CN102140184B - 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
- Publication number
- CN102140184B CN102140184B CN2011100202885A CN201110020288A CN102140184B CN 102140184 B CN102140184 B CN 102140184B CN 2011100202885 A CN2011100202885 A CN 2011100202885A CN 201110020288 A CN201110020288 A CN 201110020288A CN 102140184 B CN102140184 B CN 102140184B
- Authority
- CN
- China
- Prior art keywords
- composite flame
- flame retardant
- black lead
- expansible black
- nucleocapsid structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
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, in the development of the national economy and people's lives, plays a part very important.But so the inflammableness of macromolecular material or flammable has become very important safety-problems, research and development flame retardant type macromolecular material extremely urgent (A.B.Morgan, et al.John Wily Sons, Inc.Hoboken, NJ, 2007) mostly.
Halogen-free flame retardants has become the 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 Marinco H.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 received and pays close attention to widely and study.
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; After in RPUF, adding the EG of 25wt%, 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 through 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 be closed in the gas that is produced when intercalation oxygenant between the graphite flake layer is heated and also be not able to do in time just to have fled from the complete distending of graphite flake layer out, the expanding volume that can embody its flame retardant resistance has been reduced between the lamella.Behind the EG and pEG particle that in RPUF, add 10wt% 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 composite flame-retardant agent that the objective of the invention is to be directed against the deficiency of prior art existence and a kind 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 process step and the condition of this method are following:
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, constant temperature refluxed reaction 10-15min; 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-s 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 filtrating, 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 Pottasium 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 being the median size of using the very thin terpolycyantoamino-formaldehyde resin of one deck to coat, fire retardant provided by the invention formed nucleocapsid structure type flame retardant particle 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 opening graphite flake layer fully, discharge 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 superior to 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 through preparation method provided by the invention through regulating the mass ratio of pEG and MF, the pEG-MF composite particles that obtains different clad ratios satisfies different requirement.
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 be worth explanation is that following examples can not be interpreted as the restriction to protection domain of the present invention; The person skilled in the art in this field is according to the content of the invention described above, and improvement and the adjustment of the present invention being made some non-intrinsically safe property still belong to protection scope of the present invention.
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; Constant temperature refluxed reaction 13min promptly gets clear soln, and 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, under the ultrasonic agitation effect, disperse 30min, 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-s 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 filtrating, 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; Constant temperature refluxed reaction 15min promptly gets clear soln, and 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, under the ultrasonic agitation effect, disperse 30min, 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-s 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 filtrating, 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; Constant temperature refluxed reaction 10min promptly gets clear soln, and 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, under the ultrasonic agitation effect, disperse 30min, 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-s 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 filtrating, 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; Constant temperature refluxed reaction 10min promptly gets clear soln, and 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, under the ultrasonic agitation effect, disperse 30min, 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-s 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 filtrating, 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; Constant temperature refluxed reaction 12min promptly gets clear soln, and 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, under the ultrasonic agitation effect, disperse 30min, 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-s 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 filtrating, 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; Above each embodiment prepared composite fire retardant is got 1g pEG-MF respectively 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 with sem, the result sees Fig. 1,2.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 pEG particle surface of the uncoated that Fig. 2 showed 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 result sees Fig. 3.As can beappreciated from fig. 3 the shell material of the nucleocapsid structure composite flame-retardant agent particle of the present invention's preparation is a terpolycyantoamino-formaldehyde resin.
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 result sees Fig. 4.As can be seen from Figure 4, the diffraction peak of expansible black lead-terpolycyantoamino-formaldehyde resin nucleocapsid structure composite flame-retardant agent particle has reduced many than the diffraction peak of uncoated expansible black lead particle.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) with the nucleocapsid structure flame retardant particle of above each embodiment preparation according to following method; 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 result sees table 2.
The concrete operations step of preparation hard polyurethane foams fire retardant material method is: 10wt%pEG-MF (10wt% the refers to pEG) particle that at first various embodiments of the present invention is 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 process step and the condition of this method are following:
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, constant temperature refluxed reaction 10-15min; 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-s that obtains of step, 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 filtrating, 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 Pottasium 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100202885A CN102140184B (en) | 2011-01-18 | 2011-01-18 | Composite flame retardant with core-shell structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100202885A CN102140184B (en) | 2011-01-18 | 2011-01-18 | Composite flame retardant with core-shell structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140184A CN102140184A (en) | 2011-08-03 |
| CN102140184B true CN102140184B (en) | 2012-07-04 |
Family
ID=44407992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100202885A Expired - Fee Related CN102140184B (en) | 2011-01-18 | 2011-01-18 | Composite flame retardant with core-shell structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140184B (en) |
Families Citing this family (7)
| 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 |
| 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 |
| 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 |
| CN105086030B (en) * | 2014-05-14 | 2017-03-15 | 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 |
| 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 |
| EP3993094A4 (en) * | 2019-06-28 | 2023-12-20 | Zeon Corporation | Composite particle for electrochemical element and production method therefor, binder composition for electrochemical element functional layer and production method therefor, conductive material paste for electrode mixture layer and production method therefor, slurry for electrode mixture 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0611422D0 (en) * | 2006-06-09 | 2006-07-19 | Ciba Sc Holding Ag | Polymeric particles and their preparation |
-
2011
- 2011-01-18 CN CN2011100202885A patent/CN102140184B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102140184A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102140184B (en) | Composite flame retardant with core-shell structure and preparation method thereof | |
| Nabipour et al. | Zeolitic imidazolate framework-8/polyvinyl alcohol hybrid aerogels with excellent flame retardancy | |
| CN103333370B (en) | Organic and inorganic microcapsule coating expansible graphite preparation method | |
| Lu et al. | Study of the fire performance of magnesium hydroxide sulfate hydrate whisker flame retardant polyethylene | |
| CN105037811B (en) | A kind of ammonium polyphosphate flame retardant and preparation method thereof | |
| CN104804218A (en) | Nanocellulose surface-modified core-shell structure fire retardant, and preparation method and application of fire retardant | |
| CN106700135A (en) | Flame-retardant polystyrene insulation material and preparation method thereof | |
| CN101168607A (en) | Phosphorus nitrogen series expansion type anti-flaming nano composite material with high thermal stability | |
| CN113980551B (en) | Hydrotalcite-based water-based epoxy resin intumescent fire-retardant coating | |
| CN110041636B (en) | Halogen-free flame-retardant antistatic wood-plastic composite material and preparation method thereof | |
| Gao et al. | Creating multilayer-structured polystyrene composites for enhanced fire safety and electromagnetic shielding | |
| Hou et al. | Synergistic effect of silica aerogels and hollow glass microspheres on microstructure and thermal properties of rigid polyurethane foam | |
| Cao et al. | Self-assembled biobased chitosan hybrid carrying N/P/B elements for polylactide with enhanced fire safety and mechanical properties | |
| Luo et al. | Enhanced Thermal Insulation and Flame‐Retardant Properties of Polyvinyl Alcohol‐Based Aerogels Composited with Ammonium Polyphosphate and Chitosan | |
| Mao et al. | A self-healable and highly flame retardant TiO2@ MXene/P, N-containing polyimine nanocomposite for dual-mode fire sensing | |
| Kang et al. | Fabrication of highly flame-retardant paper by in situ loading of magnesium hydroxide/basic magnesium chloride onto cellulose fibers | |
| WO2024036756A1 (en) | Multifunctional phosphorus and nickel doped graphite-like carbon nitride nanosheet, preparation method therefor, and abs material | |
| Öktem et al. | Development of Flame Retardant Shape Memory Polymer (SMP) Flax Fiber Composite by Using Organic Polydopamine (PDA) Coating and Nanoparticles | |
| Qiang et al. | In situ nanoarchitectonics of magnesium hydroxide particles for property regulation of carboxymethyl cellulose/poly (vinyl alcohol) aerogels | |
| CN106397963A (en) | Expanded halogen-free flame-retardant EVA-based composite material and preparation method thereof | |
| CN112920470B (en) | Fire-resistant environment-friendly curtain wall and preparation method thereof | |
| Cheng et al. | Mineralized black phosphorus@ silica nanofiber multi-scale enhanced hydrogel coating for fire protection of polyurethane foams | |
| Zhang et al. | The synergistic effect of inorganic hybrid nanofibers and phytic acid-based nanosheets towards improving the fire retardancy and comprehensive performance of epoxy resin. | |
| Turku et al. | Progress in Achieving Fire-Retarding Cellulose-Derived Nano/Micromaterial-Based Thin Films/Coatings and Aerogels: A Review | |
| Dong et al. | Structure regulation of boron‐doped calcium hydroxystannate and its enhancement on flame retardancy and mechanical properties of PVC |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110803 Assignee: Chengdu Chuanke Chemical Engineering Co., Ltd. Assignor: Sichuan University Contract record no.: 2012510000127 Denomination of invention: Core-shell structure type composite flame retardant and preparation method thereof Granted publication date: 20120704 License type: Exclusive License Record date: 20121121 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20180118 |