CN112759527A - Phosphate, preparation method and application thereof - Google Patents
Phosphate, preparation method and application thereof Download PDFInfo
- Publication number
- CN112759527A CN112759527A CN202011495115.4A CN202011495115A CN112759527A CN 112759527 A CN112759527 A CN 112759527A CN 202011495115 A CN202011495115 A CN 202011495115A CN 112759527 A CN112759527 A CN 112759527A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- stirring
- dar
- reducing agent
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 37
- 239000010452 phosphate Substances 0.000 title claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- MBXIRNHACKAGPA-UHFFFAOYSA-N 4,6-dinitroresorcinol Chemical compound OC1=CC(O)=C([N+]([O-])=O)C=C1[N+]([O-])=O MBXIRNHACKAGPA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000011085 pressure filtration Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- GAKFXHZPQGSWHQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;hydrochloride Chemical compound Cl.NC1=CC(N)=C(O)C=C1O GAKFXHZPQGSWHQ-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 9
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- -1 DAR phosphate Chemical class 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
Abstract
The invention discloses a phosphate and a preparation method and application thereof, relating to the technical field of material chemical industry and comprising the following steps: (1) dissolving 4, 6-dinitroresorcinol in a methanol solvent, and adding a reducing agent, a catalyst and a polyphosphoric acid solution; (2) adding hydrogen into the mixture in the step (1), heating and stirring to obtain milky turbid liquid, and filtering out the catalyst; (3) adding a reducing agent, sodium bicarbonate and ethanol into the filtrate obtained in the step (2), stirring, heating and filtering to obtain white powder, namely a DAR phosphate crude product; (4) dissolving the white powder obtained in the step (3) in a phosphoric acid solution, adding activated carbon, stirring until the solution is decolorized, and adding ethanol to obtain milky turbid liquid; (5) and (4) cooling and crystallizing the milky white turbid liquid in the step (4), performing pressure filtration to obtain a white refined salt cake, and drying to obtain white powder crystals. Phosphoric acid is used as one of raw materials of the PBO reaction system, other substances are not introduced, the dissolution and removal speed is high, and the storage stability is better compared with hydrochloride.
Description
Technical Field
The invention relates to the technical field of material chemical industry, in particular to phosphate and a preparation method and application thereof.
Background
4,6 diamino resorcinol hydrochloride (DAR) is an important monomer of poly (p-Phenylene Benzobisoxazole) (PBO) fiber, but DAR is required to be degassed firstly when the DAR is used as a raw material to prepare the PBO, HCL generated by degassing corrodes equipment, wastes manpower and material resources, and greatly prolongs the production time due to degassing, so that the production efficiency is low.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the technical problem that HCL generated by degassing 4, 6-diaminoresorcinol hydrochloride can corrode equipment, the invention provides phosphate and a preparation method and application thereof, wherein phosphoric acid is used as one of raw materials of a PBO reaction system, other substances are not introduced, the dissolution and desorption speed is high, and the storage stability is good.
2. Technical scheme
In order to solve the problems, the technical scheme provided by the invention is as follows: the phosphate and the preparation method and the application thereof comprise the following steps:
(1) dissolving 4, 6-dinitroresorcinol in a methanol solvent, adding a reducing agent, a catalyst and a polyphosphoric acid solution, and uniformly stirring;
(2) adding hydrogen into the mixture in the step (1), heating and stirring to obtain milky turbid liquid, and filtering out the catalyst;
(3) adding a reducing agent, sodium bicarbonate and ethanol into the filtrate obtained in the step (2), stirring, heating and filtering to obtain white powder, namely a DAR phosphate crude product;
(4) dissolving the white powder obtained in the step (3) in a phosphoric acid solution, adding activated carbon, stirring until the solution is decolorized, and adding ethanol to obtain milky turbid liquid;
(5) and (4) cooling and crystallizing the milky white turbid liquid in the step (4), performing filter pressing to obtain a white refined salt cake, spraying a reducing agent solution on the surface of the white refined salt cake, and drying to obtain white powder crystals, namely DAR phosphate.
Optionally, the catalyst is palladium on carbon.
Optionally, the concentration of the polyphosphoric acid solution is 50-85%.
Optionally, the molar ratio of the 4, 6-dinitroresorcinol to the polyphosphoric acid in the step (1) is 30-2.
Optionally, the stirring time in the step (1) is 20-50 min.
Optionally, both the step (1) and the step (2) are performed in a high-pressure reaction kettle, and before the reaction, the high-pressure reaction kettle is replaced with nitrogen for multiple times before use.
Optionally, the step (3) is performed in a precipitation tank, the step (4) is performed in a filter press, and the step (5) is performed in a crystallization tank and a filter press in sequence.
Optionally, the reducing agent is a stannous chloride solution.
Optionally, the DAR phosphate is in molar yield greater than 90% and in purity greater than 99%.
Optionally, the DAR phosphate skips the DAR degassing stage directly into the polymerization stage to produce PBO.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) according to the preparation method of the phosphate, phosphoric acid is used for replacing original hydrochloric acid, the phosphoric acid can be quickly dissolved in polyphosphoric acid to remove a phosphoric acid protecting group, and the phosphoric acid is changed into 4, 6-diaminoresorcinol and phosphoric acid.
(2) According to the preparation method of the phosphate, stannous chloride is used as a reducing agent and has an anti-oxidation effect, the potential of an oxidation reduction electrode of the stannous chloride is-0.15V, the reducibility is moderate in the reaction system, phosphoric acid can be reacted to generate hydrogen when the reducibility is too strong, the anti-oxidation effect cannot be achieved when the reducibility is too weak, and the trace stannous chloride can prevent oxidation and can not introduce too many metal ions.
(3) According to the preparation method of the phosphate provided by the embodiment of the application, palladium carbon and hydrogen are selected for reaction, the product is very clean, few byproducts are generated, the byproducts can be further filtered through the purification and recrystallization processes, and the DAR phosphate with high purity and high yield is obtained.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The preparation method of the phosphate provided by the invention comprises the following steps:
(1) dissolving 4, 6-dinitroresorcinol in a methanol solvent, adding a reducing agent, a catalyst and a polyphosphoric acid solution, and uniformly stirring;
(2) adding hydrogen into the mixture in the step (1), heating and stirring to obtain milky turbid liquid, and filtering out the catalyst;
(3) adding a reducing agent, sodium bicarbonate and ethanol into the filtrate obtained in the step (2), stirring, heating and filtering to obtain white powder, namely a DAR phosphate crude product;
(4) dissolving the white powder obtained in the step (3) in a phosphoric acid solution, adding activated carbon, stirring until the solution is decolorized, and adding ethanol to obtain milky turbid liquid;
(5) and (4) cooling and crystallizing the milky white turbid liquid in the step (4), performing filter pressing to obtain a white refined salt cake, spraying a reducing agent solution on the surface of the white refined salt cake, and drying to obtain white powder crystals, namely DAR phosphate.
DAR is 4, 6-diaminoresorcinol hydrochloride, the active ingredient of the DAR is 4, 6-diaminoresorcinol, the amino group in DAR has strong activity and is easy to be oxidized and deteriorated, hydrochloride is hydrogen chloride to protect the amino group from being oxidized, active groups are removed from the hydrochloride when the DAR is used, the process of removing the hydrogen chloride is called degassing, and the process consumes a great deal of time, manpower and material resources, the aqueous solution of the hydrogen chloride is hydrochloric acid, and the gas has strong corrosivity and can cause serious corrosion to equipment. The common chemical fiber production enterprises do not have the equipment. DAR phosphate replaces original hydrochloric acid with phosphoric acid, can dissolve in polyphosphoric acid fast and remove the phosphoric acid protective group, become 4, 6-diaminoresorcinol and phosphoric acid, compare hydrochloride, phosphoric acid is one of the raw materials of PBO reaction system, do not introduce other substances, dissolve and remove the speed fast, and relative hydrochloride, it is better to store stability. The intrinsic viscosity of the PBO prepared can reach 35.6 ml/g.
Catalyst:
the invention selects palladium carbon as the catalyst, has the characteristics of good selectivity, clean product, few impurities and the like, and can select Raney nickel as the catalyst in other embodiments.
Polyphosphoric acid solution:
the concentration of the polyphosphoric acid solution is 50-85%, if the concentration of the polyphosphoric acid solution is lower than 50%, the amount of the polyphosphoric acid solution required in the preparation process needs to be increased, so that waste is caused, and if the concentration of the polyphosphoric acid solution is higher than 85%, a gel-like intermediate product generated in the initial reaction stage of the 4, 6-dinitroresorcinol and the polyphosphoric acid solution is higher in proportion in a reaction system, and the stirring and dispersing effects are poor. The concentration of the polyphosphoric acid solution in this embodiment is 85%, and in other embodiments, the concentration of the polyphosphoric acid solution can be 50%, 55%, 60%, 65%, 70%.
Molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid:
in the invention, the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid is 30-2, if the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid is less than 2, part of polyphosphoric acid does not participate in the reaction and wastes, and if the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid is more than 30, part of 4, 6-dinitroresorcinol does not participate in the reaction and wastes the same way, and in the embodiment, the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid is 2.8. In other embodiments, the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid may be 30, 20, 10, 5, 2.
Stirring time:
the stirring time in the step (1) is 20-50 min, if the stirring time is less than 20min, the reaction is insufficient, and if the stirring time is more than 50min, the preparation effect is not obviously improved, and the production cost is increased. In this embodiment, the stirring time is 30min, and in other embodiments, the stirring time may be 20min, 35min, 40min, or 50 min.
Reaction equipment:
the steps (1) and (2) are carried out in a high-pressure reaction kettle, and before the reaction, the high-pressure reaction kettle is replaced for many times by using nitrogen before being used, the high-pressure reaction kettle is the most ideal device for carrying out chemical reaction under high temperature and high pressure at present, and the nitrogen is used for replacing air in the high-pressure reaction kettle, so that the reactant is prevented from being oxidized by oxygen in the air to influence the reaction effect; the method comprises the following steps of (3) performing in a precipitation tank, (4) performing in a filter press, sequentially performing in a crystallization tank and the filter press, after the reaction in the step (2) is finished, opening a discharge valve at the bottom of a high-pressure anti-bottom kettle, recovering a catalyst, enabling filtrate to enter the precipitation tank, starting stirring, adding a proper amount of sodium bicarbonate to adjust the pH to 3-4, stopping stirring, opening the discharge valve at the bottom, performing filter pressing through a filter press, discharging liquid, obtaining a crude product of white phosphate, conveying the crude product to the crystallization tank for crystallization, and performing filter pressing to obtain a white refined salt cake.
Reducing agent:
the reducing agent is stannous chloride solution, the stannous chloride is used as the reducing agent and has an anti-oxidation effect, the potential of an oxidation reduction electrode of the stannous chloride is-0.15V, the reducibility in the reaction system is moderate, phosphoric acid can be reacted to generate hydrogen when the reducibility is too strong, the anti-oxidation effect cannot be achieved when the reducibility is too weak, and the trace amount of the stannous chloride can prevent oxidation without introducing too much metal ions.
Example 1
The preparation method of the phosphate of the embodiment comprises the following steps:
the high-pressure reaction kettle is replaced by nitrogen for three times, 500g of 4, 6-dinitroresorcinol, 5g of 5% palladium carbon catalyst, 0.05g of stannous chloride and 300g of 85% polyphosphoric acid are added, hydrogen is added into the reaction kettle to 1.5MPa, stirring is started, heating is carried out at 60 ℃ for reaction for 6 hours, after the hydrogen completely reacts, turbid milky turbid liquid is obtained, 4.2g of palladium carbon catalyst is recovered by filtration, 0.5g of stannous chloride is added into filtrate, the filtrate is prevented from being oxidized, stirring is started, the pH is adjusted to 3.9 by sodium bicarbonate, 500ml of ethanol is added into the filtrate, stirring and filtering are carried out, 800g of white powder crystals are obtained, and the molar yield is about 95%.
Dissolving the obtained crude salt in 85% polyphosphoric acid to obtain a milky or light pink solution, adding activated carbon for decolorization, stirring for 1h at 65 ℃, adding 300ml of ethanol to change the solution into milky turbid liquid, cooling to 0 ℃ for crystallization, performing pressure filtration to obtain a white refined salt cake, spraying a stannous chloride solution on the surface of the refined salt cake, drying in a vacuum oven at 65 ℃, and obtaining white powder crystals after drying to obtain 773g of refined salt, namely DAR phosphate, wherein the molar yield of the DAR phosphate is about 93%, and the liquid phase determination purity is 99.563%. PBO prepared with DAR phosphate had an intrinsic viscosity of 35.6 ml/g.
The invention and its embodiments have been described above schematically, without this being limitative. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (10)
1. A method for preparing phosphate is characterized by comprising the following steps:
(1) dissolving 4, 6-dinitroresorcinol in a methanol solvent, adding a reducing agent, a catalyst and a polyphosphoric acid solution, and uniformly stirring;
(2) adding hydrogen into the mixture in the step (1), heating and stirring to obtain milky turbid liquid, and filtering out the catalyst;
(3) adding a reducing agent, sodium bicarbonate and ethanol into the filtrate obtained in the step (2), stirring, heating and filtering to obtain white powder, namely a DAR phosphate crude product;
(4) dissolving the white powder obtained in the step (3) in a phosphoric acid solution, adding activated carbon, stirring until the solution is decolorized, and adding ethanol to obtain milky turbid liquid;
(5) and (4) cooling and crystallizing the milky white turbid liquid in the step (4), performing filter pressing to obtain a white refined salt cake, spraying a reducing agent solution on the surface of the white refined salt cake, and drying to obtain white powder crystals, namely DAR phosphate.
2. The method of claim 1, wherein the catalyst is palladium on carbon.
3. The method for preparing phosphate according to claim 1, wherein the concentration of the polyphosphoric acid solution is 50-85%.
4. The phosphate according to claim 1, wherein the molar ratio of 4, 6-dinitroresorcinol to polyphosphoric acid in step (1) is 30-2.
5. The method for preparing phosphate according to claim 1, wherein the stirring time in step (1) is 20-50 min.
6. The method according to claim 1, wherein the steps (1) and (2) are performed in an autoclave, and the autoclave is replaced with nitrogen several times before use before the reaction.
7. The method for preparing phosphate according to claim 1, wherein the step (3) is performed in a precipitation tank, the step (4) is performed in a filter press, and the step (5) is performed in a crystallization tank and a filter press in this order.
8. The method for preparing phosphate according to claim 1, wherein the reducing agent is a stannous chloride solution.
9. A phosphate prepared by the method for preparing phosphate according to any one of claims 1 to 8, wherein the molar yield of the DAR phosphate is greater than 90% and the purity is greater than 99%.
10. Use of the phosphate according to claim 9 in the production of PBO, wherein the DAR phosphate is skipped over the DAR degassing stage directly into the polymerisation stage for the production of PBO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495115.4A CN112759527A (en) | 2020-12-17 | 2020-12-17 | Phosphate, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495115.4A CN112759527A (en) | 2020-12-17 | 2020-12-17 | Phosphate, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112759527A true CN112759527A (en) | 2021-05-07 |
Family
ID=75695003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011495115.4A Pending CN112759527A (en) | 2020-12-17 | 2020-12-17 | Phosphate, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112759527A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138020A (en) * | 1989-04-21 | 1992-08-11 | The Dow Chemical Company | Phosphate salts of monomers for pbz and their use in preparing pbz polymers |
| CN101074201A (en) * | 2006-05-19 | 2007-11-21 | 大连化工研究设计院 | Production of 4,6-diamino-resorcinol and its salt |
| CN104072771A (en) * | 2014-07-18 | 2014-10-01 | 四川宝利丰科技有限公司 | Preparation method of PBO |
| CN110551284A (en) * | 2019-09-16 | 2019-12-10 | 浙江鼎龙科技有限公司 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
-
2020
- 2020-12-17 CN CN202011495115.4A patent/CN112759527A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138020A (en) * | 1989-04-21 | 1992-08-11 | The Dow Chemical Company | Phosphate salts of monomers for pbz and their use in preparing pbz polymers |
| CN101074201A (en) * | 2006-05-19 | 2007-11-21 | 大连化工研究设计院 | Production of 4,6-diamino-resorcinol and its salt |
| CN104072771A (en) * | 2014-07-18 | 2014-10-01 | 四川宝利丰科技有限公司 | Preparation method of PBO |
| CN110551284A (en) * | 2019-09-16 | 2019-12-10 | 浙江鼎龙科技有限公司 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
Non-Patent Citations (1)
| Title |
|---|
| 舒鹏等: "４，６－二氨基间苯二酚二磷酸盐的合成及其催化剂的研究", 《化工新型材料》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107021983A (en) | The resource recycling Application way of butyl octanol unit rhodium-containing waste liquid | |
| IL144454A (en) | Method for producing l-phenylephrine hydrochloride | |
| CN114478321B (en) | Method, device and application for separating, refining and purifying intermediate m-xylylene diamino ethyl formate solution | |
| CN114506820A (en) | Method for directly producing electronic grade hydrogen peroxide from hydrogen and oxygen | |
| CN112759527A (en) | Phosphate, preparation method and application thereof | |
| CN112225188B (en) | Process for removing arsenic from phosphoric acid by wet method | |
| CN109438549B (en) | Method for preparing N-tert-butyl-3-oxo-4-aza-5 alpha-androstane-17 beta-formamide | |
| CN112479906B (en) | Production process of meglumine | |
| CN114524759B (en) | Environment-friendly preparation process of odor-free captan | |
| KR840000518B1 (en) | Process for the manufacture of 2,6-dichloro-4-nitroaniline | |
| CN113754538B (en) | Vigabatrin acid intermediate and preparation method thereof | |
| CN115677654B (en) | Preparation method of atecan hydrochloride | |
| CN115650264B (en) | Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process | |
| CN117820140A (en) | Method for preparing 3-methyl-2-aminobenzoic acid | |
| CN114875451B (en) | Indium sulfate electrolyte and preparation method thereof | |
| JPH0617327B2 (en) | Method for producing xylitol | |
| CN111924869A (en) | Silver nitrate lead-removing purification process | |
| CN112939843B (en) | Synthesis method of N-hydroxymethyl-3, 4,5, 6-tetrahydrophthalimide | |
| CN113773192A (en) | Method for purifying dodecyl dicarboxylic acid by using mixed extraction agent | |
| JP4164908B2 (en) | Method for recovering phosphoric acid and method for producing polybenzazole using phosphoric acid | |
| CN116675692A (en) | Synthesis method of low-impurity linagliptin | |
| CN116217015A (en) | Process for removing 8-hydroxyquinoline from o-hydroxyphenylacetic acid synthesis wastewater | |
| CN116103500A (en) | Method for recovering platinum and aluminum from insoluble agglomeration of noble metal dead catalyst | |
| CN112592273A (en) | Production process of phthalate plasticizer | |
| CN116282240A (en) | Purification method of triruthenium laurcarbonyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210507 |