CN108203440B - Solvent-free double-screw extrusion continuous synthesis process of potassium aryl trifluoroborate - Google Patents
Solvent-free double-screw extrusion continuous synthesis process of potassium aryl trifluoroborate Download PDFInfo
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- CN108203440B CN108203440B CN201611179059.7A CN201611179059A CN108203440B CN 108203440 B CN108203440 B CN 108203440B CN 201611179059 A CN201611179059 A CN 201611179059A CN 108203440 B CN108203440 B CN 108203440B
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- potassium
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- trifluoroborate
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- 238000001125 extrusion Methods 0.000 title claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 18
- 239000011591 potassium Substances 0.000 title claims abstract description 18
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title abstract description 8
- -1 aryl boric acid Chemical compound 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 25
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000011343 solid material Substances 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- PJAIMBYNTXNOCN-UHFFFAOYSA-N 3,6-dibromo-1h-indole Chemical compound BrC1=CC=C2C(Br)=CNC2=C1 PJAIMBYNTXNOCN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 1
- 239000004327 boric acid Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 235000010338 boric acid Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 4
- HDIWKNXVBQPJCO-UHFFFAOYSA-N ethyl 2-methylsulfanyl-6-oxo-1h-pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)NC1=O HDIWKNXVBQPJCO-UHFFFAOYSA-N 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- COERJHDMQUPDCV-UHFFFAOYSA-N [K].FB(F)F Chemical compound [K].FB(F)F COERJHDMQUPDCV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a solvent-free double-screw extrusion continuous synthesis process technology of potassium aryl trifluoroborate. Stirring aryl boric acid and potassium bifluoride at a high speed to obtain a uniform mixed material, continuously adding the uniform mixed material through a feed inlet of a double-screw extruder, setting the extrusion time to be 5-10 minutes, keeping the temperature at room temperature, receiving the continuously extruded solid material in a receiver filled with water, stirring to dissolve inorganic salt to obtain slurry or suspension, filtering, washing a filter cake with water, drying to obtain the potassium aryl trifluoroborate, and returning the filtrate to the extrusion material receiver for recycling. The process of the invention adopts the double-screw extruder as the reactor to realize the continuous production of the solvent-free solid phase reaction, has higher efficiency than a kettle type batch reactor, eliminates the use of organic solvent, avoids the excess and byproduct of aqueous solution of inorganic salt, can be recycled, reduces three wastes, is clean and environment-friendly, reduces the production cost and has good value of industrial application.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a solvent-free double-screw extrusion continuous synthesis process technology of potassium aryl trifluoroborate.
Background
The arylboronic acid serving as a safe and efficient arylation reagent is widely applied to scientific research and development of related fine chemicals such as medicines, pesticides, liquid crystals, OLED photoelectric materials and the like. However, because the aryl boric acid is easy to dehydrate to form anhydride, and is not stable enough to acid, alkali and oxidant, especially easy to be oxidized or decarbolized in air, the aryl boric acid has the problems of short storage time and difficult metering in practical use, even some heterocyclic aryl boric acids are gradually decomposed at room temperature, and need to be stored at a low temperature of below-30 ℃, so that the aryl boric acid loses the value in industrial production. In order to solve the problems of use due to the stability of the arylboronic acid, it is necessary to convert it into a derivative of the arylboronic ester or salt. The aryl potassium trifluoroborate has high stability, good crystallinity and reaction performance which is closest to that of corresponding aryl boric acid, and is an aryl boric acid derivative with the best industrial production application prospect. Currently, potassium aryl trifluoroborate is prepared by reacting aryl difluoroborane with potassium fluoride, reacting aryl boronic acid with potassium bifluoride, or cross-coupling aryl halides with potassium tetrafluoroborate under the catalysis of transition metals.
For example, U.S. patent (3185730) discloses a technique for forming potassium trifluoroborate from the reaction of organodifluoroborane with potassium fluoride or potassium fluoroborate, but this technique is not suitable for the synthesis of potassium aryltrifluoroborate due to the difficulty of obtaining aryldifluoroborane.
The literature (J.Org.chem.,1995,60, 3020-3027; J.Organomet.chem.,2000,598, 127-135; Eur.J.Org.chem.,2003,4313-4327 et al) discloses the synthesis of boronic acid by reacting an arylboronic acid with an excess of potassium bifluoride (KHF)2) The technical cost of the aryl potassium trifluoroborate formed by the reaction in the water/organic mixed solvent is low, the operation is simple, and the method has the industrial application value.
Chinese patent application (201010619002.0) discloses that crude arylboronic acids synthesized from aryl halohydrocarbons react directly with potassium bifluoride in the water/organic solvent mixed systems reported in the above documents without isolation to give potassium aryltrifluoroborate.
Chinese patent (CN104945426) discloses a technique for directly preparing aryl potassium trifluoroborate by reacting potassium tetrafluoroborate with aryl halohydrocarbon under the promotion of a transition metal catalyst. Compared with the known method of firstly forming aryl boric acid and then forming salt, the method changes the introduction sequence of boron/fluorine atoms and is suitable for some aryl potassium trifluoroborate which can not stably exist boric acid precursor at normal temperature. However, the potassium tetrafluoroborate salt of diboronic acid needs to be prepared from diboronic acid ester and excessive potassium bifluoride, and the cost of the palladium catalyst is high.
In the current preparation technology of the aryl potassium trifluoroborate, the aryl boric acid and excessive potassium bifluoride react in a solvent to obtain the aryl potassium trifluoroborate, and the synthesis process is the most mature, economic and feasible and has wide application range. However, the existing process adopts a batch kettle type reactor, which not only has low efficiency, but also has more three wastes. With the improvement of the environmental protection requirement, the three-waste treatment cost is increased, so that the production cost of the potassium aryl trifluoroborate is obviously increased, and the practical application of the potassium aryl trifluoroborate in industrial scale production is severely limited.
Disclosure of Invention
The invention aims to provide a solvent-free double-screw extrusion reaction process with less three wastes, low cost and industrial application prospect, and a method for synthesizing potassium aryl trifluoroborate by continuous operation.
In order to achieve the purpose, the invention adopts the following technical scheme.
A solvent-free double-screw extrusion continuous synthesis process technology of aryl potassium trifluoroborate utilizes a double-screw extruder as a reactor to carry out solvent-free solid phase reaction to prepare the aryl potassium trifluoroborate, and comprises the following steps:
(1) stirring arylboronic acid and potassium bifluoride to obtain a uniform mixed material;
(2) continuously adding the mixed material obtained in the step (1) through a feed inlet of a double-screw extruder, and setting the extrusion time to be 5-10 minutes to obtain a continuously extruded solid material; the solid material contains crude potassium aryl trifluoroborate.
(3) The extruded solid material is directly received in a receiver containing water, and inorganic salt is dissolved by stirring to obtain slurry or suspension.
(4) And (4) filtering the suspension obtained in the step (3), washing a filter cake with water, drying to obtain the potassium aryl trifluoroborate, and returning the filtrate to an extrusion material receiver for recycling.
Wherein, in the step (1),
the aryl group of the substituent of the arylboronic acid is aromatic hydrocarbon and heterocyclic group
The potassium bifluoride is dry potassium bifluoride, and can also be replaced by a potassium bifluoride solution formed by mixing hydrofluoric acid (40%) and potassium fluoride dihydrate in an equal molar ratio.
The molar ratio of the arylboronic acid to the potassium bifluoride is 1: 2-3.
When a potassium bifluoride solution formed by mixing hydrofluoric acid (40%) (40% by mass of hydrofluoric acid) and potassium fluoride dihydrate in an equal molar ratio is adopted, the molar ratio of the arylboronic acid to the hydrofluoric acid is 1: 3; the molar ratio of arylboronic acid to potassium fluoride dihydrate was 1: 3.
Stirring arylboronic acid and potassium bifluoride at a high speed of 500rpm to obtain a uniform mixed material.
Wherein, in the step (2),
the extrusion time is 5 to 10 minutes, preferably 8 minutes.
The temperature was 25 ℃.
Wherein, in the step (3),
the mass ratio of the solid material to the water is 1: 1.
Wherein, in the step (4),
specifically, the steps include:
(1) aryl boric acid and 2 or 3 times of molar weight of potassium bifluoride are stirred at high speed of 500rpm to obtain a uniform mixed material.
(2) And (2) continuously adding the material obtained in the step (1) through a feed inlet of a double-screw extruder, setting the extrusion time to be 5-10 minutes and the temperature to be room temperature, and obtaining the continuously extruded solid material.
(3) The extruded solid material is directly received in a receiver containing water, and inorganic salt is dissolved by stirring to obtain slurry or suspension.
(4) And (4) filtering the suspension obtained in the step (3), washing a filter cake, drying the filter cake with hot air to obtain potassium aryl trifluoroborate, and returning the filtrate to an extrusion material receiver for recycling.
The invention has the beneficial effects that:
(1) the process of the invention adopts the double-screw extruder as the reactor to realize continuous production, and has higher efficiency than a kettle type batch reactor.
(2) The process adopts a solvent-free solid-phase reaction mode, eliminates the use of an organic solvent, and is clean and environment-friendly.
(3) The process is used for removing the excessive and byproduct aqueous solution of inorganic salt, can be recycled, reduces three wastes, is clean and environment-friendly, and reduces the production cost.
(4) The yield of the process is high and is 86-98%.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
50 g (0.41 mol) of phenylboronic acid and 64 g (0.82 mol) of potassium bifluoride are stirred at a high speed of 500rpm for 10 minutes to obtain a uniformly mixed material, the uniformly mixed material is continuously added through a feed inlet of a double-screw extruder, the extrusion time is set to be 5 minutes, the extruded material is directly received in a receiver filled with water with the same weight as that of a solid material, stirring and dispersing are carried out to obtain slurry, filtering is carried out, filtrate is returned to the receiver, and filter cake is washed by water and then dried by hot air to obtain 67.0 g (89%) of potassium phenyltrifluoroborate.
Example 2
The same as example 1, but 96 g (1.23 mol) of potassium bifluoride, the extrusion time was set to 8 minutes, the extruded material was directly received in a receiver containing the mother liquor filtered in example 1, stirred and dispersed to obtain slurry, filtered, the filtrate was returned to the receiver, and the filter cake was washed with water and dried with hot air to obtain 73.2 g (97%) of potassium phenyltrifluoroborate.
Example 3
The same as example 2, but the extrusion time is set to 5 minutes, the extruded material is directly received in a receiver containing the filtered mother liquor of example 2, and is stirred and dispersed to obtain slurry, the slurry is filtered, the filtrate is returned to the receiver, and the filter cake is washed by water and dried by hot air to obtain a product of 72.0 (95%) of potassium phenyltrifluoroborate.
Example 4
50 g (0.41 mol) of phenylboronic acid, 62 g (40%, 1.23 mol) of hydrofluoric acid and 116 g (1.23 mol) of potassium fluoride dihydrate are stirred at a high speed of 500rpm for 10 minutes to obtain uniformly mixed slurry, the uniformly mixed slurry is continuously added through a feed inlet of a double-screw extruder, the extrusion time is set to be 8 minutes, the extruded material is directly received in a receiver containing the filtered mother liquor of example 3, the mixture is stirred and dispersed to obtain suspension, the suspension is filtered, the filtrate is returned to the receiver, and a filter cake is washed by water and then dried by hot air to obtain 64.1 g (85%) of potassium phenyltrifluoroborate.
Examples 5 to 14
Aryl boric acid (1 time of molar weight) and potassium bifluoride (3 times of molar weight) are stirred at a high speed of 500rpm for 10 minutes to obtain a uniformly mixed powder material, the powder material is continuously added through a feed inlet of a double-screw extruder, the extrusion time is set to 8 minutes, the extruded material is directly received in a receiver filled with water with the same weight as that of a solid material, the mixture is stirred and dispersed to obtain slurry, the slurry is filtered, the filtrate is returned to the receiver, and a filter cake is washed by water and then dried by hot air to obtain a potassium aryl trifluoroborate product (Table 1).
TABLE 1 Experimental results for examples 5-14
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (3)
1. A solvent-free double-screw extrusion continuous synthesis method of aryl potassium trifluoroborate is characterized in that a double-screw extruder is used as a reactor to carry out solvent-free solid-phase reaction to prepare the aryl potassium trifluoroborate, and comprises the following steps:
(1) mixing arylboronic acid and potassium bifluoride to obtain a mixed material;
(2) continuously adding the mixed material obtained in the step (1) through a feed inlet of a double-screw extruder to obtain a continuously extruded solid material, namely potassium aryl trifluoroborate; wherein the extrusion time is 5-10 minutes, and the temperature is 25 ℃ at room temperature;
(3) directly receiving extruded solid material potassium aryl trifluoroborate in an extrusion material receiver filled with water, and stirring to dissolve inorganic salt to obtain slurry or suspension;
(4) filtering the slurry or suspension obtained in the step (3), washing a filter cake with water, drying to obtain potassium aryl trifluoroborate, and returning the filtrate to an extrusion material receiver for recycling;
wherein aryl in the arylboronic acid is aryl, p-methylphenyl, 2-ethylphenyl, p-chlorophenyl, 4-acetylphenyl, 2-furyl, 3-pyridyl, 2- (2-methoxycarbonylethyl) phenyl, 4-trifluoromethylphenyl and 4-cyanophenyl;
in the step (1), the potassium bifluoride is dried potassium bifluoride or a potassium bifluoride solution formed by mixing 40% by mass of hydrofluoric acid and potassium fluoride dihydrate in an equimolar mode.
2. The synthesis method according to claim 1, wherein in the step (1), the molar ratio of the arylboronic acid to the potassium bifluoride is 1: 2-3.
3. The synthesis method according to claim 1, wherein in the step (1), the arylboronic acid and the potassium bifluoride are stirred at a high speed of 500rpm to obtain a homogeneous mixed material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880033A (en) * | 2014-03-13 | 2014-06-25 | 广东宇星阻燃新材有限公司 | Method for producing aluminum borate or magnesium borate through reaction extrusion technology |
| CN104945426A (en) * | 2015-06-12 | 2015-09-30 | 沧州普瑞东方科技有限公司 | Novel method for synthesizing potassium aryl trifluoroborate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6958420B2 (en) * | 2002-07-19 | 2005-10-25 | Board Of Trustees Of Michigan State University | Synthesis of aminoarylboronic esters and substituted anilines from arenes via catalytic C-H activation/borylation/amination and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880033A (en) * | 2014-03-13 | 2014-06-25 | 广东宇星阻燃新材有限公司 | Method for producing aluminum borate or magnesium borate through reaction extrusion technology |
| CN104945426A (en) * | 2015-06-12 | 2015-09-30 | 沧州普瑞东方科技有限公司 | Novel method for synthesizing potassium aryl trifluoroborate |
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