CN-119431736-B - Aliphatic amine-containing cardanol basic sign mechanical reinforced flame-retardant epoxy resin and preparation method thereof

CN119431736BCN 119431736 BCN119431736 BCN 119431736BCN-119431736-B

Abstract

The invention discloses a cardanol basic sign mechanical reinforced flame-retardant epoxy resin containing aliphatic amine and a preparation method thereof, belonging to the technical field of flame retardance, wherein the preparation method comprises the steps of introducing aldehyde groups on benzene rings of cardanol and then reacting with diamine to form epoxy resin precursor substances, fully mixing and reacting the epoxy resin precursor substances, epichlorohydrin, a phase transfer catalyst and alkaline substances to obtain the cardanol basic sign flame-retardant and mechanical reinforced epoxy resin, solving the problems of high brittleness, flammability, incapability of both flame retardant performance and mechanical performance and the like caused by nonrenewable raw materials of the traditional bisphenol A epoxy resin, taking biomass cardanol with wide sources and low cost as raw materials, combining flexibility of aliphatic chains and rigidity of aromatic hydrocarbon, improving the flame retardant efficiency of a matrix of the cardanol, and improving the mechanical performance of the cardanol, wherein the cured epoxy resin system has excellent thermal stability, flame retardance and mechanical performance and has excellent popularization and application prospects.

Inventors

ZHI MAOYONG
SU BINGJIAN
PAN ZHIHENG
ZHAO HAIHUI

Assignees

中国民用航空飞行学院

Dates

Publication Date: 20260512
Application Date: 20241126

Claims (9)

1. The cardanol basic character mechanics reinforced flame-retardant epoxy resin containing fatty amine is characterized in that the molecular structural formula of the flame-retardant epoxy resin is as follows: ; Wherein R is an aliphatic linear chain having 4 to 12 carbon atoms and derivatives thereof; The preparation method of the cardanol basic feature mechanical reinforced flame-retardant epoxy resin containing fatty amine comprises the following steps of S1 is cashew phenol aldehyde-based, S2 is a take seat alkali-introducing structure, S3 is epoxidation, and the specific steps are as follows: Step S1, fully mixing hydrogenated cardanol, a surfactant and tin tetrachloride in an organic solvent at room temperature, adding paraformaldehyde, stirring for 30min, reacting in a reaction container under the protection of nitrogen, and purifying the mixture to obtain the aldehyde cardanol, wherein the aldehyde cardanol has the following molecular structural formula: ; Step S2, fully mixing the aldehyde cardanol obtained in the step S1 with diamine in an organic solvent, reacting in a reaction vessel under the protection of nitrogen, and purifying to obtain a cardanol-based epoxy resin precursor containing a Schiff base structure, wherein the molecular structural formula of the epoxy resin precursor is shown as follows: ; And step S3, fully mixing and reacting epoxy chloropropane, the epoxy resin precursor obtained in the step S2, a phase transfer catalyst and an alkaline substance, reacting in a reaction container under the protection of nitrogen, and purifying to obtain the cardanol basic feature mechanical reinforcing flame-retardant epoxy resin.
2. The aliphatic amine-containing cardanol basic-feature-mechanics-enhanced flame-retardant epoxy resin as claimed in claim 1, wherein the molar ratio of hydrogenated cardanol, surfactant, stannic tetrachloride, paraformaldehyde and organic solvent in the step S1 is 0.8-1.2:0.08-0.15:0.08-0.12:1.2-1.8:2.0-3.0, and the reaction temperature in the step S1 is 80-100 ℃, and the reaction time is 8-9 hours.
3. The aliphatic amine-containing cardanol basic-mechanical-strength-enhancing flame-retardant epoxy resin of claim 2, wherein the surfactant comprises one or more of benzyltriethylammonium chloride TEBA and tetrabutylammonium bromide TBAB, and the organic solvent in step S1 is toluene or triethylamine.
4. The aliphatic amine-containing cardanol mechanical enhancement flame-retardant epoxy resin of claim 1, wherein the molar ratio of the cardanol, diamine and organic solvent in the step S2 is 0.8-1.2:0.3-0.6:2.0-3.0, the reaction temperature in the step S2 is 70-90 ℃, the reaction time is 5-6 hours, and the diamine is aliphatic linear diamine with 4-12 carbon atoms and its derivatives.
5. The aliphatic amine containing cardanol mechanical enhancement flame retardant epoxy resin of claim 4, wherein the organic solvent in step S2 is N, N-dimethylacetamide DMAC.
6. The cardanol basic character mechanical enhancement flame-retardant epoxy resin containing aliphatic amine as set forth in claim 1, wherein the molar ratio of epoxy resin precursor, epichlorohydrin, phase transfer catalyst and alkaline substance in the step S3 is 0.8-1.2:15-25:0.08-0.15:1.5-2.5, the reaction temperature in the step S3 is 70-90 ℃, and the reaction time is 5-8 hours.
7. The aliphatic amine-containing cardanol basic mechanical enhancement flame-retardant epoxy resin as defined in claim 6, wherein the phase transfer catalyst comprises one or more of quaternary ammonium salt, polyether and quaternary phosphonium salt, the quaternary ammonium salt is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride, the polyether is chain polyethylene glycol, the quaternary phosphonium salt is one or more of tetraphenyl phosphine chloride, triphenylphosphine and derivatives thereof, the alkaline substance is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate, and the concentration of the alkaline substance is 10mol/L.
8. The cardanol basic feature mechanical reinforcing flame retardant epoxy resin containing aliphatic amine as set forth in claim 1, wherein in step S2 and step S3, the purification process comprises the steps of separating and drying: The separation step comprises extracting and separating the reacted mixture with ethyl acetate and distilled water for several times until the upper organic liquid is clear; The drying step is specifically to sequentially dry the organic liquid by using a drying agent and a vacuum drying box, and the drying agent is used for removing moisture and organic impurities in the organic liquid.
9. The aliphatic amine containing cardanol mechanical enhancement flame retardant epoxy resin of claim 8, wherein the drying agent is one or more of sodium sulfate, sodium carbonate, potassium carbonate, calcium chloride, calcium sulfate, calcium oxide, and the drying temperature is 50-80 ℃.

Description

Aliphatic amine-containing cardanol basic sign mechanical reinforced flame-retardant epoxy resin and preparation method thereof Technical Field The invention relates to the technical field of flame retardance of high polymer materials, in particular to a cardanol basic feature mechanics reinforced flame retardance epoxy resin containing fatty amine and a preparation method thereof. Background Thermosetting epoxy resins are three-dimensional network polymers formed by crosslinking epoxy monomers or oligomers with curing agents, which are unique in their insolubility and insolubility. Such materials exhibit excellent thermodynamic properties, excellent chemical resistance, and excellent dimensional stability, and thus are widely used in various fields such as aerospace, paints, high-performance composite materials, and electronic encapsulants. Currently, more than 90% of the epoxy resins worldwide are composed of bisphenol a diglycidyl ether synthesized from bisphenol a and epichlorohydrin. Bisphenol A is a compound derived from non-renewable petroleum resources. The excessive exploitation and the excessive use of the energy source can not only aggravate the energy crisis, but also form a potential threat to the health of human bodies. In view of the above-mentioned health, energy and environmental considerations, the current scientific research field is actively working on exploring and developing suitable biomass raw materials in order to achieve effective substitution of petroleum-based bisphenol a. The research direction not only accords with the concept of sustainable development, but also opens up a new path for the future development of the epoxy resin industry. The bio-based epoxy resin, which is an innovative synthetic material, shows remarkable characteristics of green, environment protection and reproducibility by adopting renewable raw materials to partially or fully replace traditional resin components, and has great potential in production and living application. The material can be used as an ideal substitute for traditional petroleum-based plastics and coatings, effectively relieves the crisis of petroleum resource shortage, and obviously reduces the environmental pollution degree. The cardanol is derived from natural cashew nut shell liquid, has wide and easily available resource sources, is a unique alkylphenol, has wide practical value in the preparation of thermosetting polymers, and is regarded as a precious biological monomer source. In the prior art, cardanol-based derivative toughened flame-retardant epoxy resin is also available, so that the flame retardance and mechanical properties of the epoxy resin can be effectively improved. The invention patent CN114524927A reports the application of cardanol bio-based polyol in flexible package adhesive, and effectively solves the problem of solvent-free ink dissolution. The invention patent CN114920989A reports an application method of cardanol on rubber, and the method can effectively improve the performance of rubber products in rubber mixing. Also disclosed are bio-based tougheners containing rigid-flexible structures, which are used in epoxy resins, which can improve the toughness of the epoxy resins to some extent by utilizing the toughness of the fatty chains in the molecular structure, but which have lower mechanical properties due to the altered steric hindrance of the epoxy resin itself, and which increase the complexity and economic costs of the preparation process thereof. Therefore, there is a need for an epoxy resin system which has excellent mechanical properties, degradability and flame retardant properties, and which is simple to prepare, low in cost and easy for industrial mass production. Disclosure of Invention The invention aims to overcome the defects of the prior art, provides a cardanol basic feature mechanics reinforced flame-retardant epoxy resin containing fatty amine and a preparation method thereof, and belongs to the technical field of flame retardance; the preparation method comprises the steps of introducing aldehyde groups on benzene rings of cardanol, reacting with diamine to form epoxy resin precursor substances, fully mixing and reacting the epoxy resin precursor substances, epoxy chloropropane, a phase transfer catalyst and alkaline substances to obtain the cardanol basic sign flame-retardant and mechanical reinforced epoxy resin, solving the problems that raw materials of the traditional bisphenol A epoxy resin are not renewable, the brittleness is large, the flame retardance and the mechanical properties cannot be considered, and the like caused by a molecular structure, taking biomass cardanol with wide sources and low cost as raw materials, combining the flexibility of aliphatic chains and the rigidity of aromatic hydrocarbons, improving the mechanical properties of the matrix flame-retardant efficiency of the matrix of the cardanol, and the cured epoxy resin system has excellent thermal stability, flam