CN109796495A - Three phosphazene derivative of ring of phosphate ester-containing and its preparation method and application - Google Patents
Three phosphazene derivative of ring of phosphate ester-containing and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of three phosphazene derivative of ring of phosphate ester-containing, and in particular to the preparation method and application of three phosphazene derivative of ring of phosphate ester-containing belongs to field of fire-proof technology.Phosphate compounds and hexachlorocyclotriph,sphazene are placed in the tetrahydrofuran solution under alkaline condition, nucleophilic substitution is brought it about, filters, be concentrated later, washing obtains three phosphazene derivative of ring of phosphate ester-containing.Reaction condition of the present invention is mild, easily controllable, reproducible, and compound obtained has good flame retardation effect, and fire-retardant additive amount can reach good flame retardant effect less, while heating is not easily decomposed, and can be used as a kind of good fire retardant use.
Description
Technical field
The invention belongs to a kind of novel nitrogen phosphorus system additive flame retardant technical fields.Three phosphonitrile of ring for being related to phosphate ester-containing spreads out
Biology and preparation method thereof, and be applied to and prepare textile and coating, polyester material and special engineering plastics and bionical
The multifunction finishing agent or additive of material etc..
Background technique
China is organic material produce big country and using big country, people caused by the fire caused every year by organic material burning
Body property loss is serious, and most of organic material is heated or easily discharges a large amount of toxic gases when burning, and is not appropriate for as more
The food packaging of secondary heating and biological affinitive material use, and are less useful for fire incident people from scene caused of burning because of organic material
Member's escape.All the time, it all pays much attention to open the research of the flame retardant type biology affinitive material of Environmental Safety and product both at home and abroad
Hair, expensive high-end fire retardant only a small amount of at present can be applied in advanced bio affinity type material, in view of it
Fancy price and function restriction are not widely applied.Therefore to having environmental protection, safety is nontoxic, efficient biology affinity type function
The research and development of energy fire retardant, is still one of the important research direction of current fire retardant.
Currently, fire retardant used in China mainly includes halogen system and phosphorus system, wherein phosphorus flame retardant have it is fire-retardant, heat-insulated,
Oxygen-impermeable function, and generation smoke is few, also is not easy to form toxic and harmful gas, adapts to various environmental requirements.Phosphonitrile class is fire-retardant
Agent is a kind of phosphonium flame retardant that flame retardant effect is excellent, due to high-content phosphorus nitrogen and have excellent flame retardant property, by right
The modification of the active site of phosphorus on its phosphonitrile monomer can be transformed into the officials such as a variety of hydroxyls, amino, halogen and charcoal carbonyl
The phosphonitrile fire-retardant agent that can be rolled into a ball, and it is widely used in the material of various different performances.Phosphonitrile fire-retardant agent does not need generally
Other auxiliary flame retardants are added, meanwhile, thermal stability is good, and nontoxic, smoke amount is small, has self-extinguishment, is acknowledged as hindering from now on
Fire one of the developing direction of agent.
There are many phosphonitrile fire-retardant agent type, and due to its cheap price, good material is affine performance and it is flexible
Application method, application field are also quite extensive.Its kind has water-soluble and oil-soluble, is suitable for a variety of occasions and uses, both may be used
It to be used for a variety of natural fibers such as cotton, fiber crops, silk, and can be applied to the synthetic materials such as polyester, aeronautical material can also be applied to.
However it is applied to organic synthesis material, biological affinitive material, while having heating nontoxic, the safety of characteristics such as it is not easily decomposed
There is not been reported for fire retardant.
Summary of the invention
To overcome the shortcomings of the prior art, the main object of the present invention is to provide a kind of phosphorus phosphorus-nitrogen coordinated fire-retardant agent,
By reacting three phosphonitrile of ring with phosphate compounds, a kind of three phosphazene derivative of ring of phosphate ester-containing is made, with good
Good flame retardant property.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of three phosphazene derivative fire retardant of ring of phosphate ester-containing of the invention is the phosphoric acid using three phosphonitrile of ring as basic framework
Ester type compound replaces six chlorine atoms to form hub-and-spoke configuration, and specific structure is as follows:
The integer of m in formula, n expression 0-2.
The present invention uses following specific technical solution:
A kind of six alkoxycyclotriphosphderivative preparation method of high-purity, substantially includes: (1) hexachlorocyclotriph,sphazene and methylol
The reaction step of diethyl phosphate；(2) reaction step of hexachlorocyclotriph,sphazene and 2- ethoxy dimethyl phosphate.
(1) response feature of hexachlorocyclotriph,sphazene and methylol diethyl phosphate is as follows:
Reaction condition: acid binding agent is sodium hydride, triethylamine；Temperature is at 65-70 DEG C, reaction time 12-72h.
Solvent for use of the present invention is tetrahydrofuran.
White solid is obtained by the purification of the methods of suction filtration, concentration, organic solvent washing, column chromatography.
Preparation method used comprises the following specific steps that:
A. the methylol diethyl phosphate for being dissolved in anhydrous tetrahydro furan is slowly dropped to dissolved with hexachlorocyclotriph,sphazene and three
Ethamine, sodium hydride anhydrous tetrahydrofuran solution in, be warming up to 65-70 DEG C of reaction 12-72h, thin-layered chromatography monitoring reaction；
The molar ratio of hexachlorocyclotriph,sphazene and methylol diethyl phosphate is 1:6-7, hexachlorocyclotriph,sphazene and acid binding agent
Molar ratio is 1:7-9；
B. reaction temperature is down to room temperature, adds appropriate tetrahydrofuran during this period；
C. it filters, is filtered with Buchner funnel, tetrahydrofuran elutes filter cake, obtains colorless and transparent filtrate；
D. it is concentrated, filtrate is concentrated to get colorless semi-solid under vacuum conditions；
E. it washs, is successively washed with petroleum ether, n-hexane, ethyl acetate, obtain finished product white solid；
F. column chromatographs, and solvent is methylene chloride: methanol: acetic acid=200:10:1.
Reaction equation of the invention is as follows:
(2) response feature of hexachlorocyclotriph,sphazene and 2- ethoxy dimethyl phosphate is as follows:
Reaction condition: acid binding agent is sodium hydride, triethylamine；Temperature is at 65-70 DEG C, reaction time 12-72h.
Solvent for use of the present invention is tetrahydrofuran.
White solid is obtained by the purification of the methods of suction filtration, concentration, organic solvent washing.
Preparation method used comprises the following specific steps that:
A. the 2- ethoxy dimethyl phosphate for being dissolved in anhydrous tetrahydro furan is slowly dropped to dissolved with hexachlorocyclotriph,sphazene and
Triethylamine, sodium hydride anhydrous tetrahydrofuran solution in, be warming up to 65-70 DEG C of reaction 12-72h, thin-layered chromatography monitoring reaction.
The molar ratio of hexachlorocyclotriph,sphazene and 2- ethoxy dimethyl phosphate is 1:6-7, hexachlorocyclotriph,sphazene and acid binding agent
Molar ratio be 1:7-9.
B. reaction temperature is down to room temperature, adds appropriate tetrahydrofuran during this period.
C. it filters, is filtered with Buchner funnel, tetrahydrofuran elutes filter cake, obtains colorless and transparent filtrate.
D. it is concentrated, filtrate is concentrated to get colorless oil under vacuum conditions.
E. it washs, is successively washed with petroleum ether, n-hexane, ethyl acetate, obtain finished product white solid.
Reaction equation of the invention is as follows:
Three phosphazene derivative of phosphate ester-containing ring of the invention is as follows as the application of fire retardant:
Three phosphazene derivative of phosphate ester-containing ring (HPCTP) is formed and gathered as flame-retardant additive and polylactic acid (PLA) compounding
The limit oxygen index (LOI) of condensation material, pure PLA is only 19.6%, and under nitrogen atmosphere, temperature of initial decomposition (T5%) is 319
DEG C, carbon yield when degradation hot arc is concentrated mainly on 350-410 DEG C or so, 800 DEG C is 0.When the additive amount of HPCTP is 5wt%
When, HPCTP (5wt%)/PLA LOI has certain improvement, can reach 26.8%, there is molten drop generation, and UL-94 is V-2 etc.
Grade, temperature of initial decomposition are 330 DEG C, degrade 50% (T50%) when carbon yield of temperature when being 367 DEG C, 800 DEG C be 2.6%.
When HPCTP additive amount is 10%, the variation of HPCTP (10wt%)/PLA LOI value is 29.6% less, there is the production of molten drop phenomenon
Raw, UL-94 is still V-2 grade, and temperature of initial decomposition is 342 DEG C, degrade 50% (T50%) when temperature be 383 DEG C, 800
DEG C when carbon yield be 4.3%.When HPCTP additive amount is 20%, HPCTP (20wt%)/PLA LOI value has very big
It improves, can reach 35.6%, no molten drop phenomenon generates, and UL-94 can reach V-0 grade, and temperature of initial decomposition is initial decomposition
Temperature is 362 DEG C, degrade 50% (T50%) when carbon yield of temperature when being 402 DEG C, 800 DEG C be 8.5%.The addition of HPCTP
So that the LOI value and UL-94 grade of PLA have been improved, show to be a kind of more efficient fire retardant for PLA.
Detailed description of the invention
Fig. 1 is three phosphazene derivative of ring of the diethyl phosphate containing methylol1HNMR
Fig. 2 is three phosphazene derivative of ring of the diethyl phosphate containing methylol31PNMR；
Fig. 3 is the infrared spectroscopy of three phosphazene derivative of ring of the diethyl phosphate containing methylol；
Fig. 4 is the thermogravimetic analysis (TGA) of three phosphazene derivative of ring of the diethyl phosphate containing methylol；
Fig. 5 is three phosphazene derivative of ring of the diethyl phosphate of ethoxy containing 2-1HNMR；
Fig. 6 is three phosphazene derivative of ring of the diethyl phosphate of ethoxy containing 2-31PNMR；
Fig. 7 is the infrared spectroscopy of three phosphazene derivative of ring of the diethyl phosphate of ethoxy containing 2-；
Fig. 8 is the thermogravimetic analysis (TGA) of three phosphazene derivative of ring of the diethyl phosphate of ethoxy containing 2-.
Specific embodiment
The invention will be further elaborated With reference to embodiment:
Embodiment 1:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and sodium hydride 2.42g is added in three times, the 14.51g for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Methylol diethyl phosphate is warming up to 65-70 DEG C of reaction 36h, thin-layered chromatography monitoring reaction.Reaction terminate milky is suspended
Liquid is filtered with Buchner funnel, and tetrahydrofuran elutes filter cake, and filtrate is concentrated into to obtain colorless and transparent half under vacuum conditions admittedly
Body is successively washed with petroleum ether, n-hexane, ethyl acetate, is finally precipitated in ethyl acetate and is obtained white solid containing methylol
The three phosphazene derivative 10.36g of ring of diethyl phosphate, yield 63.4%, purity >=85%.
Embodiment 2:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and sodium hydride 2.76g is added in five times, the 15.72g for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Methylol diethyl phosphate is warming up to 65-70 DEG C of reaction 12h, thin-layered chromatography monitoring reaction.Reaction terminate milky is suspended
Liquid is filtered with Buchner funnel, and tetrahydrofuran elutes filter cake, and filtrate is concentrated into to obtain colorless and transparent half under vacuum conditions admittedly
Body is successively washed with petroleum ether, n-hexane, ethyl acetate, is finally precipitated in ethyl acetate and is obtained white solid containing methylol
The three phosphazene derivative 10.32g of ring of diethyl phosphate, yield 63.1%, purity >=85%.
Embodiment 3:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and sodium hydride 3.11g is added in five times, the 16.93g for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Methylol diethyl phosphate is warming up to 65-70 DEG C of reaction 18h, thin-layered chromatography monitoring reaction.Reaction terminate milky is suspended
Liquid is filtered with Buchner funnel, and tetrahydrofuran elutes filter cake, and filtrate is concentrated into to obtain colorless and transparent half under vacuum conditions admittedly
Body is successively washed with petroleum ether, n-hexane, ethyl acetate, is finally precipitated in ethyl acetate and is obtained white solid containing methylol
The three phosphazene derivative 10.53g of ring of diethyl phosphate, yield 64.4%, purity >=85%.
Embodiment 4:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and triethylamine 10.19g is added, the 14.50g methylol for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Diethyl phosphate is warming up to 65-70 DEG C of reaction 65h, thin-layered chromatography monitoring reaction.Reaction terminates to obtain milky suspension, uses
Buchner funnel filters, and tetrahydrofuran elutes filter cake, filtrate is concentrated under vacuum conditions to obtain colorless and transparent semisolid, successively
It is washed with petroleum ether, n-hexane, ethyl acetate, is finally precipitated in ethyl acetate and obtains white solid p diethylaminobenzoic acid containing methylol
The three phosphazene derivative 10.22g of ring of ester, yield 62.5%, purity >=87%.
Embodiment 5:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and triethylamine 13.10g is added, the 16.93g methylol for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Diethyl phosphate is warming up to 65-70 DEG C of reaction 72h, thin-layered chromatography monitoring reaction.Reaction terminates to obtain milky suspension, uses
Buchner funnel filters, and tetrahydrofuran elutes filter cake, filtrate is concentrated under vacuum conditions to obtain colorless and transparent semisolid, successively
It is washed with petroleum ether, n-hexane, column chromatography obtains three phosphazene derivative of ring of white solid diethyl phosphate containing methylol
9.21g, yield 56.3%, purity >=90%.
Embodiment 6:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and triethylamine 10.20g is added, the 13.30g2- hydroxyl second for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Base dimethyl phosphate is warming up to 65-70 DEG C of reaction 72h, thin-layered chromatography monitoring reaction.Reaction terminates to obtain milky suspension,
It being filtered with Buchner funnel, tetrahydrofuran elutes filter cake, filtrate is concentrated under vacuum conditions to obtain colorless and transparent semisolid, according to
It is secondary to be washed with petroleum ether, n-hexane, ethyl acetate, it is finally precipitated in ethyl acetate and obtains the white solid phosphoric acid of ethoxy containing 2-
The three phosphazene derivative 8.39g of ring of diethylester, yield 55.4%, purity >=85%.
Embodiment 7:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and triethylamine 11.64g is added, the 13.30g2- hydroxyl second for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Base dimethyl phosphate is warming up to 65-70 DEG C of reaction 72h, thin-layered chromatography monitoring reaction.Reaction terminates to obtain milky suspension,
It being filtered with Buchner funnel, tetrahydrofuran elutes filter cake, filtrate is concentrated under vacuum conditions to obtain colorless and transparent semisolid, according to
It is secondary to be washed with petroleum ether, n-hexane, ethyl acetate, it is finally precipitated in ethyl acetate and obtains the white solid phosphoric acid of ethoxy containing 2-
The three phosphazene derivative 8.44g of ring of diethylester, yield 55.7%, purity >=85%.
Embodiment 8:
A dry 500ml three-necked bottle is taken, three times with nitrogen displacement, 5g hexachlorocyclotriph,sphazene is added, 200ml is added in stirring
Tetrahydrofuran is completely dissolved to it, and triethylamine 13.09g is added, the 15.51g2- hydroxyl second for being dissolved in 20ml tetrahydrofuran is slowly added dropwise
Base dimethyl phosphate is warming up to 65-70 DEG C of reaction 72h, thin-layered chromatography monitoring reaction.Reaction terminates to obtain milky suspension,
It being filtered with Buchner funnel, tetrahydrofuran elutes filter cake, filtrate is concentrated under vacuum conditions to obtain colorless and transparent semisolid, according to
It is secondary to be washed with petroleum ether, n-hexane, ethyl acetate, it is finally precipitated in ethyl acetate and obtains the white solid phosphoric acid of ethoxy containing 2-
The three phosphazene derivative 8.53g of ring of diethylester, yield 56.3%, purity >=85%.
Embodiment 9:
It regard three phosphazene derivative (HPCTP) of ring of the diethyl phosphate containing methylol as flame-retardant additive and polylactic acid
(PLA) compounding forms polymeric material, and the limit oxygen index (LOI) of pure PLA is only 19.6%, under nitrogen atmosphere, initial decomposition
Temperature (T5%) is 319 DEG C, and carbon yield when degradation hot arc is concentrated mainly on 350-410 DEG C or so, 800 DEG C is 0.Work as HPCTP
Additive amount be 5wt% when, HPCTP (5wt%)/PLA LOI has certain improvement, can reach 26.8%, there is molten drop production
Raw, UL-94 is V-2 grade, and temperature of initial decomposition is 330 DEG C, degrade 50% (T50%) when temperature be 367 DEG C, 800 DEG C
When carbon yield be 2.6%.When HPCTP additive amount is 10%, the variation of HPCTP (10wt%)/PLA LOI value less, is
29.6%, there is the generation of molten drop phenomenon, UL-94 is still V-2 grade, and temperature of initial decomposition is 342 DEG C, and degrade 50% (T50%)
When carbon yield of temperature when being 383 DEG C, 800 DEG C be 4.3%.When HPCTP additive amount is 20%, HPCTP (20wt%)/
The LOI value of PLA is greatly improved, and can reach 35.6%, and no molten drop phenomenon generates, and UL-94 can reach V-0 grade, just
Beginning decomposition temperature is that temperature of initial decomposition is 362 DEG C, degrade 50% (T50%) when temperature be 402 DEG C, 800 DEG C when carbon residue
Rate is 8.5%.The addition of HPCTP shows it is one for PLA so that the LOI value and UL-94 grade of PLA have been improved
The more efficient fire retardant of kind.
Embodiment 10:
It regard three phosphazene derivative of ring (HDCTP) of the dimethyl phosphate of ethoxy containing 2- as flame-retardant additive and polylactic acid
(PLA) compounding forms polymeric material, and the limit oxygen index (LOI) of pure PLA is only 19.6%, under nitrogen atmosphere, initial decomposition
Temperature (T5%) is 319 DEG C, and carbon yield when degradation hot arc is concentrated mainly on 350-410 DEG C or so, 800 DEG C is 0.Work as HDCTP
Additive amount be 5wt% when, HPCTP (5wt%)/PLA LOI has certain improvement, can reach 24.9%, there is molten drop production
Raw, UL-94 is V-2 grade, and temperature of initial decomposition is 335 DEG C, degrade 50% (T50%) when temperature be 351 DEG C, 800 DEG C
When carbon yield be 2.6%.When HPCTP additive amount is 10%, HPCTP (10wt%)/PLA LOI value is 28.4%, is had molten
Phenomenon is dripped to generate, UL-94 is still V-2 grade, and temperature of initial decomposition is 339 DEG C, degrade 50% (T50%) when temperature be
Carbon yield at 357 DEG C, 800 DEG C is 3.4%.When HPCTP additive amount is 20%, HPCTP (20wt%)/PLA LOI value has
Very big raising can reach 33.2%, and no molten drop phenomenon generates, and UL-94 can reach V-0 grade, and temperature of initial decomposition is
Temperature of initial decomposition is 352 DEG C, degrade 50% (T50%) when carbon yield of temperature when being 373 DEG C, 800 DEG C be 9.0%.
The addition of HDCTP so that the LOI value and UL-94 grade of PLA have been improved, show be for PLA it is a kind of more efficiently
Fire retardant.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of three phosphazene derivative of ring of phosphate ester-containing, chemical structure are as follows:
The integer of m in formula, n expression 0-2.
2. three phosphazene derivative of phosphate ester-containing ring as described in claim 1 characterized by comprising di(2-ethylhexyl)phosphate containing methylol
Three phosphazene derivative of ring of three phosphazene derivative of ring of ethyl ester, the diethyl phosphate of ethoxy containing 2-.
3. three phosphazene derivative of phosphate ester-containing ring as described in claim 1, it is characterised in that: the diethyl phosphate containing methylol
The preparation route of three phosphazene derivative of ring:
Preparation method comprises the following specific steps that:
A. the methylol diethyl phosphate for being dissolved in reaction dissolvent is slowly dropped to dissolved with the anti-of hexachlorocyclotriph,sphazene and acid binding agent
It answers in the solution of solvent, temperature reaction, thin-layered chromatography monitoring reaction；
B. reaction temperature is down to room temperature, adds appropriate reaction dissolvent during this period；
C. it filters, is filtered with Buchner funnel, reaction dissolvent elutes filter cake, obtains colorless and transparent filtrate；
D. it is concentrated, filtrate is concentrated to get colorless semi-solid under vacuum conditions；
E. it washs, is successively washed with petroleum ether, n-hexane, ethyl acetate, obtain finished product white solid；
F. column chromatographs, and solvent is methylene chloride: methanol: acetic acid=200:10:1.
4. three phosphazene derivative of phosphate ester-containing ring as claimed in claim 1 or 2, it is characterised in that: reaction dissolvent is anhydrous four
Hydrogen furans；Acid binding agent is sodium hydride, triethylamine；Reaction temperature is 65-70 DEG C, reaction time 12-72h；Hexachlorocyclotriph,sphazene
It is 1:6-7 with the molar ratio of methylol diethyl phosphate, the molar ratio of hexachlorocyclotriph,sphazene and acid binding agent is 1:7-9.
5. three phosphazene derivative of phosphate ester-containing ring as claimed in claim 1 or 2, it is characterised in that: the di(2-ethylhexyl)phosphate of ethoxy containing 2-
The preparation route of three phosphazene derivative of ring of ethyl ester:
Preparation method comprises the following specific steps that:
A. the 2- ethoxy dimethyl phosphate for being dissolved in reaction dissolvent is slowly dropped to dissolved with hexachlorocyclotriph,sphazene and acid binding agent
In the solution of reaction dissolvent, temperature reaction, thin-layered chromatography monitoring reaction；
B. reaction temperature is down to room temperature, adds appropriate reaction dissolvent during this period；
C. it filters, is filtered with Buchner funnel, reaction dissolvent elutes filter cake, obtains colorless and transparent filtrate；
D. it is concentrated, filtrate is concentrated to get colorless oil under vacuum conditions；
E. it washs, is successively washed with petroleum ether, n-hexane, ethyl acetate, obtain finished product white solid.
6. three phosphazene derivative of phosphate ester-containing ring as claimed in claim 5, it is characterised in that: reaction dissolvent is anhydrous tetrahydro furan
It mutters；Acid binding agent is sodium hydride, triethylamine；Reaction temperature is 65-70 DEG C, reaction time 12-72h；Hexachlorocyclotriph,sphazene and 2-
The molar ratio of ethoxy dimethyl phosphate is 1:6-7, and the molar ratio of hexachlorocyclotriph,sphazene and acid binding agent is 1:7-9.
7. application of three phosphazene derivative of phosphate ester-containing ring described in claim 1 as fire retardant.
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| CN110256490A (en) * | 2019-07-10 | 2019-09-20 | 中国科学技术大学 | One kind is containing phosphonate fire retardant and preparation method thereof |
| CN111440434A (en) * | 2020-05-18 | 2020-07-24 | 新昌县同生生物技术股份有限公司 | Flame-retardant composite material of polyurethane-polylactic acid block copolymer and preparation method thereof |
| CN114921870A (en) * | 2022-06-24 | 2022-08-19 | 武汉纺织大学 | Flame-retardant polylactic acid fabric and preparation method thereof |
| CN115536703A (en) * | 2021-06-29 | 2022-12-30 | 张家港市国泰华荣化工新材料有限公司 | Phosphonic acid dialkyl ester methyleneoxy pentafluorocyclotriphosphazene compound and preparation method thereof |
| CN115536702A (en) * | 2021-06-29 | 2022-12-30 | 张家港市国泰华荣化工新材料有限公司 | Phosphonic acid difluoro alkyl ester methylene oxygen group pentafluoro ring triphosphazene compound and its preparation |
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| CN114921870A (en) * | 2022-06-24 | 2022-08-19 | 武汉纺织大学 | Flame-retardant polylactic acid fabric and preparation method thereof |
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