CN103936971B - A kind of organic polymer phosphonium flame retardant - Google Patents
A kind of organic polymer phosphonium flame retardant Download PDFInfo
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Abstract
The invention provides a kind of organic polymer phosphonium flame retardant, the structural formula of described organic polymer phosphonium flame retardant is:
wherein, n be more than or equal to 1 integer; This organic polymer phosphonium flame retardant is polymkeric substance, can be better compatible with macromolecular material, not easily move, in addition, reactive group is not had in the molecular structure of this organic polymer phosphonium flame retardant, the degradation temperature that self degradation temperature compares conventional flame retardant is higher, better thermostability can be shown in heat, make the shape of the macromolecular material of compound with it, structure more stable, therefore, this organic polymer phosphonium flame retardant can be applicable in the macromolecular material of high temperature process, and the scope of application is larger; Further, after this organic polymer phosphonium flame retardant degradation, carbon left is higher than the carbon left of conventional flame retardant, and therefore, the flame retarding efficiency of this organic polymer phosphonium flame retardant is higher.
Description
Technical field
The present invention relates to organic chemistry filed, more specifically, relate to a kind of organic polymer phosphonium flame retardant.
Background technology
At present, 9, assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, as a kind of BACN intermediate, uses the fire retardant of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivative synthesis thereof to have the advantages such as Halogen is nontoxic.
But 9, the molecular weight of assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and derivative thereof is general lower, therefore, containing 9, the general molecular weight of fire retardant of assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) or derivatives thereof of 10-dihydro-9-oxy is also lower, with the poor compatibility of macromolecular material, easily move; In addition, 9, the degradation temperature of assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and derivative thereof is low, poor heat stability, easily be heated in high temperature process and melting degraded, the macromolecular material having fire retardant is easily plastified, cause generating molten drop in macromolecular material combustion processes, and after degraded 9, the carbon left of assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) or derivatives thereof of 10-dihydro-9-oxy is low, flame retarding efficiency is declined, therefore can not be applied in high temperature process material.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.
For this reason, the invention provides that a kind of molecular weight is high, Heat stability is good, carbon yield is high after degraded, flame retarding efficiency is stablized, can be used for the organic polymer phosphonium flame retardant of macromolecular material.
The embodiment of first aspect present invention provides a kind of organic polymer phosphonium flame retardant, and the structural formula of described organic polymer phosphonium flame retardant is:
wherein, n be more than or equal to 1 integer.
This organic polymer phosphonium flame retardant is polymkeric substance, can be better compatible with macromolecular material, not easily move, in addition, reactive group is not had in the molecular structure of this organic polymer phosphonium flame retardant, the degradation temperature that self degradation temperature compares conventional flame retardant is higher, better thermostability can be shown in heat, make the shape of the macromolecular material of compound with it, structure more stable, therefore, this organic polymer phosphonium flame retardant can be applicable in the macromolecular material of high temperature process, and the scope of application is larger; Further, after this organic polymer phosphonium flame retardant degradation, the carbon left of this organic polymer phosphonium flame retardant is higher than the carbon left of conventional flame retardant, and therefore, the flame retarding efficiency of this organic polymer phosphonium flame retardant is higher.
The embodiment of second aspect present invention provides a kind of preparation method of above-mentioned organic polymer phosphonium flame retardant, flame retardant intermediate and tetramethylolmethane and derivatives reaction thereof is adopted to synthesize DOPP, DOPP described in chemical condensation becomes described organic polymer phosphonium flame retardant again, described DOPP is synthetic molecules, and its structural formula is:
Do not have reactive group in the organic polymer phosphonium flame retardant molecular structure prepared in this way of profit, therefore, the degradation temperature that self degradation temperature compares conventional flame retardant is higher, can show better thermostability in heat; In addition, preparation method is simple, is easy to manufacture.
In addition, the preparation method of the organic polymer phosphonium flame retardant in above-described embodiment provided by the invention can also have following additional technical feature:
According to one embodiment of present invention, the reaction formula synthesizing described DOPP is:
Wherein, PAT is tetramethylolmethane and derivative thereof, and its structural formula is:
dOPO is flame retardant intermediate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and its structural formula is:
According to one embodiment of present invention, DOPP described in chemical condensation becomes the reaction formula of described organic polymer phosphonium flame retardant to be:
According to one embodiment of present invention, described flame retardant intermediate also comprises the derivative of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
According to one embodiment of present invention, the structural formula of the derivative of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is one of following structural formula:
According to one embodiment of present invention, the preparation method of organic polymer phosphonium flame retardant is specially:
A. by 9.5g9,10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound of mixing is dissolved in the 20ml toluene in container, continue to blast nitrogen 30 minutes in container, then container is placed in 100 DEG C of oil baths and carries out magnetic agitation, make 9, assorted-10-phospho hetero phenanthrene-10-the oxide compound of 10-dihydro-9-oxy dissolves, completely until solution clear;
B. 0.44g triethylamine, triethyl-boron or 2,2'-Diisopropyl azodicarboxylate are added in described container as catalyzer, obtain the toluene solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
C. 3.52g tetramethylolmethane or derivatives thereof is dissolved in toluene the toluene solution obtaining tetramethylolmethane or derivatives thereof, and by described 9, the mix toluene solution of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy dropwise joins in the toluene solution of described tetramethylolmethane or derivatives thereof, and the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dripped off for 5 hours;
D. after the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide drips off, in described container, add catalyst for polymerization benzoyl peroxide, continue reaction 5 hours;
E. viscous product in described container is shifted out, ventilation volatilization 2 days, obtain described organic polymer phosphonium flame retardant.
According to one embodiment of present invention, in described preparation method, the reaction formula of a ~ c is:
According to one embodiment of present invention, in described preparation method, the reaction formula of d is:
The embodiment of third aspect present invention provides a kind of purposes of above-mentioned organic polymer phosphonium flame retardant, described organic polymer phosphonium flame retardant adds to as functional agent to be prepared in polyolefine, urethane, epoxy resin, binding agent, coating, rubber or fiber, to improve the flame retardant properties of described polyolefine, urethane, epoxy resin, binding agent, coating, rubber or fiber.
This organic polymer phosphonium flame retardant is of many uses, all can relate to from industrial macromolecular material to life macromolecular material, this organic polymer phosphonium flame retardant can carry out fire-retardant to macromolecular material from gas phase and solid phase two aspect, has larger use range and the service efficiency of Geng Gao.
Additional aspect of the present invention and advantage become obvious by description part below, or are recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 is the schematic diagram of the structural formula of organic polymer phosphonium flame retardant of the present invention, wherein n be more than or equal to 1 integer;
Fig. 2 is solid state nmr collection of illustrative plates (NMR) figure of the organic polymer phosphonium flame retardant according to one embodiment of the invention;
Fig. 3 is reactant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) according to one embodiment of the invention and target product DOPP thermogravimetric curve under a nitrogen (TGA) figure;
Fig. 4 is once differentiation curve (DTG) figure of Fig. 3 curve;
Fig. 5 is reactant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) according to one embodiment of the invention and target product DOPP thermogravimetric curve under air (TGA) figure;
Fig. 6 is once differentiation curve (DTG) figure of Fig. 5 curve;
Fig. 7 is thermal analysis curve (DSC) figure of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) according to one embodiment of the invention and target product DOPP.
Embodiment
In order to more clearly understand above-mentioned purpose of the present invention, feature and advantage, below in conjunction with the drawings and specific embodiments, the present invention is further described in detail.It should be noted that, when not conflicting, the feature in the embodiment of the application and embodiment can combine mutually.
Set forth a lot of detail in the following description so that fully understand the present invention; but; the present invention can also adopt other to be different from mode described here to implement, and therefore, protection scope of the present invention is not by the restriction of following public specific embodiment.
As shown in Figure 1, a kind of organic polymer phosphonium flame retardant provided in some embodiments of the present invention, the structural formula of described organic polymer phosphonium flame retardant is:
wherein, n be more than or equal to 1 integer.
This organic polymer phosphonium flame retardant is polymkeric substance, can better melt mutually with macromolecular material, not easily move, in addition, reactive group is not had in the molecular structure of this organic polymer phosphonium flame retardant, the degradation temperature that self degradation temperature compares conventional flame retardant is higher, better thermostability can be shown in heat, make the shape of the macromolecular material of compound with it, structure more stable, therefore, this organic polymer phosphonium flame retardant can be applicable in the macromolecular material of high temperature process, and the scope of application is larger; Further, after this organic polymer phosphonium flame retardant degradation, the carbon left of this organic polymer phosphonium flame retardant is higher than the carbon left of conventional flame retardant, and therefore, the flame retarding efficiency of this organic polymer phosphonium flame retardant is higher.
The embodiment of second aspect present invention provides a kind of preparation method of above-mentioned organic polymer phosphonium flame retardant, flame retardant intermediate and tetramethylolmethane and derivatives reaction thereof is adopted to synthesize DOPP, DOPP described in chemical condensation becomes described organic polymer phosphonium flame retardant again, described DOPP is synthetic molecules, and its structural formula is:
Reactive group is not had in the organic polymer phosphonium flame retardant molecular structure that profit is prepared in this way, therefore, the degradation temperature that self degradation temperature compares conventional flame retardant is higher, as shown in Figures 3 to 6, from reactant 9, mix-10-phospho hetero phenanthrene-10-oxide compound and the thermogravimetric curve figure of target product DOPP in nitrogen and air of 10-dihydro-9-oxy can find out, the thermostability of DOPP and final residual volume are all higher than 9, 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, in a nitrogen atmosphere, 9, the mix temperature of initial decomposition of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is 199 DEG C, the temperature of initial decomposition of DOPP is 360 DEG C, the temperature of initial decomposition of DOPP compares 9, the mix temperature of initial decomposition of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy improves 161 DEG C, better thermostability can be shown in heat, plastification can not be played to body material, not easily produce molten drop, continue to compare, DOPP compares 9, 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, maximum heat weightless temperature is increased to 460 DEG C by 271 DEG C, carbon left when 600 DEG C is increased to 11.9% by 0.334%, the raising of carbon left makes DOPP have higher fire-retardant rate, in air atmosphere 9, the mix temperature of initial decomposition of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is 230 DEG C, the temperature of initial decomposition of DOPP is 341 DEG C, improve 141 DEG C, 600 DEG C time, the carbon left of DOPP is 22.4%, and the carbon left of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 3.84%, as can be seen from DSC curve (as shown in Figure 7), fail in target product to detect 9,10-dihydro-9-oxy is mixed the feature melting peak of-10-phospho hetero phenanthrene-10-oxide compound, illustrate that the purity of DOPP is very high, in addition it can also be seen that target product is non-crystalline state from DSC graphic representation, coincide with apparent colourless transparent glass shape crystal, in addition, this organic polymer phosphonium flame retardant preparation method is simple, is easy to manufacture.
In addition, the preparation method of the organic polymer phosphonium flame retardant in above-described embodiment provided by the invention can also have following additional technical feature:
In one embodiment of the invention, the reaction formula synthesizing described DOPP is:
Wherein, PAT is tetramethylolmethane and derivative thereof, and its structural formula is:
DOPO is flame retardant intermediate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and its structural formula is:
Further, DOPP described in chemical condensation becomes the reaction formula of described organic polymer phosphonium flame retardant to be:
The nuclear magnetic spectrum figure of organic polymer phosphonium flame retardant described in this as shown in Figure 2, in the solid state nmr figure spectrogram of this organic polymer phosphonium flame retardant, 2.3 ~ 2.7 places detected the C=C characteristic peak of PAT, can judge thus in this organic polymer phosphonium flame retardant process of preparation, in the C=C successful scion grafting of PAT 9, on the assorted-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, synthesize target product DOPP, make organic polymer phosphonium flame retardant have above-mentioned higher flame retarding efficiency.
Preferably, described flame retardant intermediate also comprises the derivative of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Particularly, the structural formula of the derivative of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is one of following structural formula:
Utilize 9,10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide derivative of mixing is grafted on the active pentaerythritol derivative with two reactive groups, the material had with DOPP similar quality can be prepared under catalyst action, therefore, the invention provides organic polymer phosphonium flame retardant comprise but be not limited to this kind of structure provided by the present invention.
In one particular embodiment of the present invention, the preparation method of organic polymer phosphonium flame retardant is specially:
A. by 9.5g9,10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound of mixing is dissolved in the 20ml toluene in container, continue to blast nitrogen 30 minutes in container, then container is placed in 100 DEG C of oil baths and carries out magnetic agitation, make 9, assorted-10-phospho hetero phenanthrene-10-the oxide compound of 10-dihydro-9-oxy dissolves, completely until solution clear;
B. 0.44g triethylamine, triethyl-boron or 2,2'-Diisopropyl azodicarboxylate are added in described container as catalyzer, obtain the toluene solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
C. 3.52g tetramethylolmethane or derivatives thereof is dissolved in toluene the toluene solution obtaining tetramethylolmethane or derivatives thereof, and by described 9, the mix toluene solution of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy dropwise joins in the toluene solution of described tetramethylolmethane or derivatives thereof, and the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dripped off for 5 hours;
D. after the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide drips off, in described container, add catalyst for polymerization benzoyl peroxide, continue reaction 5 hours;
E. viscous product in described container is shifted out, ventilation volatilization 2 days, obtain described organic polymer phosphonium flame retardant.
Wherein, in described preparation method, the reaction formula of a ~ c is:
Wherein, in described preparation method, the reaction formula of d is:
The embodiment of third aspect present invention provides a kind of purposes of above-mentioned organic polymer phosphonium flame retardant, described organic polymer phosphonium flame retardant adds to as functional agent to be prepared in polyolefine, urethane, epoxy resin, binding agent, coating, rubber or fiber, to improve the flame retardant properties of described polyolefine, urethane, epoxy resin, binding agent, coating, rubber or fiber.
As shown in table 1, add above-mentioned organic polymer phosphonium flame retardant to can significantly improve this polyurethane-base matrix material in urethane flame retardant properties.
Table 1 is the limiting oxygen index(LOI) of the polyurethane-base matrix material of different content
Wherein: the ratio of filler is massfraction ratio (gram).
The data drawn are tested as can be seen from above-mentioned table 1, adopt DOPP as the organic polymer phosphonium flame retardant of the present invention that compound is made add the polyurethane-base matrix material obtained in urethane limiting oxygen index(LOI), obviously be greater than the limiting oxygen index(LOI) adopting DOPO to add the polyurethane-base matrix material obtained in urethane as the conventional flame retardant that filler is made, visible, organic polymer phosphonium flame retardant of the present invention can significantly improve the flame retardant resistance of polyurethane-based material.
This organic polymer phosphonium flame retardant is of many uses, all can relate to from industrial macromolecular material to life macromolecular material, this organic polymer phosphonium flame retardant can carry out fire-retardant to macromolecular material from gas phase and solid phase two aspect, therefore, has larger use range and the service efficiency of Geng Gao.
In the description of this specification sheets, if occur, specific features, structure, material or feature that the description of term " embodiment ", " some embodiments ", " specific embodiment " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. an organic polymer phosphonium flame retardant, is characterized in that, the structural formula of described organic polymer phosphonium flame retardant is:
Wherein, n be more than or equal to 1 integer.
2. a preparation method for organic polymer phosphonium flame retardant as claimed in claim 1, is characterized in that,
Adopt flame retardant intermediate and pentaerythritol derivative Reactive Synthesis DOPP, then DOPP described in chemical condensation becomes described organic polymer phosphonium flame retardant, described DOPP is synthetic molecules, and its structural formula is:
3. the preparation method of organic polymer phosphonium flame retardant according to claim 2, is characterized in that,
The reaction formula synthesizing described DOPP is:
Wherein, PAT is pentaerythritol derivative, and its structural formula is:
DOPO is flame retardant intermediate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and its structural formula is:
4. the preparation method of organic polymer phosphonium flame retardant according to claim 3, is characterized in that, DOPP described in chemical condensation becomes the reaction formula of described organic polymer phosphonium flame retardant to be:
5. the preparation method of the organic polymer phosphonium flame retardant according to any one of claim 2 to 4, is characterized in that,
A. by 9.5g9,10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound of mixing is dissolved in the 20ml toluene in container, continue to blast nitrogen 30 minutes in container, then container is placed in 100 DEG C of oil baths and carries out magnetic agitation, make 9, assorted-10-phospho hetero phenanthrene-10-the oxide compound of 10-dihydro-9-oxy dissolves, completely until solution clear;
B. 0.44g triethylamine, triethyl-boron or 2,2'-Diisopropyl azodicarboxylate are added in described container as catalyzer, obtain the toluene solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
C. 3.52g pentaerythritol derivative is dissolved in toluene the toluene solution obtaining pentaerythritol derivative, and by described 9, the mix toluene solution of-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy dropwise joins in the toluene solution of described pentaerythritol derivative, and the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dripped off for 5 hours;
D. after the toluene solution of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide drips off, in described container, add catalyst for polymerization benzoyl peroxide, continue reaction 5 hours;
E. viscous product in described container is shifted out, ventilation volatilization 2 days, obtain described organic polymer phosphonium flame retardant.
6. the preparation method of organic polymer phosphonium flame retardant according to claim 5, is characterized in that,
In described preparation method, the reaction formula of a ~ c is:
7. the preparation method of organic polymer phosphonium flame retardant according to claim 5, is characterized in that,
In described preparation method, the reaction formula of d is:
8. the purposes of organic polymer phosphonium flame retardant as claimed in claim 1, is characterized in that,
Described organic polymer phosphonium flame retardant adds to as functional agent to be prepared in polyolefine, urethane, binding agent, coating, rubber or fiber, can improve the flame retardant properties of described polyolefine, urethane, binding agent, coating, rubber or fiber.
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| 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 |
| CN110733093B (en) * | 2019-10-25 | 2021-01-19 | 福建省顺昌县升升木业有限公司 | Fir flame-retardant modification treatment method |
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| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
| CN102276907A (en) * | 2011-07-26 | 2011-12-14 | 东华大学 | Synergic antiflaming thermoplastic resin and preparation method thereof |
| CN103012847A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant |
| EP2581379A2 (en) * | 2011-10-14 | 2013-04-17 | Schill + Seilacher "Struktol" GmbH | Halogen-free material containing phosphorous |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
| CN102276907A (en) * | 2011-07-26 | 2011-12-14 | 东华大学 | Synergic antiflaming thermoplastic resin and preparation method thereof |
| EP2581379A2 (en) * | 2011-10-14 | 2013-04-17 | Schill + Seilacher "Struktol" GmbH | Halogen-free material containing phosphorous |
| CN103012847A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant |
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