CN103113620A - Phosphine-oxide flame retardant and preparation method thereof - Google Patents
Phosphine-oxide flame retardant and preparation method thereof Download PDFInfo
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- CN103113620A CN103113620A CN2013100466628A CN201310046662A CN103113620A CN 103113620 A CN103113620 A CN 103113620A CN 2013100466628 A CN2013100466628 A CN 2013100466628A CN 201310046662 A CN201310046662 A CN 201310046662A CN 103113620 A CN103113620 A CN 103113620A
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Abstract
The invention relates to a phosphine-oxide flame retardant and a preparation method thereof. The preparation method of the phosphine-oxide flame retardant, of which the structure is disclosed in the specification, is implemented by the following two reaction steps: reacting phenyl phosphine and formaldehyde to synthesize dihydroxymethylphenyl phosphine intermediate, and oxidizing to obtain the end product. The compound has the characteristics of high phosphorus content, accessible raw materials, simple and feasible synthesis technique and the like. The phosphine-oxide flame retardant can be widely used in most flame-retardant high polymer materials, and is especially suitable for copolymerization flame retardancy of polyesters, polyurethanes and other high polymers.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to a kind of phosphine oxide flame retardant and preparation method thereof, particularly relate to fire-retardant dihydroxymethyl phenyl phosphine oxide such as the polymer that can be used for polyester, urethane and preparation method thereof.
Background technology
Twentieth century is since the eighties, and fire retardant has become the auxiliary agent of the synthetic materials consumption maximum that is only second to softening agent.Along with expanding economy, people's environmental protection and awareness of safety have had large increase, and ecotope and value of life are also more paid close attention to.Traditional halogenated flame retardant is used for the production of fire retardant material in a large number because its flame retarding efficiency is high, but a large amount of smog and poisonous corrosive gases have been produced due to the halogenated flame retardant product when burning, have a strong impact on fire rescue and evacuating personnel, caused the secondary disaster to occur.Therefore, increasing country begins to forbid that halogen is the use of flame retardant products, and halogen-free flame retardants owing to having the environmentally friendly characteristics such as low cigarette, low toxicity, is used widely gradually at this moment.Use efficient, low cigarette, halogen-free flame retardants nontoxic or low toxicity will become the inexorable trend of following fire retardant material development, inorganic fill fire retardant and phosphorus flame retardant are subject to common concern in recent years.
Phosphorus flame retardant enjoys attention because flame retarding efficiency is high in the halogen-free flameproof field.Therefore traditional phosphorus flame retardant great majority have volatility, and the defectives such as facile hydrolysis are developed the macromole low volatility, the phosphorus flame retardant of facile hydrolysis is not the emphasis of Future Development.With among covalent linkage form embedded polymer thing parent, in use the migration volatilization does not occur to the response type organophosphorous fire retardant in flame retardant molecule due to flame retardant molecule, and is fire-retardant more lasting, efficient, therefore becomes the focus of fire retardant research field.Simultaneously, when organophosphorous fire retardant uses, outstanding advantage is arranged on cost performance, be in the halogenated flame retardant surrogate the most competitive kind it
Summary of the invention
The invention belongs to technical field of organic synthesis, relate to a kind of preparation method of phosphine oxide flame retardant, particularly relate to a kind of preparation method who can be used for the fire-retardant dihydroxymethyl phenyl phosphine oxide of engineering plastics.This compound has the characteristics such as phosphorus content is high, and raw material is easy to get, and synthesis technique is simple and easy to do.Can be widely used in most of flame retarded polymeric materials, the copolymerization that is particularly useful for the superpolymer such as polyester, urethane is fire-retardant.Its structural formula is shown below:
The preparation method of new type phosphine oxide flame retardant disclosed by the invention, adopt two-step reaction:
The first step: the Phenylphosphine and the formaldehyde that are 1:2 ~ 2.5 with mol ratio drop into reaction vessel, add solvent, under nitrogen protection, fully stir, and then holding temperature is warming up to 60-100 ℃ and continues reaction 2-6 hour 10 ~ 50 ℃ of reactions 4 ~ 10 hours.After reacting completely, collect reaction intermediate, standby.
Second step: add hydrogen peroxide at above-mentioned reaction intermediate, stir, holding temperature after vacuum distilling desolvation and low volatile, obtains the phosphine oxide flame retardant 20 ~ 60 ℃ of reactions 3 ~ 12 hours.
The solvent of the first step as above reaction indication is one or more the mixture in water, dioxane, benzene,toluene,xylene, chloroform, chlorobenzene and ethylene dichloride.
It is 0.8-1.2 mole of H that second step reaction as above adds the amount of hydrogen peroxide
2O
2/ mole Phenylphosphine.
Beneficial effect
1. to adopt Phenylphosphine and formaldehyde be the synthetic phosphine oxide fire retardant of raw material in the present invention, have phosphorus content high-and be diatomic alcohol compounds, be the high molecular efficient copoly type fire retardants such as polyester, urethane.
2. phosphine oxide fire retardant of the present invention and preparation method thereof, raw material is easy to get, and reactions steps and equipment requirements simple, environment is not polluted, be applicable to suitability for industrialized production.
3. to have a phosphorus content high for this compound of dihydroxymethyl phenyl phosphine oxide of synthesizing of the present invention, the characteristics such as raw material is easy to get, and synthesis technique is simple and easy to do.Can be widely used in most of flame retarded polymeric materials, the copolymerization that is particularly useful for the superpolymer such as polyester, urethane is fire-retardant.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and need not limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modification to the present invention after having read the content that the present invention lectures, these equivalent form of values fall within the appended where claim limited range of the application equally.
A kind of phosphine oxide flame retardant of the present invention, concrete structure is as follows:
Embodiment 1
Be furnished with agitator, reflux adds Phenylphosphine 22g in the three-necked flask of thermometer; add 35% formaldehyde solution 34.3g, add entry 40ml, stir under nitrogen protection; then holding temperature slowly is warming up to 100 ℃ 10 ℃ of reactions 10 hours, reacts 2 hours.React complete after, collect reaction intermediate standby.
Add 200 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 60 ℃ of holding temperatures, reacted 3 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 2
Be furnished with agitator, reflux adds Phenylphosphine 22.0kg in 200 liters of enamel reaction stills of thermometer; add 35% formaldehyde solution 42.8kg, add dioxane 50kg, stir under nitrogen protection; then holding temperature slowly is warming up to 60 ℃ 30 ℃ of reactions 6 hours, reacts 6 hours.React complete after, collect reaction intermediate standby.
Add the 160kg34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 40 ℃ of holding temperatures, reacted 6 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 3
Be furnished with agitator, reflux adds Phenylphosphine 44g in the three-necked flask of thermometer; add 35% formaldehyde solution 75.4g, add benzene 200ml, stir under nitrogen protection; then holding temperature slowly is warming up to 80 ℃ 30 ℃ of reactions 8 hours, reacts 5 hours.React complete, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the organic phosphine flame retardant.
Add 480 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 20 ℃ of holding temperatures, reacted 12 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 4
Be furnished with agitator, reflux adds Phenylphosphine 66g in the three-necked flask of thermometer; add 35% formaldehyde solution 102.9g, add toluene 180ml, stir under nitrogen protection; then holding temperature slowly is warming up to 90 ℃ 15 ℃ of reactions 8 hours, reacts 3 hours.React complete after, collect reaction intermediate standby.
Add 630 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 50 ℃ of holding temperatures, reacted 5 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 5
Be furnished with agitator, reflux adds Phenylphosphine 110g in the three-necked flask of thermometer; add 35% formaldehyde solution 105g, add dimethylbenzene 250ml, stir under nitrogen protection; then holding temperature slowly is warming up to 70 ℃ 35 ℃ of reactions 7.5 hours, reacts 9 hours.React complete after, collect reaction intermediate standby.
Add 1025 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 60 ℃ of holding temperatures, reacted 4 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 6
Be furnished with agitator, reflux adds Phenylphosphine 132g in the three-necked flask of thermometer; add 35% formaldehyde solution 216g, add chloroform 1200ml, stir under nitrogen protection; then holding temperature slowly is warming up to 85 ℃ 40 ℃ of reactions 6 hours, reacts 4 hours.React complete after, collect reaction intermediate standby.
Add 1080 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 40 ℃ of holding temperatures, reacted 8 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 7
Be furnished with agitator, reflux adds 11 kilograms of Phenylphosphines in the three-necked flask of thermometer; add 18.5 kilograms of 35% formaldehyde solutions, add 20 kilograms of entry, stir under nitrogen protection; then holding temperature slowly is warming up to 100 ℃ 10 ℃ of reactions 10 hours, reacts 4 hours.React complete after, collect reaction intermediate standby.
Add 85 kilograms of 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 35 ℃ of holding temperatures, reacted 8 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Embodiment 8
Be furnished with agitator, reflux adds Phenylphosphine 44g in the three-necked flask of thermometer; add 35% formaldehyde solution 72g, add ethylene dichloride 140ml, stir under nitrogen protection; then holding temperature slowly is warming up to 65 ℃ 25 ℃ of reactions 10 hours, reacts 5 hours.React complete after, collect reaction intermediate standby.
Add 380 gram 34%(quality in above-mentioned reaction intermediate) superoxol, fully stir 45 ℃ of holding temperatures, reacted 11 hours, react complete after, change the back flow reaction device into vacuum distillation plant, be distilled to and no longer include liquid and distillate, stop distillation, obtain the phosphine oxide fire retardant.
Claims (4)
1. phosphine oxide flame retardant, it is characterized in that: described phosphine oxide flame retardant is dihydroxymethyl phenyl phosphine oxide, and its structure is as follows:
2. phosphine oxide flame retardant as claimed in claim 1 is characterized in that described preparation method adopts two-step reaction:
The first step: the Phenylphosphine and the formaldehyde that are 1:2 ~ 2.5 with mol ratio drop into reaction vessel, add solvent, under nitrogen protection, fully stir, and then holding temperature is warming up to 60-100 ℃ and continues reaction 2-6 hour 10 ~ 50 ℃ of reactions 4 ~ 10 hours; After reacting completely, collect reaction intermediate, standby;
Second step: add hydrogen peroxide at above-mentioned reaction intermediate, stir, holding temperature after vacuum distilling desolvation and low volatile, obtains the phosphine oxide flame retardant 20 ~ 60 ℃ of reactions 3 ~ 12 hours.
3. preparation method as claimed in claim 2, is characterized in that, the solvent of described the first step reaction indication is one or more the mixture in water, dioxane, benzene,toluene,xylene, chloroform, chlorobenzene and ethylene dichloride.
4. preparation method as claimed in claim 2, wherein, it is 0.8 ~ 1.2 mole of H that described second step reaction adds the amount of hydrogen peroxide
2O
2/ mole Phenylphosphine.
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| CN2013100466628A CN103113620A (en) | 2013-02-05 | 2013-02-05 | Phosphine-oxide flame retardant and preparation method thereof |
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| CN2013100466628A CN103113620A (en) | 2013-02-05 | 2013-02-05 | Phosphine-oxide flame retardant and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037715A (en) * | 2014-12-02 | 2015-11-11 | 淮安市欣佳尼龙有限公司 | Preparation method of flame-retarding nylon 610 and toothbrush hair produced therefrom |
| CN106349288A (en) * | 2016-08-26 | 2017-01-25 | 东华大学 | Tris(hydroxymethyl)phosphine oxide glycidyl ether and preparation method thereof |
| CN107573479A (en) * | 2017-09-25 | 2018-01-12 | 天津科技大学 | Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant |
| CN113195576A (en) * | 2018-12-21 | 2021-07-30 | 斯塔尔国际有限公司 | Process for preparing halogen-free flame-retardant aqueous polyurethane dispersions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1023387A (en) * | 1962-06-14 | 1966-03-23 | Kalk Chemische Fabrik Gmbh | Process for preparing polyesters containing phosphorus |
| US4127565A (en) * | 1977-12-22 | 1978-11-28 | Monsanto Company | Process for making fiber-forming polyesters |
-
2013
- 2013-02-05 CN CN2013100466628A patent/CN103113620A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1023387A (en) * | 1962-06-14 | 1966-03-23 | Kalk Chemische Fabrik Gmbh | Process for preparing polyesters containing phosphorus |
| US4127565A (en) * | 1977-12-22 | 1978-11-28 | Monsanto Company | Process for making fiber-forming polyesters |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037715A (en) * | 2014-12-02 | 2015-11-11 | 淮安市欣佳尼龙有限公司 | Preparation method of flame-retarding nylon 610 and toothbrush hair produced therefrom |
| CN106349288A (en) * | 2016-08-26 | 2017-01-25 | 东华大学 | Tris(hydroxymethyl)phosphine oxide glycidyl ether and preparation method thereof |
| CN107573479A (en) * | 2017-09-25 | 2018-01-12 | 天津科技大学 | Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant |
| CN113195576A (en) * | 2018-12-21 | 2021-07-30 | 斯塔尔国际有限公司 | Process for preparing halogen-free flame-retardant aqueous polyurethane dispersions |
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Application publication date: 20130522 |