CN114539623A - Application of chitosan-based flame retardant in polyurethane - Google Patents
Application of chitosan-based flame retardant in polyurethane Download PDFInfo
- Publication number
- CN114539623A CN114539623A CN202210175574.7A CN202210175574A CN114539623A CN 114539623 A CN114539623 A CN 114539623A CN 202210175574 A CN202210175574 A CN 202210175574A CN 114539623 A CN114539623 A CN 114539623A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- phytic acid
- flame retardant
- microspheres
- modified
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of flame-retardant composite materials, and discloses an application of a chitosan-based flame retardant in polyurethane, which comprises the following steps: s1: taking 12ml of phytic acid solution, adding 1.6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.5g of N-hydroxysuccinimide, and stirring for 40min to prepare a mixed solution A; s2: adding 15g of chitosan microspheres into 160ml of 1% acetic acid solution, carrying out ultrasonic treatment for 1.5h, and adding the mixture into the mixed solution A to enable phytic acid to react with the chitosan microspheres. The invention forms a novel flame retardant which integrates an acid source, a carbon source and a synergist, can generate flame-retardant related chemical reactions in a combustion process more timely, plays a role in synergistic flame retardance, can effectively solve the problem of dispersibility of chitosan or phytate added into a polyurethane matrix, can obviously improve the flame retardant property of a polyurethane material, and has less loss of mechanical property.
Description
Technical Field
The invention relates to the technical field of flame-retardant composite materials, in particular to application of a chitosan-based flame retardant in polyurethane.
Background
Based on the understanding of environmental protection, materials of biological origin are increasingly regarded as flame retardants, phytic acid exists in plants and contains a large amount of phosphorus elements, and in recent research reports, phytic acid can improve the flame retardant performance of polypropylene, cotton fibers, paper and the like. In addition, phytic acid is easy to chelate with metal ions, and some transition group metal elements can promote the interaction between an acid source and a carbon source in the intumescent flame retardant, so that the flame retardant efficiency is improved. Maldong et al (academic paper of northern and Central university of China, "preparation of Bio-based flame retardant and research on flame-retardant Polypropylene") selects metal ion Zn2+、Ni2+、Co2+The acetate is used as a reactant, zinc phytate (PA-Zn), nickel phytate (PA-Ni) and cobalt phytate (PA-Co) are prepared by reacting with PA (phytic acid), the three synergists are compounded with ammonium polyphosphate APP/pentaerythritol PER (3:1 wt%: wt%) to form an IFR (intumescent flame retardant) system, the flame-retardant PP (polypropylene) composite material is prepared by melt blending, and finally the three phytates play a good synergistic flame-retardant role in the PP/IFR system.
Compared with the acid source APP (ammonium polyphosphate) of the traditional intumescent flame retardant, the phytic acid as the acid source has poor effect, but the APP cannot realize the three-in-one effect. Therefore, in the research process, a part of APP is introduced to be compounded with the flame retardant. In addition, the academic thesis "preparation of chitosan microsphere bio-based flame retardant and application thereof in polylactic acid" in the third chapter, phytic acid is coated on chitosan microspheres as a flame retardant to be applied to polylactic acid flame retardation. Experiments show that when the phytic acid modified chitosan microspheres and APP are compounded and applied to rigid polyurethane foam, the mechanical property of the material is improved, but compared with the traditional flame retardant, such as expandable graphite, the flame retardant effect needs to be improved. Therefore, the phytic acid is adopted to modify the chitosan microspheres and the synergist is introduced at the same time, so that the transition metal ions are introduced. Of course, if the metal ions are compounded alone, the dispersion in the matrix is not good. In view of the above, in the experiment, the three phytate salts and IFR are compounded and added into rigid polyurethane foam (RPUF)/IFR (APP: chitosan microspheres), the flame retardant test result is not ideal, and the prepared phytate salts are not well dispersed in a polyurethane matrix. The chitosan is a biological charring agent which is concerned in recent years, and after the chitosan is prepared into microspheres, the chitosan microspheres have better flame retardant effect than chitosan powder under the condition of the same adding amount, and if the chitosan microspheres are prepared into charcoal microspheres after being modified and roasted, the effect is better, and the dispersibility in a matrix is better.
Therefore, the present invention proposes an application of a chitosan-based flame retardant in polyurethane for solving the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides application of a chitosan-based flame retardant in polyurethane.
In a first aspect of the invention, a chitosan-based flame retardant is provided for use in polyurethane.
Preferably, the chitosan-based flame retardant is phytic acid nickel-modified chitosan-based carbon microspheres.
In a second aspect of the present invention, a preparation process of a chitosan-based flame retardant is further provided, wherein the preparation of the phytic nickel modified chitosan-based carbon microspheres comprises the following steps:
weighing 8-10g of chitosan-based carbon microspheres modified by phytic acid, dispersing in 50-60ml of deionized water, stirring at 38-45 ℃, weighing 7-8g of Ni (Ac)2·4H2Adding O into the reaction kettle, continuously heating and stirring for 1-2h, performing suction filtration and washing, performing vacuum drying on the product at 62-70 ℃ for 1-2h, transferring the product into a tubular furnace, introducing nitrogen for carbonization, and preparing the chitosan-based carbon microsphere modified by nickel phytate.
On the other hand, it is also proposed that the preparation of the chitosan-based carbon microsphere modified by phytic acid comprises the following steps:
s1: adding 1.0-2.0g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.2-1.0g of N-hydroxysuccinimide into 5-20ml of phytic acid solution, and fully stirring for 20-40min to prepare a mixed solution A;
s2: adding 10-16g of chitosan microspheres into 150-250ml of acetic acid solution with the concentration of 1-2%, carrying out ultrasonic treatment for 1-2h, adding into the mixed solution A, fully reacting phytic acid and the chitosan microspheres at 48-62 ℃, fully stirring for 1.5-2h, adding into 180-220ml of absolute ethanol, uniformly stirring, carrying out suction filtration, washing and suction filtration by using absolute ethanol and deionized water in sequence, and finally carrying out vacuum drying at 60-68 ℃ to obtain the chitosan-based carbon microspheres modified by the phytic acid.
Preferably, the phytic acid modified chitosan-based carbon microspheres are mixed with Ni (Ac)2·4H2The mass ratio of O is 9: (7-8).
Preferably, the temperature of the carbonization is 200-300 ℃.
Preferably, the temperature is slowly raised to 200 ℃ in a tube furnace.
Compared with the prior art, the invention has the beneficial effects that: firstly, chitosan is made into microspheres, phytic acid is grafted to the surfaces of the microspheres by chemical modification, phytic acid is easily chelated with metal ions, and metal nickel ions are introduced to the surfaces of the phytic acid, so that a novel flame retardant integrating an acid source, a carbon source and a synergist is finally formed, a flame-retardant chemical reaction can be more timely generated in the combustion process, and a synergistic flame-retardant effect is achieved. According to the invention, on one hand, the dispersibility problem existing when the chitosan or phytate is added into the polyurethane matrix independently or in a compounding manner can be effectively improved, the obtained flame retardant acts on the rigid polyurethane foam, the flame retardant effect is greatly improved, and on the other hand, the influence of the addition of the flame retardant on the mechanical property of the rigid polyurethane foam material is small, and the stability is high.
Drawings
FIG. 1 is an infrared spectrum of CS, CSM, PA @ CSM and Ni-PA @ CSM of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The amount of chitosan, phytic acid, transition metal ions in the flame retardant of the present invention can be varied. Compared with chitosan and phytic acid, the additive amount (wt%) of the transition metal ions is relatively small, and the flame retardant disclosed by the invention is a flame retardant integrating an acid source, a carbon source and a synergist.
Examples
The invention provides an application of a chitosan-based flame retardant in polyurethane, which comprises the following steps:
preparation of phytic acid modified chitosan-based carbon microsphere (PA @ CSM)
S1: taking 12ml of phytic acid solution, adding 1.6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.5g of N-hydroxysuccinimide, and fully stirring for 40min to prepare a mixed solution A;
s2: adding 15g of chitosan microspheres into 160ml of 1% acetic acid solution, carrying out ultrasonic treatment for 1.5h, then adding the mixture into the mixed solution A, fully reacting phytic acid with the chitosan microspheres at the temperature of 60 ℃, fully stirring for 2h, then adding the mixture into 200ml of absolute ethyl alcohol, uniformly stirring, carrying out suction filtration, successively carrying out suction filtration washing by using absolute ethyl alcohol and deionized water, and finally carrying out vacuum drying at the temperature of 62 ℃ to obtain the phytic acid modified chitosan-based carbon microspheres.
Preparation of chitosan-based carbon microspheres (Ni-PA @ CSM) modified by nickel phytate
Weighing 9g of the phytic acid modified chitosan-based carbon microspheres obtained by preparation, dispersing the weighed 9g of the chitosan-based carbon microspheres in 50ml of deionized water, fully stirring the mixture at 40 ℃, and weighing 7.5g of Ni (Ac)2·4H2And O is added into the reaction kettle, the heating and the stirring are continued for 1 hour, the filtration and the washing are carried out, the product is dried in vacuum for 2 hours at 65 ℃, then the product is transferred into a tubular furnace to be introduced with nitrogen for carbonization, and the temperature is slowly raised to 200 ℃ to prepare the chitosan-based carbon microsphere modified by the phytic acid nickel.
Correlation analysis with respect to CSM, PA @ CSM, and Ni-PA @ CSM
1. Infrared analysis
As shown in FIG. 1, in CSM (Chitosan microsphere) infrared spectrum, at 1650cm-1And a characteristic peak of C ═ N double bonds appears nearby, which indicates that amino groups in CS (chitosan) react with aldehyde groups in glutaraldehyde, and indicates that the crosslinked chitosan microspheres are generated. 1650cm in CSM-1The peak is not disappeared, which shows that the microsphere is still in a cross-linked state. 1570cm-1The N-H deformation vibration peak in the primary amino group is weakened, which shows that the amino group reacts with the phosphoric acid group in PA (phytic acid). In PA @ CSM, 1127cm-1The characteristic peak of P ═ O in PA appears at 1062cm-1The peak at (A) is in the structure of CSThe characteristic peak of the six-membered cyclic ether, which is still present in PA @ CSM, indicates that the cyclic structure of CS is not destroyed. Therefore, the successful synthesis of the phytic acid grafted chitosan microsphere can be proved. For Ni-PA @ CSM, 1639cm can be observed-1The characteristic peak of stretching vibration at position of O-P-O, 1137cm-1Is P ═ O stretching vibration peak, 2848-2940 cm-1Is a C-H stretching vibration characteristic peak, 2800cm-1Absorption peak for P-OH, and 690cm-1And 611cm-1Is the absorption peak of nickel salt.
2. Limiting oxygen index analysis
In the experiment, the addition amount of CS (chitosan) or a modified product thereof is always 3.13g, the addition amount of APP (ammonium polyphosphate) is always 9.37g, the mass ratio of the CS to the APP is always 1:3, the polyurethane A is an isocyanate component, and the polyurethane B is a combination of polyol and other small materials. The details are shown in table 1 below:
table 1 shows the limiting oxygen index of different polyurethanes
As can be seen from Table 1, the limiting oxygen index of the neat RPUF-0 is 20.0%, and the addition of the flame retardant significantly increases the oxygen index of the polyurethane. When CS is used as a char-forming agent to be compounded with APP in a ratio of 1:3, the limiting oxygen index of RPUF-1 reaches 25.8%; when CS is made into microspheres and CSM is used as a char forming agent, the limiting oxygen index is improved to 26.2%; however, after the chitosan microspheres are further modified by phytic acid, the oxygen index of RPUF-3 is obviously improved to 26.5 percent. We believe this is most likely due to the microsphere structure facilitating the dispersion of chitosan in the polyurethane matrix. And the oxygen index of the RPUF-4 of the carbon microsphere which is modified by adding nickel phytate and is subjected to carbonization treatment is obviously improved to 29.6 percent. This is probably due to the introduction of the transition group metal ions which results in a good synergistic effect between the flame retardant and the matrix and a good dispersion of the flame retardant in the matrix. Compared with RPUF-3, the oxygen index of the polyurethane is obviously improved by 2.8 percent due to the introduction of the synergist in the Ni-PA @ CSM of the RPUF-4. It can thus be seen in the limiting oxygen index of the listed samples: RPUF (polyurethane) with CS; RPUF and CSM; RPUF and PA @ CSM; RPUF and Ni-PA @ CSM, the last group of Ni-PA @ CSM limit oxygen index is the best, flame retardant effect is the best.
3. Mechanical property test analysis
Because the polyurethane foam belongs to a hard and brittle material, the compressive strength of the polyurethane foam when the polyurethane foam is damaged by compression is measured by using a universal tensile testing machine, and the mechanical properties of different polyurethanes are obtained. The sample size used for the experiment was 50mm by 50 mm.
In general, the mechanical properties of the polymer material are significantly reduced by the addition of the additive, and the mechanical properties of the flame-retardant composite material obtained by adding the related flame retardant into the polyurethane foam are shown in table 2. When pure polyurethane foam is foamed, a large number of uniform air holes are formed inside, and when the pure polyurethane foam is damaged, the compression strength of RPUF-0 is 3.7 Mpa. The loss of the mechanical property of the material is maximum due to the addition of the flame retardant APP and CS powder, and the compression strength of RPUF-1 is only 1.7 MPa. In the RPUF-2 and the RPUF-3, the microsphere structure of the chitosan is more beneficial to filling polyurethane pores, so that the mechanical property is improved to a certain extent compared with that of the RPUF-1. And the chitosan microspheres in the RPUF-3 are modified by phytic acid and then are combined with the foam pores more tightly, so that the reinforcement effect is achieved, and the mechanical property is improved compared with that of the RPUF-2. The presence of the catalyst may affect the foaming behavior of the polyurethane. Thus, the addition of Ni-PA @ CSM to RPUF-4 results in the creation of more cells, the enhancement is more pronounced and the loss of mechanical properties is much less than pure.
TABLE 2 compression Properties of rigid polyurethane foams
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. An application of chitosan-based flame retardant in polyurethane.
2. The use according to claim 1, wherein the chitosan-based flame retardant is nickel phytate modified chitosan-based carbon microspheres.
3. The use according to claim 2, wherein the preparation of the phytic nickel modified chitosan-based carbon microspheres comprises the following steps:
weighing 8-10g of chitosan-based carbon microspheres modified by phytic acid, dispersing in 50-60ml of deionized water, stirring at 38-45 ℃, weighing 7-8g of Ni (Ac)2·4H2Adding O into the reaction kettle, continuously heating and stirring for 1-2h, performing suction filtration and washing, performing vacuum drying on the product at 62-70 ℃ for 1-2h, transferring the product into a tubular furnace, introducing nitrogen for carbonization, and preparing the chitosan-based carbon microsphere modified by nickel phytate.
4. The use according to claim 3, wherein the preparation of the phytic acid modified chitosan-based carbon microspheres comprises the following steps:
s1: adding 1.0-2.0g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.2-1.0g of N-hydroxysuccinimide into 5-20ml of phytic acid solution, and fully stirring for 20-40min to prepare a mixed solution A;
s2: adding 10-16g of chitosan microspheres into 150-250ml of acetic acid solution with the concentration of 1-2%, carrying out ultrasonic treatment for 1-2h, adding into the mixed solution A, fully reacting phytic acid and the chitosan microspheres at 48-62 ℃, fully stirring for 1.5-2h, adding into 180-220ml of absolute ethanol, uniformly stirring, carrying out suction filtration, washing and suction filtration by using absolute ethanol and deionized water in sequence, and finally carrying out vacuum drying at 60-68 ℃ to obtain the chitosan-based carbon microspheres modified by the phytic acid.
5. The use according to claim 3, wherein the phytic acid modified chitosan-based carbon particleBalls with Ni (Ac)2·4H2The mass ratio of O is 9: (7-8).
6. The use according to claim 3, wherein the temperature of the carbonization is 200-300 ℃.
7. Use according to claim 6, characterised in that the temperature is slowly raised to 200 ℃ in a tube furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210175574.7A CN114539623B (en) | 2022-02-24 | 2022-02-24 | Application of chitosan-based flame retardant in polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210175574.7A CN114539623B (en) | 2022-02-24 | 2022-02-24 | Application of chitosan-based flame retardant in polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114539623A true CN114539623A (en) | 2022-05-27 |
| CN114539623B CN114539623B (en) | 2023-06-30 |
Family
ID=81679293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210175574.7A Active CN114539623B (en) | 2022-02-24 | 2022-02-24 | Application of chitosan-based flame retardant in polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114539623B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141292A (en) * | 2022-07-18 | 2022-10-04 | 福州大学 | Full-biomass self-assembly single-component intumescent flame retardant and preparation method and application thereof |
| CN115558164A (en) * | 2022-09-20 | 2023-01-03 | 江西龙泰新材料股份有限公司 | Nano flame retardant with core-shell structure and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN106833079A (en) * | 2016-12-26 | 2017-06-13 | 中国科学院海洋研究所 | A kind of Porous Chitosan Microspheres for coating corrosion inhibiter and its preparation and application |
| CN107778446A (en) * | 2017-10-18 | 2018-03-09 | 圆容生物医药无锡有限公司 | Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break |
| CN109880267A (en) * | 2019-01-30 | 2019-06-14 | 华南理工大学 | A kind of high oxygen barrier polymer nanocomposite membrane and preparation method thereof |
| CN110038170A (en) * | 2019-04-04 | 2019-07-23 | 凯斯蒂南京医疗器械有限公司 | A kind of degradable polyurethane compound and application thereof |
| CN112011093A (en) * | 2020-08-06 | 2020-12-01 | 湖北工程学院 | Modified ammonium polyphosphate composite intumescent flame retardant and preparation method and application thereof |
| CN112063163A (en) * | 2020-08-25 | 2020-12-11 | 广州大学 | Anti-static heat-conducting flame-retardant composite material and preparation method thereof |
| US20210095102A1 (en) * | 2019-09-11 | 2021-04-01 | American University | Chitosan as an intumescing, thermoformable flame retardant |
| CN113214539A (en) * | 2021-06-23 | 2021-08-06 | 河北科技大学 | Bio-based flame retardant microcapsule and preparation method thereof |
| CN113354680A (en) * | 2021-06-23 | 2021-09-07 | 河北科技大学 | Bio-based reactive flame retardant, flame-retardant waterborne polyurethane emulsion and preparation method |
| CN113512270A (en) * | 2021-07-22 | 2021-10-19 | 同济大学 | Organic metal phosphonate @ boron nitride/epoxy composite material and preparation method thereof |
| CN113754900A (en) * | 2020-06-22 | 2021-12-07 | 北京化工大学 | Chitosan microsphere flame retardant and preparation method and application thereof |
| CN113754931A (en) * | 2020-06-22 | 2021-12-07 | 北京化工大学 | Chitosan microsphere bio-based flame retardant with core-shell structure and preparation method and application thereof |
-
2022
- 2022-02-24 CN CN202210175574.7A patent/CN114539623B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN106833079A (en) * | 2016-12-26 | 2017-06-13 | 中国科学院海洋研究所 | A kind of Porous Chitosan Microspheres for coating corrosion inhibiter and its preparation and application |
| CN107778446A (en) * | 2017-10-18 | 2018-03-09 | 圆容生物医药无锡有限公司 | Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break |
| CN109880267A (en) * | 2019-01-30 | 2019-06-14 | 华南理工大学 | A kind of high oxygen barrier polymer nanocomposite membrane and preparation method thereof |
| CN110038170A (en) * | 2019-04-04 | 2019-07-23 | 凯斯蒂南京医疗器械有限公司 | A kind of degradable polyurethane compound and application thereof |
| US20210095102A1 (en) * | 2019-09-11 | 2021-04-01 | American University | Chitosan as an intumescing, thermoformable flame retardant |
| CN113754900A (en) * | 2020-06-22 | 2021-12-07 | 北京化工大学 | Chitosan microsphere flame retardant and preparation method and application thereof |
| CN113754931A (en) * | 2020-06-22 | 2021-12-07 | 北京化工大学 | Chitosan microsphere bio-based flame retardant with core-shell structure and preparation method and application thereof |
| CN112011093A (en) * | 2020-08-06 | 2020-12-01 | 湖北工程学院 | Modified ammonium polyphosphate composite intumescent flame retardant and preparation method and application thereof |
| CN112063163A (en) * | 2020-08-25 | 2020-12-11 | 广州大学 | Anti-static heat-conducting flame-retardant composite material and preparation method thereof |
| CN113354680A (en) * | 2021-06-23 | 2021-09-07 | 河北科技大学 | Bio-based reactive flame retardant, flame-retardant waterborne polyurethane emulsion and preparation method |
| CN113214539A (en) * | 2021-06-23 | 2021-08-06 | 河北科技大学 | Bio-based flame retardant microcapsule and preparation method thereof |
| CN113512270A (en) * | 2021-07-22 | 2021-10-19 | 同济大学 | Organic metal phosphonate @ boron nitride/epoxy composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LORENZA MADDALENA: "Layer-by-layer assembly of efficient flame retardant coatings based on high aspect ratio graphene oxide and chitosan capable of preventing ignition of PU foam", POLYMER DEGRADATION AND STABILITY * |
| 张冰: "三聚氰胺植酸改性硬质聚氨酯泡沫的制备及性能", 南京工业大学学报 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141292A (en) * | 2022-07-18 | 2022-10-04 | 福州大学 | Full-biomass self-assembly single-component intumescent flame retardant and preparation method and application thereof |
| CN115558164A (en) * | 2022-09-20 | 2023-01-03 | 江西龙泰新材料股份有限公司 | Nano flame retardant with core-shell structure and preparation method thereof |
| CN115558164B (en) * | 2022-09-20 | 2023-10-24 | 江西龙泰新材料股份有限公司 | Nanometer flame retardant with core-shell structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114539623B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114539623B (en) | Application of chitosan-based flame retardant in polyurethane | |
| Meng et al. | Effects of expandable graphite and ammonium polyphosphate on the flame‐retardant and mechanical properties of rigid polyurethane foams | |
| Zeng et al. | Green flame-retardant flexible polyurethane foam based on cyclodextrin | |
| CN103382267B (en) | Organic amine modified ammonium polyphosphate, preparation method and applications thereof | |
| Li et al. | Influence of expandable graphite particle size on the synergy flame retardant property between expandable graphite and ammonium polyphosphate in semi-rigid polyurethane foam | |
| US20190153145A1 (en) | Composite polyurethane foam comprising graphene, processes for preraring the same use thereof | |
| CN112225945A (en) | Magnesium hydroxide-microcapsule flame retardant and preparation method thereof | |
| CN103193561B (en) | Explosive with low mechanical sensitivity and preparation method thereof | |
| Liu et al. | Synergistic effect of nano magnesium amino-tris-(methylenephosphonate) and expandable graphite on improving flame retardant, mechanical and thermal insulating properties of rigid polyurethane foam | |
| CN103554428A (en) | Core-shell synergistic flame retardant polyurethane microencapsulation expandable graphite and application thereof in rigid polyurethane foaming plastic | |
| CN101982497B (en) | Flame-retardant acrylonitrile-butadiene-styrene (ABS) composite material | |
| CN105542101A (en) | Compound intumescent flame retardant for hard polyurethane foam | |
| CN105037811A (en) | Ammonium polyphosphate flame retardant and preparing method thereof | |
| KR20200082851A (en) | Graphene oxide filler with aminated flame retardant, and polypropylene nanocomposite using the same | |
| CN110563944B (en) | Polyphosphazene covalent triazine polymer and preparation method and application thereof | |
| CN113637229B (en) | Modified MCA flame retardant and preparation method thereof | |
| CN107459492A (en) | A kind of organically-modified melamine polyphosphate and preparation method thereof | |
| CN109082017B (en) | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof | |
| CN113024933A (en) | High-toughness pearl wool material and preparation method thereof | |
| CN100475905C (en) | Process for preparing urea-formaldehyde resin additive, preparation method and uses | |
| CN112210629B (en) | Biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and preparation method thereof | |
| CN104844793A (en) | Preparation method and application of novel flame-retardant polyether glycol | |
| CN101967275A (en) | Nano magnesium carbonate modified fire protection engineering plastic and preparation method thereof | |
| CN101972620B (en) | Method for preparing microcapsule coated ammonium polyphosphate | |
| CN113980360B (en) | Bio-based flame retardant applied to polylactic acid film, and manufacturing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |