CN103214633B - Preparation method of graphite-base flame-retardant char forming agent - Google Patents
Preparation method of graphite-base flame-retardant char forming agent Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 28
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910021382 natural graphite Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-pentenoic acid compound Chemical class 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VJDDQSBNUHLBTD-GGWOSOGESA-N [(e)-but-2-enoyl] (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(=O)\C=C\C VJDDQSBNUHLBTD-GGWOSOGESA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- NEDHQDYBHYNBIF-UHFFFAOYSA-N pent-4-enoyl pent-4-enoate Chemical compound C=CCCC(=O)OC(=O)CCC=C NEDHQDYBHYNBIF-UHFFFAOYSA-N 0.000 claims description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 2
- VJDDQSBNUHLBTD-UHFFFAOYSA-N trans-crotonic acid-anhydride Natural products CC=CC(=O)OC(=O)C=CC VJDDQSBNUHLBTD-UHFFFAOYSA-N 0.000 claims description 2
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 8
- 150000003254 radicals Chemical class 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 229920002223 polystyrene Polymers 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract 2
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009422 external insulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of a flame-retardant char forming agent, and particularly relates to a preparation method of the graphite-base flame-retardant char forming agent. The invention aims to solve the problems of poor compatibility and difficult dispersion of flame-retardant expansible graphite in a polystyrene matrix and polymer solution. The preparation method comprises the following steps of: I, preparing expansible graphite with carboxyl on the surface; II, preparing acylating chlorination expansible graphite; III, preparing OH-C60/expansible graphite copolymer; and IV, preparing the graphite-base flame-retardant char forming agent. The graphite-base flame-retardant char forming agent and a free radical polymer can form a copolymer which is highly compatible to the free radical polymer matrix. Chemical bond combination is carried out on fullerene and the expansible graphite, so that the flame retardance is improved. The preparation method is simple and low in cost, and is used for preparing the graphite-base flame-retardant char forming agent.
Description
Technical field
The present invention relates to the preparation method of fire-retardant char-forming agent.
Background technology
In China, along with the raising of living standards of the people, building energy consumption such as heating, air-conditioning, hot water service, illumination etc. increase sharply, and therefore building energy conservation becomes the key object of China's energy-saving and emission-reduction.The Main Means reducing building energy consumption is building construction external insulation system.In large-scale application building energy-saving heat-insulating material, mainly contain the product such as expanded polystyrene foams (EPS), polyurethane foam (PU).And along with the continuous increase of polystyrene foam plate lagging material usage quantity and Application Areas, its inflammableness is also progressively exposed out, and serious harm is to the security of the lives and property of the people.
Expansible black lead is widely used in the preparation of inorganic fire-retarded auxiliary agent due to the flame retardant properties of its excellence.Expansible black lead is that find up to now only can be used for severe condition and have the swelling agent of enough expansion strengths.Expansible black lead can form the charring layer of expanded polystyrene veneer in combustion, and this charring layer has excellent fire-retardant, heat insulation and resistance to elevated temperatures.Therefore, expansible black lead is distributed in polystyrene foamed, utilizes its expansion to stop burning, damp down a fire, play the effect of heat insulation oxygen barrier simultaneously, realize the fire retardation of graphite to polystyrene foamed.But due to expansible black lead surface inertness, be difficult to effectively disperse in polystyrene matrix and in polymers soln, and then limit the application of expansible black lead in flame retardant area.
Summary of the invention
The present invention will solve flame retardant resistance expansible black lead poor compatibility in polystyrene matrix and polymers soln thereof, is difficult to the problem of disperseing, and the preparation method of the fire-retardant char-forming agent of a kind of graphite-based provided.
A preparation method for the fire-retardant char-forming agent of graphite-based, specifically prepares according to following steps:
One, natural graphite powder is dispersed in perchloric acid/nitric acid mixed solution, oxidation and preexpanding process is carried out again under temperature is 50 DEG C of conditions, obtain the expansible black lead of surface with carboxyl, wherein the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution is 20: 500 ~ 2000;
Two, the expansible black lead that step one obtains is mixed with thionyl chloride, then under temperature is 20 DEG C ~ 120 DEG C conditions, 1min ~ 360min is kept, vacuum drying treatment again, obtain chloride expansible black lead, wherein the mass ratio of the expansible black lead that obtains of step one and thionyl chloride is 1 ~ 10: 100;
Three, by mass concentration be 0.05% ~ 5.0% polyhydroxy fullerene chloroformic solution join in the chloroformic solution of the chloride expansible black lead that step 2 obtains, then under temperature is 20 DEG C ~ 100 DEG C conditions, 10min ~ 480min is kept, vacuum drying treatment again, obtains OH-C
60/ expansible black lead multipolymer, wherein the mass concentration of the chloroformic solution of chloride expansible black lead is 0.05% ~ 2%, OH-C
60oH-C in/expansible black lead multipolymer
60be 0.01 ~ 2 with the mass ratio of expansible black lead;
Four, OH-C step 3 obtained
60/ expansible black lead multipolymer and unsaturated compound put into chloroform, carry out esterification, obtain the fire-retardant char-forming agent of a kind of graphite-based under temperature is 60 DEG C ~ 100 DEG C conditions, wherein the OH-C that obtains of step 3
60the mass ratio of/expansible black lead multipolymer and unsaturated compound is 100: 1 ~ 50.
The present invention adopts polyhydroxy fullerene to be medium, unsaturated double-bond is introduced into expansible black lead surface, and then realizes itself and cinnamic in-situ copolymerization, realizes graphite flame retardant in polystyrene dispersed.Compared with the preparation method of conventional graphite flame retardant, it is simple that the fire-retardant char-forming agent of graphite-based prepared by the present invention has synthesis, good dispersity, be easy to the advantages such as extensive preparation, and in use rate of migration is little, substantially stop polyester material in use procedure because fire retardant moves the frosting phenomenon brought.
The invention has the beneficial effects as follows: 1, the fire-retardant char-forming agent of graphite-based that obtains of the present invention and free radical polyalcohol can form multipolymer, this multipolymer and free radical polyalcohol matrix have extraordinary consistency, this greatly reduces in use procedure and becomes into agent migration in the base, has stopped because char-forming agent moves the frosting phenomenon caused; 2, soccerballene and expanded graphite are carried out chemical bonds by the present invention, improve the two cooperative flame retardant ability significantly; 3, preparation method of the present invention is simple, and cost is low, and the required solvent of synthesis is single, is easy to Collection and utilization, is conducive to large-scale production, therefore have extraordinary application prospect.
The present invention is for the preparation of the fire-retardant char-forming agent of graphite-based.
Accompanying drawing explanation
Fig. 1 is graphite-based fire-retardant char-forming agent transmission electron microscope picture prepared by embodiment one.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of the fire-retardant char-forming agent of a kind of graphite-based of present embodiment, specifically prepare according to following steps:
One, natural graphite powder is dispersed in perchloric acid/nitric acid mixed solution, oxidation and preexpanding process is carried out again under temperature is 50 DEG C of conditions, obtain the expansible black lead of surface with carboxyl, wherein the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution is 20: 500 ~ 2000;
Two, the expansible black lead that step one obtains is mixed with thionyl chloride, then under temperature is 20 DEG C ~ 120 DEG C conditions, 1min ~ 360min is kept, vacuum drying treatment again, obtain chloride expansible black lead, wherein the mass ratio of the expansible black lead that obtains of step one and thionyl chloride is 1 ~ 10: 100;
Three, by mass concentration be 0.05% ~ 5.0% polyhydroxy fullerene chloroformic solution join in the chloroformic solution of the chloride expansible black lead that step 2 obtains, then under temperature is 20 DEG C ~ 100 DEG C conditions, 10min ~ 480min is kept, vacuum drying treatment again, obtains OH-C
60/ expansible black lead multipolymer, wherein the mass concentration of the chloroformic solution of chloride expansible black lead is 0.05% ~ 2%, OH-C
60oH-C in/expansible black lead multipolymer
60be 0.01 ~ 2 with the mass ratio of expansible black lead;
Four, OH-C step 3 obtained
60/ expansible black lead multipolymer and unsaturated compound put into chloroform, carry out esterification, obtain the fire-retardant char-forming agent of a kind of graphite-based under temperature is 60 DEG C ~ 100 DEG C conditions, wherein the OH-C that obtains of step 3
60the mass ratio of/expansible black lead multipolymer and unsaturated compound is 100: 1 ~ 50.
The beneficial effect of present embodiment is: 1, the fire-retardant char-forming agent of graphite-based that obtains of present embodiment and free radical polyalcohol can form multipolymer, this multipolymer and free radical polyalcohol matrix have extraordinary consistency, this greatly reduces in use procedure and becomes into agent migration in the base, has stopped because char-forming agent moves the frosting phenomenon caused; 2, soccerballene and expanded graphite are carried out chemical bonds by present embodiment, improve the two cooperative flame retardant ability significantly; 3, present embodiment preparation method is simple, and cost is low, and the required solvent of synthesis is single, is easy to Collection and utilization, is conducive to large-scale production, therefore have extraordinary application prospect.
Embodiment two: present embodiment and embodiment one unlike: in step one, in perchloric acid/nitric acid mixed solution, the volume ratio of perchloric acid and nitric acid is 30: 70.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one unlike: in step one, the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution is 20: 550 ~ 1900.Other is identical with embodiment one.
Embodiment four: present embodiment and embodiment one unlike: under temperature is 30 DEG C ~ 110 DEG C conditions, keep 10min ~ 300min in step 2.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment one unlike: in step 2, the mass ratio of expansible black lead and thionyl chloride is 2 ~ 8: 100.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one unlike: in step 3, the mass concentration of polyhydroxy fullerene chloroformic solution is 1.0% ~ 4.0%.Other is identical with embodiment one.
Embodiment seven: present embodiment and embodiment one unlike: in step 4, unsaturated compound is the one or more combination in unsaturated acid anhydride, unsaturated acyl chlorides and unsaturated acid.Other is identical with embodiment one.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: in step 4, unsaturated acid anhydride is the one or more combination in acrylic anhydride, crotonic anhydride, maleic anhydride and 4-pentenoic acid anhydride.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to seven unlike: in step 4, unsaturated acyl chlorides is the one or more combination in acrylate chloride, crotonyl chloride, malenyl chloride and 4-prenyl chloride.Other is identical with one of embodiment one to seven.
Embodiment ten: one of present embodiment and embodiment one to seven unlike: in step 4, unsaturated acid is the one or more combination in vinylformic acid, butenoic acid, toxilic acid and 4-pentenoic acid compound.Other is identical with one of embodiment one to seven.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
The preparation method of the fire-retardant char-forming agent of a kind of graphite-based of the present embodiment, specifically prepares according to following steps:
One, natural graphite powder is dispersed in perchloric acid/nitric acid mixed solution, oxidation and preexpanding process is carried out again under temperature is 50 DEG C of conditions, obtain the expansible black lead of surface with carboxyl, wherein the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution is 20: 500;
Two, the expansible black lead that step one obtains is mixed with thionyl chloride, then under temperature is 100 DEG C of conditions, 160min is kept, vacuum drying treatment again, obtains chloride expansible black lead, and wherein the mass ratio of the expansible black lead that obtains of step one and thionyl chloride is 2: 100;
Three, by mass concentration be 2.0% polyhydroxy fullerene chloroformic solution join in the chloroformic solution of the chloride expansible black lead that step 2 obtains, then under temperature is 80 DEG C of conditions, keep 380min, then vacuum drying treatment, obtain OH-C
60/ expansible black lead multipolymer, wherein the mass concentration of the chloroformic solution of chloride expansible black lead is 0.5%, OH-C
60oH-C in/expansible black lead multipolymer
60be 1 with the mass ratio of expansible black lead;
Four, OH-C step 3 obtained
60/ expansible black lead multipolymer and unsaturated compound put into chloroform, under temperature is 90 DEG C of conditions, carry out esterification, obtain the fire-retardant char-forming agent of a kind of graphite-based, wherein the OH-C that obtains of step 3
60the mass ratio of/expansible black lead multipolymer and unsaturated compound is 100: 5.
In the present embodiment, in step 4, unsaturated compound is acrylic anhydride.
The transmission electron microscope picture of the fire-retardant char-forming agent of the present embodiment graphite-based as shown in Figure 1.
Char-forming agent prepared by the present embodiment and PS consistency good, greatly reduce char-forming agent migration in the base in use procedure, stopped because char-forming agent moves the frosting phenomenon caused.
The char-forming agent prepared by above-described embodiment and PS carry out melting mixing, and mixture is pressed into flame retardant test exemplar, and to the oxygen index of blend, become charcoal to prevent dripping sign, the relation of its performance and composition is as follows:
The fire-retardant char-forming agent of the graphite-based that the present invention obtains and free radical polyalcohol can form multipolymer, this multipolymer and free radical polyalcohol matrix have extraordinary consistency, this greatly reduces in use procedure and becomes into agent migration in the base, has stopped because char-forming agent moves the frosting phenomenon caused; Soccerballene and expanded graphite are carried out chemical bonds by the present invention, improve the two cooperative flame retardant ability significantly; Preparation method of the present invention is simple, and cost is low, and the required solvent of synthesis is single, is easy to Collection and utilization, is conducive to large-scale production, therefore have extraordinary application prospect.
Claims (10)
1. a preparation method for the fire-retardant char-forming agent of graphite-based, is characterized in that the preparation method of the fire-retardant char-forming agent of a kind of graphite-based, specifically prepares according to following steps:
One, natural graphite powder is dispersed in perchloric acid/nitric acid mixed solution, oxidation and preexpanding process is carried out again under temperature is 50 DEG C of conditions, obtain the expansible black lead of surface with carboxyl, wherein the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution is 20: 500 ~ 2000;
Two, the expansible black lead that step one obtains is mixed with thionyl chloride, then under temperature is 20 DEG C ~ 120 DEG C conditions, 1min ~ 360min is kept, vacuum drying treatment again, obtain chloride expansible black lead, wherein the mass ratio of the expansible black lead that obtains of step one and thionyl chloride is 1 ~ 10: 100;
Three, by mass concentration be 0.05% ~ 5.0% polyhydroxy fullerene chloroformic solution join in the chloroformic solution of the chloride expansible black lead that step 2 obtains, then under temperature is 20 DEG C ~ 100 DEG C conditions, 10min ~ 480min is kept, vacuum drying treatment again, obtains OH-C
60/ expansible black lead multipolymer, wherein the mass concentration of the chloroformic solution of chloride expansible black lead is 0.05% ~ 2%, OH-C
60oH-C in/expansible black lead multipolymer
60be 0.01 ~ 2 with the mass ratio of expansible black lead;
Four, OH-C step 3 obtained
60/ expansible black lead multipolymer and unsaturated compound put into chloroform, carry out esterification, obtain the fire-retardant char-forming agent of a kind of graphite-based under temperature is 60 DEG C ~ 100 DEG C conditions, wherein the OH-C that obtains of step 3
60the mass ratio of/expansible black lead multipolymer and unsaturated compound is 100: 1 ~ 50.
2. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that the volume ratio of perchloric acid and nitric acid in perchloric acid in step one/nitric acid mixed solution is 30: 70.
3. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that the mass ratio of natural graphite powder and perchloric acid/nitric acid mixed solution in step one is 20: 550 ~ 1900.
4. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that under temperature is 30 DEG C ~ 110 DEG C conditions, keeping 10min ~ 300min in step 2.
5. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that the mass ratio of expansible black lead and thionyl chloride in step 2 is 2 ~ 8: 100.
6. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that the mass concentration of polyhydroxy fullerene chloroformic solution in step 3 is 1.0% ~ 4.0%.
7. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 1, is characterized in that in step 4, unsaturated compound is the one or more combination in unsaturated acid anhydride, unsaturated acyl chlorides and unsaturated acid.
8. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 7, is characterized in that in step 4, unsaturated acid anhydride is the one or more combination in acrylic anhydride, crotonic anhydride, maleic anhydride and 4-pentenoic acid anhydride.
9. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 7, is characterized in that in step 4, unsaturated acyl chlorides is the one or more combination in acrylate chloride, crotonyl chloride, malenyl chloride and 4-prenyl chloride.
10. the preparation method of the fire-retardant char-forming agent of a kind of graphite-based according to claim 7, is characterized in that in step 4, unsaturated acid is the one or more combination in vinylformic acid, butenoic acid, toxilic acid and 4-pentenoic acid compound.
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| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| CN102583303A (en) * | 2012-02-24 | 2012-07-18 | 中国科学院化学研究所 | Method for preparing high water solubility fullerol |
| CN102744996A (en) * | 2012-07-30 | 2012-10-24 | 哈尔滨工业大学 | Graphene oxide inkjet recording material and manufacturing method thereof |
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