# US 2023/0265261 A1 · Nanocomposite Flame Retardant, Flame Retardant Bismaleimide Resin and Preparation Method Thereof

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- Number: US 2023/0265261 A1
- Document ID: US20230265261A1
- Status: Published application
- Kind: A1
- Application number: 18/111,589
- Filed: 2023-02-19
- Published: 2023-08-24
- Earliest claimed: 2022-02-19
- Assignees: Nanjing Tech University
- Applicants: Nanjing Tech University
- Inventors: ZHIRONG WANG; HAOBO ZHOU; JUNLING WANG; YANGYAN ZHENG
- Web page: https://patentgrep.com/patent/US20230265261A1

## CPC

- C08K 3/22: of metals
- C08G 73/12: Unsaturated polyimide precursors
- C08G 73/126: {the unsaturated precursors being wholly aromatic}
- C08K 7/00: Use of ingredients characterised by shape
- C08L 79/085: {Unsaturated polyimide precursors}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C08K 2003/2248: {of copper}
- C08K 2201/005: Additives being defined by their particle size in general
- C08K 2201/011: Nanostructured additives
- C08K 2201/014: Additives containing two or more different additives of the same subgroup in C08K
- C08L 2201/02: Flame or fire retardant/resistant
- Y02E 60/10: Energy storage using batteries
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present application discloses a nanocomposite flame retardant. The nanocomposite flame retardant includes 9.7-9.8 wt % of MXene nanosheets, 72.7-76.5 wt % of bimetallic hydroxide and 13.8-17.5 wt % of cuprous oxide particles. The present disclosure further discloses flame-retardant bismaleimide resin added with the nanocomposite flame retardant and a preparation method of the flame-retardant bismaleimide resin. According to the present disclosure, the flame retardant is prepared from magnesium and aluminum elements, so the production cost of the flame retardant is reduced; and meanwhile, the particle size of the cuprous oxide particles is reduced, the specific surface area of cuprous oxide is increased, the catalytic efficiency of the cuprous oxide per unit mass can be improved, and then the flame-retardant and toxicity-reducing effects of products are improved.

## Claims

### Claim 1

A nanocomposite flame retardant, comprising:
9.7-9.8 wt % of MXene nanosheets,
72.7-76.5 wt % of bimetallic hydroxide, and
13.8-17.5 wt % of cuprous oxide particles.

### Claim 2 (depends on 1)

The nanocomposite flame retardant according to claim 1, wherein
a particle size of the cuprous oxide particles is 5 to 10 nm.

### Claim 3 (depends on 1)

The nanocomposite flame retardant according to claim 1, prepared by the following preparation method:
etching and stripping Ti3AlC2 to obtain the MXene nanosheets;
enabling Cu, Mg and Al trimetal LDH to grow on a single-layer MXene nanosheet to obtain MXene/LDH composite particles; and
then reducing Cu2+ in the MXene/LDH into the cuprous oxide particles in situ by ascorbic acid so as to obtain powdery MXene/LDH/Cu2O, namely the nanocomposite flame retardant, wherein the nanocomposite flame retardant is a ternary nanocomposite flame retardant.

### Claim 4 (depends on 3)

The nanocomposite flame retardant according to claim 3, wherein the preparation method comprises the following steps:
(1) preparation of MXene nanosheets:
dissolving lithium fluoride powder in hydrochloric acid to prepare a mixed solution containing hydrofluoric acid; adding Ti3AlC2 powder into the mixed solution, and maintaining stirring to realize etching reaction; after etching, carrying out first centrifugal treatment to obtain Ti3C2Tx; centrifugally washing Ti3C2Tx with deionized water until the pH value is 6-7; after washing, dispersing Ti3C2Tx in deionized water and performing ultrasonic treatment for stripping; finally, carrying out second centrifugal treatment, and collecting an upper suspension to obtain an MXene nanosheet suspension containing the MXene nanosheets;
(2) preparation of MXene/LDH composite particles:
dissolving CuCl2·2H2O, MgCl2·6H2O and AlCl3·6H2O in deionized water to prepare a solution A;
dissolving NaOH and Na2CO3 in water to prepare a solution B;
adding deionized water into the MXene nanosheet suspension for dilution and stirring to prepare MXene dispersion liquid;
adding dropwise the solution A into the MXene dispersion liquid to obtain a solution C;
then regulating the pH value of the solution C to be about 9.5-10.5 with the solution B; maintaining stirring for coprecipitation reaction; after the reaction, carrying out third centrifugal treatment to obtain a third precipitate; washing the third precipitate with water and ethyl alcohol; and then carrying out vacuum drying to obtain the MXene/LDH composite particles;
(3) preparation of MXene/LDH/Cu2O:
dispersing MXene/LDH composite particles in deionized water and performing ultrasonic stirring to obtain MXene/LDH dispersion liquid; then adding dropwise an ascorbic acid solution, and maintaining stirring for reduction reaction; after the reaction, carrying out fourth centrifugal treatment to obtain a fourth precipitate; washing the fourth precipitate with water and ethyl alcohol; and carrying out vacuum drying to obtain the MXene/LDH/Cu2O composite particles.

### Claim 5 (depends on 4)

The nanocomposite flame retardant according to claim 4, wherein
in the step (1), the concentration of lithium fluoride in a lithium fluoride solution is 50 g/L, and the concentration of hydrochloric acid is 9-12 mol/L; and during etching reaction, the reaction temperature is 35-45° C., and the reaction time is 24-48 h; and MXene is subjected to ultrasonic treatment in deionized water for 0.5-1 h;
the first centrifugal treatment is carried out for 5 min under a condition of 3,500 rpm;
the second centrifugal treatment is carried out for 10 min under a condition of 3,500 rpm;
the mass ratio of lithium fluoride to Ti3AlC2 powder is 1:1.

### Claim 6 (depends on 4)

The nanocomposite flame retardant according to claim 4, wherein
in the step (2), when MXene/LDH composite particles are prepared, the volume ratio of the solution A to the MXene dispersion liquid is 1:6;
in the solution A, the total concentration of CuCl2·2H2O, MgCl2·6H2O and AlCl3·6H2O is 140.2 g/L; and in the solution A, the molar ratio of CuCl2·2H2O to MgCl2·6H2O to AlCl3·6H2O is 3:2:2;
in the MXene dispersion liquid, the concentration of MXene is 1 g/L;
in the solution B, the concentration of NaOH is 1.6 mol/L, and the concentration of Na2CO3 is 0.8 mol/L;
in the coprecipitation reaction, the reaction temperature is 25-30° C., and the reaction time is 12-24 h.

### Claim 7 (depends on 4)

The nanocomposite flame retardant according to claim 4, wherein
the mass concentration of the MXene/LDH composite particles in the MXene/LDH solution is 10 g/L;
the concentration of ascorbic acid in the ascorbic acid solution is 0.1 mol/L; and the pH value is regulated to be 9-10 by a 0.4 mol/L NaOH solution;
the mass ratio of the ascorbic acid to the MXene/LDH composite particles is 3:2;
in the reduction reaction, the reaction temperature is 50° C., and the reaction time is 8-10 h.

### Claim 8 (depends on 1)

A flame-retardant bismaleimide resin, containing the nanocomposite flame retardant of any one of claim 1.

### Claim 9 (depends on 8)

The flame-retardant bismaleimide resin according to claim 8, wherein the content of the nanocomposite flame retardant is 2-6 wt %.

### Claim 10 (depends on 8)

A production method of the flame-retardant bismaleimide resin of claim 8, comprising the following steps:
mixing Mxene/LDH/Cu2O powder and 2,2′-diallyl bisphenol A, and performing ultrasonic stirring for 30 min in a water bath at 80° C. to obtain a first mixed solution;
adding N,N′-(4,4′-methylenediphenyl)bismaleimide into the first mixed solution and stirring for 20-30 min in an oil bath at 130° C. to obtain a prepolymer;
pouring the prepolymer into a mold and subjected to vacuum degassing for 30 min at 130° C.; transferring the prepolymer into a drying oven for curing after vacuum degassing; and after curing, naturally cooling the prepolymer to obtain the flame-retardant bismaleimide resin;
wherein the temperature control in curing is as follows in sequence: firstly, the temperature is increased to be 150° C. for the first time, and the temperature is maintained for 2 h; then the temperature is increased to be 180° C. for the second time, and the temperature is maintained for 2 h; the temperature is increased to be 200° C. for the third time, and the temperature is maintained for 2 h; the temperature is increased to be 220° C. for the fourth time, and the temperature is maintained for 2 h; and finally, the temperature is increased to be 240° C. for the fifth time, and the temperature is maintained for 4 h; and wherein
the mass ratio of 2,2′-diallyl bisphenol A to N,N′-(4,4′-methylenediphenyl)bismaleimide is 2:3.