CN102140184A - Composite flame retardant with core-shell structure and preparation method thereof - Google Patents
Composite flame retardant with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite flame retardant with a core-shell structure, which is formed into dark gray solid particles. The cores of the particles are expansible graphite with an average particle size of 100 to 200 mu m, and the shells of the particles are melamine formaldehyde resin. After the composite flame retardant is subjected to heat treatment at a high temperature of 900 DEG C for 15 seconds, the volume expansibility of the composite flame retardant is 58 to 74ml/g according to measurement. The invention also discloses a preparation method of the composite flame retardant with the core-shell structure. As the flame retardant provided by the invention is formed by coating the expansible graphite particles with a layer of very thin melamine formaldehyde resin, when the particles of the flame retardant with the core-shell structure is heated, the gas generated by the expansible graphite particles cannot escape to the outside immediately due to the protection of the shell layer formed by polymer on outer layer, instead the gas is released after the graphite sheet layer is opened completely; and thus, the expanded volume of the expansible graphite is increased, and the flame retarding performance is improved greatly. The method provided by the invention adopts simple process, is high in operability and makes the realization of large scale production easy.
Description
Technical field
The invention belongs to nucleocapsid structure composite flame-retardant agent and preparing technical field thereof, be specifically related to a kind of with formed nucleocapsid structure composite flame-retardant agent of terpolycyantoamino-formaldehyde resin (MF) coating expansible black lead and preparation method thereof.
Background technology
Along with progress of science and technology, macromolecular material has been widely used in fields such as building materials, automobile, electronics and space flight, plays a part very important in the development of the national economy and people's lives.But so the inflammableness or the combustibility of macromolecular material have become very important safety problem, research and development flame retardant type macromolecular material extremely urgent (A.B.Morgan, et al.John Wily ﹠amp mostly; Sons, Inc.Hoboken, NJ, 2007).
Halogen-free flame retardants has become the important research direction of world's flame retardant area owing to its environmental friendliness, efficient and low cigarette.In the halogen-free flame retardants of present Application and Development, have with ammonium polyphosphate (APP), tetramethylolmethane (PER), trimeric cyanamide (MA) to be the expansion type flame retardant of representative and to be the Halogen additive flame retardant of representative with the magnesium hydroxide.And expansible black lead is as a kind of novel inorganic expansion type fire retardant, because addition is few and good flame-retardant effect has been subjected to paying close attention to widely and studying.
Expansible black lead (hereinafter to be referred as EG) is that a kind of chemistry and method of physics utilized has a formed crystalline compounds of carbon hexagonal network two dimensional structure with what intercalator (generally selecting sulfuric acid for use) was inserted into graphite layers.Expansible black lead is when being heated, interlayer inserts the material decomposes or vaporization can produce a large amount of swelling heats, and this swelling heat is far longer than the Van der Waals force of graphite layers, and the junction that makes the sheet interlayer is by the air-flow distending, the graphite layers distance enlarges once more, has formed the vermiform expanded graphite.This swelling heat be come from EG time more than 200 ℃ take place following redox reaction (Clarke R, et al.Advances in Physics, 1984,33:469):
24nC+mH
2SO
4+1/2O
2→C
24n +(HSO
4 -)(m-1)H
2SO
4+1/2H
2O
When the polymer composite decomposes that is added with EG or when burning, its surface energy generates one deck " vermiform " expanding layer, and that this expanding layer has is heat insulation, oxygen barrier, press down the function of cigarette and anti-molten drop, finally plays the incendiary effect that stops.For example: EG flame retarded rigid polyurethane foams (RPUF) just demonstrates the excellent fire retardant effect, add the EG of 25wt% in RPUF after, its oxygen index can be brought up to 42vol% (Duquesne S, et al.Polymer Degradable Stability from 22vol%, 2002,77:333).Also find simultaneously, when EG adds in the high molecular polymer matrix, because the multi-disc layer structure that EG is made up of graphite flake, very big gap is arranged between the graphite flake layer, the graphite particle yardstick is bigger in addition, thereby the consistency between graphite and the matrix is relatively poor, causes matrix material machinery performance to reduce.For example: after in RPUF, adding the EG of 20wt%, its compressive strength drops to 8.9Mpa from the 14.4MPa of pure RPUF, modulus of compression also drops to 205.5Mpa (Lei Shi from 258.6Mpa, et al.Polymer-Plastics Technology and Engineering, 2005,44:1323).In order to address this problem, the inventor once proposed technical measures by refinement EG particle (hereinafter to be referred as pEG) and reaches and do not influence or weaken the influence of EG to the matrix mechanical property.But, I had never expected after the size of particles of EG reduces, brought a new problem again, promptly being closed in the gas that is produced when intercalation oxygenant between the graphite flake layer is heated also is not able to do in time the complete distending of graphite flake layer, just fled from out between the lamella, the expanding volume that allows to embody its flame retardant resistance has reduced.Behind the EG and pEG particle that add 10wt% in RPUF respectively, its oxygen index is respectively 32.5vol% and 23.5vol%, flame retardant properties obviously descend (Lei Shi, et al.Polymer International, 2006,55:862).
Summary of the invention
The objective of the invention is the deficiency that exists at prior art and a kind of composite flame-retardant agent of nucleocapsid structure is provided, this nucleocapsid structure can make the expanding volume of fire retardant obtain to increase, thereby improves its flame retardant resistance greatly.
Another object of the present invention provides a kind of method for preparing the composite flame-retardant agent of above-mentioned nucleocapsid structure, and preparation technology is simple for this method, is easy to industrializing implementation.
The composite flame-retardant agent of nucleocapsid structure provided by the invention, it is characterized in that this composite flame-retardant agent is for being dimmed solid particulate, particulate nuclear is median size 100-200 μ m expansible black lead, shell is a terpolycyantoamino-formaldehyde resin, and it records its cubical expansivity at 900 ℃ of high-temperature heat treatment 15s is 58-74ml/g.
The method of the nucleocapsid structure composite flame-retardant agent that preparation provided by the invention is above-mentioned, the processing step and the condition of this method are as follows:
1) first trimeric cyanamide is added, be mixed with the aqueous solution that weight percent concentration is 5-20% in the entry, then with alkali metal hydroxide regulator solution pH value to 8-9, be warming up to 50-70 ℃, stirring and refluxing adds formaldehyde solution behind the 30min at least, back flow reaction 10-15min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 3-5.;
2) be that the expansible black lead of 100-200 μ m adds in the entry with median size, under ultrasonic and stirring action, the preparation weight percent concentration is the expansible black lead aqueous suspension of 20-40%, and to make the mass ratio of expansible black lead and trimeric cyanamide be 2.5-8: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 50-70 ℃ of stirring and refluxing earlier at least behind the 30min, again with acid for adjusting pH value to 3-4, stirring reaction 90-150min stops to stir, and leaves standstill 6h at least;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 50-80 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Used alkali metal hydroxide is sodium hydroxide or potassium hydroxide in the above method.
Used acid is hydrochloric acid or acetic acid in the above method.
The present invention compared with prior art has the following advantages:
1, because fire retardant provided by the invention is formed nucleocapsid structure type flame retardant particle with the median size that the very thin terpolycyantoamino-formaldehyde resin of one deck coats by 100-200 μ m expansible black lead particle; thereby when this nucleocapsid structure flame retardant particle is heated; because the protection of outer layer copolymer shell; the gas that the pEG particle is produced is not easy to escape out immediately; but after being opened fully, graphite flake layer discharges again; the expanding volume of pEG particle certainly will obtain increasing like this, and flame retardant properties also must obtain bigger improvement.
2, because the outer terpolycyantoamino-formaldehyde resin that coats of fire retardant provided by the invention also is a kind of have high mechanical strength, good compactness and thermoset amino resin of thermostability, thereby it is when improving pEG particle rate of expansion, owing to self possess flame retardant properties, can improve flame retardant effect jointly with the pEG particle.
3, the flame retardant properties with composite flame-retardant agent adding hard polyurethane foams provided by the invention not only obviously is better than the flame retardant properties (see Table 2) of pEG in hard polyurethane foams, and it also can be applied to the fire-retardant of other macromolecular material.
4, can be by preparation method provided by the invention by regulating the mass ratio of pEG and MF, the pEG-MF composite particles that obtains different clad ratios satisfies different requirements.
5, the not only used shell raw material of preparation method provided by the invention is the commercial reagent, and wide material sources are cheap, and technology is simple, and strong operability is easy to realize fairly large production.
Description of drawings
Fig. 1 is the electron scanning micrograph of the prepared flame retardant particle of the inventive method embodiment 4;
Fig. 2 is the electron scanning micrograph without the pEG particle of terpolycyantoamino-formaldehyde resin coating;
The pEG particle that Fig. 3 is the prepared flame retardant particle of the inventive method embodiment 4, coat without terpolycyantoamino-formaldehyde resin and the fourier infrared spectrogram of terpolycyantoamino-formaldehyde resin;
Fig. 4 is the X-ray diffraction photo of prepared flame retardant particle of the inventive method embodiment 4 and the pEG particle that coats without terpolycyantoamino-formaldehyde resin.
Embodiment
Provide specific embodiment below so that technical scheme of the present invention is described further; but what deserves to be explained is that following examples can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field does the improvement of some non-intrinsically safes and adjusts still to belong to protection scope of the present invention to the present invention according to the content of the invention described above.
Embodiment 1
1) earlier trimeric cyanamide is added that to be mixed with weight percent concentration in the entry be 20% the aqueous solution, regulate pH value of water solution to 9 with the NaOH solution of concentration 10% then, be warming up to 50 ℃ of stirring and refluxing and add formaldehyde solution behind the 30min at least, back flow reaction 13min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 5.;
2) be that the expansible black lead of 120 μ m adds in the entry with median size, disperse 30min under the ultrasonic agitation effect, the preparation weight percent concentration is 40% expansible black lead aqueous suspension, and to make the mass ratio of expansible black lead and trimeric cyanamide be 2.5: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 50 ℃ of stirring and refluxing earlier at least behind the 30min, regulate pH value to 3 with 10% acetum again, stirring reaction 150min stops stirring, leaves standstill 12h;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 60 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Embodiment 2
1) earlier trimeric cyanamide is added that to be mixed with weight percent concentration in the entry be 5% the aqueous solution, regulate pH value of water solution to 8 with the KOH solution of concentration 10% then, be warming up to 50 ℃ of stirring and refluxing and add formaldehyde solution behind the 30min at least, back flow reaction 15min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 4;
2) be that the expansible black lead of 100 μ m adds in the entry with median size, disperse 30min under the ultrasonic agitation effect, the preparation weight percent concentration is 40% expansible black lead aqueous suspension, and to make the mass ratio of expansible black lead and trimeric cyanamide be 3: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 50 ℃ of stirring and refluxing earlier at least behind the 30min, regulate pH value to 3 with 10% hydrochloric acid soln again, stirring reaction 150min stops stirring, leaves standstill 24h;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 60 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Embodiment 3
1) earlier trimeric cyanamide is added that to be mixed with weight percent concentration in the entry be 9.1% the aqueous solution, regulate pH value of water solution to 9 with the KOH solution of concentration 10% then, be warming up to 65 ℃ of stirring and refluxing and add formaldehyde solution behind the 30min at least, back flow reaction 10min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 3.;
2) be that the expansible black lead of 150 μ m adds in the entry with median size, disperse 30min under the ultrasonic agitation effect, the preparation weight percent concentration is 30% expansible black lead aqueous suspension, and to make the mass ratio of expansible black lead and trimeric cyanamide be 4: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 65 ℃ of stirring and refluxing earlier at least behind the 30min, regulate pH value to 4 with 10% acetum again, stirring reaction 120min stops stirring, leaves standstill 12h;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 80 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Embodiment 4
1) earlier trimeric cyanamide is added that to be mixed with weight percent concentration in the entry be 5% the aqueous solution, regulate pH value of water solution to 8 with the NaOH solution of concentration 10% then, be warming up to 70 ℃ of stirring and refluxing and add formaldehyde solution behind the 30min at least, back flow reaction 10min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 3.;
2) be that the expansible black lead of 200 μ m adds in the entry with median size, disperse 30min under the ultrasonic agitation effect, the preparation weight percent concentration is 20% expansible black lead aqueous suspension, and to make the mass ratio of expansible black lead and trimeric cyanamide be 6: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 70 ℃ of stirring and refluxing earlier at least behind the 30min, regulate pH value to 3 with 10% acetum again, stirring reaction 90min stops stirring, leaves standstill 6h;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 50 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Embodiment 5
1) earlier trimeric cyanamide is added that to be mixed with weight percent concentration in the entry be 20% the aqueous solution, regulate pH value of water solution to 8 with the NaOH solution of concentration 10% then, be warming up to 70 ℃ of stirring and refluxing and add formaldehyde solution behind the 30min at least, back flow reaction 12min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 4.;
2) be that the expansible black lead of 100 μ m adds in the entry with median size, disperse 30min under the ultrasonic agitation effect, the preparation weight percent concentration is 40% expansible black lead aqueous suspension, and to make the mass ratio of expansible black lead and trimeric cyanamide be 8: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 70 ℃ of stirring and refluxing earlier at least behind the 30min, regulate pH value to 4 with 10% hydrochloric acid soln again, stirring reaction 100min stops stirring, leaves standstill 6h;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 80 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
Variation for expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent rate of expansion of investigating the present invention preparation, the composite flame-retardant agent that above each embodiment is prepared is got 1g pEG-MF respectively and is put into 900 ℃ of retort furnace high-temperature heat treatment 15s respectively with the expansible black lead particle 1g that coats without terpolycyantoamino-formaldehyde resin, survey the variation of its expanding volume, its result such as table 1.
Table 1
Secondly, also respectively expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent the particle and the uncoated expansible black lead particle of the present invention's preparation are carried out morphologic observation, the results are shown in Figure 1,2 with scanning electronic microscope.Can find out obviously that from Fig. 1 the pEG particle surface has coated one layer of polymeric, and clad structure is complete, and the shown uncoated pEG particle surface of Fig. 2 both had metalluster, can observe the laminated structure of graphite again.
The 3rd, the prepared flame retardant particle of the inventive method embodiment 4, the pEG particle and the terpolycyantoamino-formaldehyde resin that coat without terpolycyantoamino-formaldehyde resin have been carried out the fourier infrared test, the results are shown in Figure 3.The shell material of the nucleocapsid structure composite flame-retardant agent particle of the present invention's preparation is a terpolycyantoamino-formaldehyde resin as can be seen from Figure 3.
The 4th, prepared flame retardant particle of the inventive method embodiment 4 and the pEG particle that coats without terpolycyantoamino-formaldehyde resin have been advanced the X-ray diffraction analysis, the results are shown in Figure 4.As can be seen from Figure 4, the diffraction peak of the more uncoated expansible black lead particle of diffraction peak of expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent particle has reduced many.This is because terpolycyantoamino-formaldehyde resin is crosslinked and polymkeric substance no crystallization crystal formation, so minimizing along with expansible black lead particle shared weight percent in the composite flame-retardant agent particle, resulting X-ray diffraction peak-to-peak value weakens gradually, so can further judge and successfully prepared nucleocapsid structure composite flame-retardant agent particle.
In addition, in order to investigate flame retardant properties with the prepared hard polyurethane foams fire retardant material of nucleocapsid structure flame retardant particle provided by the invention, the present invention at first prepares hard polyurethane foams fire retardant material (application examples 1-5) in accordance with the following methods with the nucleocapsid structure flame retardant particle of above each embodiment preparation, and then with the flame retardant properties of its prepared hard polyurethane foams fire retardant material with using the pEG particle that coats without terpolycyantoamino-formaldehyde resin respectively by ASTM D2863-97 and ASTM D 3801-96 and ASTM D 635-98 standard testing the limiting oxygen index(LOI) of matrix material (LOI), vertical combustion and horizontal firing the results are shown in Table 2.
The concrete operations step of preparation hard polyurethane foams fire retardant material method is: at first 10wt%pEG-MF (10wt% the refers to pEG) particle that various embodiments of the present invention are prepared is added in the polyether glycol respectively together with other auxiliary agent (identical with the auxiliary agent of prior art for preparing hard polyurethane foams) and stirs, and then adding polymethine polyphenyl polyisocyanate stirs 30s (mass ratio of polyether glycol and polymethine polyphenyl polyisocyanate 100: 180), pour in the mould and foam, at 100 ℃ of following slaking 4h, promptly obtaining density is 0.2 ± 0.01g/cm again
3Rigid polyurethane foam composite.
Table 2
Claims (4)
1. the composite flame-retardant agent of a nucleocapsid structure, it is characterized in that this composite flame-retardant agent is for being dimmed solid particulate, particulate nuclear is median size 100-200 μ m expansible black lead, shell is a terpolycyantoamino-formaldehyde resin, and it records its cubical expansivity at 900 ℃ of high-temperature heat treatment 15s is 58-74ml/g.
2. method for preparing the described nucleocapsid structure composite flame-retardant agent of claim 1, the processing step and the condition of this method are as follows:
1) first trimeric cyanamide is added, be mixed with the aqueous solution that weight percent concentration is 5-20% in the entry, then with alkali metal hydroxide regulator solution pH value to 8-9, be warming up to 50-70 ℃, stirring and refluxing adds formaldehyde solution behind the 30min at least, back flow reaction 10-15min under the constant temperature, promptly get clear soln, the mol ratio of added trimeric cyanamide and formaldehyde is 1: 3-5.;
2) be that the expansible black lead of 100-200 μ m adds in the entry with median size, under ultrasonic and stirring action, the preparation weight percent concentration is the expansible black lead aqueous suspension of 20-40%, and to make the mass ratio of expansible black lead and trimeric cyanamide be 2.5-8: 1;
3) with the 1st) settled solution that obtains of step pours the 2nd into) in the suspension that obtains, be warming up to 50-70 ℃ of stirring and refluxing earlier at least behind the 30min, again with acid for adjusting pH value to 3-4, stirring reaction 100-150min stops to stir, and leaves standstill 6h at least;
4) with the solution decompression suction filtration that obtains, and be washed with water to filtrate, 50-80 ℃ of oven dry down, promptly obtain expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent pressed powder then for neutral.
3. the method for preparing the nucleocapsid structure composite flame-retardant agent according to claim 2, used alkali metal hydroxide is sodium hydroxide or potassium hydroxide in this method.
4. according to claim 2 or the 3 described methods that prepare the nucleocapsid structure composite flame-retardant agent, used acid is hydrochloric acid or acetic acid in this method.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288998A (en) * | 2013-07-01 | 2013-09-11 | 四川大学 | Core-shell structure type composite flame retardant and preparation method thereof |
| CN103333370A (en) * | 2013-07-25 | 2013-10-02 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN103819735A (en) * | 2014-03-03 | 2014-05-28 | 中国科学院青岛生物能源与过程研究所 | Inflatable graphite/melamine salt synergic intumescent flame retardant and preparation method thereof |
| CN105086030A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Low-smoke flame-retardant powdered styrene butadiene rubber and preparation method thereof |
| CN106928491A (en) * | 2017-03-13 | 2017-07-07 | 南京大学 | A kind of microencapsulation expansible graphite and its preparation method and the application in composite polyurethane rigid foam is prepared |
| CN114008821A (en) * | 2019-06-28 | 2022-02-01 | 日本瑞翁株式会社 | Composite particle for electrochemical element and method for producing same, binder composition for electrochemical element functional layer and method for producing same, conductive material paste for electrode composite layer and method for producing same, slurry for electrode composite layer, electrode for electrochemical element, and electrochemical element |
| WO2024065703A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Expandable microsphere and preparation thereof, electrode sheet comprising expandable microsphere, and secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007141123A2 (en) * | 2006-06-09 | 2007-12-13 | Ciba Holding Inc. | Polymeric particles and their preparation |
-
2011
- 2011-01-18 CN CN2011100202885A patent/CN102140184B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007141123A2 (en) * | 2006-06-09 | 2007-12-13 | Ciba Holding Inc. | Polymeric particles and their preparation |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288998A (en) * | 2013-07-01 | 2013-09-11 | 四川大学 | Core-shell structure type composite flame retardant and preparation method thereof |
| CN103333370A (en) * | 2013-07-25 | 2013-10-02 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN103333370B (en) * | 2013-07-25 | 2015-05-13 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN103819735A (en) * | 2014-03-03 | 2014-05-28 | 中国科学院青岛生物能源与过程研究所 | Inflatable graphite/melamine salt synergic intumescent flame retardant and preparation method thereof |
| CN103819735B (en) * | 2014-03-03 | 2016-03-02 | 中国科学院青岛生物能源与过程研究所 | Expansible black lead/melamine salt synergistic expanding fire retardant and preparation method thereof |
| CN105086030A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Low-smoke flame-retardant powdered styrene butadiene rubber and preparation method thereof |
| CN106928491A (en) * | 2017-03-13 | 2017-07-07 | 南京大学 | A kind of microencapsulation expansible graphite and its preparation method and the application in composite polyurethane rigid foam is prepared |
| CN106928491B (en) * | 2017-03-13 | 2019-10-29 | 南京大学 | A kind of microencapsulation expansible graphite and its preparation method and preparing the application in composite polyurethane rigid foam |
| CN114008821A (en) * | 2019-06-28 | 2022-02-01 | 日本瑞翁株式会社 | Composite particle for electrochemical element and method for producing same, binder composition for electrochemical element functional layer and method for producing same, conductive material paste for electrode composite layer and method for producing same, slurry for electrode composite layer, electrode for electrochemical element, and electrochemical element |
| WO2024065703A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Expandable microsphere and preparation thereof, electrode sheet comprising expandable microsphere, and secondary battery |
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