CN105733024A - Phosphorus/nitrogen/sulfur-containing flame retardant and preparation method thereof - Google Patents

Phosphorus/nitrogen/sulfur-containing flame retardant and preparation method thereof Download PDF

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CN105733024A
CN105733024A CN201610054450.8A CN201610054450A CN105733024A CN 105733024 A CN105733024 A CN 105733024A CN 201610054450 A CN201610054450 A CN 201610054450A CN 105733024 A CN105733024 A CN 105733024A
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phosphorus
fire retardant
preparation
nitrogen containing
element sulphur
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CN105733024B (en
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戴李宗
林康彬
陈国荣
邵志恒
袁丛辉
许一婷
曾碧榕
罗伟昂
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a phosphorus/nitrogen/sulfur-containing flame retardant and a preparation method thereof, relating to multielement synergic flame-retardant compounds. The preparation method comprises the following steps: sequentially adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diaminodiphenyl sulfone, carbon tetrachloride and a solvent into a container provided with a stirring device, magnetically stirring to uniformly mix the system, adding an acid-binding agent into the reaction system under an ice bath condition, removing the ice bath, continuing reacting, filtering, carrying out extraction eluting, concentrating, and precipitating with a precipitant, thereby obtaining the light-yellow solid phosphorus/nitrogen/sulfur-containing flame retardant. The flame retardant simultaneously contains phosphorus, nitrogen and sulfur which have the synergic flame-retardant effects in the combustion process. Besides, the preparation method has the advantages of simple preparation process, mild conditions and accessible raw materials, and can easily implement industrial production. The flame retardant is applicable to flame retardancy for epoxy resins and polyester materials.

Description

A kind of fire retardant of phosphorus-nitrogen containing element sulphur and preparation method thereof
Technical field
The present invention relates to multielement cooperative resistance combustion compound, especially relate to fire retardant and the preparation thereof of a kind of phosphorus-nitrogen containing element sulphur Method.
Background technology
Along with developing rapidly of Macromolecular materials industry, fire retardant and fire proofing development, produce and apply and the most quickly sent out Exhibition.Owing to the requirement of material property and environmental protection is increasingly stricter, development and application has environmental protection, low toxicity, efficient and multifunction Non-halogen fire retardant become the development trend of current fire retardant.
Phosphorus flame retardant is the fire retardant that a class range of application is wider, has the polymer beyond polyolefin and polystyrene well Flame retardant effect.Can degrade in combustion generation phosphoric acid, polyphosphoric acid of phosphorus flame retardant promotes into charcoal further and plays heat insulation Effect, thus prevent inner substrate participate in combustion process；It is permissible that phosphorus flame retardant the most also can generate PO, HPO Catch H and HO in gas phase, reduce the efficiency of burning.DOPO based flameproofing is the phosphorus flame retardant that research is more, has heat steady Qualitative height, hydrolysis, the feature that non-volatile and polymer compatibility is good.Utilize the activity of the P-H key of DOPO, can prepare and contain The halogen-free flame retardants of many ignition-proof elements, not only plays the fire resistance of DOPO, moreover it is possible to meet the requirement of international flame-proof environmental protection.
Simple phosphonium flame retardant can not meet the requirement of special material or high flame retardant, and then increasing researcher is opened Begin to pay close attention to cooperative flame retardant system, many phosphorous synergistic fire retardant systems occur in recent years, such as phosphorus-nitrogen combustion inhibitor, phosphorus-silicon fire retardant Deng.Cooperative flame retardant system can be effectively improved flame retarding efficiency effectively by the cooperative flame retardant effect between different elements, reduce fire retardant Addition.As Chinese patent CN104403128A discloses a kind of phosphorus nitrogen synergistic fire retardant containing two kinds of ignition-proof elements.This is fire-retardant Agent is made up of the miscellaneous luxuriant and rich with fragrance oxide of hexachlorocyclotriph,sphazene, hydroxy benzaldehyde, para-aminophenol and phosphine, this fire retardant have ring phosphonitrile, The molecular structure of phospho hetero phenanthrene, Heat stability is good, phosphorus nitrogen synergism has higher flame retarding efficiency simultaneously, when the addition of fire retardant When being only 10.6wt%, the limited oxygen index of epoxy resin cured product is brought up to 36.6% by 21.7%.Chinese patent CN102181058A describes a kind of novel phosphorus-silicon synergistic flame retardant being applied to polyester, and this fire retardant is former with DOPO and siloxanes Material, is obtained by double bond additive reaction.This fire retardant contains phosphorus element silicon, the two synergism flame-retardant polyester material, Ji Keyou Imitate fire-retardant, the molten drop phenomenon of polyester material can be suppressed again.Chinese patent CN102775431A describe a kind of by Silicon chloride., four Bromine bisphenol-A diepoxypropyl ether and epoxychloropropane synthesizing new silicon, chlorine, the method for bromine three element synergistic fire retardant.The resistance of synthesis It is high that combustion agent has silicon chlorine bromine trielement synergistic flame-retarded efficiency, the feature that silicate structure plasticity is good, but due to containing bromine and chlorine unit Element, it is impossible to meet American-European flame-retardant standard.
Summary of the invention
The purpose of the present invention aims to provide phosphorus element-containing, nitrogen element and element sulphur, can be used for REINFORCED PET, PBT polyester class material, Fire retardant of a kind of phosphorus-nitrogen containing element sulphur of the fire resistance of polyurethane and epoxy resin and preparation method thereof.
The chemical structural formula of the fire retardant (DDSDOPO) of described phosphorus-nitrogen containing element sulphur is as follows:
Specifically comprising the following steps that of the preparation method of the fire retardant of described phosphorus-nitrogen containing element sulphur
Be sequentially added in equipped with the container of agitating device 9,10-dihydro-9 oxa--10-phosphine miscellaneous phenanthrene-10-oxide (DOPO), DADPS (DDS), carbon tetrachloride and solvent, magnetic agitation makes system mix homogeneously, under conditions of ice bath, to instead Answering addition acid binding agent in system, then remove ice bath, filter after continuing reaction, extraction is washed, and concentrates, and precipitates with precipitant, obtains shallow The fire retardant (DDSDOPO) of yellow solid phosphorus-nitrogen containing element sulphur.
Described 9,10-dihydro-9 oxa--10-phosphine miscellaneous phenanthrene-10-oxide (DOPO), DADPS (DDS), four chlorinations Carbon, the mol ratio of acid binding agent can be (2～2.2): 1: (2.1～2.5): (2.2～2.5)；Described solvent is selected from dichloro One in methane, toluene, oxolane, ether, chloroform etc.；The reaction temperature of described ice bath can be-10～10 DEG C；Described Acid binding agent is selected from the one in triethylamine, Anhydrous potassium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide etc.；Described continuation is anti- The time answered can be 3～12h；Described precipitant can use the mixed solvent of normal hexane and ethyl acetate, in mass ratio normal hexane: Ethyl acetate can be 1: (1.5～3)；Described extraction is washed available water extraction and is washed.
The fire retardant of described phosphorus-nitrogen containing element sulphur has phosphorus nitrogen element sulphur simultaneously, can be applied to the processing of resin as flame-retardant additive In modification, improve the fire resistance of material.
Fire retardant prepared by the present invention is the most phosphorous, nitrogen, three kinds of elements of sulfur, has the effect of cooperative flame retardant in combustion, Additionally the preparation of this fire retardant is simple, and mild condition, raw material is easy to get, it is easy to industrialized production, has for epoxy resin, polyester material Material adds fire-retardant potentiality.
Compared with prior art the invention have the characteristics that:
1) molecular structure contains ignition-proof element phosphorus, nitrogen, sulfur simultaneously, be a kind of novel fire retardant having no report, due to phosphorus Can promote to form layer of charcoal with element sulphur, nitrogen can generate ammonia after burning have gas phase flame retardant effect, and synergism overcomes single fire-retardant The deficiency of element, improves flame retarding efficiency.
2) fire retardant (DDSDOPO) of the phosphorus-nitrogen containing element sulphur synthesized by the present invention has the structure of phospho hetero phenanthrene and sulfobenzide., There is higher heat stability and hydrolytic resistance.Flame retardant polyester PET, PBT and flame retardant epoxy tree can be applied to as flame-retardant additive The preparation of fat.
3) fire retardant of the phosphorus-nitrogen containing element sulphur of the present invention does not contains halogen, meets the needs of the non-halogen development of present stage fire retardant.
Accompanying drawing explanation
Fig. 1 is the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur1H NMR nuclear magnetic spectrogram.
Fig. 2 is the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur31P NMR nuclear magnetic spectrogram.
Fig. 3 is the infrared spectrum of the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur.
Detailed description of the invention
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
4.8g DOPO, 2.48g DADPS, 3.28g carbon tetrachloride and 10ml dichloromethane are joined 50ml circle In end flask, magnetic agitation 10min.Under condition of ice bath, with Dropping funnel by 5ml dichloromethane and the mixing of 2.7g triethylamine Solution is slowly added drop-wise in round-bottomed flask, and the reactant in holding flask will not local boiling.Ice bath is removed after all dripping off, Naturally it is warmed to room temperature and reacts 5h again.After reaction terminates, it is filtrated to get pale yellow solution, is washed till clarification, supernatant nothing by water extraction Water magnesium sulfate is dried, and after filtering out anhydrous magnesium sulfate, concentrated by rotary evaporation is to original 1/2nd volumes, with normal hexane and ethyl acetate matter Measuring the mixed solvent that ratio is 1: 1.5 is precipitant, and precipitation obtains 5.88g light yellow solid and is the fire retardant of phosphorus-nitrogen containing element sulphur (DDSDOPO), productivity 92%.
The phosphorus polynary synergistic fire retardant of nitrogen sulfur has been obtained by synthesis in embodiment 1.Fig. 1's1Chemical shift in H NMR nuclear magnetic spectrogram The peak of δ=7.42-7.95 is the proton peak of hydrogen, chemical shift δ=6.60 and δ=7.32 on the phenyl ring in fire retardant phospho hetero phenanthrene structure For the proton peak of hydrogen on the phenyl ring that is connected with sulfuryl on fire retardant, chemical shift δ=8.2 are the proton peak of hydrogen on fire retardant secondary amine, Chemical shift δ=3.3 are the proton peak of water, and the spike of chemical shift δ=2.5 is deuterated reagent DMSO proton peak；Fig. 2's31P NMR In nuclear magnetic spectrogram it can be seen that chemical shift δ=14.5 of raw material DOPO become the peak of δ=5.8；1H NMR nuclear magnetic spectrogram and31P NMR Nuclear magnetic spectrogram illustrates successfully to synthesize this response type phosphonium flame retardant.The infrared spectrum of the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur See Fig. 3.
Embodiment 2:
24.0g DOPO, 12.4g DADPS, 16.4g carbon tetrachloride and 50ml chloroform are joined 250ml circle In end flask, magnetic agitation 10min.Under condition of ice bath, with mixed by 25ml dichloromethane and 13.5g triethylamine of Dropping funnel Closing solution to be slowly added drop-wise in round-bottomed flask, the reactant in holding flask will not local boiling.Ice bath is removed after all dripping off, Naturally it is warmed to room temperature and reacts 8h again.After reaction terminates, it is filtrated to get pale yellow solution, is washed till clarification, supernatant nothing by water extraction Water magnesium sulfate is dried, and after filtering out anhydrous magnesium sulfate, concentrated by rotary evaporation is to original 1/2nd volumes, with ethyl acetate as precipitant, Precipitation obtains 25.9g light yellow solid and is the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur, productivity 84%.
Embodiment 3:
6.98g DOPO, 3.72g DADPS, 4.92g carbon tetrachloride and 15ml dichloromethane are joined 100ml In round-bottomed flask, magnetic agitation 10min.Under condition of ice bath, with mixed by 8ml dichloromethane and 3.5g triethylamine of Dropping funnel Closing solution to be slowly added drop-wise in round-bottomed flask, the reactant in holding flask will not local boiling.Ice bath is removed after all dripping off, Naturally it is warmed to room temperature and reacts 4.5h again.After reaction terminates, being filtrated to get pale yellow solution, be washed till clarification by water extraction, supernatant is used Anhydrous magnesium sulfate is dried, and is spin-dried for solvent and obtains yellow solid after filtering out anhydrous magnesium sulfate, yellow solid ethyl acetate is disperseed, Fully washing is dried, obtains the fire retardant (DDSDOPO) of 6.76g phosphorus-nitrogen containing element sulphur, productivity 72%.
Embodiment 4:
4.4g DOPO, 2.48g DADPS, 3.18g carbon tetrachloride and 10ml dichloromethane are joined 50ml circle In end flask, magnetic agitation 10min.Under condition of ice bath, with Dropping funnel by 5ml dichloromethane and the mixing of 2.1g triethylamine Solution is slowly added drop-wise in round-bottomed flask, and the reactant in holding flask will not local boiling.Ice bath is removed after all dripping off, Naturally it is warmed to room temperature and reacts 5h again.After reaction terminates, rotation is evaporated off solvent, and the solid obtained is respectively by distilled water and ethyl acetate Washing for several times, obtains 3.0g yellow solid after drying and is the fire retardant (DDSDOPO) of phosphorus-nitrogen containing element sulphur, productivity 48%.

Claims (9)

1. the fire retardant of a phosphorus-nitrogen containing element sulphur, it is characterised in that its chemical structural formula is as follows:
2. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 1, it is characterised in that it specifically comprises the following steps that
9,10-dihydro-9 oxa--10-phosphine miscellaneous phenanthrene-10-oxide, diaminourea two it is sequentially added in equipped with the container of agitating device Benzene sulfone, carbon tetrachloride and solvent, magnetic agitation makes system mix homogeneously, under conditions of ice bath, adds and tie up in reaction system Acid agent, then remove ice bath, filtering after continuing reaction, extraction is washed, and concentrates, and precipitates with precipitant, obtains light yellow solid phosphorus-nitrogen containing The fire retardant of element sulphur.
3. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that described 9,10-dihydro -9 oxa--10-phosphine miscellaneous phenanthrene-10-oxides, DADPS, carbon tetrachloride, the mol ratio of acid binding agent are (2～2.2): 1: (2.1～2.5): (2.2～2.5).
4. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that described solvent is selected from dichloro One in methane, toluene, oxolane, ether, chloroform.
5. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that the reaction temperature of described ice bath Degree is for-10～10 DEG C.
6. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that described acid binding agent is selected from three One in ethamine, Anhydrous potassium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide.
7. the preparation method of the as claimed in claim 2 fire retardant of phosphorus-nitrogen containing element sulphur, it is characterised in that described continuation reaction time Between be 3～12h.
8. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that described precipitant uses Normal hexane and the mixed solvent of ethyl acetate, in mass ratio normal hexane: ethyl acetate is 1: (1.5～3).
9. the preparation method of the fire retardant of phosphorus-nitrogen containing element sulphur as claimed in claim 2, it is characterised in that it is to extract with water that described extraction is washed Wash.
CN201610054450.8A 2016-01-27 2016-01-27 A kind of fire retardant and preparation method thereof of phosphorus-nitrogen containing element sulphur Expired - Fee Related CN105733024B (en)

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Cited By (15)

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CN106800644A (en) * 2017-01-16 2017-06-06 海泰纺织（苏州）有限公司 A kind of terminal hydroxy group organic nitrogen-containing thioesters compound and preparation method thereof and by its obtained flame retardant polyester fabric
CN106893369A (en) * 2017-01-19 2017-06-27 北京化工大学 A kind of synthesis of phosphorous nitrogen sulfur compound and its preparation method of intercalation modifying hydrotalcite
CN107254142A (en) * 2016-07-21 2017-10-17 广东广山新材料股份有限公司 A kind of fire-proof resin composition, compositions of thermosetting resin, composite metal substrate and flame-resistant electronic material
CN107641290A (en) * 2016-07-21 2018-01-30 广东广山新材料股份有限公司 A kind of fire-proof resin composition, compositions of thermosetting resin, anti-flammability engineering plastics and composite metal substrate
CN107641288A (en) * 2016-07-21 2018-01-30 广东广山新材料股份有限公司 A kind of sulphur phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate
CN108440598A (en) * 2018-04-08 2018-08-24 三峡大学 A kind of preparation method and applications of sulphur-nitrogen-phosphorus composite fire retardant
CN110092944A (en) * 2019-05-05 2019-08-06 三峡大学 The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO
CN110128474A (en) * 2019-05-05 2019-08-16 三峡大学 The preparation method and applications of the double DOPO thiazolium compounds of nitrogen phosphorus sulphur synergistic flame retardant
CN110128702A (en) * 2019-05-05 2019-08-16 三峡大学 Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications
CN110669074A (en) * 2019-10-18 2020-01-10 广东聚航新材料研究院有限公司 Novel organic phosphorus flame retardant and preparation method thereof
CN110183727B (en) * 2019-05-05 2021-03-23 三峡大学 Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof
CN112625249A (en) * 2020-11-20 2021-04-09 江苏集萃先进高分子材料研究所有限公司 Novel phosphorus-nitrogen-sulfur flame retardant and preparation method thereof
CN113292823A (en) * 2021-05-24 2021-08-24 南京工业大学 Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material
CN113861510A (en) * 2021-10-09 2021-12-31 常州大学 Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof
CN116854728A (en) * 2023-07-05 2023-10-10 吉林大学 Phosphorus-containing dopamine flame retardant, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN107254142A (en) * 2016-07-21 2017-10-17 广东广山新材料股份有限公司 A kind of fire-proof resin composition, compositions of thermosetting resin, composite metal substrate and flame-resistant electronic material
CN107641290A (en) * 2016-07-21 2018-01-30 广东广山新材料股份有限公司 A kind of fire-proof resin composition, compositions of thermosetting resin, anti-flammability engineering plastics and composite metal substrate
CN107641288A (en) * 2016-07-21 2018-01-30 广东广山新材料股份有限公司 A kind of sulphur phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate
CN106800644A (en) * 2017-01-16 2017-06-06 海泰纺织（苏州）有限公司 A kind of terminal hydroxy group organic nitrogen-containing thioesters compound and preparation method thereof and by its obtained flame retardant polyester fabric
CN106893369A (en) * 2017-01-19 2017-06-27 北京化工大学 A kind of synthesis of phosphorous nitrogen sulfur compound and its preparation method of intercalation modifying hydrotalcite
CN108440598A (en) * 2018-04-08 2018-08-24 三峡大学 A kind of preparation method and applications of sulphur-nitrogen-phosphorus composite fire retardant
CN108440598B (en) * 2018-04-08 2020-04-24 三峡大学 Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant
CN110128702A (en) * 2019-05-05 2019-08-16 三峡大学 Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications
CN110128474A (en) * 2019-05-05 2019-08-16 三峡大学 The preparation method and applications of the double DOPO thiazolium compounds of nitrogen phosphorus sulphur synergistic flame retardant
CN110092944A (en) * 2019-05-05 2019-08-06 三峡大学 The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO
CN110183727B (en) * 2019-05-05 2021-03-23 三峡大学 Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof
CN110128474B (en) * 2019-05-05 2021-10-19 三峡大学 Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound
CN110669074A (en) * 2019-10-18 2020-01-10 广东聚航新材料研究院有限公司 Novel organic phosphorus flame retardant and preparation method thereof
CN112625249A (en) * 2020-11-20 2021-04-09 江苏集萃先进高分子材料研究所有限公司 Novel phosphorus-nitrogen-sulfur flame retardant and preparation method thereof
CN113292823A (en) * 2021-05-24 2021-08-24 南京工业大学 Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material
CN113292823B (en) * 2021-05-24 2022-03-22 南京工业大学 Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material
CN113861510A (en) * 2021-10-09 2021-12-31 常州大学 Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof
CN113861510B (en) * 2021-10-09 2023-02-28 常州大学 Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof
CN116854728A (en) * 2023-07-05 2023-10-10 吉林大学 Phosphorus-containing dopamine flame retardant, and preparation method and application thereof

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