CN112778349A - Refining method of tetra (dimethylamino) hafnium - Google Patents
Refining method of tetra (dimethylamino) hafnium Download PDFInfo
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- CN112778349A CN112778349A CN202011590423.5A CN202011590423A CN112778349A CN 112778349 A CN112778349 A CN 112778349A CN 202011590423 A CN202011590423 A CN 202011590423A CN 112778349 A CN112778349 A CN 112778349A
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- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000007670 refining Methods 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 88
- 229920005989 resin Polymers 0.000 claims abstract description 88
- 238000001179 sorption measurement Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000004821 distillation Methods 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- -1 hafnium tetra (dimethylamino) phosphonium Chemical compound 0.000 claims description 10
- QCHIEOGZUMAQKI-SNAWJCMRSA-N (e)-3-(3-boronophenyl)prop-2-enoic acid Chemical compound OB(O)C1=CC=CC(\C=C\C(O)=O)=C1 QCHIEOGZUMAQKI-SNAWJCMRSA-N 0.000 claims description 9
- LQIMZUPFMSNHTM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxycarbonylamino]hex-5-enoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CCC=C LQIMZUPFMSNHTM-UHFFFAOYSA-N 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 239000004088 foaming agent Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 24
- 239000012043 crude product Substances 0.000 abstract description 19
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 229910052735 hafnium Inorganic materials 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- KXAVXHYIOCQWIB-UHFFFAOYSA-N n-(dimethylaminooxy)-n-methylmethanamine Chemical compound CN(C)ON(C)C KXAVXHYIOCQWIB-UHFFFAOYSA-N 0.000 description 1
- MAGVJLLHDZWQFM-UHFFFAOYSA-N n-chloro-n-methylmethanamine Chemical compound CN(C)Cl MAGVJLLHDZWQFM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Images
Classifications
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of chemical engineering, and particularly relates to a method for refining tetrakis (dimethylamino) hafnium; the method adopts the surface grafting modified adsorption resin to firstly carry out refined adsorption on the crude product of the tetra (dimethylamino) hafnium, remove a small amount of dimethylamine serving as a reaction raw material and n-butanol serving as a reaction byproduct contained in the product, then adopts a reduced pressure distillation mode to firstly remove a small amount of volatile impurities of the residual reaction raw material at a low temperature, and then heats and distills to obtain the high-purity product.
Description
Technical Field
The invention belongs to the field of chemical engineering, and particularly relates to a method for refining tetrakis (dimethylamino) hafnium.
Background
Tetrakis (dimethylamino) hafnium is mainly used for the formation of below 28nm, and is mainly used for the formation of HfN films and the formation of HKMG electrodes in copper shielding applications. The HKMG (high-k insulating layer + metal gate) technology has almost become a prerequisite technology for processes below the 45nm level.
CN102760758A discloses a metal gate structure including a high-k gate dielectric layer, a nitrogen-containing layer, a work-function metal layer, and a nitrogen trapping layer. The nitrogen-containing layer is arranged between the work function metal layer and the high-dielectric-constant grid dielectric layer; the nitrogen trapping layer is disposed between the work function metal layer and the high-k gate dielectric layer, and does not include any nitrogen ions or includes a low concentration of nitrogen ions.
CN1981386A provides an advanced gate structure comprising a fully silicided metal gate and silicided source and drain regions, wherein the fully silicided metal gate has a thickness greater than the thickness of the silicided source/drain regions. The invention also provides a method for forming the advanced gate structure.
CN105336592B proposes a gate last process for forming a high-K metal gate device, comprising: a. forming a gate oxide; b. removing the gate oxide on the core portion; c. forming silicon oxynitride layers on the input-output portion and the core portion, respectively; d. selectively etching part of the gate oxide and part of the silicon oxynitride layer, and forming a polysilicon dummy gate on the remaining gate oxide and silicon oxynitride layer; e. forming side walls on two sides of the polycrystalline silicon virtual grid; f. performing source and drain ion implantation on the substrate on two sides of the polycrystalline silicon virtual grid to form a source and a drain; g. forming an interlayer dielectric layer on the semiconductor substrate, wherein the interlayer dielectric layer exposes the top parts of the side walls and the polycrystalline silicon virtual grid; h. removing the polysilicon virtual grid; i. removing the silicon oxynitride layer; j. growing a gate oxide layer in the opening of the structure after the silicon oxynitride layer is removed; k. a high-k metal gate is formed at the gate oxide layer in the opening.
At present, no document reports a refining method of the compound in China, and a product obtained by a conventional distillation method cannot meet the requirement of the electronic industry on the use purity of the product. At present, the problem that Hf element and Zr element are difficult to separate is the most difficult problem, and the high-purity product with the purity of 99.9 percent is difficult to prepare.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for purifying tetrakis (dimethylamino) hafnium.
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80-120 parts by weight of crude product of hafnium tetra (dimethylamino) into a refining reaction kettle, adding 0.5-3 parts by weight of adsorption resin under the protection of nitrogen, controlling the temperature to be 40-80 ℃, stirring and mixing for 20-90min, filtering to remove the adsorption resin, and then introducing the crude product of hafnium tetra (dimethylamino) into a distillation kettle
Controlling the temperature to be 10-30 ℃, decompressing and pumping out volatile components, then heating to 50-130 ℃, decompressing and distilling to obtain the refined tetra (dimethylamino) hafnium finished product.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
according to the mass portion, 50-70 portions of polystyrene macroporous absorption resin are radiated by electron beams by using an electron accelerator to generate active free radicals which can be used for grafting reaction, and the radiation condition is as follows: the irradiation voltage is 3-5MeV, the irradiation dose is 15-30kGy, and the dose rate is 5-10 kGy/pass; immediately dispersing the macroporous adsorption resin into 500 parts of boiling cold pure water 200-0.6 part of gelatin and 12-18 parts of 4-allyl anisole, 0.1-0.5 part of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.1-0.5 part of 3- (2-carboxyvinyl) phenylboronic acid and 2-4 parts of benzoyl peroxide, controlling the temperature to be 70-85 ℃, stirring for grafting reaction for 120-180min, filtering out the resin, soaking the resin in ethanol for 5-10h after washing, and filtering to obtain the surface graft modified adsorption resin.
The reaction mechanism is that the active free radical of the polystyrene macroporous adsorption resin is grafted or polymerized with 4-allyl anisole, 2- (tert-butyloxycarbonylamino) -5-hexenoic acid and 3- (2-carboxyvinyl) phenylboronic acid, and the equation of partial reaction is shown as follows:
the content of the crude product of the hafnium tetra (dimethylamino) chloride is 90-95%.
The vacuum degree of the reduced pressure distillation in the distillation kettle is 0.09-0.1 MPa.
The distillation kettle is purged with dry nitrogen for 5-10min before use.
The method adopts the surface grafting modified adsorption resin to firstly carry out refined adsorption on the crude product of the tetra (dimethylamino) hafnium, remove a small amount of dimethylamine serving as a reaction raw material and n-butanol serving as a reaction byproduct contained in the product, then adopts a reduced pressure distillation mode to firstly remove a small amount of volatile impurities of the residual reaction raw material at a low temperature, and then heats and distills to obtain the high-purity product.
The surface grafting modified resin disclosed by the invention bonds tert-butyloxycarbonyl into a reaction system in a grafting or polymerization process, wherein the tert-butyloxycarbonyl is used as an amino protecting group, has a good adsorption effect on amino and a good adsorption effect on reaction raw material dimethylamine; the adsorbing resin grafts the anisole and the phenylboronic acid on the surface, is a resin which can better adsorb n-butanol which is a reaction byproduct, can prevent trace reaction raw materials, metal ions and the byproduct from being distilled into fractions along with the product, and creates conditions for obtaining a high-purity product.
Drawings
FIG. 1 is a Fourier infrared spectrum of the surface graft-modified adsorption resin prepared in example 2:
at 1610/1502/1454cm-1An absorption peak of benzene ring is present nearby, and is 2951cm-1A telescopic absorption peak of carbon hydrogen exists nearby, which indicates that D101 polystyrene macroporous adsorption resin participates in the reaction; at 1665cm-1The telescopic absorption peak of carbonyl exists nearby and is 1559cm-1An absorption peak of a nitrogen-hydrogen bond exists nearby, which indicates that the gelatin participates in the reaction; at 1728cm-1The telescopic absorption peak of the carboxyl carbonyl exists nearby and is 936cm-1An out-of-plane bending absorption peak of the carboxyl hydroxyl exists nearby, which indicates that 2- (tert-butoxycarbonylamino) -5-hexenoic acid participates in the reaction; at 1337cm-1The absorption peak of boron-oxygen bond exists nearby, which shows that the 3- (2-carboxyvinyl) phenylboronic acid participates in the reaction.
FIG. 2 is a nuclear magnetic resonance spectrum of hafnium tetra (dimethylamino) oxide prepared in example 3.
Detailed Description
The invention is further illustrated by the following specific examples:
the purity of the hafnium tetra (dimethylamino) acetate product was analyzed by nuclear magnetic resonance. The grafting ratio of the prepared adsorption resin is calculated according to the mass ratio of the product weight gain of the prepared resin to the added p-carboxyl anisole. The crude product of hafnium tetra (dimethylamino) used in the examples and comparative examples had a product content of 93.284%.
D101 polystyrene macroporous adsorption resin is selected as the polystyrene macroporous adsorption resin in the examples and the comparative examples.
Example 1
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 0.5g of adsorption resin under the protection of nitrogen, controlling the temperature to be 30 ℃, stirring and mixing for 20min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 10 ℃, decompressing and pumping volatile components, then heating to 80 ℃, decompressing and distilling to obtain the finished product of the refined tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
50g of D101 polystyrene macroporous adsorption resin is subjected to electron beam irradiation by using an electron accelerator to generate active free radicals for grafting reaction, and the irradiation conditions are as follows: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5 gy/pass; immediately dispersing the macroporous adsorption resin into 200g of boiling cold pure water, adding 0.3g of gelatin and 12g of 4-allyl anisole, 0.1g of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.1g of 3- (2-carboxyvinyl) phenylboronic acid and 2g of benzoyl peroxide, controlling the temperature to be 70 ℃, stirring for grafting reaction for 120min, filtering out the resin after completion, soaking the resin in ethanol for 5h after washing, and filtering to obtain the surface graft modified adsorption resin.
The vacuum degree of reduced pressure distillation in the distillation kettle is 15 Pa.
The still was purged with dry nitrogen for 5min before use.
Example 2
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 100g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 1.2g of adsorption resin under the protection of nitrogen, controlling the temperature to be 35 ℃, stirring and mixing for 50min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 30 ℃, decompressing and pumping volatile components, then heating to 60 ℃, decompressing and distilling to obtain the finished product of the refined tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
using an electron accelerator to perform electron beam radiation on 60g of polystyrene macroporous adsorption resin to generate active free radicals for grafting reaction, wherein the irradiation conditions are as follows: the irradiation voltage is 3.5MeV, the irradiation dose is 20gy, and the dose rate is 8 gy/pass; immediately dispersing the macroporous adsorption resin into 400g of boiling and cold pure water, adding 0.5g of gelatin, 17g of 4-allyl anisole, 0.4g of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.3g of 3- (2-carboxyvinyl) phenylboronic acid and 2.8g of benzoyl peroxide, controlling the temperature to be 77 ℃, stirring for grafting reaction for 160min, filtering out the resin after completion, soaking the resin in ethanol for 7h after washing, and filtering to obtain the surface graft modified adsorption resin.
The vacuum degree of reduced pressure distillation in the distillation kettle is 10 Pa.
The still was purged with dry nitrogen for 8min before use.
Example 3
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 120g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 3g of adsorption resin under the protection of nitrogen, controlling the temperature to be 40 ℃, stirring and mixing for 90min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 35 ℃, decompressing and removing volatile components, then heating to 50 ℃, decompressing and distilling to obtain a refined finished product of the tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
using an electron accelerator to perform electron beam irradiation on 70g of polystyrene macroporous adsorption resin to generate active free radicals for grafting reaction, wherein the irradiation conditions are as follows: the irradiation voltage is 5MeV, the irradiation dose is 30gy, and the dose rate is 10 gy/pass; immediately dispersing the macroporous adsorption resin into 500g of boiling and cold pure water, adding 0.6g of gelatin and 18g of 4-allyl anisole, 0.5g of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.5g of 3- (2-carboxyvinyl) phenylboronic acid and 4g of benzoyl peroxide, controlling the temperature to be 85 ℃, stirring for grafting reaction for 180min, filtering out the resin after completion, soaking the resin in ethanol for 10h after washing, and filtering to obtain the adsorption resin with the surface graft modification.
The vacuum degree of reduced pressure distillation in the distillation kettle is 7 Pa.
The still was purged with dry nitrogen for 10min before use.
The results of the modified resin grafting ratio and the product purity test of the above examples are shown in the following table:
| graft ratio (%) | Product purity (%) | |
| Example 1 | 82.4 | 99.911 |
| Example 2 | 83.9 | 99.943 |
| Example 3 | 85.2 | 99.970 |
Comparative example 1
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, controlling the temperature to be 10 ℃, decompressing, pumping out volatile components, then heating to 80 ℃, decompressing and distilling to obtain a refined tetra (dimethylamino) hafnium finished product.
The vacuum degree of reduced pressure distillation in the distillation kettle is 15 Pa.
The still was purged with dry nitrogen for 5min before use.
Comparative example 2
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 0.5g of adsorption resin under the protection of nitrogen, controlling the temperature to be 30 ℃, stirring and mixing for 20min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 10 ℃, decompressing and pumping volatile components, then heating to 60 ℃, decompressing and distilling to obtain the finished product of the refined tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
50g of D101 polystyrene macroporous adsorption resin is subjected to electron beam irradiation by using an electron accelerator to generate active free radicals for grafting reaction, and the irradiation conditions are as follows: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5 gy/pass; immediately dispersing macroporous adsorption resin into 200g of boiling cold pure water, adding 0.3g of gelatin, 0.1g of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.1g of 3- (2-carboxyvinyl) phenylboronic acid and 2g of benzoyl peroxide, controlling the temperature to be 70 ℃, stirring for grafting reaction for 120min, filtering out the resin after completion, soaking the resin in ethanol for 5h after washing, and filtering to obtain the adsorption resin with the surface graft modification.
The vacuum degree of reduced pressure distillation in the distillation kettle is 10 Pa.
The still was purged with dry nitrogen for 5min before use.
Comparative example 3
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 0.5g of adsorption resin under the protection of nitrogen, controlling the temperature to be 30 ℃, stirring and mixing for 20min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 10 ℃, decompressing and pumping volatile components, then heating to 50 ℃, decompressing and distilling to obtain the finished product of the refined tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
50g of D101 polystyrene macroporous adsorption resin is subjected to electron beam irradiation by using an electron accelerator to generate active free radicals for grafting reaction, and the irradiation conditions are as follows: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5 gy/pass; immediately dispersing the macroporous adsorption resin into 200g of boiling cold pure water, adding 0.3g of gelatin and 12g of 4-allyl anisole, 0.1g of 3- (2-carboxyvinyl) phenylboronic acid and 2g of benzoyl peroxide, controlling the temperature to be 70 ℃, stirring for grafting reaction for 120min, filtering out the resin after the grafting reaction is finished, soaking the resin in ethanol for 5h after the resin is washed, and filtering to obtain the adsorption resin with the surface graft modification.
The vacuum degree of reduced pressure distillation in the distillation kettle is 7 Pa.
The still was purged with dry nitrogen for 5min before use.
Comparative example 4
A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80g of crude product of the tetra (dimethylamino) hafnium into a refining reaction kettle, adding 0.5g of adsorption resin under the protection of nitrogen, controlling the temperature to be 30 ℃, stirring and mixing for 20min, filtering to remove the adsorption resin, then introducing the crude product of the tetra (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 10 ℃, decompressing and pumping volatile components, then heating to 50 ℃, decompressing and distilling to obtain the finished product of the refined tetra (dimethylamino) hafnium.
The adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
50g of D101 polystyrene macroporous adsorption resin is subjected to electron beam irradiation by using an electron accelerator to generate active free radicals for grafting reaction, and the irradiation conditions are as follows: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5 gy/pass; immediately dispersing the macroporous adsorption resin into 200g of boiling cold pure water, adding 0.3g of gelatin and 12g of 4-allyl anisole, 0.1g of 2- (tert-butoxycarbonylamino) -5-hexenoic acid and 2g of benzoyl peroxide, controlling the temperature to be 70 ℃, stirring for grafting reaction for 120min, filtering out the resin after the reaction is finished, soaking the resin in ethanol for 5h after the resin is washed clean, and filtering to obtain the adsorption resin with the surface graft modification.
The vacuum degree of reduced pressure distillation in the distillation kettle is 7 Pa.
The still was purged with dry nitrogen for 5min before use.
The results of the grafting rate and product purity measurements of the macroporous resin of the above examples are shown in the following table:
| graft ratio (%) | Product purity (%) | |
| Comparative example 1 | -- | 97.322 |
| Comparative example 2 | 80.4 | 98.476 |
| Comparative example 3 | 80.7 | 98.183 |
| Comparative example 4 | 81.6 | 99.012 |
Claims (6)
1. A method for refining tetrakis (dimethylamino) hafnium, which has the following specific scheme:
adding 80-120 parts by mass of crude tetrakis (dimethylamino) hafnium into a refining reaction kettle, adding 0.5-3 parts by mass of adsorption resin under the protection of nitrogen, controlling the temperature to be 30-40 ℃, stirring and mixing for 20-90min, filtering to remove the adsorption resin, then introducing the crude tetrakis (dimethylamino) hafnium into a distillation kettle, controlling the temperature to be 10-30 ℃, decompressing and pumping out volatile components, then heating to 40-80 ℃, decompressing and distilling to obtain a refined tetrakis (dimethylamino) hafnium finished product.
2. The method of claim 1, wherein the hafnium tetra (dimethylamino) phosphonium refining method comprises: the adsorbent resin is surface grafting modified adsorbent resin, and the preparation method comprises the following steps:
according to the mass portion, 50-70 portions of polystyrene macroporous absorption resin are radiated by electron beams by using an electron accelerator to generate active free radicals which can be used for grafting reaction, and the radiation condition is as follows: the irradiation voltage is 3-5MeV, the irradiation dose is 15-30kGy, and the dose rate is 5-10 kGy/pass; immediately dispersing the macroporous adsorption resin into 500 parts of boiling cold pure water 200-0.6 part of gelatin and 12-18 parts of 4-allyl anisole, 0.1-0.5 part of 2- (tert-butoxycarbonylamino) -5-hexenoic acid, 0.1-0.5 part of 3- (2-carboxyvinyl) phenylboronic acid and 2-4 parts of benzoyl peroxide, controlling the temperature to be 70-85 ℃, stirring for grafting reaction for 120-180min, filtering out the resin, soaking the resin in ethanol for 5-10h after washing, and filtering to obtain the surface graft modified adsorption resin.
3. The method of claim 2, wherein the hafnium tetra (dimethylamino) phosphonium refining method comprises: the acrylate monomer is hydroxyethyl acrylate or acrylic ester or isobutyl acrylate.
4. The method of claim 2, wherein the hafnium tetra (dimethylamino) phosphonium refining method comprises: the pore-foaming agent is xylene or n-heptane or tert-amyl alcohol.
5. The method of claim 1, wherein the hafnium tetra (dimethylamino) phosphonium refining method comprises: the vacuum degree of the reduced pressure distillation in the distillation kettle is 0.09-0.1 MPa.
6. The method of claim 1, wherein the hafnium tetra (dimethylamino) phosphonium refining method comprises: the distillation kettle is purged with dry nitrogen for 5-10min before use.
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| CN113277475A (en) * | 2021-05-27 | 2021-08-20 | 浙江凯圣氟化学有限公司 | Method for removing metal ions in anhydrous hydrogen fluoride |
| CN113527033A (en) * | 2021-08-24 | 2021-10-22 | 浙江巨化股份有限公司氟聚厂 | Photochlorination method preparation method of dichlorooctafluorobutane |
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