight percent content in the described catalyzer less than or equal to 50% treated old catalyzer, preferably contain weight percent content less than or equal to 35% treated old catalyzer; And the treating processes of described old catalyzer is: will use catalyzer once extremely to clarify with hot wash, then add mass percent concentration and be 20% sodium hydroxide solution, at 90 ℃ of lower stirring reaction 1h, then wash described catalyzer to pH value with water and be 9 ~ 10 and get final product.
Two ring [2.2.1] heptane-2 provided by the invention, the preparation method of 3-dicarboxylic acid disodium further may further comprise the steps:
(1) dicyclopentadiene 1 thermal degradation is generated cyclopentadiene 2;
(2) mixture with solvent and MALEIC ANHYDRIDE is cooled to below 10 ℃, slowly drips cyclopentadiene 2 under the violent stirring, and the control temperature of reaction, is warming up to 60 ℃ and continues reaction after dripping at 10 ~ 15 ℃; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-enedioic acid acid anhydride 3;
(3) under the room temperature, sodium hydroxide is joined two rings [2.2.1] heptan-5-alkene-2, and in the aqeous suspension of 3- dicarboxylic anhydride 3,80 ℃ of stirrings make and form the clarification homogeneous solution, then 75 ℃ of vacuum rotary steam desolventizings obtain two the ring [2.2.1]-heptan-5-alkene-2,3-dicarboxylic acid disodium 4.
Preferably, in the step (2), cyclopentadiene 2 is 1.025 ~ 1.100:1 with the mol ratio of MALEIC ANHYDRIDE; Described solvent is cyclohexane/ethyl acetate or petrol ether/ethyl acetate; The consumption of described solvent is 40 ~ 150% of MALEIC ANHYDRIDE weight; The time that drips cyclopentadiene 2 is 20 ~ 30min; Reaction times after the intensification is 10 ~ 30min.
More preferably, in the step (2), cyclopentadiene 2 is 1.050 ~ 1.075:1 with the mol ratio of MALEIC ANHYDRIDE, most preferably is 1.050:1; Described solvent is petrol ether/ethyl acetate, most preferably is the petrol ether/ethyl acetate that volume ratio is 1:1; The consumption of described solvent is 46 ~ 80% of MALEIC ANHYDRIDE weight; The time that drips cyclopentadiene 2 is 30min; Reaction times after the intensification is 20min.
Preferably, in the step (1), described thermal degradation adopts successive reaction-fractionation process; Heating temperature is higher than 170 ℃; Be filled with O type ring filler in the fractional column, and its D=6 ~ 10mm, h=4 ~ 7mm; Fractional column is incubated by 40 ~ 42 ℃ of recirculated waters.
Two ring [2.2.1] heptane-2 of the present invention, the preparation method's of 3-dicarboxylic acid disodium yield is high, reaches more than 98%.
Description of drawings
Fig. 1 be two the ring [2.2.1] heptan-5-alkene-2, the high-efficient liquid phase chromatogram of 3-dicarboxylic anhydride.
Fig. 2 be two the ring [2.2.1] heptan-5-alkene-2, the infrared spectrogram of 3-dicarboxylic anhydride.
Fig. 3 be two the ring [2.2.1] heptan-5-alkene-2, the standard infrared spectrogram of 3-dicarboxylic anhydride.
Fig. 4 be two the ring [2.2.1] heptan-5-alkene-2, the X-diffraction analysis collection of illustrative plates of 3-dicarboxylic anhydride.
Fig. 5 is two ring [2.2.1] heptane-2, the high-efficient liquid phase chromatogram of 3-dicarboxylic acid disodium.
Fig. 6 is two ring [2.2.1] heptane-2, the infrared spectrogram of 3-dicarboxylic acid disodium.
Fig. 7 is two ring [2.2.1] heptane-2, the X-diffraction analysis collection of illustrative plates of 3-dicarboxylic acid disodium.
Embodiment
Below by the embodiment the present invention that further explains.
Main experimental raw specification and source are as follows:
Cyclopentadiene: obtained by Dicyclopentadiene (DCPD) cracking fractionation, collect 40 ~ 42 ℃ of cuts, gas chromatographic analysis content is greater than 99.7%.
MALEIC ANHYDRIDE: analytical pure, content 〉=99.5%, Tianjin is large chemical reagent development centre production forever.40 ~ 42 ℃ of cuts are collected in distillation before using.
Sherwood oil: analytical pure, 60 ~ 90 ℃ of boiling ranges, content 〉=99.5%, Tianjin Da Mao chemical reagent factory.
Ethyl acetate: analytical pure, content 〉=99.5%, Tianjin Da Mao chemical reagent factory.
Hexanaphthene: analytical pure, content 〉=99.5%, Tianjin Da Mao chemical reagent factory.
Hydrogen: industrial goods, the huge foreign flavour body in Changchun limited liability company.
Sodium hydroxide: analytical pure, content 〉=96.0%, the north, Tianjin day medical chemistry chemical reagent work.
Ni-Al:20 ~ 40 orders, 40 ~ 80 orders, 80 ~ 120 orders, catalyzer company limited of Suzhou City Xinhua.
Adopt successive reaction-fractionation process that the Dicyclopentadiene (DCPD) thermal degradation is generated cyclopentadiene; Heating temperature is 170 ℃; Be filled with O type ring filler in the fractional column, and its D(external diameter)=6mm, h(length)=4mm; Fractional column is incubated by 40 ℃ of recirculated waters.
The content analysis of cyclopentadiene: analytical instrument is sky, GC7900(Shanghai U.S. Instr Ltd.), be furnished with the FID hydrogen flame detector.Analysis condition: SE-54 capillary chromatographic column (15m * 0.25mm, 0.33 μ m), 150 ℃ of vaporizer temperature, 220 ℃ of detector temperatures, the column temperature program: 40 ℃ of initial temperatures, keep 15min, rise to 180 ℃ with 20 ℃ of speed, keep 10min.The quantitative analysis of cyclopentadiene adopts area normalization method to carry out.The result: content is greater than 99.7%.
Embodiment 2
In the four-hole boiling flask that agitator, constant pressure funnel, reflux condensing tube and thermometer are housed, be petrol ether/ethyl acetate and the 11.77g(0.12mol of 1:1 with the 5g volume ratio) the mixture of MALEIC ANHYDRIDE be cooled to below 10 ℃, slowly drip the cyclopentadiene of 0.126mol under the violent stirring, the time that drips cyclopentadiene is 30min, and the control temperature of reaction is at 10 ~ 15 ℃; After dripping, be warming up to 60 ℃ and continue reaction 20min; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-alkene-2, the 3-dicarboxylic anhydride.Yield is 99.0%.
Two the ring [2.2.1] heptan-5-alkene-2, the content analysis of 3-dicarboxylic anhydride and sign:
Content analysis adopts high performance liquid chromatography.Laboratory apparatus: Shimadzu LC-20AB high performance liquid chromatograph, join the SPD-M20A diode-array detector, Japanese Shimadzu company.Chromatographic condition: chromatographic column: Shimadzu VP-ODS C18 post (150 * 4.6mm, 5 μ m).Moving phase: A is that 0.1% phosphate aqueous solution, B are methyl alcohol; A:B=82:18.Flow velocity: 1mL/min.The detection wavelength is: 210nm.Measuring temperature is 40 ℃.Sample size: 20 μ L.Two the ring [2.2.1] heptan-5-alkene-2, the high-efficient liquid phase chromatogram of 3-dicarboxylic anhydride is seen Fig. 1.By Fig. 1 obtain two the ring [2.2.1] heptan-5-alkene-2, the purity of 3-dicarboxylic anhydride is 99.5%.
Fusing point test: WRS-1B numeral melting point instrument, Shanghai are easily surveyed plant and instrument company limited, and thermometer is not calibrated.Measurement result: two the ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride fusing point is 164.2 ~ 165.8 ℃, conforms to 163 ~ 165 ℃ of literature values.
Ultimate analysis: Vario MICRO cube type elemental analyser, German elementar company.Results of elemental analyses sees Table 1.As can be seen from Table 1, two the ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride results of elemental analyses conforms to each element theory value.
Table 1 two ring [2.2.1] heptan-5-alkene-2, the results of elemental analyses of 3-dicarboxylic anhydride
Infrared spectroscopy: in two rings [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride Infrared spectroscopy is undertaken by your NICOLET6700 of company limited type Fourier transformation infrared spectrometer of U.S. Sai Mo-fly generation, the KBr compressing tablet, and infrared spectrogram is seen Fig. 2.Fig. 3 be two the ring [2.2.1] heptan-5-alkene-2, the standard infrared spectrogram of 3-dicarboxylic anhydride (derives from: http://www.sigmaaldrich.com/china-mainland.htmL).Fig. 2 and Fig. 3 are compared, can find out, both main absorption peak position and intensity are basic identical.
X-diffraction analysis: carry out the material phase analysis of crystal at the German Brooker ADVANCE D8 of company type X diffractometer, CuK alpha-ray source, scintillometer, sweep voltage 40kV, sweep current 40mA, 4-66 ° of 2 θ sweep limit, sweep velocity 0.2s/ step.Fig. 4 be two the ring [2.2.1] heptan-5-alkene-2, the X-diffraction analysis collection of illustrative plates of 3-dicarboxylic anhydride.By Fig. 4 and database are compared voluntarily, show products obtained therefrom be two the ring [2.2.1] heptan-5-alkene-2, the 3-dicarboxylic anhydride.
In the four-hole boiling flask that agitator, constant pressure funnel, reflux condensing tube and thermometer are housed, be cyclohexane/ethyl acetate and the 11.77g(0.12mol of 1:1 with the 18g volume ratio) the mixture of MALEIC ANHYDRIDE be cooled to below 10 ℃, slowly drip the cyclopentadiene of 0.129mol under the violent stirring, the time that drips cyclopentadiene is 20min, and the control temperature of reaction is at 10 ~ 15 ℃; After dripping, be warming up to 60 ℃ and continue reaction 30min; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, yield are 98.4%.Structural characterization is consistent with embodiment 2.
Embodiment 4
In the four-hole boiling flask that agitator, constant pressure funnel, reflux condensing tube and thermometer are housed, be petrol ether/ethyl acetate and the 11.77g(0.12mol of 1:1 with the 6g volume ratio) the mixture of MALEIC ANHYDRIDE be cooled to below 10 ℃, slowly drip the cyclopentadiene of 0.123mol under the violent stirring, the time that drips cyclopentadiene is 30min, and the control temperature of reaction is at 10 ~ 15 ℃; After dripping, be warming up to 60 ℃ and continue reaction 10min; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, yield are 99.2%.Structural characterization is consistent with embodiment 2.
Embodiment 5
In the four-hole boiling flask that agitator, constant pressure funnel, reflux condensing tube and thermometer are housed, be petrol ether/ethyl acetate and the 11.77g(0.12mol of 1:1 with the 9.5g volume ratio) the mixture of MALEIC ANHYDRIDE be cooled to below 10 ℃, slowly drip the cyclopentadiene of 0.132mol under the violent stirring, the time that drips cyclopentadiene is 30min, and the control temperature of reaction is at 10 ~ 15 ℃; After dripping, be warming up to 60 ℃ and continue reaction 20min; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, yield are 99.5%.Structural characterization is consistent with embodiment 2.
Embodiment 6
Under the room temperature, with 1.6g(0.04mol) sodium hydroxide joins 3.28g(0.02mol) two rings [2.2.1] heptan-5-alkene-2, in the 20mL aqeous suspension of 3-dicarboxylic anhydride, 80 ℃ of stirrings made and form clarification homogeneous solution (can be directly used in next step reaction) in 2 hours, then 75 ℃ of vacuum rotary steam desolventizings obtain two the ring [2.2.1]-heptan-5-alkene-2,3-dicarboxylic acid disodium.
Embodiment 7
In the 100mL beaker, place 1g alumel and 20mL distilled water, the rotation beaker mixes it, then adds the 1.6g solid sodium hydroxide in batches, and the time add shaking by swirling.The strong reaction heat release, and have a large amount of hydrogen to overflow.Control the adding speed of alkali, do not overflow with foam and be advisable, till overflowing without obvious hydrogen.Then reactant is placed 10min in room temperature, then in 70 ℃ of water-baths, be incubated 0.5h.The supernatant liquid that inclines respectively washs 3 times with distilled water and 95% ethanol successively with decantation.Then the catalyzer for preparing being added a small amount of ethanol covers for subsequent use.During use ethanol is inclined.
Simple and easy normal pressure catalytic hydrogenation device is comprised of 100mL round-bottomed flask (hydrogenation bottle), storage hydrogen cylinder, separating funnel (equilibration flask) and induction stirring.In the hydrogenation bottle, add 4.52g(0.02mol) firm two rings [2 that prepare, 2,1] heptan-5-alkene-2,3-dicarboxylic acid disodium, it is mixed with 50% methanol solution, place 25 ℃ of waters bath with thermostatic control, 20 ~ 40 order alumino nickel catalyzer that adding 1.10g prepares carry out catalytic hydrogenation 90min.After reaction finishes, remove by filter catalyzer, then filtrate is changed in the 100mL round-bottomed flask,,, while hot product is poured in the furnace pot when more epitaxial occurring to the round-bottomed flask 80 ℃ of lower solvent removed in vacuo with Rotary Evaporators, at room temperature cooling, separate out white solid, be drying to obtain two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium at 80 ℃.Yield is 99.3%.
Two ring [2.2.1] heptane-2, content analysis and the sign of 3-diacid carboxylic disodium:
Content analysis adopts high performance liquid chromatography.Laboratory apparatus: Shimadzu LC-20AB high performance liquid chromatograph, join the SPD-M20A diode-array detector, Japanese Shimadzu company.Chromatographic condition: chromatographic column: Shimadzu VP-ODS C18 post (150 * 4.6mm, 5 μ m).Moving phase: 0.1% phosphate aqueous solution.Flow velocity: 1mL/min.The detection wavelength is: 207nm.Measuring temperature is 40 ℃.Sample size: 20 μ L.Two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium liquid chromatogram is seen Fig. 5.Obtain two ring [2.2.1] heptane-2 by Fig. 5, the purity of 3-dicarboxylic acid disodium is 99.5%.
Fusing point test: WRS-1B numeral melting point instrument, Shanghai are easily surveyed plant and instrument company limited, and thermometer is not calibrated.Two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium fusing point conforms to greater than 300 ℃ with literature value greater than 300 ℃.
Ultimate analysis: Vario MICRO cube type elemental analyser, German elementar company.Results of elemental analyses sees Table 2.As can be seen from Table 2, two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium results of elemental analyses conforms to each element theory value.
Table 2 two ring [2.2.1] heptane-2, the results of elemental analyses of 3-dicarboxylic acid disodium
Infrared spectroscopy: two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium Infrared spectroscopy is undertaken by your NICOLET6700 of company limited type Fourier transformation infrared spectrometer of U.S. Sai Mo-fly generation, the KBr compressing tablet, infrared spectrogram is seen Fig. 6.Infrared spectrogram in Fig. 6 and the bibliographical information is compared, and main absorption peak conforms to.
X-diffraction analysis: carry out the material phase analysis of crystal at the German Brooker ADVANCE D8 of company type X diffractometer, CuK alpha-ray source, scintillometer, sweep voltage 40kV, sweep current 40mA, 4-66 ° of 2 θ sweep limit, sweep velocity 0.2s/ step.Fig. 7 is two ring [2.2.1] heptane-2, the X-diffraction analysis collection of illustrative plates of 3-dicarboxylic acid disodium.The result of analytical test and structural characterization shows that products obtained therefrom meets two ring [2.2.1] heptane-2, the constitutional features of 3-dicarboxylic acid disodium.
Embodiment 9
Simple and easy normal pressure catalytic hydrogenation device is comprised of 100mL round-bottomed flask (hydrogenation bottle), storage hydrogen cylinder, separating funnel (equilibration flask) and induction stirring.In the hydrogenation bottle, add 4.52g(0.02mol) firm two rings [2 that prepare, 2,1] heptan-5-alkene-2,3-dicarboxylic acid disodium, it is mixed with 60% ethanolic soln, place 30 ℃ of waters bath with thermostatic control, 40 ~ 80 order alumino nickel catalyzer that adding 1.75g prepares carry out catalytic hydrogenation 100min.After reaction finishes, remove by filter catalyzer, then filtrate is changed in the 100mL round-bottomed flask, with Rotary Evaporators 80 ℃ of lower solvent removed in vacuo, when more epitaxial occurring to the round-bottomed flask, while hot product is poured in the furnace pot, at room temperature white solid is separated out in cooling, is drying to obtain two ring [2.2.1] heptane-2 at 80 ℃, 3-dicarboxylic acid disodium, yield are 99.1%.Structural characterization is consistent with embodiment 8.
Simple and easy normal pressure catalytic hydrogenation device is comprised of 100mL round-bottomed flask (hydrogenation bottle), storage hydrogen cylinder, separating funnel (equilibration flask) and induction stirring.In the hydrogenation bottle, add 4.52g(0.02mol) firm two rings [2 that prepare, 2,1] heptan-5-alkene-2,3-dicarboxylic acid disodium, it is mixed with 40% aqueous isopropanol, place 20 ℃ of waters bath with thermostatic control, 80 ~ 120 order alumino nickel catalyzer that adding 1.25g prepares carry out catalytic hydrogenation 120min.After reaction finishes, remove by filter catalyzer, then filtrate is changed in the 100mL round-bottomed flask, with Rotary Evaporators 80 ℃ of lower solvent removed in vacuo, when more epitaxial occurring to the round-bottomed flask, while hot product is poured in the furnace pot, at room temperature white solid is separated out in cooling, is drying to obtain two ring [2.2.1] heptane-2 at 80 ℃, 3-dicarboxylic acid disodium, yield are 99.0%.Structural characterization is consistent with embodiment 8.
Embodiment 11
Take by weighing a certain amount of 20 ~ 40 order alumino nickel catalyzer that used once, oven dry, then place the beaker of 50ml, with the extremely clarification of hot wash catalyzer, the adding mass percent concentration is 20% sodium hydroxide solution, at 90 ℃ of lower stirring reaction 1h, then wash catalyzer to pH value with water and be 9 ~ 10, for subsequent use.Above-mentioned treated old catalyzer is mixed according to weight percent 1:1 with freshly prepd 20 ~ 40 order alumino nickel catalyzer, as the catalytic hydrogenation catalyzer.
Simple and easy normal pressure catalytic hydrogenation device is comprised of 100mL round-bottomed flask (hydrogenation bottle), storage hydrogen cylinder, separating funnel (equilibration flask) and induction stirring.In the hydrogenation bottle, add 4.52g(0.02mol) two rings [2,2,1] of just preparation heptan-5-alkene-2,3-dicarboxylic acid disodium, with its methanol solution that is configured to 30%, place 25 ℃ of waters bath with thermostatic control, add 20 ~ 40 above-mentioned order alumino nickel catalyzer of 1.10g and carry out catalytic hydrogenation 110min.After reaction finishes, remove by filter catalyzer, then filtrate is changed in the 100mL round-bottomed flask, with Rotary Evaporators 80 ℃ of lower solvent removed in vacuo, when more epitaxial occurring to the round-bottomed flask, while hot product is poured in the furnace pot, at room temperature white solid is separated out in cooling, is drying to obtain two ring [2.2.1] heptane-2 at 80 ℃, 3-dicarboxylic acid disodium, yield are 99.2%.Structural characterization is consistent with embodiment 8.
It will be understood by those skilled in the art that under the instruction of this specification sheets, can make some modifications or variation to the present invention.These modifications and variations also should be within claim limited range of the present invention.
Claims (9)
1. a ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, described preparation method may further comprise the steps:
Two rings [2.2.1]-heptan-5-alkene-2,3-dicarboxylic acid disodium 4 carries out catalytic hydrogenation and obtains two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium 5;
Wherein, the catalyzer of described catalytic hydrogenation use is 20 ~ 120 order alumino nickels; In two rings [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid disodium 4 is 0.02mol:1.10g ~ 1.75g with the amount ratio of described catalyzer; The temperature of described reaction is 15 ~ 40 ℃; The pressure of described reaction is normal pressure.
2. according to claim 1 two encircle [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, described catalyzer is 20 ~ 40 order alumino nickels; In two rings [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid disodium 4 is 0.02mol:1.10g with the amount ratio of described catalyzer; The temperature of described reaction is 20 ~ 35 ℃; The time of described reaction is 90 ~ 180min.
3. according to claim 1 and 2 two encircle [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, the solvent of described catalytic hydrogenation is methyl alcohol, ethanol or Virahol.
4. according to claim 1 ~ 3 each described two the ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium, it is characterized in that, the preparation process of described catalyzer is: according to the 1g alumel: the ratio of 20mL distilled water is mixed, and adds the solid sodium hydroxide of 1.6 times of alumel weight after mixing in batches; The adding speed of control sodium hydroxide is not overflowed reaction vessel with foam and is advisable, till overflowing without obvious hydrogen; Then reactant is placed 10min in room temperature, then in 70 ℃ of water-baths, be incubated 0.5h; The supernatant liquid that inclines respectively washs 3 times with distilled water and 95% ethanol successively with decantation.
5. according to claim 1 ~ 4 each described two the ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium, it is characterized in that, contain weight percent content in the described catalyzer less than or equal to 50% treated old catalyzer, preferably contain weight percent content less than or equal to 35% treated old catalyzer; And the treating processes of described old catalyzer is: will use catalyzer once extremely to clarify with hot wash, then add mass percent concentration and be 20% sodium hydroxide solution, at 90 ℃ of lower stirring reaction 1h, then washing described catalyzer to pH value with water is 9 ~ 10.
6. according to claim 1 ~ 5 each described two the ring [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, described method further may further comprise the steps:
(1) dicyclopentadiene 1 thermal degradation is generated cyclopentadiene 2;
(2) mixture with solvent and MALEIC ANHYDRIDE is cooled to below 10 ℃, slowly drips cyclopentadiene 2 under the violent stirring, and the control temperature of reaction, is warming up to 60 ℃ and continues reaction after dripping at 10 ~ 15 ℃; Then reaction mixture is cooled to below 10 ℃, filtration under diminished pressure, vacuum-drying obtain two the ring [2.2.1] heptan-5-enedioic acid acid anhydride 3;
(3) under the room temperature, sodium hydroxide is joined two rings [2.2.1] heptan-5-alkene-2, and in the aqeous suspension of 3-dicarboxylic anhydride 3,80 ℃ of stirrings make and form the clarification homogeneous solution, then 75 ℃ of vacuum rotary steam desolventizings obtain two the ring [2.2.1]-heptan-5-alkene-2,3-dicarboxylic acid disodium 4.
7. according to claim 6 two encircle [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, in the step (2), cyclopentadiene 2 is 1.025 ~ 1.100:1 with the mol ratio of MALEIC ANHYDRIDE; Described solvent is cyclohexane/ethyl acetate or petrol ether/ethyl acetate; The consumption of described solvent is 40 ~ 150% of MALEIC ANHYDRIDE weight; The time that drips cyclopentadiene 2 is 20 ~ 30min; Reaction times after the intensification is 10 ~ 30min.
8. according to claim 7 two encircle [2.2.1] heptane-2, the preparation method of 3-dicarboxylic acid disodium is characterized in that, in the step (2), cyclopentadiene 2 is 1.050 ~ 1.075:1 with the mol ratio of MALEIC ANHYDRIDE, is preferably 1.050:1; Described solvent is petrol ether/ethyl acetate, is preferably the petrol ether/ethyl acetate that volume ratio is 1:1; The consumption of described solvent is 46 ~ 80% of MALEIC ANHYDRIDE weight; The time that drips cyclopentadiene 2 is 30min; Reaction times after the intensification is 20min.
9. each described two ring [2.2.1] heptane-2 according to claim 6 ~ 8, the preparation method of 3-dicarboxylic acid disodium is characterized in that, in the step (1), described thermal degradation adopts successive reaction-fractionation process; Heating temperature is higher than 170 ℃; Be filled with O type ring filler in the fractional column, and its, D=6 ~ 10mm, h=4 ~ 7mm; Fractional column is incubated by 40 ~ 42 ℃ of recirculated waters.
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