CN114874264B - Synthetic method of flame retardant DDPS - Google Patents
Synthetic method of flame retardant DDPS Download PDFInfo
- Publication number
- CN114874264B CN114874264B CN202210499667.5A CN202210499667A CN114874264B CN 114874264 B CN114874264 B CN 114874264B CN 202210499667 A CN202210499667 A CN 202210499667A CN 114874264 B CN114874264 B CN 114874264B
- Authority
- CN
- China
- Prior art keywords
- reaction
- ddps
- flame retardant
- solvent
- stirring
- 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.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 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 29
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 20
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 38
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 8
- 239000011230 binding agent Substances 0.000 abstract description 8
- 238000005580 one pot reaction Methods 0.000 abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- HWSUUGHIDOOOOJ-UHFFFAOYSA-N dioxaphosphinane Chemical compound C1COOPC1 HWSUUGHIDOOOOJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- -1 halogen phosphate Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- CIFZCCWGXMYJEU-UHFFFAOYSA-N dithiodiphosphoric acid Chemical compound OP(O)(=S)OP(O)(O)=S CIFZCCWGXMYJEU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
Abstract
The invention relates to a synthetic method of a flame retardant DDPS, which has the chemical structural formula:
Description
Technical Field
The invention belongs to the technical field of flame retardance, and particularly relates to a flame retardant DDPS prepared by a one-pot method in an environment-friendly method.
Background
Flame retardants are adjuvants used to improve the flame resistance of materials, i.e., to prevent the material from igniting and to inhibit flame propagation. The organic phosphorus flame retardant with various flame retardants is the most complex and most fully studied, and most of the organic phosphorus flame retardants have the advantages of low smoke, no toxicity, low halogen and no halogen, accord with the development direction of the flame retardant, and have good development prospect. The phosphate flame retardant is widely applied due to abundant resources and low price, is divided into halogen-free and halogen-containing, and has the characteristics of flame retardance and plasticization, the plasticization function can enable the processing fluidity of plastics to be good when the plastics are molded, residues after combustion can be inhibited, the halogen-containing phosphate has high flame retardance difficulty due to the fact that the halogen and the phosphorus are contained simultaneously, and the halogen-containing phosphate is a plasticization flame retardant, but the non-halogen phosphate is a development direction of a non-toxic flame retardant. The viscose is the most commonly used textile fiber, but the viscose is extremely easy to burn when meeting water, the limiting oxygen index is only about 17%, the use of the viscose in the fields of life, industry and the like is limited, and flame-retardant modification is carried out on the viscose, so that the flame-retardant viscose with good flame-retardant performance is one of the problems of fiber modification research.
The dithio-pyrophosphate of neopentyl glycol is an effective and most classical additive blending type flame retardant for viscose fiber, which is prepared by two steps of reaction, takes neopentyl glycol and phosphorus trichloride as intermediates prepared by starting materials, and then reacts with water to prepare a target product. In industrial production, the separation of the intermediate is difficult, so that the process is complicated and the cost is increased, the synthesis process of the flame retardant for the viscose fiber is improved, the solvent, the acid binding agent and the like are optimized, the one-pot production process is realized under the condition that the intermediate is not separated, the production cost is greatly reduced, and the environmental pollution is reduced.
When the intermediate is prepared, nitrogen is blown to replace triethylamine to discharge hydrogen chloride gas generated by the reaction, the use of an acid-binding agent is completely avoided, under the condition of not separating the intermediate, water is used as a solvent, and calcium oxide is used as alkali to synthesize the flame retardant.
Disclosure of Invention
The invention aims to solve the main problems that the preparation of the flame retardant DDPS in the process uses an acid-binding agent to cause the defect of relatively large smell, relatively strong pressure and toxicity caused by the environment and harm to production operators, and provides a method for preparing the phosphorus-containing flame retardant DDPS by using a green, environment-friendly and one-pot method.
The technical scheme of the invention is as follows:
a phosphorus flame retardant DDPS, the chemical structural formula of the compound being:
a method for preparing a flame retardant DDPS by a green, environment-friendly and one-pot method, which comprises the following steps:
(1) Preparation of intermediate DDSP: dissolving neopentyl glycol in a solvent, adding phosphorus oxychloride, stirring to dissolve the neopentyl glycol, and introducing nitrogen to react until no hydrogen chloride gas is generated, thus obtaining an intermediate DDSP after the reaction is finished;
(2) Preparation of the target compound DDPS: under the condition of not separating the intermediate, adding water into the intermediate DDSP, stirring at room temperature to dissolve the intermediate DDSP, adding calcium oxide powder, reacting until no hydrogen chloride gas is generated, washing the solid separated out after the reaction is finished by absolute ethyl alcohol, filtering and drying to obtain the flame retardant DDPS.
In the step 1, the feeding mole ratio of neopentyl glycol to phosphorus oxychloride to calcium oxide is 1:0.5-1.5:0.5-1.5; in the step 1, nitrogen is supplied by a nitrogen cylinder, and the exhaust gas quantity is 20-30L/min.
The reaction temperature in the step 1 is 0-60 ℃ and the reaction time is 1-4h; the reaction temperature in the step 2 is 0-40 ℃ and the reaction time is 12-24h.
The organic solvent used in the step 1 is acetonitrile or dimethyl sulfoxide; the solvent used in the reaction step 2 is deionized water.
The step 1 and the step 2 are prepared by a one-pot method, and the intermediate does not need a step of separation and purification.
Triethylamine or pyridine is not needed as an acid-binding agent in both the step 1 and the step 2.
The solvent in the step 2 is water, which is a green solvent, and after the reaction is finished, acetonitrile or a mixed solvent of dimethyl sulfoxide and water can be recycled.
The invention has the following beneficial effects:
1. the invention discloses a method for preparing a target compound by using neopentyl glycol and phosphorus oxychloride as raw materials, exhausting hydrogen chloride gas generated by reaction through nitrogen bubbling and reacting at room temperature.
2. The invention overcomes the defect that the traditional process needs triethylamine or pyridine as an acid-binding agent to cause larger odor, and causes strong pressure and toxicity to the environment, and the harm to the health of production operators, prepares the flame retardant intermediate DDSP based on nitrogen bubbling, and provides a novel method with low preparation cost, simple operation and high reaction efficiency.
3. The invention discloses a method for synthesizing a flame retardant DDPS by taking water as a solvent to replace the traditional process toluene or xylene, which takes water as the solvent, is beneficial to the hydrolysis of the reaction to be carried out towards the positive reaction direction, and simultaneously, the generated byproduct inorganic salt can be well dissolved in the water to enable the reaction to be fully contacted in one phase for reaction.
4. The invention discloses a hydrogen chloride gas generated during an absorption reaction by taking calcium oxide as alkali, which avoids the defects of strong pressure and toxicity caused by the traditional process that triethylamine or pyridine is required as an acid-binding agent and causes a large amount of smell, and the harm to the health of production operators is strong, and meanwhile, the generated byproducts can be well dissolved in an aqueous solvent, so that the post-treatment process is simplified, and the novel method with low preparation cost, simple operation and high reaction efficiency is provided.
5. The invention prepares the phosphorus-containing flame retardant DDPS, the compound is used as a common and important phosphorus-containing structural unit, has a ring-shaped carbon skeleton structure similar to a benzene ring structure, has stable property, high phosphorus content and good flame retardant effect, and is a hot spot for synthesizing the flame retardant in recent years.
6. The process for preparing the phosphorus-containing flame retardant DDPS is one-pot preparation, and the intermediate does not need a step of separation and purification. And the second step is water. Is a green reaction process.
Drawings
Fig. 1: nuclear magnetic resonance hydrogen spectrum of neopentyl glycol dithio-pyrophosphate (DDPS) 1 H NMR) map.
Fig. 2: nuclear magnetic resonance carbon spectrum of neopentyl glycol dithio-pyrophosphate (DDPS) 13 C NMR) map.
Detailed Description
The present invention will be further illustrated by the following examples, but the scope of the invention is not limited to the examples.
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 65℃with the remainder being conventional laboratory equipment: ACO series electromagnetic air pump, SHZ-E type circulating water vacuum pump, DZE-6120 type vacuum drying box, EB2005A electronic balance, DFX-5L/30 low temperature constant temperature reaction bath and 2YZ-4A type rotary vane vacuum oil pump. The reagents used were all analytically pure.
Example 1
A method of preparing DDPS comprising the experimental steps of:
weighing 0.52g (5 mmol) of neopentyl glycol into a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring by a magnetic stirrer to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen cylinder to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at room temperature to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing by absolute ethyl alcohol, filtering and drying after the reaction is completed to obtain 752mg of the target compound DDPS. The yield thereof was found to be 87%.
1 H NMR(400MHz,CDCl 3 )δ4.48(d,J＝10.8Hz,4H),4.04–3.94(m,4H),1.33(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.
Example 2
A method for preparing DDPS (DDPS) takes dimethyl sulfoxide as a solvent for reaction, and comprises the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol in a 50ml double-necked flask, adding 2ml of dimethyl sulfoxide solvent, adding 0.766g (5 mmol) of phosphorus trichloride into the double-necked flask, stirring by a magnetic stirrer to dissolve the phosphorus trichloride, setting the exhaust gas of a nitrogen bottle to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at room temperature to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing by absolute ethyl alcohol, filtering and drying to obtain 742mg of the target compound DDPS. The yield was 85%.
Example 3
A method for preparing DDPS using nitrogen gas with an exhaust gas of 20L/min, comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol into a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring by a magnetic stirrer to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen cylinder to be 20L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at room temperature to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing by absolute ethyl alcohol, filtering and drying after the reaction is completed to obtain the target compound DDPS 519mg. The yield was 60%.
Example 4
A method of preparing DDPS, producing an intermediate in an open state, comprising the experimental steps of:
neopentyl glycol 0.52g (5 mmol) is weighed into a 50ml double-necked flask, 2ml acetonitrile solvent is added, 0.766g (5 mmol) of phosphorus oxychloride is added into the double-necked flask, the solution is stirred by a magnetic stirrer to be dissolved, a piston of the double-necked flask is opened, mechanical stirring is carried out for 1h, after the reaction is completed, 2ml deionized water is added into the double-necked flask under the condition of not separating an intermediate, stirring is carried out at room temperature to be dissolved, 0.28g (5 mmol) of calcium oxide powder is started to be added, mechanical stirring is carried out for 12h, precipitation is carried out in the reaction process, and after the reaction is completed, absolute ethyl alcohol is used for washing, filtering and drying to obtain the target compound DDPS 415mg. The yield was 48%.
Example 5
A method for preparing DDPS, gram-scale experiments, comprising the experimental steps of:
2.08g (20 mmol) of neopentyl glycol is weighed into a 100ml double-necked flask, 8ml of acetonitrile solvent is added, 3.06g (20 mmol) of phosphorus oxychloride is added into the double-necked flask, the phosphorus oxychloride is stirred by a magnetic stirrer to be dissolved, the exhaust gas of a nitrogen cylinder is set to be 30L/min, nitrogen is introduced into the double-necked flask, the mechanical stirring is carried out for 1h, after the reaction is completed, 8ml of deionized water is added into the double-necked flask under the condition that intermediates are not separated, the stirring is carried out at room temperature to be dissolved, 1.12g (20 mmol) of calcium oxide powder is started to be added, the mechanical stirring is carried out for 2h, and ethanol is used for washing, filtering and drying after the reaction is completed, thus obtaining 2.76g of target compound DDPS. The yield was 80%.
Example 6
A process for preparing DDPS using urea as base comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol into a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus trichloride into the double-necked flask, stirring by a magnetic stirrer to dissolve the phosphorus trichloride, setting the exhaust gas of a nitrogen bottle to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at room temperature to dissolve the intermediate, starting to add 0.3g (5 mmol) of urea particles, mechanically stirring for 12h, precipitating during the reaction, washing by absolute ethyl alcohol after the reaction is completed, filtering and drying to obtain the target compound DDPS328mg. The yield was 38%.
Example 7
A method for preparing DDPS using 50% aqueous acetone as a solvent, comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol into a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring by a magnetic stirrer to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen bottle to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 1ml of deionized water and 1ml of acetone into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at room temperature to dissolve the deionized water and 1ml of acetone, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing by absolute ethyl alcohol, filtering and drying to obtain the target compound DD519 mg after the reaction is completed. The yield thereof was found to be 61%.
Example 8
A method for preparing DDPS, the reaction being carried out at 0 ℃, comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol in a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring at 0 ℃ to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen cylinder to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at 0 ℃ to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing with absolute ethyl alcohol, filtering and drying after the reaction is completed to obtain the target compound DDPS674mg. The yield was 78%.
Example 9
A method for preparing DDPS, the reaction being carried out at 40 ℃, comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol in a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring at 40 ℃ to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen cylinder to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at 40 ℃ to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing with absolute ethyl alcohol, filtering and drying after the reaction is completed to obtain 717mg of the target compound DDPS. The yield thereof was found to be 82%.
Example 10
A method for preparing DDPS, the reaction being carried out at 60 ℃, comprising the following experimental steps:
weighing 0.52g (5 mmol) of neopentyl glycol in a 50ml double-necked flask, adding 2ml of acetonitrile solvent, adding 0.766g (5 mmol) of phosphorus oxychloride into the double-necked flask, stirring at 60 ℃ to dissolve the phosphorus oxychloride, setting the exhaust gas of a nitrogen cylinder to be 30L/min, introducing nitrogen into the double-necked flask, mechanically stirring for 1h, adding 2ml of deionized water into the double-necked flask under the condition of not separating an intermediate after the reaction is completed, stirring at 60 ℃ to dissolve the intermediate, starting to add 0.28g (5 mmol) of calcium oxide powder, mechanically stirring for 12h, precipitating during the reaction, washing with absolute ethyl alcohol, filtering and drying after the reaction is completed to obtain 622mg of the target compound DDPS. The yield was 72%.
The invention provides a method for avoiding the defect of high manufacturing cost caused by the traditional process for preparing DDPS by using toluene and dimethylbenzene, and also avoiding the environmental problem caused by using triethylamine; the method for preparing the intermediate DDSP by replacing hydrogen chloride gas generated by triethylamine absorption reaction by a nitrogen bubbling method and preparing the target compound DDPS by replacing triethylamine by calcium oxide has the advantages of low preparation cost, simple operation and high reaction efficiency.
The foregoing embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without collision. The protection scope of the present invention 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 invention are also within the scope of the invention.
Claims (3)
1. The synthesis method of the flame retardant DDPS is characterized by comprising the following steps:
(1) Preparation of intermediate DDSP: dissolving neopentyl glycol in a solvent, adding phosphorus trichloride, stirring to dissolve the neopentyl glycol, introducing nitrogen during the reaction until no hydrogen chloride gas is generated, and obtaining an intermediate DDSP after the reaction is finished, wherein the used organic solvent is acetonitrile or dimethyl sulfoxide;
(2) Preparation of the target compound DDPS: without isolation of the intermediate, water was added to the intermediate DDSP, which was then dissolved by stirring at room temperature, and then calcium oxide powder was added, the molar ratio of neopentyl glycol, phosphorus oxychloride and calcium oxide being 1:0.5-1.5:0.5-1.5; the nitrogen gas is introduced into the reactor at a concentration of 20-30L/min, the reaction is carried out until no hydrogen chloride gas is generated, and the solid precipitated after the reaction is washed by absolute ethyl alcohol, filtered and dried to obtain the flame retardant DDPS.
2. The process according to claim 1, wherein the reaction temperature in step (1) is 0 to 60 ℃ and the reaction time is 1 to 4 hours.
3. The process according to claim 1, wherein the reaction temperature in step (2) is 0-40 ℃ and the reaction time is 12-24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210499667.5A CN114874264B (en) | 2022-05-09 | 2022-05-09 | Synthetic method of flame retardant DDPS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210499667.5A CN114874264B (en) | 2022-05-09 | 2022-05-09 | Synthetic method of flame retardant DDPS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114874264A CN114874264A (en) | 2022-08-09 |
| CN114874264B true CN114874264B (en) | 2023-12-19 |
Family
ID=82674321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210499667.5A Active CN114874264B (en) | 2022-05-09 | 2022-05-09 | Synthetic method of flame retardant DDPS |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114874264B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH625806A5 (en) * | 1976-11-02 | 1981-10-15 | Sandoz Ag | Process for the preparation of pyrophosphorus compounds |
| CN101974167A (en) * | 2010-10-22 | 2011-02-16 | 天津工业大学 | Intumescent flame retardant and synthesis method thereof |
-
2022
- 2022-05-09 CN CN202210499667.5A patent/CN114874264B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH625806A5 (en) * | 1976-11-02 | 1981-10-15 | Sandoz Ag | Process for the preparation of pyrophosphorus compounds |
| CN101974167A (en) * | 2010-10-22 | 2011-02-16 | 天津工业大学 | Intumescent flame retardant and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 尹志刚主编.有机磷化学.北京：化学工业出版社,2011,196-197. * |
| 张海滨等.阻燃剂2,2'-二氧[5.5-二甲基-1,3,2-二氧磷杂环]2,2'-二硫化物的 合成.精细化工中间体.1981,第40卷(第1期),61-62、65. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114874264A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111440357B (en) | All-bio-based flame retardant, flame-retardant PLA composite material and preparation method thereof | |
| CN108440598B (en) | Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant | |
| CN110357987B (en) | Intumescent flame retardant and preparation method thereof | |
| CN114349968B (en) | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof | |
| CN110183727A (en) | Benzothiazole nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO units, preparation method and applications | |
| CN101880294B (en) | Novel phosphorus series bisphenols and manufacture method of derivatives thereof | |
| CN113264961A (en) | Novel phosphorus-nitrogen-containing DOPO flame retardant and preparation method and application thereof | |
| CN111073037B (en) | High-thermal-stability intumescent flame retardant and preparation method thereof | |
| CN112979498A (en) | Preparation method of 3-fluoro-4-trifluoromethyl benzonitrile | |
| CN110981912B (en) | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof | |
| CN114874264B (en) | Synthetic method of flame retardant DDPS | |
| CN114685563B (en) | Preparation method and application of flame retardant DDSP | |
| CN114085246A (en) | Bio-based phosphorus-containing flame retardant and preparation method and application thereof | |
| CN111606948B (en) | Efficient phosphine-nitrogen flame retardant and preparation method and application thereof | |
| CN107056839A (en) | A kind of synthetic method of novel reaction type bicyclic phosphate fire retardant | |
| CN110128474B (en) | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound | |
| CN113337006A (en) | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof | |
| CN113337004A (en) | Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof | |
| CN109851639B (en) | Alkyl bridged chain DOPO derivative and preparation method and application thereof | |
| CN110092944A (en) | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO | |
| CN113264960A (en) | Novel phosphorus-nitrogen flame retardant containing Schiff base DOPO derivative and preparation method and application thereof | |
| CN114702525B (en) | Preparation method of flame retardant dithio-pyrophosphate | |
| CN113024605A (en) | Synthesis method of hexaphenoxycyclotriphosphazene flame retardant | |
| CN113214656A (en) | Intumescent flame retardant taking octacyclodextrin POSS as carbon source and application thereof | |
| CN112457344A (en) | Synthesis method of p-xylyl bis (diphenylphosphine) oxide |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |