CN104744507A - Aminomethyl phenyl phosphinic acid and preparation method thereof - Google Patents
Aminomethyl phenyl phosphinic acid and preparation method thereof Download PDFInfo
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- CN104744507A CN104744507A CN201510163749.2A CN201510163749A CN104744507A CN 104744507 A CN104744507 A CN 104744507A CN 201510163749 A CN201510163749 A CN 201510163749A CN 104744507 A CN104744507 A CN 104744507A
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Abstract
The invention relates to aminomethyl phenyl phosphinic acid and a preparation method thereof, and particularly provides aminomethyl phenyl phosphinic acid prepared by carrying out halogenation reaction and ammonolysis reaction of hydroxymethyl phenyl phosphinic acid successively, and a preparation method thereof. The preparation method disclosed by the invention comprises the following steps: heating and reacting hydroxymethyl phenyl phosphinic acid, sulfoxide chloride and ether in a reaction kettle at a certain mol ratio at first, preparing chloromethyl phenyl phosphinic acid after completing reaction, and carrying out ammonolysis reaction by introducing ammonia gas in a sodium hydroxide solution so as to obtain the aminomethyl phenyl phosphinic acid. The aminomethyl phenyl phosphinic acid disclosed by the invention is high in content, good in fire resistance and high in molecular activity; when the aminomethyl phenyl phosphinic acid is added into other materials, the advantages of being low in addition amount, good in compatibility and fire resistance and the like can be realized; and furthermore, the performance of a fire-resistant material is further improved.
Description
Technical field
The invention belongs to BACN field of material technology, relate to a kind of aminomethyl phenyl phosphinic acid and preparation method thereof, particularly provide a kind of priority to carry out aminomethyl phenyl phosphinic acid obtained by halogenating reaction and aminating reaction and preparation method thereof to hydroxymethyl phenyl phospho acid.
Background technology
Along with the development of Chinese synthetic material industry and the continuous expansion of Application Areas, fire retardant has wide market outlook in the every field such as chemical building material, electronic apparatus, communications and transportation, space flight and aviation, household furniture, upholstery, clothing, food, lodging and transportion--basic necessities of life.Along with the enhancing day by day of people's environmental protection, safety, health perception, countries in the world start using environment friendly flame retardant as the emphasis researched and developed and apply, and have achieved certain achievement.Effective element classification pressed by fire retardant, can be divided into phosphorus system, chlorine system, bromine system and antimony base, aluminium base, boryl fire retardant etc.
The difference of fire retardant using method can be divided into addition type and response type, the fire retardant that current market uses is substantially based on additive flame retardant, melting can be divided into again to add and polymerization interpolation, this kind of ignition dope can only be evenly distributed in fire retardant material when adding, and this fire retardant phosphorus content is low, to reach good flame retardant effect, just must increase fire retardant addition, this will cause declining to a great extent of fire retardant material performance.
Phospho acid salt flame retardant products density is lower, and amount of flame-retardant agent is less, in electronic apparatus industry, have good application prospect.Clariant company of Germany, Pennwalt company of the U.S. and Ticona company are all to the exploitation of hypophosphite fire retardant and should be used as a lot of research.The synthetic method of various metal phosphinate fire retardant is also found out successively.As in the invention CN 98811621.9 of Clariant company in the basic conditions, prepare the method for metal phosphinate from yellow phosphorus, alkylogen, metal hydroxides; And the method that CN 200410104692.0, CN 102164934 A, CN 102164930 adopt the mode of free radical reaction from phospho acid source in the patent such as A, CN 1660858A, alkene or olefin oxide, source metal prepare metal phosphinate fire retardant.A lot of painstaking effort have also been poured into the exploitation of phosphinate flame retardant by domestic many scholars and company, and achieve a lot of achievement.As CN 101747368 A provides a kind of preparation method and application of partially alkylated phosphinic acid nonalkali metal salt; CN 101830926 A provides a kind of synthetic process of dialkyl metal phosphinate adopting free radical reaction to prepare from alkyl dichloro phosphorus.
Current phosphinates based flame retardant almost all based on metal phosphinate class, and is applied in polybutylene terephthalate and nylon 6, nylon66 fiber more, respond well.About the research of non-metal phosphinate flame retardant, at present and few.Publication number is the preparation method providing a kind of melamine hypophosphite fire retardant in CN 101570518A, and this method adopts Aqueous phase preparation from trimeric cyanamide and phospho acid.This method to be limited as raw material single, and be subject to the impact of phospho acid strong reducing property, trimeric cyanamide and phospho acid must be added, otherwise phospho acid be heated and can be oxidized to phosphoric acid in air ambient simultaneously.
Summary of the invention
The present invention relates to a kind of aminomethyl phenyl phosphinic acid and preparation method thereof, particularly provide a kind of priority to carry out aminomethyl phenyl phosphinic acid obtained by halogenating reaction and aminating reaction and preparation method thereof to hydroxymethyl phenyl phospho acid.The present invention first by hydroxymethyl phenyl phospho acid, sulfur oxychloride and ether according to certain mol proportion reacting by heating in a kettle., chloromethyl phenyl phospho acid obtained after completing pass into ammonia in sodium hydroxide solution to carry out aminating reaction and obtains aminomethyl phenyl phosphinic acid.Described aminomethyl phenyl phosphinic acid phosphorus content is high, good flame resistance, molecular activity are high, can reach the objects such as addition is few, consistency good, good flame resistance, improving the performance of fire retardant material further when adding in other materials.
A kind of aminomethyl phenyl phosphinic acid of the present invention, its structural formula is:
The preparation method of a kind of aminomethyl phenyl phosphinic acid of the present invention, by hydroxymethyl phenyl phospho acid, sulfur oxychloride and ether reacting by heating in a kettle., reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal;
Chloromethyl phenyl phospho acid crystal is joined in sodium hydroxide solution, passes into ammonia, again filter after reaction for some time, and by water cleaned screening repeatedly, then after super-dry obtained aminomethyl phenyl phosphinic acid.
As preferred technical scheme:
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, the mol ratio that adds of described hydroxymethyl phenyl phospho acid, sulfur oxychloride and ether is 1:1:3 ~ 10, and the chemical equation of correlated response is
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, described ether is methyl-phenoxide, phenyl ether, Chloromethyl methyl ether, chloromethyl ether, ethyl vinyl ether, phenyl methyl ether, ethylene glycol monomethyl ether or glycol dimethyl ether.Ethers boiling point is lower, is a kind of conventional low-temperature solvent.
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, the temperature of described reacting by heating is 40 ~ 80 DEG C, and the reaction times is 3 ~ 6 hours, and described cooling down to 20 ~ 30 DEG C are filtered.This reaction is temperature required low, and the time is short, can effective production control cost, and after cooling, Crystal solubility reduces and separates out, and more easily carries out lock out operation.
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, the mol ratio that adds of described sodium hydroxide and chloromethyl phenyl phospho acid is 1 ~ 1.2:1, and the concentration of sodium hydroxide solution is 2 ~ 50wt%.Relevant chemical equation is
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, it is 0.1 ~ 0.5MPa that described ammonia adds fashionable reaction pressure, and excess of ammonia gas can ensure carrying out completely of reaction, and under the pressure of ammonia, is conducive to the carrying out of accelerated reaction.
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, described reaction for some time refers to 1 ~ 8 hour.
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, described repeatedly cleaning refer to wash number be 1 ~ 10 time until described filtrate pH value reaches 6 ~ 8.The sodium hydroxide solution used in the preparation process of aminomethyl phenyl phosphinic acid is strong basicity, if it can not be cleaned from fire retardant, will make a big impact to the result of use of aminomethyl phenyl phosphinic acid.
The preparation method of a kind of aminomethyl phenyl phosphinic acid as above, the temperature of described drying is 50 ~ 100 DEG C, and time of drying is 4 ~ 8 hours.The fire retardant of abundant drying, in use can directly add in production process, avoids moisture and introduces the negative impact caused; The qualitative filter paper that the filter paper that described filtration uses is 30 ~ 120 microns, aperture.
Beneficial effect:
The preparation method of a kind of fire retardant aminomethyl phenyl phosphinic acid of the present invention, design is unique, and step is easy, and fire retardant addition is few, successful.
Aminomethyl phenyl phosphinic acid of the present invention is a kind of BACN, and this flame retardant molecule amount is little, and phosphorus content is high.The phosphoric of the phenyl in this flame retardant molecule structure, the nitrogen element in amino and fire retardant all has good flame retardant effect, by the combination of concentrated ignition-proof element, make this fire retardant that fire retardant material just can be made to reach good flame retardant effect when addition is little.In addition, amino in fire retardant can react with the functional group in most of macromolecular material, thus improve consistency and the bonding force of fire retardant and macromolecular material, macromolecular material can not only be allowed to have good flame retardant resistance, the mechanical property of macromolecular material can also be improved to a certain extent.
Aminomethyl phenyl phosphinic acid of the present invention, this fire retardant is easy to process, lower to equipment requirements, and production technique is easy, can production control cost significantly, more can guarantee that the safety of producing is carried out.The fire retardant precision of preparation is high, and moisture is few, directly can add use.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
A kind of aminomethyl phenyl phosphinic acid of the present invention, structural formula is:
Embodiment 1
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:3, sulfur oxychloride and methyl-phenoxide reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 40 DEG C, reaction times is 3 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 20 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 2wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1:1, pass into ammonia, it is 0.1MPa that ammonia adds fashionable reaction pressure, react and again filter after 1 hour, to filter the filter paper used be 30 ~ 120 microns, aperture qualitative filter paper, and clean 1 time with water and reach 8 to filtrate pH value, then at temperature is 50 DEG C obtained aminomethyl phenyl phosphinic acid after dry 4 hours.
Embodiment 2
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:10, sulfur oxychloride and phenyl ether reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 80 DEG C, reaction times is 6 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 30 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 50wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1.1:1, pass into ammonia, it is 0.5MPa that ammonia adds fashionable reaction pressure, react and again filter after 8 hours, to filter the filter paper used be 30 ~ 120 microns, aperture qualitative filter paper, and clean 10 times with water and reach 7 to filtrate pH value, then at temperature is 100 DEG C obtained aminomethyl phenyl phosphinic acid after dry 8 hours.
Embodiment 3
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:5, sulfur oxychloride and chloromethyl ether reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 50 DEG C, reaction times is 5 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 25 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 5wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1.2:1, pass into ammonia, it is 0.3MPa that ammonia adds fashionable reaction pressure, react and again filter after 3 hours, to filter the filter paper used be 30 ~ 120 microns, aperture qualitative filter paper, and clean 5 times with water and reach 7.5 to filtrate pH value, then at temperature is 80 DEG C obtained aminomethyl phenyl phosphinic acid after dry 6 hours.
Embodiment 4
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:8, sulfur oxychloride and Chloromethyl methyl ether reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 60 DEG C, reaction times is 4 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 20 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 30wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1.2:1, pass into ammonia, it is 0.3MPa that ammonia adds fashionable reaction pressure, react and again filter after 7 hours, filter the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture, and clean 8 times until filtrate pH value reaches 6 with water, then obtain aminomethyl phenyl phosphinic acid after dry 4 hours at temperature is 100 DEG C.
Embodiment 5
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:6, sulfur oxychloride and phenyl methyl ether reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 40 DEG C, reaction times is 6 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 30 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 40wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1:1, pass into ammonia, it is 0.5MPa that ammonia adds fashionable reaction pressure, react and again filter after 2 hours, to filter the filter paper used be 30 ~ 120 microns, aperture qualitative filter paper, and clean 3 times with water and reach 8 to filtrate pH value, then at temperature is 50 DEG C obtained aminomethyl phenyl phosphinic acid after dry 4 hours.
Embodiment 6
A preparation method for aminomethyl phenyl phosphinic acid, synthesis step is:
Be the hydroxymethyl phenyl phospho acid of 1:1:9, sulfur oxychloride and glycol dimethyl ether reacting by heating in a kettle. by mol ratio, the temperature of reacting by heating is 50 DEG C, reaction times is 5 hours, reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal to 26 DEG C, filters the qualitative filter paper that the filter paper of use is 30 ~ 120 microns, aperture;
It is in the sodium hydroxide solution of 45wt% that chloromethyl phenyl phospho acid crystal is joined concentration, the mol ratio of sodium hydroxide and chloromethyl phenyl phospho acid is 1.1:1, pass into ammonia, it is 0.2MPa that ammonia adds fashionable reaction pressure, react and again filter after 5 hours, to filter the filter paper used be 30 ~ 120 microns, aperture qualitative filter paper, and clean 6 times with water and reach 7.5 to filtrate pH value, then at temperature is 90 DEG C obtained aminomethyl phenyl phosphinic acid after dry 7 hours.
Claims (10)
1. an aminomethyl phenyl phosphinic acid, is characterized in that structural formula is:
2. a preparation method for aminomethyl phenyl phosphinic acid, is characterized in that synthesis step is:
By hydroxymethyl phenyl phospho acid, sulfur oxychloride and ether reacting by heating in a kettle., reaction terminates rear cooling down and carries out filtering obtained chloromethyl phenyl phospho acid crystal;
Chloromethyl phenyl phospho acid crystal is joined in sodium hydroxide solution, passes into ammonia, again filter after reaction for some time, and by water cleaned screening repeatedly, then after super-dry obtained aminomethyl phenyl phosphinic acid.
3. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, the mol ratio that adds of described hydroxymethyl phenyl phospho acid, sulfur oxychloride and ether is 1:1:3 ~ 10.
4. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 3, it is characterized in that, described ether is methyl-phenoxide, phenyl ether, Chloromethyl methyl ether, chloromethyl ether, ethyl vinyl ether, phenyl methyl ether, ethylene glycol monomethyl ether or glycol dimethyl ether.
5. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, the temperature of described reacting by heating is 40 ~ 80 DEG C, and the reaction times is 3 ~ 6 hours, and described cooling down to 20 ~ 30 DEG C are filtered.
6. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, the mol ratio of described sodium hydroxide and chloromethyl phenyl phospho acid crystal is 1 ~ 1.2:1, and the concentration of sodium hydroxide solution is 2 ~ 50wt%.
7. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, described ammonia adds makes reaction pressure be 0.1 ~ 0.5MPa.
8. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, described reaction for some time refers to 1 ~ 8 hour.
9. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, described repeatedly cleaning refer to wash number be 1 ~ 10 time until described filtrate pH value reaches 6 ~ 8.
10. the preparation method of a kind of aminomethyl phenyl phosphinic acid according to claim 2, is characterized in that, the temperature of described drying is 50 ~ 100 DEG C, and time of drying is 4 ~ 8 hours; The qualitative filter paper that the filter paper that described filtration uses is 30 ~ 120 microns, aperture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153228A (en) * | 2015-10-20 | 2015-12-16 | 什邡市太丰新型阻燃剂有限责任公司 | Novel organic phosphorus-nitrogen flame retardant as well as preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332987A (en) * | 1963-06-24 | 1967-07-25 | Pennsalt Chemicals Corp | Aminoalkylphosphinic acids |
| CN1059148A (en) * | 1990-08-17 | 1992-03-04 | 赫彻斯特股份公司 | The method for making of aminomethane phosphonic acids and amino methyl-phospho acid |
| CN1871245A (en) * | 2003-08-22 | 2006-11-29 | 孟山都技术公司 | Process for the preparation of N-phosphonomethylglycine and derivatives thereof |
| PL203028B1 (en) * | 2005-11-07 | 2009-08-31 | Politechnika Wroclawska | Method for the manufacture of 1-aminoalkyl (organo) phosphane acids and their N, - substituted derivatives |
| CN102863383A (en) * | 2011-07-08 | 2013-01-09 | 华东理工大学 | Preparation method of oxygen bleaching activator tribasic copper chloride (TBCC) |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332987A (en) * | 1963-06-24 | 1967-07-25 | Pennsalt Chemicals Corp | Aminoalkylphosphinic acids |
| CN1059148A (en) * | 1990-08-17 | 1992-03-04 | 赫彻斯特股份公司 | The method for making of aminomethane phosphonic acids and amino methyl-phospho acid |
| CN1871245A (en) * | 2003-08-22 | 2006-11-29 | 孟山都技术公司 | Process for the preparation of N-phosphonomethylglycine and derivatives thereof |
| PL203028B1 (en) * | 2005-11-07 | 2009-08-31 | Politechnika Wroclawska | Method for the manufacture of 1-aminoalkyl (organo) phosphane acids and their N, - substituted derivatives |
| CN102863383A (en) * | 2011-07-08 | 2013-01-09 | 华东理工大学 | Preparation method of oxygen bleaching activator tribasic copper chloride (TBCC) |
Non-Patent Citations (1)
| Title |
|---|
| POPOFF, I. C.ET AL.: "α-Aminophosphinic acids and α-aminophosphine oxides. I.", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153228A (en) * | 2015-10-20 | 2015-12-16 | 什邡市太丰新型阻燃剂有限责任公司 | Novel organic phosphorus-nitrogen flame retardant as well as preparation method and application thereof |
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