CN105348578A - Preparation method of novel nanoscale fire retardant - Google Patents
Preparation method of novel nanoscale fire retardant Download PDFInfo
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- CN105348578A CN105348578A CN201510887060.4A CN201510887060A CN105348578A CN 105348578 A CN105348578 A CN 105348578A CN 201510887060 A CN201510887060 A CN 201510887060A CN 105348578 A CN105348578 A CN 105348578A
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Abstract
A preparation method of a novel nanoscale fire retardant comprises the following steps: first, performing reduction on oxidized graphene; then, grafting para aminobenzoic acid on graphene to functionalize reduced graphene oxide; finally, grafting phosphonitrilic chloride trimer to further enhance the stability, and grafting chlorine element and phosphorus element on graphene, that is, combining a graphene flame retardant, a phosphorus flame retardant and a halogen flame retardant to prepare the nanoscale flame retardant. Base materials into which the novel nanoscale flame retardant can be added comprise natural rubber, EPDM (Ethylene Propylene Diene Monomer), butadiene styrene rubber and polypropene plastics. Compared with a traditional intumescent flame retardant and a traditional halogen flame retardant, the novel nanoscale flame retardant prepared by the preparation method can effectively solve the problems that the traditional flame retardant is poor in dispersity in material base bodies, weak in surface migration resisting capability, large in addition amount, poor in compatibility, un-ideal in flame-retardant effect, weak in carbon forming capability and the like, so that the flame retardant property of the composite and the compatibility between the flame retardant and the material base body are greatly improved.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant.
Background technology
Along with the develop rapidly of science and technology, the means that the mankind take precautions against fire emerge in an endless stream.The fire prevention such as smoke detector, spray plays an important role in fire escape, extensively praises by people.And as the invention of great significance of mankind's fireproofing technique, fire retardant is the second largest plastics additive being only second to softening agent, is widely used in electric, the field such as furniture fabric, material of construction, vehicles.It in fact from we very close to, have its figure in mobile phone, computer, TV, dormitory, classroom, subway, high ferro.It erects one fireproof brickwork for us dumbly, stops or slows down the generation of fire or spread.Halogen flame is the fire retardant be found at first, its fire-retardant principle mainly utilize halogen element produce after combustion a large amount of non-combustible gas stop material burn further.Expansion type flame retardant is that a class develops the environment friendly flame retardant be exceedingly fast.Expansion type flame retardant is main ignition-proof element with phosphorus nitrogen, simultaneously can produce the uniform layer of charcoal of one deck on surface when superpolymer is heated, and heat insulation, oxygen barrier, presses down cigarette and can prevent molten drop, and can not produce toxic gas.
But in order to reach desirable flame retardant effect, usually need to add relatively large expansion type flame retardant, this will cause declining to a great extent of material mechanical performance.Simultaneously, due to conventional expanded type fire retardant easy reunion and the reason with material matrix poor compatibility in material matrix, fire retardant can be caused to occur in material matrix, and dispersion is uneven, easily to phenomenons such as matrix surface migration and poor heat stability, this have impact on the flame retardant properties of material greatly.
Summary of the invention
For the problems referred to above, the invention provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, in daily life and production, widely used natural rubber and acrylic plastering are as base material, in the solvent of tetrahydrofuran (THF) and under nitrogen and triethylamine be the condition of catalyzer, graphene functionalized grafting phosphoric and halogen element are generated the nano level flame retardant of good flame retardation effect from molecular designing angle.
For realizing above-mentioned purpose of the present invention, the invention provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, comprising the following steps.
Step 1,1 ~ 2g para-amino benzoic acid and 0.2 ~ 0.4g sodium hydroxide join in reaction vessel, and add 50 ~ 100ml distilled water; Then at 0 ~ 5 DEG C, slowly add 0.5 ~ 1g Sodium Nitrite and 5 ~ 10ml concentration is the HCl of 20%, and stir 45 ~ 60min; 0.2 ~ 0.5g reduced graphene after ultrasonic is joined in solution, and stirs 3 ~ 4h at 0 ~ 5 DEG C; The pH value of gained solution is transferred to 2 ~ 3, and with dialysis membrane dialysis 2 ~ 3 times, then products obtained therefrom organic solvent is washed neutrality, obtain phenylformic acid functionalization graphene.
Step 2, by 1 ~ 3g phenylformic acid functionalization graphene, ultrasonic disperse is in 100ml tetrahydrofuran (THF), then solution being poured into is full of in the 500ml there-necked flask of nitrogen, under condition of ice bath, add 5 ~ 12g triethylamine and stir 1 ~ 2h, add 3 ~ 5g hexachlorocyclotriphosphazene again and stir 2h, then filling stirring 5 ~ 8h under nitrogen condition, phenylformic acid/hexachlorocyclotriphosphazene functionalization graphene is obtained, i.e. Performances of Novel Nano-Porous meter level fire retardant.
In described step 1, organic solvent is ethanol, chloroform, N-N dimethyl formamide.
The base material that Performances of Novel Nano-Porous meter level fire retardant can add to comprises natural rubber, terpolymer EP rubber, styrene-butadiene rubber(SBR), styrene-butadiene rubber(SBR), acrylic plastering.
Compared with prior art beneficial effect of the present invention.
The preparation method of Performances of Novel Nano-Porous meter level fire retardant provided by the invention, first grafting para-amino benzoic acid on Graphene, reduce graphene oxide, solve the easy agglomeration traits of Graphene; Then connect hexachlorocyclotriphosphazene, by redox graphene functionalization, strengthen its stability further; Again chlorine element and phosphoric in hexachlorocyclotriphosphazene are grafted on Graphene, namely fire-retardant, the phosphorous flame-retardant of Graphene, halogen system is fire-retardant combines, thus substantially increases the flame retardant properties of matrix material and the consistency between fire retardant and material matrix.Compare with halogen flame with conventional expanded type fire retardant, this Performances of Novel Nano-Porous meter level fire retardant effectively can improve the problems such as conventional flame retardant bad dispersibility, resistance to surface transfer ability in material matrix are weak, addition large, poor compatibility, flame retardant effect are undesirable, become charcoal ability weak.
Accompanying drawing explanation
Fig. 1 is the synthesis mechanism figure of phenylformic acid functionalization graphene.
Fig. 2 is the synthesis mechanism figure of Performances of Novel Nano-Porous meter level fire retardant of the present invention.
Embodiment
The present invention is further described below in conjunction with specific embodiment.
Embodiment 1.
Refer to Fig. 1, Fig. 2, the present embodiment provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, comprises the following steps.
Step 1,1g para-amino benzoic acid and 0.3g sodium hydroxide join in reaction vessel, and add 80ml distilled water; Then at 5 DEG C, slowly add 0.5g Sodium Nitrite and 5ml concentration is the HCl of 20%, and stir 50min; 0.4g reduced graphene after ultrasonic is joined in solution, and stirs 3h at 5 DEG C; The pH value of gained solution is transferred to 2 ~ 3, and dialyses 3 times with dialysis membrane, then products obtained therefrom organic solvent is washed neutrality, obtain phenylformic acid functionalization graphene.
Step 2, get 1g phenylformic acid functionalization graphene, then its ultrasonic disperse in the middle of 100ml tetrahydrofuran (THF), then solution is poured into and is full of in the 500ml there-necked flask of nitrogen; Then under condition of ice bath, add 10.82g triethylamine and stir 1.5h, then add 3g hexachlorocyclotriphosphazene and stir 2h, finally stirring 8h filling under nitrogen condition, obtain phenylformic acid/hexachlorocyclotriphosphazene functionalization graphene, i.e. Performances of Novel Nano-Porous meter level fire retardant.
Get the present embodiment nano level flame retardant 5 parts by weight, natural rubber 100 parts, 1.2 parts, sulphur, accelerant CZ 0.8 part, Vulcanization accelerator TMTD 0.35 part, stearic acid 4 parts, 5 parts, zinc oxide, (4010) 1 parts, anti-aging agent, whiteruss 1 part, carbon black 35 parts be placed in mill, mixing at the temperature of 55 DEG C, obtain flame retardant rubber.
Embodiment 2.
The present embodiment provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, comprises the following steps.
Step 1,2g para-amino benzoic acid and 0.4g sodium hydroxide join in reaction vessel, and add 100ml distilled water; Then at 5 DEG C, slowly add 0.8g Sodium Nitrite and 10ml concentration is the HCl of 20%, and stir 55min; 0.5g reduced graphene after ultrasonic is joined in solution, and stirs 3.5h at 5 DEG C; The pH value of gained solution is transferred to 2 ~ 3, and dialyses 2 times with dialysis membrane, then products obtained therefrom organic solvent is washed neutrality, obtain phenylformic acid functionalization graphene.
Step 2, get 2g phenylformic acid functionalization graphene, then its ultrasonic disperse in the middle of 100ml tetrahydrofuran (THF), then solution is poured into and is full of in the 500ml there-necked flask of nitrogen.Then under condition of ice bath, add 11g triethylamine and stir 2h, then add 4g hexachlorocyclotriphosphazene and stir 2h, finally stirring 6h filling under nitrogen condition, obtain phenylformic acid/hexachlorocyclotriphosphazene functionalization graphene, i.e. Performances of Novel Nano-Porous meter level fire retardant.
Get the present embodiment nano level flame retardant 5 parts, thermoplastics base-material polypropylene 100 parts, silver-loaded zirconium phosphate inorganic antiseptic 15 parts, dispersion agent stearic acid 0.3 part, aluminate coupling agent 0.3 part, maleic anhydride toughner 1 part, sodium stearate stablizer 1 part by weight; processing temperature is 180 DEG C; make single-size through double-screw extruding pelletizing unit turnover pelletizing, obtain flame retardant plastics.
Claims (3)
1. a preparation method for Performances of Novel Nano-Porous meter level fire retardant, is characterized in that, comprises the following steps:
Step 1,1 ~ 2g para-amino benzoic acid and 0.2 ~ 0.4g sodium hydroxide join in reaction vessel, and add 50 ~ 100ml distilled water; Then at 0 ~ 5 DEG C, slowly add 0.5 ~ 1g Sodium Nitrite and 5 ~ 10ml concentration is the HCl of 20%, and stir 45 ~ 60min; 0.2 ~ 0.5g reduced graphene after ultrasonic is joined in solution, and stirs 3 ~ 4h at 0 ~ 5 DEG C; The pH value of gained solution is transferred to 2 ~ 3, and with dialysis membrane dialysis 2 ~ 3 times, then products obtained therefrom organic solvent is washed neutrality, obtain phenylformic acid functionalization graphene;
Step 2, by 1 ~ 3g phenylformic acid functionalization graphene, ultrasonic disperse is in 100ml tetrahydrofuran (THF), then solution being poured into is full of in the 500ml there-necked flask of nitrogen, under condition of ice bath, add 5 ~ 12g triethylamine and stir 1 ~ 2h, add 3 ~ 5g hexachlorocyclotriphosphazene again and stir 2h, then filling stirring 5 ~ 8h under nitrogen condition, phenylformic acid/hexachlorocyclotriphosphazene functionalization graphene is obtained, i.e. Performances of Novel Nano-Porous meter level fire retardant.
2. organic solvent as claimed in claim 1, it is characterized in that, in described step 1, organic solvent is ethanol, chloroform, N-N dimethyl formamide etc.
3. Performances of Novel Nano-Porous meter level fire retardant as claimed in claim 1, it is characterized in that, the base material that described Performances of Novel Nano-Porous meter level fire retardant can add to is: natural rubber, terpolymer EP rubber, styrene-butadiene rubber(SBR), styrene-butadiene rubber(SBR), acrylic plastering etc.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146922A (en) * | 2016-07-04 | 2016-11-23 | 沈阳化工大学 | A kind of anti-flaming function rubber and preparation method thereof |
| CN106632958A (en) * | 2016-09-29 | 2017-05-10 | 四川大学 | Method for preparing a flame-retardant water-based polyurethane based on reactive graphene flame retardant |
| CN107090107A (en) * | 2017-06-12 | 2017-08-25 | 泉州信和石墨烯研究院有限公司 | Abrasive rubber that a kind of graphene is modified and preparation method thereof |
| CN108611880A (en) * | 2018-04-27 | 2018-10-02 | 新乡市新科防护科技有限公司 | A kind of cotton fabric durable flame-retardant, conduction and grey black dye a step processing method |
| CN109912845A (en) * | 2019-02-22 | 2019-06-21 | 四川大学 | A kind of graphene oxide and its epoxy nano composite material that epoxy radicals end-blocking is modified |
| CN110615928A (en) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
| WO2022233108A1 (en) * | 2021-05-06 | 2022-11-10 | 福建师范大学泉港石化研究院 | Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method therefor |
| CN116925541A (en) * | 2022-06-13 | 2023-10-24 | 台州俪盛塑料有限公司 | Halogen-free environment-friendly flame-retardant nylon with high glow wire |
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| CN103407999A (en) * | 2013-07-21 | 2013-11-27 | 西北工业大学 | Method for microwave-assisted preparation of hyperbranched polycyclophosphazene grafted graphene |
| CN104910447A (en) * | 2015-05-28 | 2015-09-16 | 沈阳化工大学 | Flame-retardant rubber |
| CN105037801A (en) * | 2015-08-03 | 2015-11-11 | 苏州大学 | Phosphorus-containing hybridization graphene oxide and preparation method thereof |
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| CN103407999A (en) * | 2013-07-21 | 2013-11-27 | 西北工业大学 | Method for microwave-assisted preparation of hyperbranched polycyclophosphazene grafted graphene |
| CN104910447A (en) * | 2015-05-28 | 2015-09-16 | 沈阳化工大学 | Flame-retardant rubber |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146922A (en) * | 2016-07-04 | 2016-11-23 | 沈阳化工大学 | A kind of anti-flaming function rubber and preparation method thereof |
| CN106632958A (en) * | 2016-09-29 | 2017-05-10 | 四川大学 | Method for preparing a flame-retardant water-based polyurethane based on reactive graphene flame retardant |
| CN106632958B (en) * | 2016-09-29 | 2019-04-12 | 四川大学 | The preparation method of fire-retardant water-based polyurethane based on response type Graphene fire retardant |
| CN107090107A (en) * | 2017-06-12 | 2017-08-25 | 泉州信和石墨烯研究院有限公司 | Abrasive rubber that a kind of graphene is modified and preparation method thereof |
| CN108611880A (en) * | 2018-04-27 | 2018-10-02 | 新乡市新科防护科技有限公司 | A kind of cotton fabric durable flame-retardant, conduction and grey black dye a step processing method |
| CN109912845A (en) * | 2019-02-22 | 2019-06-21 | 四川大学 | A kind of graphene oxide and its epoxy nano composite material that epoxy radicals end-blocking is modified |
| CN110615928A (en) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
| CN110615928B (en) * | 2019-09-30 | 2022-03-08 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
| WO2022233108A1 (en) * | 2021-05-06 | 2022-11-10 | 福建师范大学泉港石化研究院 | Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method therefor |
| CN116925541A (en) * | 2022-06-13 | 2023-10-24 | 台州俪盛塑料有限公司 | Halogen-free environment-friendly flame-retardant nylon with high glow wire |
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| CN105348578B (en) | 2017-11-10 |
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Address after: 110141 Yao village, Yuhong Township, Yuhong District, Liaoning, Shenyang Applicant after: Shenyang Shunfeng New Materials Co., Ltd Address before: 110141 Yao village, Yuhong Township, Yuhong District, Liaoning, Shenyang Applicant before: Shenyang Shunfeng Metro Building Materials Co., Ltd. |
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Address after: 110141 Yao village, Yuhong Township, Yuhong District, Liaoning, Shenyang Patentee after: Liaoning Shunfeng New Material Technology Co.,Ltd. Address before: 110141 Yao village, Yuhong Township, Yuhong District, Liaoning, Shenyang Patentee before: SHENYANG SHUNFENG NEW MATERIAL Co.,Ltd. |