CN104558684A - DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof - Google Patents
DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof Download PDFInfo
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- CN104558684A CN104558684A CN201510028921.3A CN201510028921A CN104558684A CN 104558684 A CN104558684 A CN 104558684A CN 201510028921 A CN201510028921 A CN 201510028921A CN 104558684 A CN104558684 A CN 104558684A
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- flame retardant
- dopo
- dioxygen
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- phosphate flame
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Abstract
The invention discloses a DOPO-containing dioxacaprophosphate flame retardant. The flame retardant is prepared by the following steps: reacting DOPO and p-benzoquinone in an organic solvent so as to obtain an intermediate I; preparing an intermediate II from neopentyl glycol and phosphorus oxychloride under the action of chloroform; and reacting the intermediate I and the intermediate II in an organic solvent, thereby obtaining the flame retardant. The flame retardant is white in appearance, high in thermal stability and high in flame retardant rate and has the purity of 99.5 percent. The flame retardant can serve as a reactive flame retardant to be used in an epoxy resin, an ABS resin, polyurethane and other thermosetting resins, also can serve as an additive flame retardant, is used for meeting the halogen-free flame retardant requirements on ABS, nylon and other engineering plastics with high heat resistance requirements on the flame retardant and is wide in application prospects.
Description
Technical field
In dioxygen containing DOPO of the present invention is own, phosphoric acid ester belongs to phosphorus flame retardant technical field, be specifically related to preparation method and the application thereof of oneself interior phosphate flame retardant of a kind of dioxygen containing DOPO, this fire retardant both can be used as reactive flame retardant and had prepared halogen-free flame-retardant resin, can be used as again the halogen-free flame retardants of additive flame retardant for engineering plastics.
Background technology
High polymer material is widely used in each department of the national economy such as industry, agricultural, military affairs, but most of superpolymer belongs to petroleum base combustible matl, during burning, heat release rate is high, calorific value is large, flame propagation speed, not easily extinguish, generally also can produce thick smoke and toxic gas, to grave danger that the security of the lives and property of people causes.There is the secondary harm such as thickness, poisonous or corrosive gases releasing during traditional Halogen fire retardant material burning, serious threat is constituted to personnel safety.Therefore, people are more and more stricter to the requirement that macromolecular material is fire-retardant, and the environmental protection fire retarding agent of Halogen, low cigarette, low toxicity, high heat resistance has started the target becoming people's pursuit.Phosphorus flame retardant has become the main force in fire retardant, phosphate flame retardant have low cigarette, nontoxic, Halogen, with the advantage such as material compatibility is good, flame retardant effect is lasting, water-fast, heat-resisting, resistance to migration, in macromolecular material, play the effects such as fire-retardant and plasticising, there is good development prospect.
DOPO is BACN intermediate, containing active phosphorus-hydrogen bond in its structure, activity is had to alkene, epoxy bond and carbonyl, can react and generate many derivatives, DOPO and derivative thereof are owing to containing cyclohexyl biphenyl and phenanthrene ring structure in molecular structure, and particularly phosphorus group in side is introduced in the mode of ring-type O=P-O key, organophosphate thermostability and the chemical stability of the non-Cheng Huan of ratio are high, flame retardant properties is better, and Halogen, smokeless, environmental protection, not easily move.But the fire-retardant existence 180 DEG C that DOPO monomer is directly used in macromolecular material just starts the shortcoming of decomposing, and can not meet the processing temperature of most polymer material.
Summary of the invention
The object of the invention is to overcome above-mentioned weak point of the prior art, provide that a kind of technique is simple, production cost is low, overcome DOPO low-temperature decomposition, the dioxygen containing DOPO of excellent flame retardancy in oneself phosphate flame retardant and preparation method and application.
The object of the invention is such realization: phosphate flame retardant in a kind of dioxygen containing DOPO is own, this compound has following chemical structural formula:
Preparation method containing oneself the interior phosphate flame retardant of dioxygen of DOPO:
A: under nitrogen protection; DOPO is joined in organic solvent and dissolves; add para benzoquinone again; stir at 90-120 DEG C and react 3-8h (more preferably stir at 100 DEG C and react 5h); after having reacted, gained throw out is cooled to room temperature to filter; by recrystallizing methanol, can obtain intermediate I after drying, reaction equation is as follows:
B: after neopentyl glycol, chloroformic solution mixing, stir and drip phosphorus oxychloride, after dripping off, 5-9h (more preferably reacting 6h at 65 DEG C) is reacted at 50-80 DEG C, after reaction terminates, chloroform and excessive phosphorus oxychloride are steamed, obtains the own interior phosphoryl chloride intermediate II of dioxygen heterocycle;
C: add organic solvent in intermediate II, stirring adds intermediate compound I after making it dissolve, drip triethylamine under ice cooling, 4, dropwise, (be more preferably warming up to 70 DEG C) after being warming up to 60-90 DEG C gradually, adopt TLC to follow the tracks of reaction process, after having reacted, steam solvent, filtration obtains light yellow solid, and recrystallization obtains white crystalline powder:
This fire retardant both can be used as reactive flame retardant and had prepared halogen-free flame-retardant resin, can be used as again the halogen-free flame retardants of additive flame retardant for engineering plastics.
The own interior phosphate flame retardant of dioxygen containing DOPO is as the application of the phosphorus nitrogen cooperative flame retardant additive of epoxy resin, urethane, ABS.
Beneficial effect of the present invention is as follows:
(1) the own interior phosphate flame retardant of the dioxygen containing DOPO provided by the invention, simple to operate, technique is advanced, solvent recoverable;
(2) fire retardant provided by the invention is by DOPO, is incorporated in oneself interior phosphoric acid ester of dioxygen to phenoxy group structural unit, there is higher phosphorus content, thermotolerance and high temperature charring rate, both can as reactive flame retardant, be linked in the thermosetting resin such as epoxy resin, urethane and used, again can as additive flame retardant, for meeting the halogen-free flameproof to the higher engineering plastics such as ABS, nylon of fire retardant heat resistant requirements;
(3) product of the present invention's synthesis, thermally-stabilised good, fire-retardant rate is high, and purity reaches 99.5%;
(4) raw material used in the present invention is easy to get, technique is advanced, be easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
In order to develop the higher fire retardant of flame retarding efficiency, the core texture segment of DOPO, the own interior phosphate compounds of dioxygen heterocycle rationally being assembled and modifying, synthesizes the composite fire retardant of oneself the interior phosphoric acid ester of dioxygen containing DOPO.
Embodiment 1:
Containing a preparation method for oneself the interior phosphate flame retardant of dioxygen of DOPO, step is:
Under nitrogen protection in three-necked flask, add 12g DOPO (0.055mol) and 300mL toluene, heated and stirred arrives, and after DOPO is dissolved in toluene completely, adds 5g para benzoquinone (0.046mol), stirring reaction 5h at 100 DEG C.Gained throw out is cooled to room temperature to filter, heavily tie product with methyl alcohol, drying obtains intermediate I, white solid.
52.0g (0.5mo1) neopentyl glycol and 200mL chloroform are joined in flask, under agitation, slowly drips 84.3g (0.55mo1) phosphorus oxychloride, after dripping, at 65 DEG C of reaction 6h.After having reacted, steam chloroform and excessive phosphorus oxychloride, obtain white solid, obtain intermediate II through recrystallization, drying, yield 91.2%.
In the round-bottomed flask that 100mL acetonitrile is housed, add intermediate I 3.24g (0.01mol)), stir and make it dissolve, add 4.23g (0.023mol) intermediate II in batches, 2.33g (0.022mo1) triethylamine is dripped in ice bath, stir, dropwise, be heated to 70 DEG C gradually, TLC follows the tracks of reaction process, steam acetonitrile after reaction terminates, adularescent solid is separated out, and filters and obtains light yellow solid.With acetone-water mixed solvent recrystallization twice, white solid, productive rate 89.8%.
The chemical equation that the present invention prepares compound is:
The compound outward appearance that the present invention obtains is white crystal, and fusing point is 233-235 DEG C; Its better heat stability, when temperature reaches 85 DEG C, weightless 1.5%, when temperature reaches 550 DEG C, weightlessness is 13.5%, 800 DEG C of charring rates is 46.3%; This compound can be dissolved in DMSO solvent.
Oneself analytical results of interior phosphoric acid ester of a kind of dioxygen containing DOPO that the present invention obtains is as follows:
Its outward appearance of compound is white solid, and fusing point is 232-235 DEG C, results of IR: FT-IR (KBr), be phenyl ring C-H stretching vibration peak near v/cm-1:3025, being P-O-Ph stretching vibration peak near 1230,1042, is P=O stretching vibration peak near 1249; Proton nmr spectra analytical results:
1h NMR (DMSO-d6,400MHz): 8.17-7.95 (m, 4H, ArH), 7.68-7.43 (m, 3H, ArH), 7.38-7.29 (m, 4H, ArH), 3.56 (s, 8H, CH
2), 0.98 (s, 12H, CH
3).
Embodiment 2:
Solvent changes THF into, and other is with example one, its target compound yield 85.1%, and fusing point is 233-235 DEG C.
Solvent changes DMF into, and other is with example one, its target compound yield 83.2%, and fusing point is 233-235 DEG C.
Embodiment 3:
The amount of intermediate II is increased to 4.79g (0.026mol), other is with example one, its target compound yield 90.5%, and fusing point is 233-235 DEG C.
Embodiment 4:
The amount of intermediate II is increased to 5.15g (0.028mol), other is with example one, its target compound yield 88.3%, and fusing point is 233-235 DEG C
Embodiment 5:
The amount of intermediate II is increased to 5.52g (0.03mol), other is with example one, its target compound yield 86.3%, and fusing point is 233-235 DEG C
Oneself interior organic phosphate flame-retardant agent of dioxygen containing DOPO provided by the invention is as follows as the application of the flame-retardant additive of epoxy resin, urethane, ABS:
Make batten according to insulating laminated sheet combustionproperty testing standard, carry out limited oxygen index (LOI) test with JF-3 type oxygen index measurer respectively, FZ-5401 type vertical combustion instrument carries out the test of UL94 vertical combustion performance, and measurement result is as following table 1-3.
The fire retardant that table 1 embodiment of the present invention 1 is synthesized is as the flame retardant effect of ethoxyline resin antiflaming additive
The fire retardant that table 2 embodiment of the present invention 1 is synthesized is as the flame retardant effect of polyurethane flame-proof additive
The fire retardant that table 3 embodiment of the present invention 1 is synthesized is as the flame retardant effect of ABS flame-retardant additive
Claims (8)
1., containing the own interior phosphate flame retardant of dioxygen of DOPO, it is characterized in that, its chemical structural formula is as follows:
This fire retardant is containing DOPO and the own interior phosphate ester structure of dioxygen.
2. the synthetic method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to claim 1, is characterized in that: comprise the following steps:
A: under nitrogen protection, joins DOPO in organic solvent and dissolves, then add para benzoquinone; stir at 90-120 DEG C and react 3-8h, after having reacted, gained throw out being cooled to room temperature and filtering, by recrystallizing methanol; can obtain intermediate I after drying, reaction equation is as follows:
B: after neopentyl glycol, chloroformic solution mixing, stir and drip phosphorus oxychloride, after dripping off, reacting 5-9h at 50-80 DEG C, after reaction terminates, chloroform and excessive phosphorus oxychloride being steamed, obtains the own interior phosphoryl chloride intermediate II of dioxygen heterocycle;
C: add organic solvent in intermediate II, stirring adds intermediate compound I after making it dissolve, drip triethylamine under ice cooling, 4, dropwise, after being warming up to 60-90 DEG C gradually, adopting TLC to follow the tracks of reaction process, after having reacted, steam solvent, filtration obtains light yellow solid, and recrystallization obtains white crystalline powder:
3. the preparation method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to claim 2, is characterized in that:
A: under nitrogen protection, joins DOPO in organic solvent and dissolves, then add para benzoquinone, stirs and react 5h at 100 DEG C, after having reacted, gained throw out is cooled to room temperature and filters, by recrystallizing methanol, can obtain intermediate I after drying;
B: after neopentyl glycol, chloroformic solution mixing, stir and drip phosphorus oxychloride, after dripping off, reacting 6h at 65 DEG C, after reaction terminates, chloroform and excessive phosphorus oxychloride being steamed, obtains the own interior phosphoryl chloride intermediate II of dioxygen heterocycle;
C: add organic solvent in intermediate II, stirring adds intermediate compound I after making it dissolve, drip triethylamine under ice cooling, 4, dropwise, after being warming up to 70 DEG C gradually, adopt TLC to follow the tracks of reaction process, solvent is steamed after having reacted, filtration obtains light yellow solid, and recrystallization obtains white crystalline powder, is the own interior phosphate flame retardant of dioxygen containing DOPO.
4. the preparation method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to Claims 2 or 3, it is characterized in that: in steps A, organic solvent is toluene, and DOPO is 1:1.1-1.5 with the ratio of the amount of substance of para benzoquinone, the weight of toluene be DOPO, para benzoquinone gross weight 8-12 doubly.
5. the preparation method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to Claims 2 or 3, it is characterized in that: in step B, neopentyl glycol is 1:1.0-1:1.5 with the ratio of the amount of substance of phosphorus oxychloride, the weight of chloroform be phosphorus oxychloride, neopentyl glycol gross weight 5-8 doubly.
6. the preparation method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to Claims 2 or 3, it is characterized in that: in step C, the ratio of the amount of substance of intermediate I, intermediate II is 1:2.3-3.0, and the weight of organic solvent is 5-9 times of intermediate I and intermediate II gross weight.
7. the preparation method of oneself interior phosphate flame retardant of the dioxygen containing DOPO according to claim 6, is characterized in that: organic solvent described in step C is any one in acetonitrile, tetrahydrofuran (THF), DMF.
8. the application of phosphate flame retardant on the flame-retardant additive of epoxy resin, urethane, ABS in the dioxygen containing DOPO described in any one described in claim 1-7 is own.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945710A (en) * | 2015-06-18 | 2015-09-30 | 宁波高新区卓尔化工科技有限公司 | Halogen-free polyethylene composition for pipe preparation |
| CN104945830A (en) * | 2015-06-18 | 2015-09-30 | 宁波高新区卓尔化工科技有限公司 | Inflaming retarding ABS plastic |
| CN104962066A (en) * | 2015-06-18 | 2015-10-07 | 宁波高新区卓尔化工科技有限公司 | Conductive flame-retardant polyphenyl ether resin composition |
| CN104962072A (en) * | 2015-06-18 | 2015-10-07 | 宁波高新区卓尔化工科技有限公司 | Flame-retardant PPO/PA (poly-p-phenylene oxide /poly-A) alloy |
| CN105038173A (en) * | 2015-06-18 | 2015-11-11 | 宁波高新区卓尔化工科技有限公司 | Halogen-free flame retardant pc/abs alloy |
| CN105295300A (en) * | 2015-09-10 | 2016-02-03 | 东华大学 | DOPO derivative flame retardant as well as preparation and application of DOPO derivative flame retardant |
| CN105693774A (en) * | 2016-03-16 | 2016-06-22 | 三峡大学 | Phosphaphenanthrene phosphate flame retardant with xenyl and preparation method and application thereof |
| CN107082909A (en) * | 2017-04-18 | 2017-08-22 | 三峡大学 | A kind of preparation method and applications of the hydroquinones biphosphonate fire retardant containing DOPO |
| WO2018095362A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Phosphaphenanthrene-structure reactive fire retardant and application thereof |
| CN111040548A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Environment-friendly flame-retardant mildew-proof powder coating |
| CN113265089A (en) * | 2020-02-17 | 2021-08-17 | 内蒙古浩普科技有限公司 | Flame retardant intermediate and preparation method and application thereof |
| CN114213462A (en) * | 2021-12-04 | 2022-03-22 | 江苏三吉利化工股份有限公司 | O-phenylenedioxy bis-neopentyl glycol phosphate and its synthesis method |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104945710A (en) * | 2015-06-18 | 2015-09-30 | 宁波高新区卓尔化工科技有限公司 | Halogen-free polyethylene composition for pipe preparation |
| CN104945830A (en) * | 2015-06-18 | 2015-09-30 | 宁波高新区卓尔化工科技有限公司 | Inflaming retarding ABS plastic |
| CN104962066A (en) * | 2015-06-18 | 2015-10-07 | 宁波高新区卓尔化工科技有限公司 | Conductive flame-retardant polyphenyl ether resin composition |
| CN104962072A (en) * | 2015-06-18 | 2015-10-07 | 宁波高新区卓尔化工科技有限公司 | Flame-retardant PPO/PA (poly-p-phenylene oxide /poly-A) alloy |
| CN105038173A (en) * | 2015-06-18 | 2015-11-11 | 宁波高新区卓尔化工科技有限公司 | Halogen-free flame retardant pc/abs alloy |
| CN105295300A (en) * | 2015-09-10 | 2016-02-03 | 东华大学 | DOPO derivative flame retardant as well as preparation and application of DOPO derivative flame retardant |
| CN105693774A (en) * | 2016-03-16 | 2016-06-22 | 三峡大学 | Phosphaphenanthrene phosphate flame retardant with xenyl and preparation method and application thereof |
| WO2018095362A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Phosphaphenanthrene-structure reactive fire retardant and application thereof |
| US10618923B2 (en) | 2016-11-23 | 2020-04-14 | Xiamen University | Preparation method of phosphaphenanthrene-structure reactive flame retardant and application thereof |
| CN107082909A (en) * | 2017-04-18 | 2017-08-22 | 三峡大学 | A kind of preparation method and applications of the hydroquinones biphosphonate fire retardant containing DOPO |
| CN111040548A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Environment-friendly flame-retardant mildew-proof powder coating |
| CN111040548B (en) * | 2019-12-27 | 2021-10-08 | 浙江新灿新材料有限公司 | Environment-friendly flame-retardant mildew-proof powder coating |
| CN113265089A (en) * | 2020-02-17 | 2021-08-17 | 内蒙古浩普科技有限公司 | Flame retardant intermediate and preparation method and application thereof |
| CN114213462A (en) * | 2021-12-04 | 2022-03-22 | 江苏三吉利化工股份有限公司 | O-phenylenedioxy bis-neopentyl glycol phosphate and its synthesis method |
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Application publication date: 20150429 |