CN103588990B - Heat-resisting reaction type phosphorate containing flame retardant with maleimide structure and preparation method thereof - Google Patents
Heat-resisting reaction type phosphorate containing flame retardant with maleimide structure and preparation method thereof Download PDFInfo
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- CN103588990B CN103588990B CN201310562528.3A CN201310562528A CN103588990B CN 103588990 B CN103588990 B CN 103588990B CN 201310562528 A CN201310562528 A CN 201310562528A CN 103588990 B CN103588990 B CN 103588990B
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Abstract
The invention discloses a heat-resisting reaction type phosphorate containing flame retardant with a maleimide structure and a preparation method thereof. The preparation method is characterized in that maleimide based phenol and phosphoryl chloride or phosphoryl bromide are added into a reactor, a reaction solvent is added into the reactor, then an inert gas is fed into the reactor, and materials in the reactor are heated to 70-100 DEG C; continuous stirring is performed during heating, and stirring is continued during a constant temperature reaction until no hydrogen halide gas is released; the materials are cooled to a room temperature, distillation under reduced pressure is performed to remove the reaction solvent, and an obtained orange-yellow product is the heat-resisting reaction type phosphorate containing flame retardant with the maleimide structure. The prepared heat-resisting reaction type phosphorate containing flame retardant with the maleimide structure can serve as a reaction type flame retardant to react with a polymer resin matrix, is not prone to movement and has superior service durability and good flame-retardant effect, and the heat resistance of a material can be improved simultaneously.
Description
Technical field
The invention belongs to halogen-free phosphorus-containing fire retardant agent technical field, be specifically related to phosphonium flame retardant of a kind of maleimide structure of resistance to thermal-reactive and preparation method thereof.
Background technology
At present, the feature of polymer-based composite and excellent performance light with its quality, is just becoming a more and more important class novel material, is replacing traditional material and be widely used in life and production all respects.Be widely used in reinforced composite field based on the thermosetting resin of epoxy resin, unsaturated polyester etc.The performance that the matrix material strengthened possesses that cheap, high tensile, quality are light, chemical resistant properties etc. is excellent, is applied to building, chemical industry, communications and transportation, shipbuilding, the field such as electric.But thermosetting resin is mostly elementary composition by C, H, O etc., comparatively easy firing and cause fire, produces a large amount of toxic gases in combustion processes simultaneously, causes very large threat to limit widely using of matrix material to safety of life and property simultaneously.Therefore, a hot issue urgently to be resolved hurrily is become to such thermosetting resin fire-retardant.
Fire retardant adds in resin or polymkeric substance an analog assistant that material can be stoped to ignite or suppress propagation of flame.Fire retardant of a great variety, but the fire retardant using more at present mainly halogen containing flame-retardant, metal hydroxides and phosphonium flame retardant.As CN1803918A, CN102634182A, CN101885860A report additive flame retardant as decabromodiphenyl oxide, antimonous oxide, aluminium hydroxide, phosphorous Intumscent Flame Retardant System flameproof unsaturated polyester and epoxy resin.Chinese patent CN1869098A discloses a kind of synthetic method of response type heat-proof combustion-resistant unsaturated polyester, by the N-(2 of synthesis, 4,6 tribromo phenyl) maleimide monomer and vinylbenzene are jointly as cross-linking monomer, and synthesis obtains the unsaturated polyester with heat-resisting and fire-retardant dual property.Although halogen containing flame-retardant comparatively effectively and be widely used, easily discharge irritant and corrosive gases when burning, people's health is endangered, and European Union has ordered to prohibit the use some halogen containing flame-retardant.Metal hydroxide combustion inhibitor could meet flame-retardancy requirements owing to needing the consumption added up to 40% ~ 60%, cause mixed with resin, shaping time poor fluidity, the processing of material and mechanicalness are declined.In addition, phosphorus nitrogen expansion type combustion inhibitor can Substitute For Partial halogen containing flame-retardant, but most of expansion type flame retardant still exists that addition is large, the easy moisture absorption of fire retardant, with matrix poor compatibility, easily move, reduce the mechanical property of material, flame retardant properties and work-ing life.Reactive flame retardant can while raising resins fire retardant performance, and do not damage or damage less the mechanical property of resin, resin is often transparent, represents the direction that thermosetting resin is flame-retardant modified.But existing reactive flame retardant existence reaction, the shortcoming that purification process is loaded down with trivial details, flame retarding efficiency is low, in addition, the low heat decomposition temperature of organophosphorous fire retardant causes the resistance toheat of material to decline, and makes it apply and is restricted.
Summary of the invention
For solving the weak point existing for above-mentioned prior art, the invention provides phosphonium flame retardant of a kind of maleimide structure of resistance to thermal-reactive and preparation method thereof, to can improve the flame retarding efficiency of fire retardant and the resistance toheat of material simultaneously.
Technical solution problem of the present invention, adopts following technical scheme:
The phosphonium flame retardant of the present invention's maleimide structure of resistance to thermal-reactive, its feature is: the molecular structure of described phosphonium flame retardant is:
Wherein, n is 1 or 2, R
1for
Wherein, R
2for-CH
2cH
2-,-CH
2cH
2cH
2-or-(CH
3)
2c (CH
2)
2-;
R
3for-CH
3,-OCH
3,-CH
2cH
3,-OCH
2cH
3, phenyl or phenoxy group.
The preparation method of the phosphonium flame retardant of the present invention's maleimide structure of resistance to thermal-reactive, its feature is: by dimaleoyl imino phenol and phosphoryl chloride or phosphoryl bromide in molar ratio 1:1 or 2:1 add in reactor, and add reaction solvent in the reactor, in reactor, pass into rare gas element again and material in reactor is heated to 70 ~ 100 DEG C, constantly stir in heating simultaneously, continue to be stirred to non-halogen hydrogen while isothermal reaction to release, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, the chemical equation of described maleimide phenol and phosphoryl chloride or phosphoryl bromide is as shown in Equation 1:
Wherein, A is dimaleoyl imino phenol; B is phosphoryl chloride or phosphoryl bromide; C is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive; N be 1 or 2, X be chlorine atom or bromine atoms, R
1for
R
2for-CH
2cH
2-,-CH
2cH
2cH
2-or-(CH
3)
2c (CH
2)
2-;
R
3for-CH
3,-OCH
3,-CH
2cH
3,-OCH
2cH
3, phenyl or phenoxy group.
Described reaction solvent is tetrahydrofuran (THF), acetonitrile or toluene.
Described reaction solvent carries out the process that dewaters before adding reactor.
Described rare gas element is nitrogen, argon gas or helium.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive 1, prepared by the present invention can react as reactive flame retardant and polymer resin matrix, not easily moves, has excellent weather resistance and good flame retardation effect;
The phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive 2, prepared by the present invention belongs to halogen-free flame retardants, is conducive to environmental protection;
Containing maleimide structure in the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive 3, prepared by the present invention, the resistance toheat of material can be improved, overcome the infringement of phosphonium flame retardant to matrix resistance toheat;
4, the present invention carries out esterification by dimaleoyl imino phenol and phosphoryl chloride or phosphoryl bromide and sloughs the phosphonium flame retardant that small molecules hydrogen halide obtains the maleimide structure of resistance to thermal-reactive, method is simple, be easy to realize, and without the need to using catalyzer, last handling process is simple;
The phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive 5, prepared by the present invention be applicable to unsaturated polyester, epoxy resin fire-retardant; When flameproof unsaturated polyester, its limiting oxygen index(LOI) (LOI) has had raising by a relatively large margin, improves second-order transition temperature simultaneously.
Embodiment
Further describe the preparation method of the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive of the present invention and the mensuration to unsaturated polyester limiting oxygen index(LOI), miniature calorimetric and second-order transition temperature thereof by the following examples.
Embodiment 1
Being equipped with agitator, have in the 500ml there-necked flask of nitrogen inlet and prolong add 37.8g(0.2mol) dimaleoyl imino phenol, 250ml anhydrous tetrahydro furan and 29.7g(0.1mol) pentaerythritol diphosphate two phosphoryl chloride, pass into nitrogen, and material in reactor is heated to 70 DEG C, heating is constantly stirred simultaneously, continue after constant temperature to be stirred to and release without HCl gas, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, and productive rate is 90%.
The hydrogen nuclear magnetic resonance spectrum analysis of products therefrom, the peak position of chemical shift at 6.80-6.85ppm place is the hydrogen vibration signal in the double bond on nitrogenous five-ring, the peak of chemical shift between 7.05-7.11ppm and between 7.12-7.14ppm is benzene ring hydrogen vibration signal, and the peak of chemical shift between 4.18-4.25ppm is the hydrogen vibration signal on methylene radical; The chemical shift of nucleus magnetic resonance phosphorus spectrum display products therefrom phosphorus atom is-7.11ppm.Illustrate thus, the fire retardant of synthesis is consistent with the structure of target product.
Get the phosphonium flame retardant 2.1g of the maleimide structure of resistance to thermal-reactive of above-mentioned preparation, unsaturated polyester 27.9g, 10min is stirred at about 80 DEG C, then heating unit is removed, be cooled to after room temperature until unsaturated polyester, add 0.3g benzoyl peroxide, after continuing to stir 20min, vacuum defoamation, finally sample to be cast in the mould of the long 100mm be made up of tetrafluoroethylene, wide 6.5mm, thick 3mm 70 DEG C of solidifications 3 hours, 120 DEG C solidify 3 hours, naturally cool to room temperature, the demoulding obtains solidified sample.
Measured by solidified sample oxygen index instrument, its oxygen index is up to 26.0%; The heat release rate peak value of miniature calorimeter (MCC) result display solidified sample is only 271w/g, and total heat release (THR) is 14.8KJ/g; The second-order transition temperature that dsc (DSC) measures unsaturated polyester is 135 DEG C.
Embodiment 2
Being equipped with agitator, have in the 500ml there-necked flask of Ar inlet and prolong add 18.9g(0.1mol) dimaleoyl imino phenol, 150ml anhydrous acetonitrile and 18.5g(0.1mol) neopentyl glycol phosphoryl chloride, pass into argon gas, and material in reactor is heated to 85 DEG C, heating is constantly stirred simultaneously, continue after constant temperature to be stirred to and release without HCl gas, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, and productive rate is 92%.
The hydrogen nuclear magnetic resonance spectrum analysis of products therefrom, the peak position of chemical shift at 6.80-6.86ppm place is the hydrogen vibration signal in the double bond on nitrogenous five-ring, the peak of chemical shift between 7.06-7.11ppm and between 7.11-7.14ppm is benzene ring hydrogen vibration signal, hydrogen vibration signal on the peak position methylene radical of chemical shift between 3.87-3.93ppm, the peak of chemical shift between 0.93-0.97ppm is the vibration signal of the hydrogen on methyl; The chemical shift of nucleus magnetic resonance phosphorus spectrum display products therefrom phosphorus atom is-6.13ppm.Illustrate thus, the fire retardant of synthesis is consistent with the structure of target product.
Get the phosphonium flame retardant 2.1g of the response type maleimide structure of above-mentioned preparation, unsaturated polyester 27.9g, stir 10min at about 80 DEG C, then remove heating unit, after unsaturated polyester cooling, add 0.3g benzoyl peroxide, continue to stir after 20min, vacuum defoamation, finally sample to be cast in the mould of the long 100mm be made up of tetrafluoroethylene, wide 6.5mm, thick 3mm 70 DEG C of solidifications 3 hours, 120 DEG C solidify 3 hours, naturally cool to room temperature, the demoulding obtains solidified sample.
Solidified sample oxygen index instrument measures its oxygen index, oxygen index up to 28.0%; The heat release rate peak value of miniature calorimeter (MCC) result show sample is only 265w/g, and total heat release (THR) is 13.9KJ/g; The second-order transition temperature that dsc (DSC) measures unsaturated polyester is 130 DEG C.
Embodiment 3
Being equipped with agitator, have in the 500ml there-necked flask of helium entrance and prolong add 37.8g(0.2mol) dimaleoyl imino phenol, 250ml dry toluene and 21.1g(0.1mol) dichloro-phenyl-phosphate, pass into helium, and material in reactor is heated to 100 DEG C, heating is constantly stirred simultaneously, continue after constant temperature to be stirred to and release without HCl gas, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, and productive rate is 88%.
The hydrogen nuclear magnetic resonance spectrum analysis of products therefrom, the peak position of chemical shift at 6.80-6.86ppm place is the hydrogen vibration signal in the double bond on nitrogenous five-ring, the peak of chemical shift between 7.05-7.11ppm and between 7.12-7.14ppm is maleimide structure benzene ring hydrogen vibration signal, and the peak of chemical shift between 7.14-7.18ppm and between 7.32-7.38ppm is dichloro-phenyl-phosphate structure benzene ring hydrogen vibration signal; The chemical shift of nucleus magnetic resonance phosphorus spectrum display products therefrom phosphorus atom is-1.51ppm.Illustrate thus, the fire retardant of synthesis is consistent with the structure of target product.
Get the phosphonium flame retardant 2.1g of the response type maleimide structure of above-mentioned preparation, unsaturated polyester 27.9g, stir 10min at about 80 DEG C, then remove heating unit, after unsaturated polyester cooling, add 0.3g benzoyl peroxide, continue to stir after 20min, vacuum defoamation, finally sample to be cast in the mould of the long 100mm be made up of tetrafluoroethylene, wide 6.5mm, thick 3mm 70 DEG C of solidifications 3 hours, 120 DEG C solidify 3 hours, naturally cool to room temperature, the demoulding obtains solidified sample.
Solidified sample oxygen index instrument is measured its oxygen index, oxygen index up to 25.5%; The heat release rate peak value of miniature calorimeter (MCC) result show sample is only 270w/g, and total heat release (THR) is 15.9KJ/g; The second-order transition temperature that dsc (DSC) measures unsaturated polyester is 133 DEG C.
Embodiment 4
Being equipped with agitator, have in the 500ml there-necked flask of nitrogen inlet and prolong add 37.8g(0.2mol) dimaleoyl imino phenol, 250ml anhydrous acetonitrile and 38.7g(0.1mol) pentaerythritol diphosphate two phosphoryl bromide, pass into nitrogen, and material in reactor is heated to 85 DEG C, heating is constantly stirred simultaneously, continue after constant temperature to be stirred to and release without HBr gas, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, and productive rate is 90%.
The hydrogen nuclear magnetic resonance spectrum analysis of products therefrom, the peak position of chemical shift at 6.80-6.84ppm place is the hydrogen vibration signal in the double bond on nitrogenous five-ring, the peak of chemical shift between 7.05-7.11ppm and between 7.12-7.15ppm is benzene ring hydrogen vibration signal, and the peak of chemical shift between 4.18-4.26ppm is the hydrogen vibration signal on methylene radical; The chemical shift of nucleus magnetic resonance phosphorus spectrum display products therefrom phosphorus atom is-7.09ppm.Illustrate thus, the fire retardant of synthesis is consistent with the structure of target product.
Get the phosphonium flame retardant 2.1g of the response type maleimide structure of above-mentioned preparation, unsaturated polyester 27.9g, stir 10min at about 80 DEG C, then remove heating unit, after unsaturated polyester cooling, add 0.3g benzoyl peroxide, continue to stir after 20min, vacuum defoamation, finally sample to be cast in the mould of the long 100mm be made up of tetrafluoroethylene, wide 6.5mm, thick 3mm 70 DEG C of solidifications 3 hours, 120 DEG C solidify 3 hours, naturally cool to room temperature, the demoulding obtains solidified sample.
Solidified sample oxygen index instrument measures its oxygen index, oxygen index up to 26.0%; The heat release rate peak value of miniature calorimeter (MCC) result show sample is only 268w/g, and total heat release (THR) is 14.0KJ/g; The second-order transition temperature that dsc (DSC) measures unsaturated polyester is 131 DEG C.
Claims (5)
1. the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive is used for a purposes for unsaturated polyester and ethoxyline resin antiflaming, it is characterized in that: the molecular structure of described phosphonium flame retardant is:
Wherein, n is 1 or 2, R
1for
Wherein, R
2for-CH
2cH
2-or-CH
2cH
2cH
2-;
R
3for-CH
3,-OCH
3,-CH
2cH
3or phenoxy group.
2. the preparation method of the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive of purposes according to claim 1, it is characterized in that: by dimaleoyl imino phenol and phosphoryl chloride or phosphoryl bromide in molar ratio 1:1 or 2:1 add in reactor, and add reaction solvent in the reactor, in reactor, pass into rare gas element again and material in reactor is heated to 70 ~ 100 DEG C, constantly stir in heating simultaneously, continue to be stirred to non-halogen hydrogen while isothermal reaction to release, be cooled to room temperature, underpressure distillation removing reaction solvent, gained orange product is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive, the chemical equation of described dimaleoyl imino phenol and phosphoryl chloride or phosphoryl bromide is as shown in Equation 1:
Wherein, A is dimaleoyl imino phenol; B is phosphoryl chloride or phosphoryl bromide; C is the phosphonium flame retardant of the maleimide structure of resistance to thermal-reactive; N be 1 or 2, X be chlorine atom or bromine atoms, R
1for
R
2for-CH
2cH
2-or-CH
2cH
2cH
2-;
R
3for-CH
3,-OCH
3,-CH
2cH
3or phenoxy group.
3. preparation method according to claim 2, is characterized in that: described reaction solvent is tetrahydrofuran (THF), acetonitrile or toluene.
4. preparation method according to claim 3, is characterized in that: described reaction solvent carries out the process that dewaters before adding reactor.
5. preparation method according to claim 2, is characterised in that: described rare gas element is nitrogen, argon gas or helium.
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| CN107759636A (en) * | 2017-10-25 | 2018-03-06 | 无锡福祈制药有限公司 | A kind of vitamin D3Spiro-phosphate and preparation method thereof |
| CN109575076B (en) * | 2018-11-08 | 2020-11-27 | 中北大学 | Preparation of phosphorus-containing bismaleimide and application of phosphorus-containing bismaleimide in flame-retardant epoxy resin |
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| Title |
|---|
| Studies of Phosphonate-Containing Bismaleimide Resins. I. Synthesis and Characteristics of Model Compounds and Polyaspartimides;Wei-JYE SHU et al;《Journal of Applied Polymer Science》;20021231;第83卷;p1919-1933 * |
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