CN101613374B - Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof - Google Patents
Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof Download PDFInfo
- Publication number
- CN101613374B CN101613374B CN2009101442022A CN200910144202A CN101613374B CN 101613374 B CN101613374 B CN 101613374B CN 2009101442022 A CN2009101442022 A CN 2009101442022A CN 200910144202 A CN200910144202 A CN 200910144202A CN 101613374 B CN101613374 B CN 101613374B
- Authority
- CN
- China
- Prior art keywords
- dihydro
- flame retardant
- oxy
- assorted
- preparation
- 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
Abstract
The invention discloses a polymeric phosphorus-containing flame retardant with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a lateral group and a preparation method thereof. The preparation method is characterized by comprising the following steps: placing aromatic dihydric phenol and pentaerythritol diphosphate diphosphoryl chloride (or bromine) which are modified by the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an anhydrous acetonitrile solvent based on reaction mol ratio, heating the obtained mixture to 80 DEG C in an inert atmosphere, agitating and reacting until no halogen hydride is released, cooling the obtained mixture to the room temperature, and depressurizing the mixture to remove the solvent. The obtained product has high phosphorus content, very good expansibility and char formation, and good flame retardation effect. When flame retardation is performed on epoxy resin, the limiting oxygen index of the obtained product is greatly improved and the vertical burning scale reaches V-0 level; and the polymeric phosphorus-containing flame retardant has the advantage of overcoming the disadvantages of low thermal decomposition temperature, poor compatibility with polymer matrix and easy migration in the existing micromolecular phosphorus flame retardants. The preparation method has the advantages of being simple and feasible, using no catalyst and simple post-treatment process.
Description
Technical field
The invention belongs to the phosphonium flame retardant technical field, being specifically related to side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO) and preparation method thereof.
Background technology
At present, be all respects that the goods of raw material have been widely used in life and have produced with polymkeric substance such as epoxy resin, unsaturated polyester and polymeric amide, but they are inflammable material mostly, are prone to lead to fire, and safety of life and property is caused very big threat.Therefore, polymer materials fire-retardant becomes a hot issue that needs to be resolved hurrily.Extensively be employed at present and add fire retardant in each base polymer to improve its flame retardant properties.Advantages such as phosphorus flame retardant is efficient with it, low toxicity, environmental protection have obtained lot of domestic and foreign scholar's broad research.
The preparation method of a kind of phosphonium flame retardant that one Chinese patent application publication number CN1910263A introduces; Take organo phosphorous compounds DOPO and unsaturated acid or its acid anhydrides are reacted in alkylene glycol; But the prepared phosphonium flame retardant of this method is some small molecules P contained compounds; Bad with the polymeric matrix consistency, there is the leaching problem.
The organic cpds that contains many DOPO of one Chinese patent application publication number CN1835960A report is to carry out addition reaction through DOPO with the alkynes class that has reactivity or ester group to form.This addition reaction must just can be carried out under the condition that catalyzer exists, and used catalyzer is some heavy metal salts, and toxicity is bigger.
The preparation method of a kind of polymer type phosphor-containing fire retardant that one Chinese patent application publication number CN1563152A proposes; Adopt the Resorcinol of DOPO modification or be response matrix, thereby obtain phosphorated polymer-type fire retardant naphthalenediol, the substituted dichloro of phenyl or naphthyl (bromine) oxygen phosphorus.Catalyzer to be used in the preparation process of this fire retardant, a large amount of precipitation agents will be used in the sepn process, bigger to the pollution of environment.
Summary of the invention
The objective of the invention is to propose a kind of side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound and preparation method thereof, to overcome the above-mentioned defective of prior art.
Side group of the present invention is 9, the 10-dihydro-9-oxy is assorted-and the preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that 9; The 10-dihydro-9-oxy is assorted-the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying; With pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides, add in the reactor drum, under the protection of rare gas element by the reaction mol ratio; In the anhydrous acetonitrile solvent, be heated to 80 ℃; Stirring reaction to non-halogen hydrogen is emitted, and is cooled to room temperature, removal of solvent under reduced pressure; It is 9 that resulting pink solid product is side group, the 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound;
Said process can be expressed as with reaction formula:
Wherein polymerization degree n is 1~50 integer, and X is chlorine atom or bromine atoms, and R is one or more in the following structure:
Said rare gas element can be selected nitrogen, argon gas or helium for use.
Employed anhydrous acetonitrile is used after preferably heavily steaming before use again in the above-mentioned reaction.
Side group by method for preparing of the present invention is 9; The 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound; Be characterised in that its be have a following general structure contain pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides (1) and 9, the 10-dihydro-9-oxy is assorted-polymkeric substance of 10-phospho hetero phenanthrene-10-oxide compound substituted aromatic dihydric phenol (2) structure:
Wherein, X is chlorine atom or bromine atoms, and R is one or more in the following structure (phenyl, naphthyl, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound is substituted to diphenyl methyl):
This fire retardant has following repeating unit:
Polymerization degree n=1~50 wherein, R is phenyl, naphthyl or substituted-phenyl.
Because the present invention takes 9; The 10-dihydro-9-oxy is assorted-and the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying and pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides carry out polyreaction; This preparation method is simple; Need not to use catalyzer, last handling process is very easy.
The side group that adopts the inventive method to prepare is 9; The 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound compares with existing small molecules phosphorus flame retardant, overcome the shortcoming that small molecules phosphorus flame retardant heat decomposition temperature is low, poor with the polymeric matrix consistency, be prone to migration; And its phosphorus content is high, has well to expand into charcoal property, good flame retardation effect; When fire retarding epoxide resin, its limiting oxygen index(LOI) (LOI) has raising by a relatively large margin, and the vertical combustion grade has reached the V-0 level.
Embodiment
Below be 9 through embodiment further explain side group of the present invention, the 10-dihydro-9-oxy is assorted-preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound and the mensuration of oxygen index, vertical combustion and thermogravimetric analysis thereof.
Embodiment 1:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 32.4g (0.10mol) 9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-Resorcinol; Be warming up to 80 ℃, do not emit to there being HCl gas, be cooled to room temperature in the following reaction that continues to stir; Removal of solvent under reduced pressure obtains peach solid product.Productive rate reaches 95%, and fusing point is 220 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment product is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
The side group of getting above-mentioned preparation is 9, the 10-dihydro-9-oxy is assorted-and polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, epoxy resin (E-44) 40.0 grams; Stir 30min at 120 ℃; Add 20.0 gram low molecular polyamides (model: 651), be cast to after mixing in the mould of the long 10cm that processes by tetrafluoroethylene, wide 10mm, thick 3mm, solidified 1 hour then at 60 ℃; Naturally cool to room temperature, the demoulding.
Solidified sample is surveyed its oxygen index with oxygen index instrument, and oxygen index is up to 30.5; Use the vertical combustion appearance to survey its burning rank and be the V-0 level.Solidified sample is tested and can be known through thermogravimetric analyzer, the initial heat decomposition temperature of epoxy resin after fire-retardant reaches 291 ℃, and the maximum heat decomposition temperature is 350 ℃, residual massfraction 20.8% in the time of 700 ℃.
Embodiment 2:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 39.8g (0.10mol) 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound-to naphthalenediol; Be warming up to 80 ℃, reaction is not emitted to there being HCl gas under lasting the stirring, is cooled to room temperature; Removal of solvent under reduced pressure obtains peach solid product.Productive rate is 92%, and fusing point is 235 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Can know that the present embodiment product is that side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Getting the side group for preparing in the present embodiment is 9, the 10-dihydro-9-oxy is assorted-and polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, epoxy resin (E-44) 40.0 grams; Under 120 ℃ of conditions, stir 30min; Add low molecular polyamides (model: 651) 20.0 restrain, be cast to after mixing in the mould of the long 10cm that processes by tetrafluoroethylene, wide 10mm, thick 3mm, under 60 ℃ of conditions, solidified 1 hour then; Naturally cool to room temperature, the demoulding.
Used for epoxy resin oxygen index instrument after fire-retardant is surveyed its oxygen index, and oxygen index reaches 32.5; Use the vertical combustion appearance to survey its burning rank and be the V-0 level.
Embodiment 3:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 39.8g (0.10mol) 9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-dihydroxyphenyl propane; Be warming up to 80 ℃, reaction is not emitted to there being HCl gas under lasting the stirring, is cooled to room temperature; Removal of solvent under reduced pressure obtains red solid product.Productive rate is 85%, and fusing point is 240 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment products therefrom is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Getting the side group that present embodiment makes is 9, the 10-dihydro-9-oxy is assorted-and polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, epoxy resin (E-44) 40.0 grams; Under 120 ℃ of conditions, stir 30min; Add low molecular polyamides (model: 651) 20.0 restrain, be cast to after mixing in the mould of the long 10cm that processes by tetrafluoroethylene, wide 10mm, thick 3mm, under 60 ℃ of conditions, solidified 1 hour then; Naturally cool to room temperature, the demoulding.
Used for epoxy resin oxygen index instrument after fire-retardant is surveyed its oxygen index, and oxygen index is up to 35.0; Use the vertical combustion appearance to survey its burning rank and be the V-0 level.
Embodiment 4:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 38.6g (0.10mol) pentaerythritol diphosphate two phosphoryl bromides, 150ml anhydrous acetonitrile and 32.4g (0.10mol) 9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-Resorcinol, is warming up to 80 ℃, does not emit to there being HBr gas in the following reaction that continues to stir; Be cooled to room temperature; Removal of solvent under reduced pressure obtains peach solid product, and productive rate reaches 92%.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl bromides
-1The characteristic peak of the P-Br of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment product is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Claims (3)
1. a side group is 9, the 10-dihydro-9-oxy is assorted-and the preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that 9; The 10-dihydro-9-oxy is assorted-the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying; With pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides, add in the reactor drum, under the protection of rare gas element by the reaction mol ratio; In the anhydrous acetonitrile solvent, be heated to 80 ℃; Stirring reaction to non-halogen hydrogen is emitted, and is cooled to room temperature, removal of solvent under reduced pressure; It is 9 that resulting pink solid product is side group, the 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound;
Said process is expressed as with reaction formula:
Wherein polymerization degree n is 1~50 integer, and X is chlorine atom or bromine atoms, and R is one or more in the following structure:
2. side group as claimed in claim 1 is 9, the 10-dihydro-9-oxy is assorted-and the preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound, be characterised in that said rare gas element is nitrogen, argon gas or helium.
3. the side group by the said method preparation of claim 1 is 9; The 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound; Be characterised in that its be have a following general structure contain pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides (1) and 9, the 10-dihydro-9-oxy is assorted-polymkeric substance of 10-phospho hetero phenanthrene-10-oxide compound substituted aromatic dihydric phenol (2) structure:
Wherein, X is chlorine atom or bromine atoms, and R is one or more in the following structure:
This fire retardant has following repeating unit:
Polymerization degree n=1~50 wherein.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009101442022A CN101613374B (en) | 2009-07-22 | 2009-07-22 | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009101442022A CN101613374B (en) | 2009-07-22 | 2009-07-22 | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101613374A CN101613374A (en) | 2009-12-30 |
CN101613374B true CN101613374B (en) | 2012-03-14 |
Family
ID=41493280
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2009101442022A Active CN101613374B (en) | 2009-07-22 | 2009-07-22 | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101613374B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101792530A (en) * | 2010-03-19 | 2010-08-04 | 苏州兰特纳米材料科技有限公司 | Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof |
CN101880395B (en) * | 2010-06-21 | 2012-07-04 | 中国科学技术大学 | Polymer type phosphorous flame retardant containing DOPO and preparation method thereof |
CN103408596B (en) * | 2013-07-19 | 2015-09-30 | 沈阳化工大学 | A kind of phosphorous spirocyclic compound and preparation method thereof |
CN103936971B (en) * | 2014-04-04 | 2016-04-06 | 北京市建筑工程研究院有限责任公司 | A kind of organic polymer phosphonium flame retardant |
CN104830092B (en) * | 2015-04-13 | 2017-01-11 | 苏州大学 | Preparation method and applications of fire retardation dye |
CN104788770B (en) * | 2015-05-06 | 2017-06-09 | 3M中国有限公司 | Fire retardant, composition, damping fire proofing, damper, damping layer |
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 |
CN106866740B (en) * | 2017-01-16 | 2019-01-15 | 东华大学 | A kind of carboxylate and preparation method thereof |
CN106832259B (en) * | 2017-02-14 | 2019-06-11 | 北京理工大学 | A kind of preparation method for the fire retardant of polyphosphate that branch is double DOPO |
CN108976705B (en) | 2017-06-05 | 2020-01-24 | 广东生益科技股份有限公司 | Halogen-free epoxy resin composition, and prepreg and laminated board using same |
CN110564114B (en) * | 2019-08-14 | 2021-06-01 | 上海工程技术大学 | Preparation method of flame-retardant material |
CN112442077A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with reactive groups and preparation method and application thereof |
CN110527100A (en) * | 2019-09-12 | 2019-12-03 | 贵州省材料产业技术研究院 | Poly- phosphamide fire retardant and its preparation method and application |
US20230295376A1 (en) * | 2020-08-12 | 2023-09-21 | Agency For Science, Technology And Research | A halogen-free synergist |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1563152A (en) * | 2004-03-19 | 2005-01-12 | 四川大学 | Polymer type phosphatic fire retardant, preparation method and usage |
CN1835960A (en) * | 2003-06-18 | 2006-09-20 | 纺织和塑料研究协会图林根研究院 | Method for producing organic compounds contg poly-dopo, and use of the same |
CN1910263A (en) * | 2003-12-26 | 2007-02-07 | 东洋纺织株式会社 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
-
2009
- 2009-07-22 CN CN2009101442022A patent/CN101613374B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1835960A (en) * | 2003-06-18 | 2006-09-20 | 纺织和塑料研究协会图林根研究院 | Method for producing organic compounds contg poly-dopo, and use of the same |
CN1910263A (en) * | 2003-12-26 | 2007-02-07 | 东洋纺织株式会社 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
CN1563152A (en) * | 2004-03-19 | 2005-01-12 | 四川大学 | Polymer type phosphatic fire retardant, preparation method and usage |
Non-Patent Citations (4)
Title |
---|
欧育湘等.无卤本质阻燃热塑性共聚酯.《合成树脂及塑料》.2007,第24卷(第2期), * |
蒋建中.新型反应型阻燃剂中间体DOPO及其衍生物的合成.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2004,(第4期), * |
钱立军等.DOPO及其衍生物的应用综述.《2005年中国阻燃学会年会》.2005, * |
钱立军等.含磷酰杂菲共聚酯的合成及其性能研究.《2008年全国阻燃学术年会论文集》.2008, * |
Also Published As
Publication number | Publication date |
---|---|
CN101613374A (en) | 2009-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101613374B (en) | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof | |
CN101880395B (en) | Polymer type phosphorous flame retardant containing DOPO and preparation method thereof | |
Liu et al. | Synthesis, characterization, thermal properties and flame retardancy of a novel nonflammable phosphazene-based epoxy resin | |
Liang et al. | Bisphenol-S bridged penta (anilino) cyclotriphosphazene and its application in epoxy resins: synthesis, thermal degradation, and flame retardancy | |
Yang et al. | Synthesis, mechanical properties and fire behaviors of rigid polyurethane foam with a reactive flame retardant containing phosphazene and phosphate | |
Markwart et al. | Systematically controlled decomposition mechanism in phosphorus flame retardants by precise molecular architecture: P–O vs P–N | |
Liu et al. | Novel cyclotriphosphazene-based epoxy compound and its application in halogen-free epoxy thermosetting systems: Synthesis, curing behaviors, and flame retardancy | |
CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
Sun et al. | Synthesis and performance of cyclomatrix polyphosphazene derived from trispiro-cyclotriphosphazene as a halogen-free nonflammable material | |
Zhao et al. | Synthesis of a novel bridged-cyclotriphosphazene flame retardant and its application in epoxy resin | |
Xu et al. | Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance | |
Bai et al. | Novel cyclolinear cyclotriphosphazene-linked epoxy resin for halogen-free fire resistance: synthesis, characterization, and flammability characteristics | |
Sun et al. | Novel spirocyclic phosphazene-based epoxy resin for halogen-free fire resistance: synthesis, curing behaviors, and flammability characteristics | |
Zhao et al. | Aluminum hypophosphite versus alkyl-substituted phosphinate in polyamide 6: flame retardance, thermal degradation, and pyrolysis behavior | |
Gu et al. | Two novel phosphorus–nitrogen-containing halogen-free flame retardants of high performance for epoxy resin | |
El Gouri et al. | Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin | |
CN101838538B (en) | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof | |
Liu et al. | A novel nitrogen-rich phosphinic amide towards flame-retardant, smoke suppression and mechanically strengthened epoxy resins | |
TWI572614B (en) | Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers | |
CN108864193B (en) | Phosphaphenanthrene compound, and preparation method and application thereof | |
KR20100097668A (en) | Substituted phosphazene compounds and their use as flame resistance additives for organic polymers | |
CN105348326A (en) | N-P flameresistant material and preparation method thereof and application in textiles | |
CN106432340A (en) | Composite structural phosphorus fire retardant containing poly-DOPO cyclic phosphate and preparation method thereof | |
CN106496551A (en) | A kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof | |
CN106519297A (en) | Method for synthesizing flame retardant by aminolysis and phosphorous-nitrogen flame retardant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |