CN114751929A - Preparation method of semiconductor-grade diethyl aluminum ethoxide - Google Patents
Preparation method of semiconductor-grade diethyl aluminum ethoxide Download PDFInfo
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- CN114751929A CN114751929A CN202210546988.6A CN202210546988A CN114751929A CN 114751929 A CN114751929 A CN 114751929A CN 202210546988 A CN202210546988 A CN 202210546988A CN 114751929 A CN114751929 A CN 114751929A
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- diethyl aluminum
- aluminum ethoxide
- hexane
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- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000012535 impurity Substances 0.000 claims abstract description 49
- 239000012298 atmosphere Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 229910000574 NaK Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- SXFIGIUKFHASFO-UHFFFAOYSA-N diethylalumanylium;ethanolate;hexane Chemical compound CC[O-].CC[Al+]CC.CCCCCC SXFIGIUKFHASFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019080 Mg-H Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 230000002740 effect on eyes Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QKJHJLBPEPMXAR-UHFFFAOYSA-N ethoxyalumane Chemical compound C(C)O[AlH2] QKJHJLBPEPMXAR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 moisture Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
Abstract
The invention relates to a preparation method of semiconductor grade diethyl aluminum ethoxide, which comprises the steps of removing a normal hexane solvent under the protection of anhydrous oxygen-free inert atmosphere; then carrying out reduced pressure rectification, and collecting middle fractions; washing the mixture for many times by using high-purity anhydrous n-hexane under a low-temperature condition; then distilling at normal temperature and normal pressure; adding a potassium-sodium alloy desiliconization agent, stirring, and refluxing at high temperature; and finally, carrying out reduced pressure rectification and collecting intermediate fractions. Removing most organic impurities and inorganic impurities through atmospheric distillation and vacuum rectification; washing with n-hexane for multiple times to remove trace organic impurities, distilling, adsorbing trace silicon impurities by adopting a potassium-sodium alloy desiliconization agent through high-temperature reflux, and finally performing reduced pressure rectification to obtain middle distillate to finally obtain high-purity diethyl aluminum ethoxide; the organic impurities in the diethyl aluminum ethoxide can be removed, the content of all inorganic impurities is less than 1ppm, and the purity and the granularity of the obtained diethyl aluminum ethoxide can better meet the product requirements of the semiconductor industry.
Description
Technical Field
The invention relates to a preparation method of semiconductor-grade diethyl aluminum ethoxide.
Background
At present, diethyl aluminum ethoxide is a colorless flammable liquid with high boiling point, is stable at normal temperature and normal pressure, can be dissolved in organic solvents such as hydrocarbons and the like, has stimulation effect on eyes, skin, mucosal tissues and upper respiratory tracts, is very sensitive to strong oxidants, moisture, air, acid and alcohol, is stored in dry inert gas, and keeps a container sealed. The method is mainly used for combining H in a Mg-H complex compound by O in P-ALGaAs (Mg doping), thereby improving the activation efficiency of Mg; diethyl aluminum ethoxide and nickel hexafluoropentadione are combined to form a double-component catalyst which acts on oligomerization reaction, isomerization reaction and hydrogenation reaction of alkene; the organic chromium catalyst also adopts diethyl aluminum ethoxide to reduce hexavalent chromium in the preparation process.
The synthesis method of diethyl aluminum ethoxide generally comprises the following steps: synthesis of triethylaluminium and sodium ethoxide, synthesis of triethylaluminium and ethoxyaluminium, etc.
Most of the commercially available diethyl-aluminum ethoxide n-hexane solutions are 25% in purity, and the organic purity of the solutions is about 98% with good quality, and the solutions contain a small amount of impurities such as iron, silicon, n-hexane solvent and the like. The diethyl aluminum ethoxide can not be directly used as a catalyst in the semiconductor industry, and in the semiconductor industry, the diethyl aluminum ethoxide is used as an important catalyst, and the ultrahigh purity of 6N is required, namely, the content of all inorganic impurities is less than 1ppm, and the diethyl aluminum ethoxide can not contain an organic solvent, so that the diethyl aluminum ethoxide can be further purified to ensure that all technical indexes of the diethyl aluminum ethoxide can reach the 6N standard.
The research on semiconductor-grade diethyl aluminum ethoxide is carried out aiming at the applications of olefin polymerization hydrogenation catalysis and the like, and the semiconductor-grade diethyl aluminum ethoxide not only has better stability and higher vapor pressure, but also shows quite high catalytic activity, and is a hotspot in the research field of petrochemical catalysis nowadays. At present, no report is available on the preparation method of semiconductor-grade diethyl ethoxy aluminum.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of semiconductor-grade diethyl aluminum ethoxide.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the semiconductor grade diethyl aluminum ethoxide is characterized in that: the method comprises the following steps:
1) under the protection of anhydrous oxygen-free inert atmosphere, removing the normal hexane solvent;
in a water-free and oxygen-free inert atmosphere glove box, filling a diethyl aluminum ethoxide n-hexane solution into a round bottom flask, and distilling the solution by adopting a thorn-shaped distillation column under normal pressure to remove an n-hexane solvent in raw materials;
2) performing reduced pressure rectification, and collecting middle fractions;
in an inert atmosphere glove box, performing reduced pressure rectification on diethyl aluminum ethoxide by using a rectification column containing theta-shaped stainless steel filler to remove low-boiling fraction and high-boiling impurity, and collecting middle-section fraction;
3) Washing the mixture for many times by using high-purity anhydrous n-hexane under a low-temperature condition;
stirring high-purity anhydrous n-hexane and diethyl aluminum ethoxide fraction in the middle section in an inert atmosphere glove box at room temperature, reducing the temperature after stirring to separate out diethyl aluminum ethoxide, changing the diethyl aluminum ethoxide from a liquid state to a solid state, and pouring out the n-hexane solvent;
4) distilling at normal temperature and normal pressure;
in an inert atmosphere glove box, when the jacketed bottle returns to the room temperature, pouring diethyl aluminum ethoxide into a round-bottom flask, distilling the diethyl aluminum ethoxide by adopting a thorn-shaped distillation column under normal pressure, and removing a normal hexane solvent;
5) adding a potassium-sodium alloy desiliconization agent, stirring, and refluxing at high temperature;
adding a potassium-sodium alloy desiliconization agent into a round-bottomed flask, adding a magnetic stirrer, heating and stirring, refluxing at high temperature, and adsorbing trace silicon impurities;
6) vacuum rectifying, collecting intermediate fraction
In an inert atmosphere glove box, a rectification column containing theta-shaped stainless steel filler is adopted to carry out vacuum rectification on diethyl aluminum ethoxide, low boiling point fractions and high boiling point impurities are removed, middle section fractions are collected, and finally the ultra-pure diethyl aluminum ethoxide is obtained.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, in the step 2), theta-shaped stainless steel mixed packing with different sizes is adopted to fill the rectifying column.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, in the step 3), in an inert atmosphere glove box, under the room temperature condition, the high-purity anhydrous n-hexane and the diethyl aluminum ethoxide fraction of the middle section are mixed according to the proportion of 2: 1, stirring for 1 hour, cooling the temperature to about-30 ℃ to separate out diethyl aluminum ethoxide, changing the diethyl aluminum ethoxide from a liquid state to a solid state, and pouring out an n-hexane solvent; the above steps were repeated and washing was continued for 3 times.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, the ratio of n-hexane to diethyl aluminum ethoxide is 2: 1, placing the mixture into a jacketed bottle, and adding a magnetic stirrer for stirring; after the stirring, the jacketed flask was cooled to about-30 ℃ by a freezer to precipitate diethyl aluminum ethoxide, which became solid from liquid.
Further, the preparation method of the semiconductor grade diethyl aluminum ethoxide comprises the steps that the melting point of n-hexane is-95 ℃, the melting point of diethyl aluminum ethoxide is 2.5-4.5 ℃, the melting point of trace organic impurities is-70 ℃ to-90 ℃, diethyl aluminum ethoxide is separated out at about-30 ℃ according to the difference between the melting points, the liquid state is changed into the solid state, and the trace organic impurities are dissolved in the n-hexane solvent and poured out.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, in the step 5), a condensing tube connected with a refrigerator is used as a cooling device for reflux, the top of the condensing tube is connected with an air extraction head, and the air extraction head is connected with a bubble counter through a latex tube.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, in the step 6), the reduced pressure distillation is connected with a cold trap outside the glove box through a pipeline and then connected with a vacuum pump, the vacuum pump is used for vacuumizing, nitrogen is used as a protective gas, and the vacuum degree is controlled by controlling a nitrogen valve.
Further, in the preparation method of the semiconductor grade diethyl aluminum ethoxide, the inert atmosphere is nitrogen atmosphere.
Compared with the prior art, the invention has obvious advantages and beneficial effects, which are embodied in the following aspects:
firstly, removing most of organic impurities and inorganic impurities through atmospheric distillation and vacuum rectification; washing with n-hexane for multiple times to remove trace organic impurities, distilling, adsorbing trace silicon impurities by adopting a potassium-sodium alloy desiliconization agent through high-temperature reflux, and finally performing reduced pressure rectification to obtain middle distillate to finally obtain high-purity diethyl aluminum ethoxide;
According to NMR detection, organic impurities in diethyl aluminum ethoxide can be removed by the preparation method, all inorganic impurities are detected by ICP-OES, the content of all the inorganic impurities is less than 1ppm, and the purity and the granularity of the diethyl aluminum ethoxide obtained by the preparation method can better meet the product requirements of the semiconductor industry;
the preparation method disclosed by the invention does not need any ether solvent, only needs a single hydrocarbon solvent n-hexane, adopts conventional commercially available products as raw materials, greatly reduces the cost and the toxicity of the reaction, has better operability, and is good in stability, high in catalytic activity and easy for large-scale production.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description.
Detailed Description
Specific embodiments will now be described in detail in order to more clearly understand the technical features, objects, and effects of the present invention.
The preparation process of the semiconductor-grade diethyl aluminum ethoxide comprises the following steps:
1) Under the protection of anhydrous oxygen-free inert atmosphere, removing the normal hexane solvent;
in a water-free and oxygen-free inert atmosphere glove box, filling a diethyl aluminum ethoxide n-hexane solution into a round bottom flask, and distilling the solution by adopting a thorn-shaped distillation column under normal pressure to remove an n-hexane solvent in raw materials; the inert atmosphere is nitrogen atmosphere;
2) performing reduced pressure rectification, and collecting middle fractions;
in an inert atmosphere glove box, filling a rectifying column with theta-shaped stainless steel mixed fillers with different sizes to perform vacuum rectification on diethyl aluminum ethoxide, removing low-boiling-point fractions and high-boiling-point impurities, and collecting middle-section fractions;
3) washing the mixture for many times by using high-purity anhydrous n-hexane under a low-temperature condition;
in an inert atmosphere glove box, under the condition of room temperature, the high-purity anhydrous n-hexane and the diethyl aluminum ethoxide fraction of the middle section are mixed according to the proportion of 2: 1, and stirring the mixture according to the volume ratio of the n-hexane to the diethyl aluminum ethoxide of 2: 1, placing the mixture into a jacketed bottle, and adding a magnetic stirrer for stirring; after stirring, cooling the jacketed bottle to about-30 ℃ by using a refrigerator to separate out diethyl aluminum ethoxide, changing the diethyl aluminum ethoxide from a liquid state to a solid state, and pouring out the n-hexane solvent; repeating the steps, and continuously washing for 3 times;
The melting point of n-hexane is-95 ℃, the melting point of diethyl ethoxy aluminum is 2.5-4.5 ℃, the melting point of trace organic impurities is-70 ℃ to-90 ℃, diethyl ethoxy aluminum is separated out at about-30 ℃ according to the difference between the melting points, liquid is changed into solid, and the trace organic impurities are dissolved in the n-hexane solvent and poured out;
4) distilling at normal temperature and normal pressure;
in an inert atmosphere glove box, when the jacketed bottle returns to the room temperature, pouring diethyl aluminum ethoxide into a round-bottom flask, distilling the diethyl aluminum ethoxide by adopting a thorn-shaped distillation column under normal pressure, and removing a normal hexane solvent;
5) adding a potassium-sodium alloy desiliconization agent, stirring, and refluxing at high temperature;
adding a potassium-sodium alloy desiliconization agent into a round-bottomed flask, adding a magnetic stirrer, heating and stirring, refluxing at high temperature for 24 hours, wherein the reflux is performed by taking a condenser connected with a refrigerator as a cooling device, the top of the reflux is connected with an air pumping head, and the reflux is connected with a bubble counter through a latex tube to adsorb trace silicon impurities;
6) vacuum rectifying, collecting intermediate fraction
In an inert atmosphere glove box, the inert atmosphere is nitrogen atmosphere, a rectification column containing theta-shaped stainless steel filler is adopted to carry out reduced pressure rectification on diethyl aluminum ethoxide, the rectification column is connected with a cold trap outside the glove box through a pipeline and then connected with a vacuum pump, the vacuum pump is used for pumping vacuum, nitrogen is used as protective gas, the vacuum degree is controlled by controlling a nitrogen valve, low boiling point fraction and high boiling point impurities are removed, middle section fraction is collected, and finally the ultra-pure diethyl aluminum ethoxide is obtained.
Example 1
1207g of 25 percent diethyl aluminum normal hexane solution is filled into a 2L round bottom flask in a water-free and oxygen-free inert atmosphere glove box, and distilled by a thorn-shaped distillation column under normal pressure to remove the normal hexane in the raw material, thus obtaining 250g of diethyl aluminum ethoxide, wherein the organic purity is 96.43 percent by NMR, the silicon content is 10.7ppm and the iron content is 0.5ppm in ICP-OES all-element detection;
placing 250g of diethyl aluminum ethoxide in a 500ml round-bottom flask in an inert atmosphere glove box, performing reduced pressure rectification on the diethyl aluminum ethoxide by using rectification columns containing theta-type stainless steel mixed fillers with different sizes to remove 20% of low-boiling-point fractions and 20% of high-boiling-point impurities, collecting fractions with 60% of an intermediate section, and determining the organic purity to be 97.35% by NMR, the silicon content to be 4.0ppm and the iron content to be 0.1ppm in ICP-OES all-element detection;
in an inert atmosphere glove box, under the condition of room temperature, the high-purity anhydrous n-hexane and the diethyl aluminum ethoxide fraction of the middle section are mixed according to the proportion of 2: 1 into a 1L jacketed bottle, adding a magnetic stirrer for stirring, cooling the jacketed bottle to about-30 ℃ by a refrigerator after stirring for 1h to separate out diethyl aluminum ethoxide, changing the diethyl aluminum ethoxide from a liquid state to a solid state, and pouring out the n-hexane solvent. Repeating the steps, and continuously washing for 3 times;
Turning off the refrigerator, in an inert atmosphere glove box, after the jacketed bottle returns to room temperature, pouring diethyl aluminum ethoxide into a round bottom flask, distilling the flask by using a thorn-shaped distillation column under normal pressure, removing a small amount of n-hexane solvent, and measuring the organic purity of the flask by using NMR to be 99.8 percent and the silicon content in ICP-OES full-element detection to be 2.2 ppm;
adding 5g of potassium-sodium alloy desiliconization agent into a round-bottom flask, adding a magnetic stirrer, heating and stirring, taking a condenser connected with a refrigerator as a cooling device, refluxing at high temperature for 24 hours, and adsorbing trace silicon impurities;
in an inert atmosphere glove box, performing reduced pressure rectification on diethyl aluminum ethoxide by using a rectification column containing theta-shaped stainless steel mixed fillers with different sizes, removing 20% of low-boiling-point fraction and 20% of high-boiling-point impurities, collecting fraction with 60% of middle section, and finally obtaining 76g of middle fraction of diethyl aluminum ethoxide, wherein the yield is 84.4%, the organic purity is 99.95% through NMR measurement, and the content of all inorganic impurities is less than 1ppm through ICP-OES full-element detection, so that the product purity requirement of the semiconductor industry is met.
Example 2
1300g of a 25% diethyl aluminum ethoxide n-hexane solution was charged into a 2L round bottom flask in a glove box in an inert atmosphere free of water and oxygen, and distilled using a stab type distillation column under normal pressure to remove n-hexane from the raw material to obtain 268g of diethyl aluminum ethoxide having an organic purity of 96.28% by NMR, a silicon content of 9.9ppm and an iron content of 0.5ppm in ICP-OES total element detection;
Placing 268g of diethyl aluminum ethoxide in a 500ml round-bottom flask in an inert atmosphere glove box, carrying out reduced pressure rectification on the diethyl aluminum ethoxide by using rectification columns containing theta-type stainless steel mixed fillers with different sizes, removing 20% of low-boiling-point fractions and 20% of high-boiling-point impurities, collecting fractions with the middle section of 60%, and measuring the organic purity of 97.28% by NMR, wherein the silicon content and the iron content are 4.2ppm and 0.15ppm in ICP-OES all-element detection;
in an inert atmosphere glove box, under the condition of room temperature, the high-purity anhydrous n-hexane and the diethyl aluminum ethoxide fraction of the middle section are calculated according to the proportion of 3: 1 into a 2L jacketed bottle, adding a magnetic stirrer, stirring for 1h, cooling the jacketed bottle to-30 deg.C with a refrigerator to separate out diethyl aluminum ethoxide, changing from liquid to solid, and pouring out n-hexane solvent. Repeating the steps, and continuously washing for 3 times;
turning off the refrigerator, in an inert atmosphere glove box, after the jacketed bottle returns to room temperature, pouring diethyl aluminum ethoxide into a round bottom flask, distilling the flask by using a thorn-shaped distillation column under normal pressure, removing a small amount of n-hexane solvent, and measuring the organic purity of the flask by using NMR to be 99.87 percent and the silicon content in ICP-OES all-element detection to be 1.7 ppm;
Adding 3g of potassium-sodium alloy desiliconization agent into a round-bottom flask, adding a magnetic stirrer, heating and stirring, taking a condenser connected with a refrigerator as a cooling device, refluxing at high temperature for 24 hours, and adsorbing trace silicon impurities;
in an inert atmosphere glove box, performing reduced pressure rectification on diethyl aluminum ethoxide by using a rectification column containing theta-shaped stainless steel mixed fillers with different sizes, removing 20% of low-boiling-point fraction and 20% of high-boiling-point impurities, collecting fraction with 60% of middle section, and finally obtaining 70g of middle fraction of diethyl aluminum ethoxide, wherein the yield is 72.6%, the organic purity is 99.96% through NMR measurement, and the content of all inorganic impurities is less than 1ppm through ICP-OES full-element detection, so that the product purity requirement of the semiconductor industry is met.
Example 3
In a glove box in an inert atmosphere without water and oxygen, 1000g of 25% diethyl aluminum ethoxide n-hexane solution is filled into a 2L round bottom flask, and distilled by a thorn-shaped distillation column under normal pressure to remove n-hexane in the raw material, so as to obtain 235g of diethyl aluminum ethoxide, wherein the organic purity is 96.50% by NMR, and the silicon content and the iron content are 10.2ppm and 0.35ppm in ICP-OES all-element detection;
placing 235g of diethyl aluminum ethoxide in a 500ml round-bottom flask in an inert atmosphere glove box, carrying out reduced pressure rectification on the diethyl aluminum ethoxide by using rectification columns containing theta-type stainless steel mixed fillers with different sizes, removing 20% of low-boiling-point fractions and 20% of high-boiling-point impurities, collecting fractions with 60% of an intermediate section, and measuring the organic purity of 97.32% by NMR, wherein the silicon content and the iron content are 3.7ppm and 0.12ppm in ICP-OES all-element detection;
In an inert atmosphere glove box, under the condition of room temperature, the high-purity anhydrous n-hexane and the diethyl aluminum ethoxide fraction of the middle section are mixed according to the proportion of 1: 1 into a 2L jacketed bottle, adding a magnetic stirrer, stirring for 1h, cooling the jacketed bottle to-30 deg.C with a refrigerator to separate out diethyl aluminum ethoxide, changing from liquid to solid, and pouring out n-hexane solvent. Repeating the steps, and continuously washing for 3 times;
turning off the refrigerator, in an inert atmosphere glove box, after the jacketed bottle returns to room temperature, pouring diethyl aluminum ethoxide into a round bottom flask, distilling the flask by using a thorn-shaped distillation column under normal pressure, removing a small amount of n-hexane solvent, and measuring the organic purity of the flask by NMR to be 99.65 percent and the silicon content in ICP-OES all-element detection to be 2.5 ppm;
adding 8g of potassium-sodium alloy desiliconization agent into a round-bottom flask, adding a magnetic stirrer, heating and stirring, refluxing at high temperature for 24 hours by using a condenser pipe connected with a refrigerator as a cooling device, and adsorbing trace silicon impurities;
in an inert atmosphere glove box, performing reduced pressure rectification on diethyl aluminum ethoxide by using a rectification column containing theta-shaped stainless steel mixed fillers with different sizes, removing 20% of low-boiling-point fraction and 20% of high-boiling-point impurities, collecting fraction with 60% of middle section, and finally obtaining 62g of middle fraction of diethyl aluminum ethoxide, wherein the yield is 73.3%, the organic purity is 99.96% through NMR measurement, and the content of all inorganic impurities is less than 1ppm through ICP-OES full-element detection, so that the product purity requirement of the semiconductor industry is met.
In conclusion, the invention removes most organic impurities and inorganic impurities through atmospheric distillation and vacuum rectification;
then, under the condition of low temperature, washing with high-purity anhydrous n-hexane for multiple times to remove trace organic impurities;
distilling, and then refluxing at high temperature by adopting a potassium-sodium alloy desiliconization agent to adsorb trace silicon impurities;
and finally, carrying out reduced pressure rectification to remove front fractions and high-boiling-point impurities, and taking middle fractions to finally obtain the high-purity diethyl aluminum ethoxide.
According to NMR detection, the preparation method can remove organic impurities in diethyl aluminum ethoxide, the organic purity is up to more than 99.95%, and the content of all inorganic impurities is less than 1ppm through ICP-OES all-element detection, so that the product purity requirement of the semiconductor industry is met. The high-purity diethyl aluminum ethoxide can be filtered by a high-purity clean microporous filter to remove large-aperture particles influencing use, so that the product with high organic purity and granularity can be obtained, and the product requirement of the semiconductor industry can be well met.
It should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; while the foregoing description will be apparent to those skilled in the relevant art and it is intended to cover in the appended claims all such modifications and changes as fall within the true spirit of the invention.
Claims (8)
1. The preparation method of the semiconductor grade diethyl aluminum ethoxide is characterized by comprising the following steps: the method comprises the following steps:
1) under the protection of anhydrous oxygen-free inert atmosphere, removing the normal hexane solvent;
in a water-free and oxygen-free inert atmosphere glove box, filling a diethyl aluminum ethoxide n-hexane solution into a round bottom flask, and distilling the solution by adopting a thorn-shaped distillation column under normal pressure to remove an n-hexane solvent in raw materials;
2) performing reduced pressure rectification, and collecting middle fractions;
in an inert atmosphere glove box, performing reduced pressure rectification on diethyl aluminum ethoxide by using a rectification column containing theta-shaped stainless steel filler to remove low-boiling fraction and high-boiling impurity, and collecting middle-section fraction;
3) washing the mixture for many times by using high-purity anhydrous n-hexane under a low-temperature condition;
stirring high-purity anhydrous n-hexane and diethyl aluminum ethoxide fraction in the middle section in an inert atmosphere glove box at room temperature, reducing the temperature after stirring, separating out diethyl aluminum ethoxide, changing the liquid state into a solid state, and pouring out the n-hexane solvent;
4) distilling at normal temperature and normal pressure;
in an inert atmosphere glove box, when the jacketed bottle is returned to the room temperature, pouring diethyl aluminum ethoxide in the jacketed bottle into a round-bottom flask, distilling the diethyl aluminum ethoxide by using a thorn-shaped distillation column at normal pressure, and removing a normal hexane solvent in the diethyl aluminum ethoxide;
5) Adding a potassium-sodium alloy desiliconization agent, stirring, and refluxing at high temperature;
adding a potassium-sodium alloy desiliconization agent into a round-bottomed flask, adding a magnetic stirrer, heating and stirring, refluxing at high temperature, and adsorbing trace silicon impurities;
6) vacuum rectifying, collecting intermediate fraction
In an inert atmosphere glove box, a rectification column containing theta-shaped stainless steel filler is adopted to carry out reduced pressure rectification on diethyl aluminum ethoxide, low boiling point fractions and high boiling point impurities are removed, middle section fractions are collected, and finally the ultra-pure diethyl aluminum ethoxide is obtained.
2. The method of claim 1, wherein the method comprises the steps of: and 2) filling the rectifying column with theta-shaped stainless steel mixed fillers with different sizes.
3. A method of preparing semiconductor grade diethyl aluminum ethoxide according to claim 1, characterized in that: and 3) in an inert atmosphere glove box, under the room temperature condition, mixing high-purity anhydrous n-hexane and diethyl ethoxy aluminum distillate at the middle section according to the weight ratio of 2: 1, stirring, cooling the temperature to about minus 30 ℃ after stirring for 1h, separating out diethyl aluminum ethoxide, changing the liquid state into a solid state, and pouring out the n-hexane solvent; the above steps were repeated and washing was continued 3 times.
4. A method of preparing semiconductor grade diethyl aluminum ethoxide according to claim 1 or 3, characterized in that: n-hexane and diethyl aluminum ethoxide according to a ratio of 2: 1, placing the mixture into a jacketed bottle, and adding a magnetic stirrer for stirring; after the stirring, the jacketed flask was cooled to about-30 ℃ by a freezer to precipitate diethyl aluminum ethoxide, which became solid from liquid.
5. A method of preparing semiconductor grade diethyl aluminum ethoxide according to claim 1 or 3, characterized in that: the melting point of the n-hexane is-95 ℃, the melting point of the diethyl ethoxy aluminum is 2.5-4.5 ℃, the melting point of the trace organic impurities is-70 ℃ to-90 ℃, the diethyl ethoxy aluminum is separated out at about-30 ℃ according to the difference between the melting points, the diethyl ethoxy aluminum is changed from a liquid state to a solid state, and the trace organic impurities are dissolved in the n-hexane solvent and poured out.
6. The method of claim 1, wherein the method comprises the steps of: and 5) refluxing by taking a condenser pipe connected with a refrigerator as a cooling device, connecting the top of the condenser pipe with an air extraction head, and connecting the air extraction head with a bubble counter through a latex pipe.
7. The method of claim 1, wherein the method comprises the steps of: and 6) connecting the reduced pressure distillation with a cold trap outside the glove box through a pipeline, then connecting with a vacuum pump, vacuumizing through the vacuum pump, taking nitrogen as protective gas, and controlling the vacuum degree through controlling a nitrogen valve.
8. The method of claim 1, wherein the method comprises the steps of: the inert atmosphere is nitrogen atmosphere.
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