CN105348578B - A kind of preparation method of nano level flame retardant - Google Patents
A kind of preparation method of nano level flame retardant Download PDFInfo
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- CN105348578B CN105348578B CN201510887060.4A CN201510887060A CN105348578B CN 105348578 B CN105348578 B CN 105348578B CN 201510887060 A CN201510887060 A CN 201510887060A CN 105348578 B CN105348578 B CN 105348578B
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Abstract
A kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, graphene oxide is reduced first, p-aminobenzoic acid is then grafted on graphene by redox graphene functionalization, is most followed by hexachlorocyclotriph,sphazene, its stability is further enhanced, chlorine element and P elements are grafted on graphene；I.e. graphene is fire-retardant, phosphorous flame-retardant, halogen system is fire-retardant combines, and nano level flame retardant is made.The base material that the Performances of Novel Nano-Porous meter level fire retardant can be added to includes natural rubber, ethylene propylene diene rubber, butadiene-styrene rubber, butadiene-styrene rubber, polypropylene plastics.Compared with conventional expanded type fire retardant and halogen flame, Performances of Novel Nano-Porous meter level fire retardant prepared by this method can be effectively improved conventional flame retardant bad dispersibility, resistance to surface transfer ability in material matrix are weak, addition is big, poor compatibility, the problems such as flame retardant effect is undesirable, char forming ability is weak, so as to substantially increase the compatibility between the fire resistance of composite and fire retardant and material matrix.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant.
Background technology
With the rapid development of science and technology, the means that the mankind take precautions against fire emerge in an endless stream.The fire preventions such as smoke detector, spray exist
Play an important role in fire escape, extensively praised by people.And as the invention of great significance of mankind's fireproofing technique, fire retardant is only secondary
In the second largest plastic additive of plasticizer, it is widely used in the neck such as electric, furniture fabric, construction material, vehicles
Domain.It is in fact close from us, there is its figure in mobile phone, computer, TV, dormitory, classroom, subway, high ferro.It is dumbly
One of fire wall is erected for us, prevents or slow down the generation or sprawling of fire.Halogen flame is to be found fire-retardant at first
Agent, its fire-retardant principle mainly produce a large amount of non-combustible gas using halogen element and prevent material from further burning after combustion.It is swollen
Swollen type fire retardant is the environment friendly flame retardant that a kind of development is exceedingly fast.Expansion type flame retardant is using phosphorus nitrogen as main ignition-proof element, simultaneously
One layer of uniform layer of charcoal can be produced on surface when high polymer is heated, heat-insulated, oxygen barrier, suppression cigarette simultaneously can prevent molten drop, and
Toxic gas will not be produced.
However, in order to reach preferable flame retardant effect, it usually needs add larger amount of expansion type flame retardant, this will cause
Material mechanical performance declines to a great extent.Simultaneously as conventional expanded type fire retardant is easily reunited in material matrix and and material
The reason for matrix poor compatibility, can cause fire retardant occur in material matrix it is scattered it is uneven, easily to matrix surface migrate with
And phenomena such as heat endurance difference, this leverages the fire resistance of material.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, with daily life and life
Widely used natural rubber and polypropylene plastics be as base material in production, from MOLECULE DESIGN angle tetrahydrofuran solvent
In and under conditions of nitrogen and triethylamine be catalyst, graphene functionalized is grafted P elements and halogen element generation is fire-retardant
The good nano level flame retardant of effect.
To realize the above-mentioned purpose of the present invention, the present invention provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, including
Following steps.
Step 1,1~2g p-aminobenzoic acid and 0.2~0.4g sodium hydroxides are added in reaction vessel, and addition 50~
100ml distilled water；Then 0.5~1g natrium nitrosums are slowly added at 0~5 DEG C and 5~10ml concentration is 20% HCl, and are stirred
Mix 45~60min；0.2~0.5g reduced graphenes after ultrasound are added in solution, and 3~4h is stirred at 0~5 DEG C；Will
The pH value of resulting solution is transferred to 2~3, and is dialysed 2~3 times with dialysis membrane, and products obtained therefrom then is washed into neutrality with organic solvent,
Produce benzoic acid functionalization graphene.
Step 2, by 1~3g benzoic acid functionalization graphenes, ultrasonic disperse is in 100ml tetrahydrofurans, then solution
Pour into the 500ml three-necked flasks full of nitrogen, 5~12g triethylamines are added under condition of ice bath and stir 1~2h, then are added
Enter 3~5g hexachlorocyclotriph,sphazenes and stir 2h, 5~8h is then stirred under the conditions of nitrogen charging, obtains benzoic acid/hexachlorocyclotriph,sphazene work(
Can graphite alkene, i.e. Performances of Novel Nano-Porous meter level fire retardant.
Organic solvent is ethanol, chloroform, N-N dimethylformamides in the step 1.
The base material that Performances of Novel Nano-Porous meter level fire retardant can be added to includes natural rubber, ethylene propylene diene rubber, butadiene-styrene rubber, fourth
Benzene rubber, polypropylene plastics.
Beneficial effects of the present invention compared with prior art.
The preparation method of Performances of Novel Nano-Porous meter level fire retardant provided by the invention, p-aminophenyl first is grafted first on graphene
Acid, graphene oxide is reduced, solve the easy agglomeration traits of graphene；Then hexachlorocyclotriph,sphazene is connect, by reduction-oxidation graphite
Olefinic functionality, further enhance its stability；Chlorine element in hexachlorocyclotriph,sphazene and P elements are grafted on graphene again, i.e.,
Graphene is fire-retardant, phosphorous flame-retardant, halogen system is fire-retardant combines, so as to substantially increase the fire resistance of composite and resistance
Fire the compatibility between agent and material matrix.Compared with conventional expanded type fire retardant and halogen flame, Performances of Novel Nano-Porous meter level resistance
Combustion agent can be effectively improved that conventional flame retardant bad dispersibility, resistance to surface transfer ability in material matrix are weak, addition is big, compatibility
Difference, the problems such as flame retardant effect is undesirable, char forming ability is weak.
Brief description of the drawings
Fig. 1 is the synthesis mechanism figure of benzoic 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 with reference to specific embodiment.
Embodiment 1.
Fig. 1, Fig. 2 are referred to, the present embodiment provides a kind of preparation method of Performances of Novel Nano-Porous meter level fire retardant, including following step
Suddenly.
Step 1,1g p-aminobenzoic acid and 0.3g sodium hydroxides are added in reaction vessel, and add 80ml distilled water；
Then 0.5g natrium nitrosums are slowly added at 5 DEG C and 5ml concentration is 20% HCl, and stir 50min；By the 0.4g after ultrasound
Reduced graphene is added in solution, and stirs 3h at 5 DEG C；The pH value of resulting solution is transferred to 2~3, and 3 are dialysed with dialysis membrane
It is secondary, products obtained therefrom is then washed into neutrality with organic solvent, produces benzoic acid functionalization graphene.
Step 2,1g benzoic acid functionalization graphenes are taken, then its ultrasonic disperse among 100ml tetrahydrofurans, then
Solution is poured into the 500ml three-necked flasks full of nitrogen；Then 10.82g triethylamines are added under condition of ice bath and are stirred
1.5h, then add 3g hexachlorocyclotriph,sphazenes and stir 2h, 8h is finally stirred under the conditions of nitrogen charging, obtains benzoic acid/chlordene ring
Three phosphonitrile functionalization graphenes, i.e. Performances of Novel Nano-Porous meter level fire retardant.
5 parts of the present embodiment nano level flame retardant, 100 parts of natural rubber, 1.2 parts of sulphur, accelerant CZ are taken in parts by weight
0.8 part, 0.35 part of Vulcanization accelerator TMTD, 4 parts of stearic acid, 5 parts of zinc oxide, age resistor（4010）1 part, 1 part of atoleine, carbon black
35 parts are placed in mill, are kneaded at a temperature of 55 DEG C, produce 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.
Steps 1 and 2 g p-aminobenzoic acid and 0.4g sodium hydroxides are added in reaction vessel, and add 100ml distilled water；
Then 0.8g natrium nitrosums are slowly added at 5 DEG C and 10ml concentration is 20% HCl, and stir 55min；After ultrasound
0.5g reduced graphenes are added in solution, and stir 3.5h at 5 DEG C；The pH value of resulting solution is transferred to 2~3, and with dialysis
Film is dialysed 2 times, and products obtained therefrom then is washed into neutrality with organic solvent, produces benzoic acid functionalization graphene.
Step 2,2g benzoic acid functionalization graphenes are taken, then its ultrasonic disperse among 100ml tetrahydrofurans, then
Solution is poured into the 500ml three-necked flasks full of nitrogen.Then 11g triethylamines are added under condition of ice bath and stir 2h,
Then 4g hexachlorocyclotriph,sphazenes are added and stir 2h, 6h is finally stirred under the conditions of nitrogen charging, obtains benzoic acid/hexachlorocyclotriph,sphazene
Functionalization graphene, i.e. Performances of Novel Nano-Porous meter level fire retardant.
5 parts of the present embodiment nano level flame retardant, 100 parts of thermoplastic base-material polypropylene are taken in parts by weight, carry silver-colored phosphorus
Sour 15 parts of zirconium inorganic antiseptic, 0.3 part of dispersant stearic acid, 0.3 part of aluminate coupling agent, 1 part of maleic anhydride toughener, tristearin
Sour 1 part of stable sodium agent, processing temperature are 180 DEG C, and single-size is made through the disengaging pelletizing of double-screw extruding pelletizing unit, produces resistance
Fire plastics.
Claims (2)
1. a kind of preparation method of nano level flame retardant, it is characterised in that comprise the following steps：
Step 1,1~2g p-aminobenzoic acid and 0.2~0.4g sodium hydroxides are added in reaction vessel, and addition 50~
100ml distilled water；Then 0.5~1g natrium nitrosums are slowly added at 0~5 DEG C and 5~10ml concentration is 20% HCl, and are stirred
Mix 45~60min；0.2~0.5g reduced graphenes after ultrasound are added in solution, and 3~4h is stirred at 0~5 DEG C；Will
The pH value of resulting solution is transferred to 2~3, and is dialysed 2~3 times with dialysis membrane, and products obtained therefrom then is washed into neutrality with organic solvent,
Produce benzoic acid functionalization graphene；
Step 2, then 1~3g benzoic acid functionalization graphenes, ultrasonic disperse pour into solution in 100ml tetrahydrofurans
In 500ml three-necked flasks full of nitrogen, 5~12g triethylamines are added under condition of ice bath and stir 1~2h, add 3~
5g hexachlorocyclotriph,sphazenes simultaneously stir 2h, and 5~8h is then stirred under the conditions of nitrogen charging, obtains benzoic acid/hexachlorocyclotriph,sphazene functionalization
Graphene, i.e. nano level flame retardant.
2. the preparation method of nano level flame retardant as claimed in claim 1, it is characterised in that organic solvent in the step 1
For ethanol, chloroform or N-N dimethylformamides.
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| CN106146922B (en) * | 2016-07-04 | 2018-06-22 | 沈阳化工大学 | A kind of flame retarding function rubber and preparation method thereof |
| 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 |
| CN108611880B (en) * | 2018-04-27 | 2021-01-22 | 新乡市新科防护科技有限公司 | Durable flame-retardant, conductive and grey-black dyeing one-step processing method for cotton fabric |
| CN109912845B (en) * | 2019-02-22 | 2020-12-04 | 四川大学 | Epoxy-terminated modified graphene oxide and epoxy nanocomposite 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 |
| CN113174087B (en) * | 2021-05-06 | 2022-04-01 | 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 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 |
| 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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- 2015-11-27 CN CN201510887060.4A patent/CN105348578B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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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. |