CN-119955178-B - Phenylalkali metal silsesquioxane coated polyoxometallate submicron sphere, composite material and application

Abstract

The invention relates to the field of flame retardants, in particular to a phenylalkali metal silsesquioxane coated polyoxometallate submicron sphere, a composite material and application thereof, which takes polyoxometallate, phenylalkali metal silsesquioxane and a reaction solvent as raw materials, the submicron spheres are prepared by taking phenyl alkali metal silsesquioxane as a core and utilizing the strong electronegativity of polyoxometallate to carry out surface coating under the action of strong static electricity. And then the submicron spheres are compounded with the EP to obtain the EP/POM (Mo) @ POSS (Li) composite material. The composite material prepared by the invention contains phenyl alkali metal silsesquioxane with smoke suppression and char formation effects and polyoxometallate with the function of promoting the catalysis of a matrix to char, and can greatly reduce the release of heat, smoke and toxic gas in the combustion process of the EP composite material, thereby providing guarantee for the life safety of personnel in a fire scene.

Inventors

• YE XINMING
• YANG FAN
• ZHANG JINNING
• BAI JIANKUN
• LI JIE
• LI YINGCHUN
• LI FENGCHAO
• GUO JINZHU

Assignees

• 中北大学
• 中电科风华信息装备股份有限公司

Dates

Publication Date

20260508

Application Date

20250321

Claims (6)

1. 1. A preparation method of a composite material of epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometallate submicron spheres is characterized in that, The method comprises the following steps: heating epoxy resin to 120-150 ℃, adding phenyl alkali metal silsesquioxane coated polyoxometalate submicron spheres, uniformly stirring, adding a curing agent 4,4' -diaminodiphenyl sulfone, and curing to obtain an epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere composite material; the preparation method of the phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere comprises the following steps of mixing phenyl alkali metal silsesquioxane, polyoxometalate and an organic solvent, and coating by intermolecular force to obtain the phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere, wherein the polyoxometalate is phosphomolybdic acid or phosphotungstic acid.
2. 2. The method for preparing the epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere composite material according to claim 1, wherein the phenyl alkali metal silsesquioxane is an incomplete condensation cage type phenyl silsesquioxane containing alkali metal sodium or an incomplete condensation cage type phenyl silsesquioxane containing alkali metal lithium.
3. 3. The method for preparing the epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometallate submicron sphere composite material according to claim 1, wherein the organic solvent is ethanol, methanol, acetone, tetrahydrofuran, dichloromethane, chloroform or dimethyl sulfoxide.
4. 4. The preparation method of the epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere composite material is characterized in that the mass ratio of the phenyl alkali metal silsesquioxane to the polyoxometalate is 10-23:7-15.
5. 5. The method for preparing the epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometalate submicron sphere composite material according to claim 1, wherein the mixing reaction temperature of the phenyl alkali metal silsesquioxane, the polyoxometalate and the organic solvent is 50-80 ℃ and the reaction time is 18-25 h.
6. 6. The method for preparing the epoxy resin/phenyl alkali metal silsesquioxane coated polyoxometallate submicron sphere composite material according to claim 1, wherein the curing temperature is 150-200 ℃ and the curing time is 2-5 h.

Description

Phenylalkali metal silsesquioxane coated polyoxometallate submicron sphere, composite material and application Technical Field The invention relates to the field of flame retardants, in particular to a phenyl alkali metal silsesquioxane coated polyoxometallate submicron sphere, a composite material and application. Background Epoxy resins are thermosetting resins with excellent adhesion, mechanical properties, corrosion resistance and electrical insulation. The polymer is formed by reacting epichlorohydrin with bisphenol A or polyalcohol, and contains more than two epoxy groups. The epoxy resin can be subjected to a crosslinking reaction with the hardener in the curing process to form a three-dimensional network structure, so that the epoxy resin has good thermal stability, chemical stability and dimensional stability. It has wide application in the fields of electronic and electric appliances, paint, composite material, adhesive, etc. However, with the wide application of the polymer materials in the life of people, the casualties of residential fire disaster are high. Once a fire occurs, the high carbon content of the polymer material becomes one of the biggest advantaged of fire spread. There is an increasing demand for functionalized epoxy resins, and there is therefore an urgent need for epoxy resins having flame retardant properties. The flame retardants commonly used today are five of halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, inorganic metal flame retardants and silicon flame retardants. Halogen flame retardants have limited thermal stability and can release toxic or even carcinogenic substances during combustion, so that traditional halogen flame retardants are mostly disabled and are more subject to toxicity evaluation. The phosphorus flame retardant meets the halogen-free environment-friendly requirement, but still has the problems of high volatility, low stability, poor compatibility and the like, and can generate molten drops which cause secondary injury in combustion. The nitrogen flame retardant has poor thermal stability, can be decomposed in the processing process, has poor water resistance, precipitation resistance and migration resistance, and can be precipitated on the surface or dissolved in water after long-time heating or long-time hot water soaking, thereby losing the flame retardant effect. Although the inorganic metal flame retardant does not release toxic gas during combustion and has smoke suppression performance, the inorganic metal flame retardant has low flame retardant effect rate and low compatibility with polymers, and can greatly reduce the mechanical properties of materials, so the inorganic metal flame retardant is generally used as a synergistic flame retardant to be compounded with other flame retardants. The silicon flame retardant is environment-friendly halogen-free flame retardant with the advantages of low smoke, no toxicity, easy char formation, anti-molten drop and the like. The phenyl alkali metal silsesquioxane belongs to a silicon flame retardant, and is an incomplete condensation cage type phenyl silsesquioxane containing alkali metal. The metallic element can catalyze and carbonize the polymer material. The phenyl alkali metal silsesquioxane contains seven rigid phenyl groups, and the size of the phenyl alkali metal silsesquioxane is generally 1-3 nm, so that the phenyl alkali metal silsesquioxane not only can improve flame retardant property, but also can obviously improve mechanical property when being introduced into a polymer matrix. Meanwhile, the phenyl alkali metal silsesquioxane has higher specific surface area and can be used as a carrier. Polyoxometalates such as phosphomolybdic acid and phosphotungstic acid are anionic metal-oxygen clusters with high electronegativity, and thus can be coated with phenyl alkali metal silsesquioxane under the action of strong static electricity. The polyoxometalate has several flame-retardant elements of phosphorus, molybdenum and tungsten, the phosphorus is used as acid source in the flame-retardant system, the two elements of molybdenum and tungsten have catalytic action on polymer and phenyl alkali metal silsesquioxane, and the flame-retardant system can be rapidly catalyzed into carbon in the combustion process. Meanwhile, the phenyl alkali metal silsesquioxane is an excellent smoke suppressant and a char forming agent, and the simultaneous action of the polyoxometallate and the phenyl alkali metal silsesquioxane can play a better role in smoke suppression and char formation. Therefore, the polyoxometallate and the phenyl alkali metal silsesquioxane are combined by using intermolecular force, the silicon-phosphorus flame retardant is compounded for use to realize synergistic effect, and the defects of the phosphorus flame retardant and the silicon flame retardant can be avoided. Disclosure of Invention The invention provides a phenyl alkali metal silsesquioxane coated poly