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Preparation method of nitrogen, phosphorus and silicon modified graphene/shape memory polyurethane flame-retardant composite material

A flame-retardant composite material, graphene technology, applied in the field of intelligent coating and packaging, can solve the problems of no flame-retardant components, no flame-retardant function, dispersion, etc., to achieve good flame retardancy and shape memory function, excellent Flame retardant and shape memory function, effect of improving flame retardant performance

Inactive Publication Date: 2019-04-19
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Chinese patent (CN108314787A) discloses a phosphorus-nitrogen-silicon-containing polymer modified graphene oxide flame retardant and its preparation method, which is modified from MAdiDOPO, MAPOSS and GMA monomers containing phosphorus, nitrogen and silicon elements by free radical polymerization The prepared functionalized graphene has flame retardant effect, but it can only be dispersed in organic solvents, which has certain limitations. In addition, the invention is not composited with polymer matrix materials, especially with intelligent Responsive polymer matrix material
Chinese patent (CN107163211A) discloses a preparation method of shape-memory polyurethane, which is obtained by polymerization of adamantyl star-shaped polyε-caprolactone, long-chain diol and isocyanate, and has shape-memory function, but not Contains flame retardant ingredients, does not have flame retardant function, and has potential safety hazards
Chinese patent (CN108192485A) discloses a method for preparing a thermally stable flame-retardant graphene oxide polyurethane coating, which is grafted with maleic anhydride and polyolefin on the surface of graphene oxide and applied to the coating. Graphene polyurethane has certain flame retardant properties, but the effective flame retardant component on the surface of modified graphene oxide is single, and additional additives are required during the application process, and the film formation does not have shape memory function
[0006] So far, there have been no reports on the research on functionalized graphene / shape memory polyurethane composites in both shape memory and flame retardancy at home and abroad.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1: Disperse 500 g of graphene oxide in deionized water (1 mg / mL) in a single-necked flask, slowly add 1 g of polyethyleneimine (M n ≈600), nitrogen protection, reaction at room temperature for 24 h, centrifugation, and drying to obtain nitrogen-modified graphene; disperse 250 mg nitrogen-modified graphene in butanone (3 mg / mL), add 1.08 g of 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, under nitrogen protection, reacted at room temperature for 24 h, centrifuged and dried to obtain nitrogen-phosphorus-modified graphene; 200 1 g of nitrogen-phosphorus-modified graphene was dispersed in methyl ethyl ketone (3 mg / mL), 2 g of isocyanate-propyltrimethoxysilane was added, under nitrogen protection, and reacted at 80 °C for 24 h. After centrifugation, nitrogen-phosphorus-silicon-modified graphene was obtained. spare. 10 g polycaprolactone (M n =1000) was placed in a three-necked flask equipped with a stirre...

Embodiment 2

[0017] Example 2: Disperse 500 g of graphene oxide in deionized water (1 mg / mL) in a single-necked flask, and slowly add 3.33 g of polyethyleneimine (M n≈2000), nitrogen protection, reaction at room temperature for 24 h, centrifugation, and drying to obtain nitrogen-modified graphene; disperse 250 mg nitrogen-modified graphene in butanone (3 mg / mL), add 1.08 g of 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, under nitrogen protection, reacted at room temperature for 24 hours, centrifuged and dried to obtain nitrogen-phosphorus-modified graphene; 200 g Nitrogen-phosphorus-modified graphene was dispersed in methyl ethyl ketone (3 mg / mL), 2 g of isocyanate-propyltriethoxysilane was added, under nitrogen protection, reacted at 80 °C for 24 h, centrifuged to obtain nitrogen-phosphorus-silicon-modified graphene, and set aside . 10 g polybutylene adipate (M n =1000) was placed in a three-necked flask equipped with a stirr...

Embodiment 3

[0018] Example 3: Disperse 500 g of graphene oxide in deionized water (1 mg / mL) in a single-necked flask, and slowly add 3.33 g of polyethyleneimine (M n ≈2000), nitrogen protection, reaction at room temperature for 24 h, centrifugation, and drying to obtain nitrogen-modified graphene; disperse 250 mg nitrogen-modified graphene in butanone (3 mg / mL), add 1.08 g of 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, under nitrogen protection, reacted at room temperature for 24 hours, centrifuged and dried to obtain nitrogen-phosphorus-modified graphene; 200 g Nitrogen-phosphorus-modified graphene was dispersed in methyl ethyl ketone (3 mg / mL), 2 g of isocyanate-propyltriethoxysilane was added, under nitrogen protection, reacted at 80 °C for 24 h, centrifuged to obtain nitrogen-phosphorus-silicon-modified graphene, and set aside . 10 g polybutylene adipate (M n =2000) in a three-necked flask equipped with a stirrer, a ther...

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Abstract

The invention discloses a preparation method of a nitrogen, phosphorus and silicon modified graphene / shape memory polyurethane flame-retardant composite material. The composite material is formed by functional graphene modified with nitrogen, phosphorus and silicon and a polyurethane precursor through suspension polymerization, wherein the functional graphene is obtained by conducting covalent modification on graphene oxide, polyethylenimine, phosphorus-containing flame retardant and 3-isocyanatopropyl triethoxysilane. The composite material can synergistically exert the effects of the graphene and polymers containing nitrogen, phosphorus and silicon on the surface of the graphene, and a polyurethane material has the functions of good flame retardancy and shape memory. In addition, the shape memory function of the composite material can be realized based on an external heating method, and meanwhile remote operation and control can be realized under the photothermal effect o f the graphene. The preparation method is easy and convenient to operate and environmentally friendly, and the prepared composite material has the excellent functions of flame retardancy and shape memory and canbe applied to the fields of intelligent coating, packaging and others.

Description

technical field [0001] The invention relates to the field of intelligent coating and packaging, in particular to the preparation of a nitrogen-phosphorus-silicon-modified graphene / shape-memory polyurethane flame-retardant composite material. Background technique [0002] In recent years, thermotropic shape memory polymers have been widely concerned and studied, and the typical representative multi-block polyurethane materials have been widely accepted in the scientific research and engineering circles because of their excellent mechanical properties, stable chemical properties, and simple processing. Favored, and widely used in smart coatings and packaging (Progress in Polymer Science, 2015, 49-50: 3-33.). However, most polyurethane materials are combustible or combustible, which greatly limits the safety and practicality of the material. Therefore, how to endow shape memory polyurethane with excellent flame retardant properties has become a research hotspot in the fields o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L75/04C08K13/06C08K9/04C08K9/06C08K3/04
CPCC08K3/042C08K9/04C08K9/06C08K9/08C08K13/06C08L2201/02C08L2201/08C08L2201/12C08L75/04
Inventor 金勇杜卫宁金泓宇杨恒
Owner SICHUAN UNIV