CN116574133A - One-pot synthesis technology of flame retardant dithio-pyrophosphate by taking ammonia gas as acid-binding agent - Google Patents
One-pot synthesis technology of flame retardant dithio-pyrophosphate by taking ammonia gas as acid-binding agent Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 23
- 239000011230 binding agent Substances 0.000 title claims abstract description 22
- 239000003063 flame retardant Substances 0.000 title claims abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- CIFZCCWGXMYJEU-UHFFFAOYSA-N dithiodiphosphoric acid Chemical compound OP(O)(=S)OP(O)(O)=S CIFZCCWGXMYJEU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000005516 engineering process Methods 0.000 title description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 63
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 49
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 42
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- -1 dithio-pyrophosphoric acid ester Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 38
- 239000003513 alkali Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The application discloses a process for synthesizing a flame retardant dithio-pyrophosphate by using ammonia as an acid-binding agent through a one-pot method, wherein ammonia and sodium carbonate are used as the acid-binding agent, and the ammonia is used as the acid-binding agent in the first step, so that the problems of low product purity, high environmental problems during recycling and the like caused by using a large amount of organic alkali are avoided, the problems of low yield and the like caused by using solid inorganic alkali as the acid-binding agent are also avoided, and the sodium carbonate is used as the acid-binding agent in the second step. The route adopts a green synthesis process of inorganic alkali acid binding by a one-pot method, and the whole route is green, efficient and economic and has good industrial application prospect.
Description
Technical Field
The application belongs to the technical field of flame retardance, and particularly relates to a method for synthesizing a flame retardant DDPS (ddPS) in a one-pot green manner by taking ammonia gas as an acid binding agent.
Background
Polymeric materials such as fibers, plastics, rubber, etc. are widely used in industry, agriculture and people's life, most of them are inflammable in air, and their limiting oxygen index is below 21%. In recent years, fire disasters occur in various countries, and a considerable part of fire disasters are caused by ignition of high polymer materials. Therefore, the polymer material needs to be added with flame retardant to improve the flame retardant property of the material when in application. Flame retardants are classified into halogen-based, organic phosphorus-based, intumescent and inorganic flame retardants according to the type of flame retardant element. Among them, the organic phosphorus flame retardant is the most complex and studied one of various flame retardants. The organic phosphorus flame retardant has the advantages of low toxicity, low smoke, no halogen and the like, accords with the development direction of the flame retardant, and has good development prospect.
Dithio-pyrophosphate belongs to an organic phosphorus halogen-free environment-friendly flame retardant, and is a classical flame retardant applied to textile fibers. Has the advantages of hydrolysis resistance, acid-base stability, good flame retardant property and the like. The dithio-pyrophosphate is synthesized by the traditional process, 3.0-6.0 equivalents of acid-binding agent such as triethylamine or pyridine are used, and a large amount of triethylamine hydrochloride or pyridine hydrochloride is generated by adding a large amount of acid-binding agent and is wrapped in the dithio-pyrophosphate, so that the purity of the product is affected. And triethylamine and pyridine are substances with great smell, especially pyridine has great toxicity, and the triethylamine and the pyridine have great influence on the air environment and personnel of a workshop during use and recovery. It is therefore desirable to find a more green and efficient process for the synthesis of dithiopyrophosphates.
Ammonia is taken as an acid binding agent for the first step of acyl chlorination reaction, and no literature report exists at present. In the first step, the method adopts the mode of introducing ammonia gas to bind acid, and compared with the traditional process using organic alkali, the method does not need to recover an acid binding agent and separate byproduct ammonium chloride better, and is more green and efficient. Compared with the method of adding solid inorganic base acid, the method has the advantages of more complete reaction and higher yield. And in the second step, the sodium carbonate solution is used as an acid binding agent to replace triethylamine or pyridine, so that the DDPS product can be obtained efficiently, and the cost is lower and the method is more environment-friendly. The university of great company Wang Yang provides a method for synthesizing DDPS by using triethylamine as an acid binding agent through a one-pot method in the research on the synthesis and application of organic phosphorus flame retardants. Inspired by the work, the experiment adopts a one-pot synthesis process, and the first step of acyl chlorination reaction is directly put into the second step of reaction without any post treatment after the completion of the first step of acyl chlorination reaction, so that the high yield can be obtained. The process method disclosed by the application has the advantages of low cost, environment friendliness, high yield and the like, and has a good industrial application prospect.
Disclosure of Invention
The application aims to explore and provide a green and efficient process method for synthesizing dithio-pyrophosphate, which avoids using a large amount of organic alkali such as triethylamine, pyridine and the like, and has the advantages of lower cost, higher product quality and more environment friendliness.
The technical scheme of the application is as follows:
an organophosphorus flame retardant dithio-pyrophosphate, the chemical structural formula of the compound is as follows:
a one-pot green synthesis process using ammonia gas and sodium carbonate as acid binding agents comprises the following steps:
adding neopentyl glycol into a reaction bottle, then adding toluene solvent, heating and stirring, slowly adding phosphorus oxychloride for multiple times after dissolving, extending a conduit connected with an ammonia steel bottle below the liquid level, slowly opening an ammonia pressure reducing valve, setting the flow rate of ammonia by using an ammonia micro-flow meter, continuously introducing ammonia, and stirring for reacting for a period of time to obtain the intermediate thiophosphoryl chloride. After the first step of reaction is finished, the reaction temperature is set to the second step of reaction temperature, a sodium carbonate solution with a certain concentration is slowly added, the reaction is carried out for a period of time in a heat preservation way, and a large amount of white solid is precipitated in the reaction process. And (3) carrying out suction filtration to obtain a DDPS crude product, washing the DDPS crude product with water, then washing with ethanol, filtering and drying to obtain a DDPS product. The reaction formula is as follows:
the feeding mole ratio of neopentyl glycol to phosphorus oxychloride in the step is 1:0.8-1.2, preferably 1:1.
the flow rate of ammonia in the step is 5-50mL/min.
The organic solvent in the step is any one of toluene, benzene, n-heptane and n-hexane.
The reaction temperature of the first step in the steps is 25-40 ℃ and the reaction time is 0.5-4 h.
The feeding mole ratio of the intermediate thiophosphoryl chloride to sodium carbonate in the step is 1:0.5-1.5.
The reaction temperature of the second step in the steps is 50-70 ℃ and the reaction time is 6-12 h.
And in the step, after the first-step reaction is finished, directly putting the reaction product into the second-step reaction without any post-treatment.
The mass concentration of the ethanol in the ethanol washing is 95% or more.
The application has the following beneficial effects:
1. the application discloses a green and efficient method for synthesizing a flame retardant dithio-pyrophosphate by taking ammonia as an acid binding agent. The traditional process method uses a large amount of organic base such as triethylamine, pyridine and the like, the large amount of organic base has great influence on the surrounding environment and personnel in the using and recycling processes, the cost is high, and the purity of the dithio-pyrophosphate product is influenced by a large amount of byproducts. In the first step, the acid is bound by introducing a proper amount of dry ammonia, so that the problems of product quality, environmental problems and cost caused by the use of a large amount of organic alkali are avoided, the problem of insufficient reaction yield and low reaction yield in the common solid inorganic alkali acid binding process is solved, and the method is a brand-new, green, efficient and economic method.
2. The second step of the one-pot synthesis process disclosed by the application adopts sodium carbonate solution as an acid binding agent, so that the method is economical and efficient.
3. The one-pot synthesis process adopted by the application has the advantages of shorter time consumption of the whole route, less three wastes, high yield and high product purity.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectrum of dithio pyrophosphate (DDPS) 1 H NMR) map.
FIG. 2 shows nuclear magnetic resonance carbon spectrum of dithio-pyrophosphate (DDPS) 13 C NMR) map.
FIG. 3 shows nuclear magnetic resonance phosphorus spectrum of dithio-pyrophosphate (DDPS) 31 P NMR) map.
Detailed Description
Instrument and reagent:
nuclear magnetic resonance spectrum (NMR) was measured using Bruker AVANCE III MHz Plus NMR spectrometer with TMS as internal standard, CDCl 3 Is a solvent. The solvent was evaporated under reduced pressure using an EYELA SB-1100 rotary evaporator at 60℃with the remainder being conventional laboratory equipment: the system comprises an SHZ-E circulating water type vacuum pump, a DZE-6120 type vacuum drying box, an EB2005A electronic balance, a DFX-5L/30 low-temperature constant-temperature reaction bath and a 2YZ-4A rotary vane type vacuum oil pump. The reagents used were all analytically pure.
The present application will be further illustrated by the following examples, but the scope of the application is not limited to the examples.
Example 1
A method for preparing DDPS by a one-pot method comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of toluene is added, stirring is carried out under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus trichloride is slowly added, stirring reaction is carried out at 40 ℃ for 0.5h, a conduit connected with an ammonia steel bottle extends below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia trace flowmeter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed, so that 3.308g of DDPS is obtained. The yield was 95.6%.
1 H NMR(400MHz,CDCl 3 )δ4.54(d,J＝10.3Hz,4H),3.94(dd,J＝25.2,11.0Hz,4H),1.32(s,6H),0.91(s,6H).
13 C NMR(101MHz,CDCl 3 )δ79.06,79.03,78.99,77.32,77.00,76.68,32.15,32.12,32.09,21.81,19.85.
31 P NMR(162MHz,CDCl 3 )δ43.53(s).
Example 2
A method for preparing DDPS by a one-pot method comprises the following experimental steps of:
52.04g (0.5 mol) of neopentyl glycol is weighed and placed in a 1L three-necked flask, 180mL of toluene is added, stirring is carried out under heating to dissolve the neopentyl glycol, 83.93g (0.5 mol) of phosphorus oxychloride is slowly added, stirring is carried out at 40 ℃ for 0.5h, a conduit connected with an ammonia steel bottle extends below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia micro-flow meter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 53.0g (0.5 mol) of sodium carbonate, adding 132.5g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise addition is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained through suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain the product DDPS 82.094g. The yield was 94.9%.
Example 3
A method for preparing DDPS by a one-pot method optimizes alkali, which comprises the following experimental steps:
neopentyl glycol 1.041g (10 mmol) was weighed into a 100mL three-necked flask, 20mL toluene was added and dissolved by stirring under heating, then 1.20g (30 mmol) NaOH solid particles were added, 1.679g (10 mmol) phosphorus trichloride was slowly added dropwise with a constant pressure funnel, and after the addition was completed, the reaction was carried out at 40℃for 3 hours. After the first step of reaction is finished, the temperature is raised to 70 ℃, 1.06g (10 mmol) of sodium carbonate is weighed, 2.65g of pure water is added to prepare 28% sodium carbonate solution, then the prepared sodium carbonate solution is slowly added dropwise, and the reaction is carried out for 8 hours at 70 ℃ after the dropwise addition is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained through suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain the product DDPS 2.526g. The yield was 74.3%.
Example 4
A method for preparing DDPS by a one-pot method optimizes alkali, which comprises the following experimental steps:
neopentyl glycol 1.041g (10 mmol) was weighed into a 100mL three-necked flask, 20mL toluene was added and dissolved by stirring under heating, then 3.366g (30 mmol) of potassium tert-butoxide solid was added, 1.679g (10 mmol) of phosphorus oxychloride was slowly added dropwise with a constant pressure funnel, and the reaction was continued for 3 hours at 40℃after the addition was completed. After the first step of reaction is finished, the temperature is raised to 70 ℃, 1.06g (10 mmol) of sodium carbonate is weighed, 2.65g of pure water is added to prepare 28% sodium carbonate solution, then the prepared sodium carbonate solution is slowly added dropwise, and the reaction is carried out for 8 hours at 70 ℃ after the dropwise addition is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain 2.400g of DDPS product. The yield was 70.6%.
Example 5
A method for preparing DDPS by a one-pot method optimizes alkali, which comprises the following experimental steps:
neopentyl glycol 1.041g (10 mmol) was weighed into a 100mL three-necked flask, 20mL toluene was added and dissolved by stirring under heating, then 3.180g (30 mmol) of sodium carbonate solid was added, 1.679g (10 mmol) of phosphorus oxychloride was slowly added dropwise with a constant pressure funnel, and the reaction was continued at 40℃for 3 hours after the addition. After the first step of reaction is finished, the temperature is raised to 70 ℃, 1.06g (10 mmol) of sodium carbonate is weighed, 2.65g of pure water is added to prepare 28% sodium carbonate solution, then the prepared sodium carbonate solution is slowly added dropwise, and the reaction is carried out for 8 hours at 70 ℃ after the dropwise addition is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain 2.455g of DDPS product. The yield was 72.2%.
Example 6
A method for preparing DDPS by a one-pot method optimizes a solvent, and comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of benzene is added, stirring is carried out under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus trichloride is slowly added, stirring reaction is carried out at 40 ℃ for 0.5h, a conduit connected with an ammonia steel bottle extends below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia trace flowmeter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained through suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain the product DDPS 3.065g. The yield was 88.6%.
Example 7
A method for preparing DDPS by a one-pot method optimizes a solvent, and comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of n-heptane is added, stirring is carried out under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus trichloride is slowly added, stirring reaction is carried out for 0.5h at 40 ℃, a conduit connected with an ammonia steel bottle is stretched below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia trace flowmeter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained through suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain the product DDPS 2.958g. The yield was 85.5%.
Example 8
A method for preparing DDPS by a one-pot method optimizes a solvent, and comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of normal hexane is added, stirring is carried out under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus trichloride is slowly added, stirring reaction is carried out at 40 ℃ for 0.5h, a conduit connected with an ammonia steel bottle extends below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia trace flowmeter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed to obtain 2.886g of DDPS product. The yield was 83.4%.
Example 9
A method for preparing DDPS by a one-pot method optimizes a solvent, and comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of 1, 4-dioxane is added, the mixture is stirred under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus oxychloride is slowly added, the mixture is stirred at 40 ℃ to react for 0.5h, a conduit connected with ammonia in a steel bottle stretches below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of the ammonia is set to be 20mL/min by using an ammonia micro-flow meter, and the mixture is kept at 40 ℃ to react for 3h under the condition of continuously introducing the ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed, so that 2.135g of DDPS is obtained. The yield was 62.8%.
Example 10
A method for preparing DDPS by a one-pot method optimizes a solvent, and comprises the following experimental steps:
1.041g (10 mmol) of neopentyl glycol is weighed and placed in a 100mL three-necked flask, 20mL of butyl acetate is added, stirring is carried out under heating to dissolve the neopentyl glycol, 1.679g (10 mmol) of phosphorus oxychloride is slowly added, stirring reaction is carried out at 40 ℃ for 0.5h, a conduit connected with an ammonia steel bottle extends below the liquid level, an ammonia pressure reducing valve is slowly opened, the flow rate of ammonia is set to 20mL/min by using an ammonia trace flowmeter, and the reaction is carried out for 3h at 40 ℃ under the condition of continuously introducing ammonia. After the first step of reaction is finished, stopping introducing ammonia gas, heating to 70 ℃, weighing 1.06g (10 mmol) of sodium carbonate, adding 2.65g of pure water to prepare 28% sodium carbonate solution, slowly dropwise adding the prepared sodium carbonate solution, and reacting for 8 hours at 70 ℃ after the dropwise adding is finished. A large amount of white solid is precipitated in the reaction process, after the reaction is finished, the solid is obtained by suction filtration, and then the solid is washed with water, washed with ethanol, dried and weighed, so that the DDPS 1.880g is obtained. The yield was 55.3%.
The application provides a method for synthesizing a flame retardant dithio-pyrophosphate by using ammonia and sodium carbonate as acid binding agents, which avoids the problems of product quality, environment, cost and the like caused by using a large amount of organic alkali. In the first step, ammonia gas is used as an acid binding agent, so that the reaction is more efficient and the yield is higher than that of solid inorganic base. The synthesis method adopts a one-pot method, the reaction time is shorter, and the generated three wastes are less. The whole route avoids using organic alkali as an acid binding agent, ammonia gas and sodium carbonate as the acid binding agent, and a one-pot synthesis process is used, so that the whole route is green, efficient and economic, and has good industrial application prospect.
The above embodiments are merely preferred embodiments of the present application, and should not be construed as limiting the present application, and the embodiments and features of the embodiments of the present application may be arbitrarily combined with each other without collision. The protection scope of the present application is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this application are also within the scope of the application.
Claims (8)
1. A process for synthesizing a flame retardant dithio-pyrophosphate by using ammonia as an acid-binding agent through a one-pot method is characterized by comprising the following steps of:
(1) Weighing raw material neopentyl glycol in a reactor, adding an organic solvent, heating and stirring until the neopentyl glycol is dissolved, then dropwise adding phosphorus oxychloride, introducing ammonia gas after the dropwise adding is finished for carrying out heat preservation reaction, and obtaining intermediate thiophosphoryl chloride after the reaction is finished;
(2) After the intermediate thiophosphoryl chloride is heated up again, dropwise adding sodium carbonate solution, after dropwise adding, carrying out heat preservation reaction, after the reaction is finished, carrying out suction filtration to obtain a crude product, and then washing the crude product with water, washing with ethanol, filtering and drying to obtain a dithio-pyrophosphoric acid ester product, wherein the reaction formula is as follows:
2. the process according to claim 1, wherein the molar ratio of neopentyl glycol to phosphorus oxychloride is 1:0.8-1.2.
3. The process according to claim 2, wherein the molar ratio of neopentyl glycol to phosphorus oxychloride is 1:1.
4. the process according to claim 1, wherein the reaction temperature in step (1) is 25 ℃ to 40 ℃ and the reaction time is 0.5h to 4h.
5. A process according to claim 3, wherein the organic solvent in step (1) is selected from any one of toluene, benzene, n-heptane, n-hexane.
6. The process according to claim 1, wherein the flow rate of ammonia gas in the step (1) is 5-50mL/min.
7. The process according to claim 1, characterized in that the molar ratio of intermediate thiophosphoryl chloride to sodium carbonate is 1:0.5-1.5.
8. The process according to claim 1, wherein the reaction temperature in step (2) is 50-70 ℃ and the reaction time is 6-12 h.
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