CN102336403A - Preparation method of high-flame-retardancy expandable graphite - Google Patents
Preparation method of high-flame-retardancy expandable graphite Download PDFInfo
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- CN102336403A CN102336403A CN2011101793543A CN201110179354A CN102336403A CN 102336403 A CN102336403 A CN 102336403A CN 2011101793543 A CN2011101793543 A CN 2011101793543A CN 201110179354 A CN201110179354 A CN 201110179354A CN 102336403 A CN102336403 A CN 102336403A
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Abstract
The invention relates to a preparation method of high-flame-retardancy expandable graphite, which comprises the following steps: oxidizing graphite by using concentrated sulfuric acid/nitric acid mixture, nitric acid/phosphoric acid mixture, fuming nitric acid or concentrated sulfuric acid together with a solid strong oxidizer which accounts for 5-60 wt% of graphite, wherein the reaction temperature is 15-50 DEG C, and the reaction time is 10-100 minutes; after the reaction finishes, filtering, and washing with water until the pH value is 4-7, thereby obtaining the primary expandable graphite; and reacting the primary expandable graphite with guanidine salt solution at 20-80 DEG C for 20-200 minutes, carrying out repeated vacuum filtration, washing with water until the pH value is 6-7, and baking at 40-80 DEG C for 10-72 hours to obtain the high-flame-retardancy expandable graphite. The method provided by the invention intercalates guanidine salts into the interlayer of the expandable graphite, enhances the expansion ratio and flame retardancy, and can be widely used for flame retardancy for plastics, rubber, paint, foam and various other materials.
Description
Technical field
The present invention relates to a kind of graphite material preparation method, be specifically related to a kind of preparation method of high fire resistance property expandable graphite.
Background technology
Expansible black lead be natural flake graphite through the oxidation intercalation, between graphite flake layer, insert foreign atom, molecule or ion, and the novel cpd that forms with interlayer intercalation thing.When expansible black lead received high temperature action, interlayer intercalation thing received high hot vaporization rapidly, and the gas of formation produces the huge power that supports to graphite flake layer, and expansible black lead is expanded, and expansion multiple arrives hundreds of times up to tens of times.The charcoal layer that generates has splendid oxidation-resistance and high thermal resistance, can protect the material under the charcoal layer, reaches the purpose of fire-retardant fireproof.Expansible black lead is compared with conventional flame retardant has following characteristic: nontoxic, and low cigarette, rate of combustion is low, HRR is low, environment is safe from harm; Adapt to the development trend of fire retardant material, thereby obtained to pay close attention to widely, lot of documents or patent report the Preparation of Expansible Graphite method; Wherein adopt SRM 935a, nitric acid, an ammonium nitrate, Potcrate, ydrogen peroxide 50, potassium permanganate etc. as oxygenant usually, prepare as intercalator with sulfuric acid, phosphoric acid, organic acid, organic cpds etc., related patent U.S. Patent No. has: CNl462724A; CNl1884060A, CNl613757A, CNl01327926A; CNl01786618A, CN101100297A etc.
But the expansion thermal insulation layer that expansible black lead mainly leans on own vol to expand to be formed delays or the burning of inhibitory substance, and is not taken place between the fire-retardant thing or rare chemical action, is typical condensed phase fire retardant mechanism; The expansible black lead carbon-coating that the back forms that expands, adhesive power to each other a little less than, after by fire-retardant thing matrix burning; Can't form firm expansion charcoal layer, under the effect of flame pressure or heat convection current, the expanded graphite layer on surface possibly destroyed; Form " flying dust ", cause the forfeiture of adiabatic expansion layer, and then cause unburned material and lighted; Flame continues to propagate, so flame retarding efficiency is limited.And expansible black lead often shows intensive " candle wick effect " when flame-retardant polymer, and this has also weakened its fire retardancy to a certain extent.Therefore, expansible black lead is also more limited in the practical application of flame retardant area.Han Zhidong etc. insert graphite layers with a kind of P contained compound ammonium polyphosphate with flame retardant resistance and have prepared the expansible black lead with high flame retardant; Li Juan etc. have processed another kind of high fire resistance property expandable graphite with trimeric cyanamide or derivatives thereof intercalation to graphite layers.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists; A kind of preparation method of high fire resistance property expandable graphite is provided; The guanidinesalt insertion graphite layers preparation that the present invention will have flame retardant resistance has high fire resistance property expandable graphite, the expansible black lead good flame retardation effect of acquisition, high, the generation gas toxicological harmless of rate of expansion.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the nitration mixture, nitrosonitric acid or the vitriol oil that adopt nitration mixture, nitric acid and the phosphoric acid of the vitriol oil and nitric acid; With consumption be 5%～60% the solid strong oxidizer graphite oxide together of graphite quality; Temperature of reaction is 15～50 ℃; React after 10～100 minutes, it is 4～7 that filtered water is washed till pH, obtains elementary expansible black lead; Then, under 20～80 ℃ temperature, react, react after 20～200 minutes elementary expansible black lead and guanidinesalt solution, repeatedly suction filtration, wash to pH be 6～7,40～80 ℃ of down oven dry 10～72 hours, make high fire resistance property expandable graphite then.
The massfraction of above-mentioned nitrosonitric acid >=95%, the massfraction of the vitriol oil are 95%～98%, and the massfraction of phosphoric acid >=85%, the massfraction of nitric acid are 65%～68%.
Above-mentioned nitration mixture can be that volume ratio is (1～5): 1 the vitriol oil mixes with nitric acid, and also can be that volume ratio is (8～12): 1 nitric acid mixes with phosphoric acid.
Above-mentioned graphite is artificial or natural crystalline flake graphite, and its granularity is 30～800 orders.
Above-mentioned solid strong oxidizer is SRM 935a or potassium permanganate or ammonium persulphate or an ammonium nitrate.
The mass ratio of the above-mentioned graphite and the vitriol oil or nitration mixture is 1: (2～10);
The mass ratio of above-mentioned graphite and solid strong oxidizer is 1: (0.05～0.6);
Above-mentioned guanidinesalt solution is meant any or several kinds of guanidinesalt aqueous solution that water-soluble back forms in the guanidinesalts such as guanidine sulfate, Guanidinium hydrochloride, Guanidine Sulfamate 99, Guanidinium carbonate, biphosphate guanidine, phosphoric acid hydrogen two guanidines, polyphosphoric acid guanidine, phosphoric acid biguanides; Or with any or several kinds and phosphatase reaction in the guanidinesalts such as guanidine sulfate, Guanidinium hydrochloride, Guanidine Sulfamate 99, Guanidinium carbonate; Constantly stir; 35 ~ 40 ℃ of down heating, and with the back guanidinesalt phosphoric acid solution of formation in pH value to 2～9 of the phosphoric acid regulator solution of massfraction 85%.
Compared with prior art, the present invention has following beneficial effect:
Guanidinesalt is one type of environment friendly flame retardant, and is best with the flame retardant resistance of phosphoguanidine in the guanidinesalt fire retardant, and guanidinesalt is a kind of water miscible, fire retardant that can self foaming and intumescing, is used for the expansion type flame-retarding agent prescription, can serve as acid source and source of the gas simultaneously, plays dual function.Guanidinesalt is thermal endothermic decomposition at high temperature, and nitrogen moiety decomposes rapidly, absorbs a large amount of heats, and cooling effect is played on the thermal insulation layer surface, reduces the further transmission of heat, thus the ablation that slows down lower floor's thermal insulation layer; Carbonic acid gas, nitrogen, ammonia and water vapour etc. do not fire or difficult combustion gas body has diluted oxygen concentration through emitting when being heated simultaneously, have played the dilution fire retardation; The present invention enters into the guanidinesalt intercalation between expansible black lead, and but a large amount of gases are emitted in guanidinesalt decomposition at high temperature, and expansible black lead is strutted, and effectively promote graphite expansion to form adiabatic carbon-coating, play heat insulation the combustion effect, thereby obtain following effect:
1. the inventive method is inserted graphite layers with guanidinesalt; The initial expansion temperature of the high fire resistance property expandable graphite that obtains changes with guanidinesalt is different; Between 200～280 ℃; Be complementary with the complete processing of macromolecular material, can be widely used in the fire-retardant of multiple materials such as plastics, rubber, coating, foam;
2. the expansible black lead of the inventive method preparation; Guanidinesalt is at high temperature emitted gas in combustion processes; Effectively raise the rate of expansion of expansible black lead; Can effectively control the rate of expansion of expansible black lead through the kind that changes guanidinesalt, be the expansible black lead of intercalator with sulfuric acid than tradition, can improve rate of expansion 10～50ml/g;
3. can promote into charcoal after the burning of guanidine radicals phosphoric acid salt in the inventive method; The melt that forms is the exhausted hotbed of carbon of adhesion effectively; The gas of emitting is not for firing or difficult combustion gas body; Flying dust and candle wick effect to traditional expansible black lead occurred have some improvement, and the fire-retardant material of the expansible black lead of the present invention's preparation has advantages such as rate of combustion is low, HRR is low when burning;
4. intercalation material adopts guanidinesalt in the inventive method, and guanidinesalt is only emitted carbonic acid gas, nitrogen, ammonia and water vapour etc. in combustion processes, not halogen-containing, low toxicity, environmental protection.
Embodiment
Embodiment 1:
Common Preparation of Expansible Graphite method, being dissolved in 25 milliliters of massfractions to 1 grammes per square metre potassiumchromate is in 98% the vitriol oil; Then 10 grams, 50 order natural flake graphites are poured into wherein; 30 ℃ down between in stir and standing and reacting after 30 minutes, the pH that extremely filtrates of suction filtration, washing is 6～7 repeatedly; In baking oven,, obtain common expansible black lead product in 50 ℃ of oven dry 24 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 240 ml/g.
Embodiment 2:
The preparation method of high fire resistance property expandable graphite, being dissolved in 25 milliliters of massfractions to 1 grammes per square metre potassiumchromate is in 98% the vitriol oil, makes solution A; Be dissolved in 15 gram Guanidinium carbonates in 30 milliliters the phosphoric acid, make solution B; Then 10 grams, 50 order natural flake graphites are poured in the solution A, 30 ℃ down between in stir and standing and reacting after 30 minutes, the pH that suction filtration, repeated water washing, suction filtration are extremely filtrated is 4～5, obtains elementary expansible black lead; Then elementary expansible black lead is dropped in the solution B again, 30 ℃ down between in stir and leave standstill 80 minutes after, repeatedly suction filtration, washing to the pH that filtrates be 6～7; In baking oven,, obtain high fire resistance property expandable graphite in 50 ℃ of oven dry 24 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 256 ml/g.
Embodiment 3:
The preparation method of high fire resistance property expandable graphite, being dissolved in 90 milliliters of massfractions to 8 grammes per square metre potassiumchromates is in 98% the vitriol oil, makes solution A; Be dissolved in 45 gram Guanidinium carbonates in 90 milliliters the phosphoric acid, make solution B; Then 30 grams, 325 order natural flake graphites are poured in the solution A, 30 ℃ down between in stir and standing and reacting after 15 minutes, the pH that suction filtration, repeated water washing, suction filtration are extremely filtrated is 5.5～6.5, obtains elementary expansible black lead; Then elementary expansible black lead is dropped in the solution B again, 30 ℃ down between in stir and leave standstill 120 minutes after, repeatedly suction filtration, washing to the pH that filtrates be 6～7; In baking oven,, obtain high fire resistance property expandable graphite in 40 ℃ of oven dry 48 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 55 ml/g.
Comparative example: sample for preparing in the above-mentioned instance and microcapsule red phosphorus etc. are composite, add in the Vestolen PP 7052, when addition was 25-35phr, the polyacrylic oxygen index of obtained flame-retardant was 27%～30%.
Embodiment 4:
The preparation method of high fire resistance property expandable graphite, being dissolved in 25 milliliters of massfractions to 1 grammes per square metre potassiumchromate is in 98% the vitriol oil, makes solution A; Be dissolved in 30 gram Guanidine Sulfamate 99s in 40 milliliters the deionized water, make solution B; Then 10 grams, 50 order natural flake graphites are poured in the solution A, 30 ℃ down between in stir and standing and reacting after 30 minutes, the pH that suction filtration, repeated water washing, suction filtration are extremely filtrated is 4～5, obtains elementary expansible black lead; Then elementary expansible black lead is dropped in the solution B again, 30 ℃ down between in stir and leave standstill 60 minutes after, suction filtration, washing to the pH that filtrates be 6～7; In baking oven,, obtain high fire resistance property expandable graphite in 50 ℃ of oven dry 24 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 265 ml/g.
Embodiment 5:
The preparation method of high fire resistance property expandable graphite in ice-water bath, is 98% H with the 25ml massfraction
2SO
4Slowly splash into the 8ml massfraction and be 65% HNO
3In process nitration mixture A; Be dissolved in 10 gram Guanidinium carbonates in 30 milliliters the deionized water, make solution B; Then, 10g 50 order natural flake graphites are distributed to through stirring among the nitration mixture A and form pulpous state suspension-s; Then, when stirring, in suspension-s, add 2.4 gram potassium permanganate in batches, under 30 ℃, stir in, react after 30 minutes, suction filtration, repeated water washing, the suction filtration extremely pH of filtrating are 4～5, obtain elementary expansible black lead; Then elementary expansible black lead is taken out a part and drops into again in the solution B, 30 ℃ down between in stir and leave standstill 200 minutes after, suction filtration, washing are to the pH 6～7 that filtrates; In baking oven,, obtain high fire resistance property expandable graphite in 40 ℃ of oven dry 72 hours.With microwave oven 700W firepower heating 30 seconds, recording elementary expansible black lead allowance for expansion was 190ml/g in quartz beaker, and the high fire resistance property expandable graphite allowance for expansion is 230ml/g.
Embodiment 6:
The preparation method of high fire resistance property expandable graphite.With the 2ml massfraction 85% H
3PO
4Slowly splash into the 20ml massfraction and be 65% HNO
3In process nitration mixture A; Be dissolved in 15 gram Guanidinium carbonates in 30 milliliters the phosphoric acid, make solution B; Then, 10g 50 order natural flake graphites are distributed to through stirring among the nitration mixture A and form pulpous state graphite mud; Then, when stirring, in graphite mud, add 3.2 gram potassium permanganate in batches, under 50 ℃, stir in, react after 60 minutes, suction filtration, repeated water washing, the suction filtration extremely pH of filtrating are about 5, obtain elementary expansible black lead.Then elementary expansible black lead is dropped in the solution B again, 30 ℃ down between in stir and leave standstill 150 minutes after, suction filtration, washing are to the pH 6～7 that filtrates; In baking oven,, obtain high fire resistance property expandable graphite in 50 ℃ of oven dry 36 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 260 ml/g.
Embodiment 7:
The preparation method of high fire resistance property expandable graphite is distributed to 10g 50 order natural flake graphites in the nitrosonitric acid of 20ml massfraction >=95% through stirring; Then, when stirring, in suspension-s, add 1.4 grammes per square metre potassiumchromates in batches, under 25 ℃, stir in, react after 45 minutes, suction filtration, repeated water washing, the suction filtration extremely pH of filtrating are 5～6, obtain elementary expansible black lead; Then elementary expansible black lead is put in the guanidine sulfate solution (10 gram guanidine sulfates are dissolved in 30 milliliters deionized water) again, 40 ℃ down between in stir and leave standstill 120 minutes after, suction filtration, washing to the pH that filtrates be about 7; In baking oven,, obtain high fire resistance property expandable graphite in 50 ℃ of oven dry 24 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 280 ml/g.
Embodiment 8:
The preparation method of high fire resistance property expandable graphite, being dissolved in 90 milliliters of massfractions to 9 gram ammonium persulphates is in 98% the vitriol oil, makes solution A; Be dissolved in 40 gram Guanidinium carbonates in 90 milliliters the phosphoric acid, make solution B; Then 30 grams, 325 order natural flake graphites are poured in the solution A, 30 ℃ down between in stir and standing and reacting after 20 minutes, the pH that suction filtration, repeated water washing, suction filtration are extremely filtrated is 5.5～6.5, obtains elementary expansible black lead; Then elementary expansible black lead is dropped in the solution B again, 30 ℃ down between in stir and leave standstill 120 minutes after, repeatedly suction filtration, washing to the pH that filtrates be 6～7; In baking oven,, obtain high fire resistance property expandable graphite in 50 ℃ of oven dry 40 hours.Press the method for GB 10698-89 " expansible black lead " regulation, the allowance for expansion that in 950 ℃ of resistance furnaces, records is 50 ml/g.
Claims (7)
1. the preparation method of a high fire resistance property expandable graphite; It is characterized in that: the nitration mixture, nitrosonitric acid or the vitriol oil that adopt nitration mixture, nitric acid and the phosphoric acid of the vitriol oil and nitric acid; With consumption be 5%～60% the solid strong oxidizer graphite oxide together of graphite quality, temperature of reaction is 15～50 ℃, reacts after 10～100 minutes; It is 4～7 that filtered water is washed till pH, obtains elementary expansible black lead; Then, under 20～80 ℃ temperature, react, react after 20～200 minutes elementary expansible black lead and guanidinesalt solution, repeatedly suction filtration, wash to pH be 6～7,40～80 ℃ of down oven dry 10～72 hours, make high fire resistance property expandable graphite then.
2. the preparation method of high fire resistance property expandable graphite according to claim 1 is characterized in that: described guanidinesalt solution is any or several kinds of solution that water-soluble back forms in the guanidinesalts such as guanidine sulfate, Guanidinium hydrochloride, Guanidine Sulfamate 99, Guanidinium carbonate, biphosphate guanidine, phosphoric acid hydrogen two guanidines, polyphosphoric acid guanidine, phosphoric acid biguanides; Or with any or several kinds and phosphatase reaction in guanidine sulfate, Guanidinium hydrochloride, Guanidine Sulfamate 99, the Guanidinium carbonate, constantly stir, and be heated under 35 ~ 40 ℃ and finish, with the solution of phosphorus acid for adjusting pH value to the 2～9 back formation of massfraction 85% until reaction.
3. the preparation method of high fire resistance property expandable graphite according to claim 1, it is characterized in that: the guanidine in the said guanidinesalt solution has following structure:
4. the preparation method of high fire resistance property expandable graphite according to claim 1, it is characterized in that: described solid strong oxidizer is SRM 935a or potassium permanganate or ammonium persulphate or an ammonium nitrate.
5. according to the preparation method of the described high fire resistance property expandable graphite of claim l, it is characterized in that: the massfraction of nitrosonitric acid >=95%, the massfraction of the vitriol oil are 95%～98%, and the massfraction of phosphoric acid >=85%, the massfraction of nitric acid are 65%～68%; Said nitration mixture be by volume ratio for (1～5): 1 the vitriol oil mixes with nitric acid and obtains, or is (8～12) by volume ratio: 1 nitric acid mixes with phosphoric acid and obtains.
6. the preparation method of high fire resistance property expandable graphite according to claim 1, it is characterized in that: the mass ratio of the described graphite and the vitriol oil or nitration mixture is 1: (2～10).
7. the preparation method of high fire resistance property expandable graphite according to claim 1, it is characterized in that: described graphite is artificial synthetic or natural crystalline flake graphite, and its granularity is 30～800 orders.
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Cited By (8)
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| CN103881138A (en) * | 2014-03-06 | 2014-06-25 | 北京化工大学 | Guanidine sulfamate flame retardant modification grafted carbon nanotube and manufacturing method thereof |
| CN107601497A (en) * | 2017-08-22 | 2018-01-19 | 孙岩波 | A kind of expansible graphite preparation method |
| CN107936233A (en) * | 2017-12-05 | 2018-04-20 | 江苏裕兴薄膜科技股份有限公司 | A kind of flame retardant type PET/ nanometers of carbosphere composite materials and preparation method thereof |
| CN108760965A (en) * | 2018-05-29 | 2018-11-06 | 西安建筑科技大学 | A kind of the real time measure Ti-C detonator heat release amounts and its intensifying method |
| CN111169127A (en) * | 2020-01-17 | 2020-05-19 | 界首市丰杨塑业有限公司 | Sound-insulation noise-reduction composite corrugated plate tile and production process thereof |
| CN111188606A (en) * | 2020-01-14 | 2020-05-22 | 中国石油大学(华东) | Low-temperature expandable graphite for steam injection channeling sealing of heavy oil reservoir and preparation method and application thereof |
| CN112011100A (en) * | 2020-08-24 | 2020-12-01 | 李薇 | Novel halogen-free flame-retardant rubber material and preparation method thereof |
| CN114604869A (en) * | 2022-04-22 | 2022-06-10 | 宁波信远炭材料有限公司 | Antioxidant expanded graphite and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103881138A (en) * | 2014-03-06 | 2014-06-25 | 北京化工大学 | Guanidine sulfamate flame retardant modification grafted carbon nanotube and manufacturing method thereof |
| CN103881138B (en) * | 2014-03-06 | 2016-11-23 | 北京化工大学 | A kind of Guanidine Sulfamate 99 fire retardant modification grafting carbon nanotube and preparation method thereof |
| CN107601497A (en) * | 2017-08-22 | 2018-01-19 | 孙岩波 | A kind of expansible graphite preparation method |
| CN107936233A (en) * | 2017-12-05 | 2018-04-20 | 江苏裕兴薄膜科技股份有限公司 | A kind of flame retardant type PET/ nanometers of carbosphere composite materials and preparation method thereof |
| CN108760965A (en) * | 2018-05-29 | 2018-11-06 | 西安建筑科技大学 | A kind of the real time measure Ti-C detonator heat release amounts and its intensifying method |
| CN111188606A (en) * | 2020-01-14 | 2020-05-22 | 中国石油大学(华东) | Low-temperature expandable graphite for steam injection channeling sealing of heavy oil reservoir and preparation method and application thereof |
| CN111169127A (en) * | 2020-01-17 | 2020-05-19 | 界首市丰杨塑业有限公司 | Sound-insulation noise-reduction composite corrugated plate tile and production process thereof |
| CN112011100A (en) * | 2020-08-24 | 2020-12-01 | 李薇 | Novel halogen-free flame-retardant rubber material and preparation method thereof |
| CN112011100B (en) * | 2020-08-24 | 2022-11-01 | 宁波睿布尔新材料科技有限公司 | Halogen-free flame-retardant rubber material and preparation method thereof |
| CN114604869A (en) * | 2022-04-22 | 2022-06-10 | 宁波信远炭材料有限公司 | Antioxidant expanded graphite and preparation method and application thereof |
| CN114604869B (en) * | 2022-04-22 | 2023-12-15 | 宁波信远炭材料有限公司 | Antioxidant expanded graphite and preparation method and application thereof |
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Application publication date: 20120201 |