CN111205437B - Preparation method of biological basic characteristic type flame-retardant epoxy resin - Google Patents
Preparation method of biological basic characteristic type flame-retardant epoxy resin Download PDFInfo
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Abstract
The invention provides a preparation method of a biological basic characteristic type flame-retardant epoxy resin, which comprises the steps of utilizing vanillic acid to react with resorcinol to obtain trihydric alcohol containing a benzophenone structure, further introducing an epoxy group through a phenolic hydroxyl group, mixing and curing an obtained biological epoxy monomer and a curing agent under certain conditions to obtain the flame-retardant biological epoxy resin, wherein the obtained biological epoxy monomer is similar to a DGEBA structure used in the general industry. The resin has the advantages of wide raw material source, environmental protection, simple synthesis process, high thermal stability, good flame retardant property, 35% of carbon residue at 800 ℃, 34% of limit oxygen index and V-0 level of vertical combustion grade.
Description
Technical Field
The invention relates to a preparation method of a biological basic characteristic type flame-retardant epoxy resin, which uses renewable biological energy as a raw material to design the molecular structure of an epoxy monomer, so that the prepared epoxy resin has good flame-retardant performance without introducing flame-retardant elements.
Background
The petroleum-based plastic has various excellent properties, can provide various raw materials and products for various industries such as buildings, automobiles, machine manufacturing, electronic information and the like, plays an important role in modern social life, and has the characteristics of high added value of biomass resources which are increasingly emphasized along with the continuous deep understanding of people on the problems of environmental pollution, resource crisis and the like, so that renewable biomass resources are found to replace petroleum products to gain attention of people. Most biological materials are non-toxic and harmless, have rich content, can relieve the pressure of energy exhaustion and pollution aggravation, reduce the dependence of the plastic industry on petroleum-based chemical product supply, and reduce the environmental pollution caused in the production process of high polymer materials. Currently, research on bio-based polymer materials is mainly limited to some natural polymers or thermoplastic materials such as starch plastics, cellulose-based materials, PHBV, PLA, PBS, bio-based PE, etc., and research on bio-based thermosetting resins is relatively rare.
The epoxy resin is one of the most widely used thermosetting resins, the global yield is about 200 ten thousand tons per year, 85 percent of bisphenol A epoxy resin is mainly prepared from 2 raw materials of bisphenol A and epoxy chloropropane. Epichlorohydrin can be prepared from bio-based glycerol and has been industrialized, but more than 67% of bisphenol A completely depends on petrochemical resources at present. Meanwhile, bisphenol A has great threat to the health of living bodies, and the development of environment-friendly resin which can replace bisphenol A epoxy resin is significant. Meanwhile, the oxygen index of the epoxy resin is 19.8, the epoxy resin can be combusted in the air after being ignited, and the combustion speed is high, so that how to improve the flame retardant property of the epoxy resin and expand the application range of the epoxy resin is also a big subject of application type research.
The flame retardant is added into the epoxy resin, so that the flame retardant efficiency is often unsatisfactory, on one hand, in order to obtain an ideal flame retardant effect, a large amount of flame retardant needs to be added, so that the cost is increased, and on the other hand, because the flame retardant has a limited structural design and a relatively low crosslinking density, the Tg and the initial decomposition temperature of the epoxy resin are reduced along with the addition of the flame retardant, so that the mechanical property is reduced. The intrinsic flame retardance is that a structure easy to form carbon is introduced into the epoxy resin, so that the thermal stability of the epoxy resin is enhanced during the decomposition of the polymer, the aromatization and carbonization of the polymer are promoted, the carbon residue is finally increased, the migration of a flame retardant can be avoided, and the flame retardant efficiency is improved.
Vanillin and vanillin belong to cinnamic acid derivatives, which are widely found in nature, such as Vanilla planifolia, vanilla pod, Peru balsam, benzoin ointment, Java essential oil and many other plants and essential oils, and are important raw materials in bio-based polymers. Resorcinol is an important fine chemical raw material, has mature matched production technology in China, and is low in price. Chinese patent CN102532480A discloses an epoxy resin that exhibits excellent properties such as high thermal decomposition stability, high heat resistance, low thermal expansion, flame retardancy, and low moisture absorption, and a method for producing the same. The phenolic resin of the epoxy resin intermediate is obtained by reacting dihalogenated benzophenone with bisphenol or resorcinol, and then the final epoxy resin is obtained by reacting the dihalogenated benzophenone with epichlorohydrin. The resin has excellent performances such as high thermal decomposition stability, high heat resistance, low thermal expansion, flame retardancy, low hygroscopicity and the like. But the whole process flow is more complicated, the amount of the filler is more, and the industrial popularization and the mechanical property of the process are greatly influenced. Chinese patent CN101531754A discloses a preparation method of phosphorus-containing epoxy resin, which comprises a, heating and melting 200-300 parts by weight of epoxy resin; b. stirring the melted epoxy resin, and simultaneously adding 20-50 parts by weight of phosphorus-containing hydroquinone and 0.03-0.08 part by weight of a catalyst, wherein the reaction temperature is controlled at 80-160 ℃; c. and (3) preserving the heat for 8-14 hours, and then cooling to obtain a reactant, namely the phosphorus-containing epoxy resin. The phosphorus-containing epoxy resin is an environment-friendly product which has excellent flame retardant property and heat resistance and can meet the requirements of no halogen and no lead. The preparation method has the advantages of simple preparation method, low cost due to the fact that phosphorus-containing hydroquinone is used for replacing DOPO, low requirement on reaction temperature, energy-saving and environment-friendly preparation process, and no harm to human bodies. However, the additive flame retardant is different from the material in structure, and is easy to migrate in the material, so that the flame retardant efficiency is reduced. Chinese patent CN109912780A discloses a preparation method of low-viscosity heat-resistant epoxy resin, which comprises the following specific steps: firstly synthesizing low-molecular-weight thermoplastic phenolic resin by adopting phenol, formaldehyde and oxalic acid, then synthesizing an etherified intermediate by adopting the thermoplastic phenolic resin, resorcinol, bisphenol S, a catalyst, a solvent and excessive epichlorohydrin through an etherification reaction, then adding sodium hydroxide to perform a ring-closing reaction to generate epoxy resin, and finally obtaining the low-viscosity heat-resistant epoxy resin through the steps of separation, washing, neutralization, purification and the like. The thermal deformation temperature of the synthesized low-viscosity heat-resistant epoxy resin exceeds that of the low-viscosity novolac epoxy resin, but the viscosity is less than 50% of that of the low-viscosity novolac epoxy resin, and the solvent-free epoxy anticorrosive paint prepared by matching the low-viscosity novolac epoxy resin with the heat-resistant amine curing agent can be conveniently applied to the field of high-temperature anticorrosion, and avoids the application defects of the existing liquid epoxy resin. However, because of the low molecular weight, the epoxy resin has a low number of rigid benzene ring structures and thus has poor mechanical strength after curing.
The invention provides a preparation method of a biological basic characteristic type flame-retardant epoxy resin, raw materials are vanillic acid and resorcinol, the price is low, and the source is wide. And the structure of the benzophenone-containing flame retardant epoxy resin contains a plurality of aromatic groups, which is beneficial to improving the thermal stability of the epoxy resin, and the structure of the benzophenone is beneficial to improving the thermal stability and carbon residue of the resin, so that the flame retardant property of the epoxy resin is improved.
Disclosure of Invention
The invention aims to solve the problems that the traditional epoxy resin raw material is toxic and non-renewable and has poor flame retardant property, and provides a preparation method of a biological basic characteristic type flame retardant epoxy resin. The method has the advantages of wide raw material source, low price, simple steps in the whole reaction process and no need of too severe reaction conditions. The quantity of aromatic rings and epoxy groups is large, which is beneficial to improving the final crosslinking density and rigidity of the resin. Benzophenone is used as a carbon forming structure, and is beneficial to improving the flame retardant property of the epoxy resin.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows: a basic biological characteristic type flame-retardant epoxy resin is prepared through catalytic Friedel-crafts acylation reaction of vanillic acid and resorcinol, substitution reaction of vanillic acid and epichlorohydrin to obtain benzophenone epoxy monomer, and heating to mix it with curing agent DDS for solidification.
According to the preparation method of the biological basic characteristic type flame-retardant epoxy resin, the vanillic acid and the resorcinol undergo a Friedel-crafts acylation reaction under a catalytic condition, then undergo a substitution reaction with epichlorohydrin to obtain a benzophenone epoxy monomer, and the benzophenone epoxy monomer and a curing agent DDS are mixed and cured under a heating condition to obtain the biological basic characteristic type flame-retardant epoxy resin.
The preparation method of the biological basic characteristic type flame-retardant epoxy resin comprises the following synthetic steps of the benzophenone epoxy monomer:
(1) preparation of product DA: heating vanillic acid, resorcinol and boron trifluoride diethyl etherate for full reaction, cooling to room temperature, pouring sodium acetate buffer solution, standing, filtering to obtain a product, cleaning, recrystallizing for purification, and vacuum drying to obtain a product DA, wherein the reaction process is shown as the following formula:
(2) preparing a benzophenone epoxy monomer: the product DA is placed in N 2 Under the environment, epichlorohydrin is added into a flask at room temperature, heating and reacting are carried out, NaOH solution is slowly added, the reaction mixture is subjected to heat preservation reaction at the temperature, the reaction mixture is cooled to room temperature, filtering is carried out to obtain a product, the product is washed by a solvent, and then vacuum drying is carried out to obtain the benzophenone epoxy monomer, wherein the reaction process is shown as the following formula:
the molar ratio of vanillic acid to resorcinol is 0.7-1.5: 1, the molar ratio of vanillic acid to boron trifluoride diethyl etherate is 1: 3-8, the molar ratio of vanillic acid to sodium acetate is 1: 20-50, and the mass fraction of the sodium acetate buffer solution is 5-25%.
The recrystallization solvent is one of tetrahydrofuran, acetone, methanol and dichloromethane.
The mole ratio of epichlorohydrin to DA is 3-11: 1, the mole ratio of NaOH to DA is 3-12: 1, and the mass fraction of NaOH solution is 10-40%.
The cleaning solvent is one of dimethylbenzene, ethanol, butanone and dichloromethane.
The temperature of the heating reaction in the first step is 70-120 ℃, and the temperature of the heating reaction in the second step is 70-130 ℃.
Stirring benzophenone epoxy monomer at 30-80 ℃ for 8-30 min, adding curing agent DDS, stirring for 3-8 min, pouring into a preheated mold, reacting at 120 ℃ for 2h, at 150 ℃ for 2h, at 180 ℃ for 2h, and at 200 ℃ for 1 h.
The mass ratio of the benzophenone epoxy monomer to the curing agent DDS is 1: 3-6.
Has the advantages that:
(1) two raw materials, namely vanillic acid and resorcinol, for preparing the benzophenone epoxy monomer are low in price and wide in source, wherein the vanillic acid belongs to a bio-based material and is green and environment-friendly;
(2) the prepared benzophenone epoxy monomer has high aromatic ring content and a large number of epoxy groups, and is beneficial to improving the crosslinking density and the mechanical property of the final resin;
(3) the whole preparation process has few steps, simple process and no pollutant;
(4) benzophenone is a good char-forming structure, is beneficial to improving the flame retardant property of epoxy resin, the maximum limit oxygen index can reach 34 percent, the vertical combustion level can reach V-0 level, and T 5％ The carbon residue can reach 35 percent at 321 ℃.
Drawings
FIG. 1 is a nuclear magnetic spectrum of intermediate DA.
Fig. 2 is an infrared spectrum of intermediate DA.
FIG. 3 is a nuclear magnetic spectrum of benzophenone epoxy monomer.
Fig. 4 is an infrared spectrum of benzophenone epoxy monomer.
FIG. 5 is a graph showing the residual carbon content of the epoxy resin of the present invention.
Detailed Description
The following examples are used to illustrate the preparation method of a flame retardant epoxy resin with biological basic characteristics. The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
A process for preparing the basic biologic flame-retarding epoxy resin includes such steps as catalytic Friedel-crafts acylation reaction between vanillic acid and resorcin, substitution reaction with epichlorohydrin to obtain epoxy monomer, and heating the epoxy monomer and solidifying agent DDS to obtain the final resin specimen.
The synthesis steps of the bio-based epoxy monomer and the curing agent are as follows:
(1) adding a certain amount of vanillic acid, resorcinol and boron trifluoride diethyl etherate into a round-bottom flask with a condensation pipe, heating to 70-120 ℃, and keeping the mixture at the temperature for 40-120 min. And cooling to room temperature, pouring a sodium acetate buffer solution, and standing for 3-7 h. Filtering to obtain a product, washing with clear water, recrystallizing, purifying, and vacuum drying at 50-80 ℃ for 5-9 h to obtain the product DA. The molar ratio of vanillic acid to resorcinol is 0.7-1.5: 1, the molar ratio of vanillic acid to boron trifluoride diethyl etherate is 1: 3-8, the molar ratio of vanillic acid to sodium acetate is 1: 20-50, and the mass fraction of the sodium acetate buffer solution is 5-25%. The recrystallization solvent is one of tetrahydrofuran, acetone, methanol and dichloromethane.
(2) A round bottom flask with a condenser tube is charged with a certain amount of the above product and placed in N 2 And (4) under the environment. Adding epichlorohydrin into a flask at room temperature according to a certain proportion, heating to 70-130 ℃, slowly adding a certain amount of NaOH solution within 30-90 min, and keeping the reaction mixture at the temperature for 30-90 min. And cooling to room temperature, filtering to obtain a product, washing with a solvent for three times, and then drying in vacuum at 30-100 ℃ for 8-12 hours to obtain the benzophenone epoxy monomer, wherein the used washing solvent is one of xylene, ethanol, butanone and dichloromethane. The molar ratio of epichlorohydrin to DA is 3-11: 1, and the molar ratio of NaOH to DA is 312:1, wherein the mass fraction of the NaOH solution is 10-40%.
And finally, stirring the benzophenone epoxy monomer at 30-80 ℃ for 8-30 min, adding a curing agent DDS (4, 4-diaminodiphenyl sulfone) (the ratio is 1: 3-6), stirring for 3-8 min, pouring into a preheated mold, and obtaining the biological basic characteristic type flame-retardant epoxy resin, wherein the temperature is 120 ℃ for 2h, the temperature is 150 ℃ for 2h, the temperature is 180 ℃ for 2h, and the temperature is 200 ℃ for 1 h.
Example 1:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.17mol of resorcinol and 0.36mol of boron trifluoride etherate, heated to 120 ℃ and the mixture was kept at this temperature for 120 min. After cooling to room temperature, pouring a sodium acetate buffer solution with the mass fraction of 5%, wherein the sodium acetate is 2.4mol, and standing for 7 h. Filtering to obtain a product, washing with clear water, recrystallizing with dichloromethane, purifying, and vacuum drying at 80 deg.C for 9h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.24mol of epichlorohydrin was added to the flask at room temperature, heated to 130 ℃ and a 10% by weight NaOH solution, the NaOH content being 0.24mol, was added slowly over a period of 90min, and the reaction mixture was held at this temperature for 90 min. After cooling to room temperature, the product was filtered, washed three times with dichloromethane and then dried under vacuum at 100 ℃ for 12h to give benzophenone epoxy monomer.
Finally stirring the benzophenone epoxy monomer at 80 ℃ for 30min, adding a curing agent DDS (the ratio is 1:6), stirring for 8min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 2:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.17mol of resorcinol and 0.36mol of boron trifluoride etherate, heated to 70 ℃ and the mixture was kept at this temperature for 40 min. After cooling to room temperature, pouring a sodium acetate buffer solution with the mass fraction of 5%, wherein the sodium acetate is 2.4mol, and standing for 3 h. Filtering to obtain a product, washing with clear water, recrystallizing with tetrahydrofuran for purification, and vacuum drying at 50 deg.C for 5h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.24mol of epichlorohydrin was added to the flask at room temperature, heated to 70 ℃ and a 10% by mass NaOH solution was slowly added over 30min, the NaOH content being 0.24mol, and the reaction mixture was held at this temperature for 30 min. After cooling to room temperature, the product is obtained by filtration, washed three times with xylene and then dried in vacuum at 30 ℃ for 8h to obtain the benzophenone epoxy monomer.
Finally stirring benzophenone epoxy monomer for 8min at 30 ℃, adding curing agent DDS (ratio is 1:3), stirring for 3min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 3:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.17mol of resorcinol and 0.36mol of boron trifluoride etherate, heated to 80 ℃ and the mixture was kept at this temperature for 80 min. After cooling to room temperature, pouring a sodium acetate buffer solution with the mass fraction of 5%, wherein the sodium acetate is 2.4mol, and standing for 5 h. Filtering to obtain a product, washing with clear water, recrystallizing with acetone, purifying, and vacuum drying at 60 deg.C for 7 hr to obtain product DA.
(2) A round-bottomed flask with condenser was charged with 0.08mol of the above product and placed under an atmosphere of N2. 0.24mol of epichlorohydrin was added to the flask at room temperature, heated to 90 ℃ and a 10% by mass NaOH solution, the NaOH content being 0.24mol, was slowly added over 60min, and the reaction mixture was held at this temperature for 70 min. After cooling to room temperature, filtering to obtain a product, washing with butanone three times, and then drying in vacuum at 60 ℃ for 10 hours to obtain the benzophenone epoxy monomer.
Finally, stirring the benzophenone epoxy monomer at 50 ℃ for 20min, adding a curing agent DDS (the ratio is 1:5), stirring for 5min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 4:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.08mol of resorcinol and 0.96mol of boron trifluoride etherate, heated to 70 ℃ and the mixture was kept at this temperature for 40 min. After cooling to room temperature, pouring 25% sodium acetate buffer solution with the mass fraction of 6mol, and standing for 3 h. Filtering to obtain a product, washing with clear water, recrystallizing with tetrahydrofuran for purification, and vacuum drying at 50 deg.C for 5h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.88mol of epichlorohydrin was added to the flask at room temperature, heated to 70 ℃ and a 10% by mass NaOH solution was slowly added over 30min, the NaOH content being 0.96mol, and the reaction mixture was held at this temperature for 30 min. After cooling to room temperature, filtering to obtain a product, washing with xylene for three times, and then drying in vacuum at 30 ℃ for 8 hours to obtain the benzophenone epoxy monomer.
Finally stirring the benzophenone epoxy monomer at 30 ℃ for 8min, adding a curing agent DDS (the ratio is 1:3), stirring for 3min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 5:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.08mol of resorcinol and 0.96mol of boron trifluoride etherate, heated to 80 ℃ and the mixture was kept at this temperature for 70 min. After cooling to room temperature, pouring 25% sodium acetate buffer solution by mass fraction, wherein the sodium acetate is 6mol, and standing for 5 h. Filtering to obtain a product, washing with clear water, recrystallizing with acetone, purifying, and vacuum drying at 70 deg.C for 6h to obtain product DA.
(2) A round bottom flask with a condenser was charged with 0.08mol of the above product and placed under N2 atmosphere. 0.88mol of epichlorohydrin was added to the flask at room temperature, heated to 80 ℃ and a 10% by mass NaOH solution was slowly added over 60min, the NaOH content being 0.96mol, and the reaction mixture was held at this temperature for 60 min. After cooling to room temperature, the product is obtained by filtration, washed with ethanol three times and then dried in vacuum at 70 ℃ for 10h to obtain the benzophenone epoxy monomer.
Finally, stirring benzophenone epoxy monomer for 20min at 50 ℃, adding curing agent DDS (ratio of 1:4), stirring for 5min, pouring into a preheated mold, and carrying out stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 6:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.08mol of resorcinol and 0.96mol of boron trifluoride etherate, heated to 120 ℃ and the mixture was kept at this temperature for 120 min. After cooling to room temperature, pouring 25% sodium acetate buffer solution by mass fraction, wherein the sodium acetate is 6mol, and standing for 7 h. Filtering to obtain a product, washing with clear water, recrystallizing with dichloromethane, purifying, and vacuum drying at 80 deg.C for 9h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.88mol of epichlorohydrin was added to the flask at room temperature, heated to 130 ℃ and a 10% by mass NaOH solution was slowly added over 90min, the NaOH content being 0.96mol, and the reaction mixture was held at this temperature for 90 min. After cooling to room temperature, the product was filtered, washed three times with dichloromethane and then dried under vacuum at 100 ℃ for 12h to give benzophenone epoxy monomer.
Finally, stirring benzophenone epoxy monomer at 80 ℃ for 30min, adding curing agent DDS (the ratio is 1:6), stirring for 8min, pouring into a preheated mold, and carrying out stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 7:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.12mol of resorcinol and 0.6mol of boron trifluoride etherate, heated to 120 ℃ and the mixture was kept at this temperature for 120 min. After cooling to room temperature, pouring 20% sodium acetate buffer solution with the mass fraction of 3.6mol, and standing for 7 h. Filtering to obtain a product, washing with clear water, recrystallizing with dichloromethane, purifying, and vacuum drying at 80 deg.C for 9h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. Adding 0.8mol of epichlorohydrin into a flask at room temperature, heating to 130 ℃, and slowly adding NaOH solution with the mass fraction of 20% in 30minThe reaction mixture, which had a NaOH content of 0.8mol, was kept at this temperature for 30 min. After cooling to room temperature, the product was filtered, washed three times with dichloromethane and then dried under vacuum at 100 ℃ for 12h to give benzophenone epoxy monomer.
Finally stirring the benzophenone epoxy monomer at 80 ℃ for 30min, adding a curing agent DDS (the ratio is 1:6), stirring for 8min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 8:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.12mol of resorcinol and 0.6mol of boron trifluoride etherate, heated to 70 ℃ and the mixture was kept at this temperature for 40 min. After cooling to room temperature, pouring 20% sodium acetate buffer solution with the mass fraction of 3.6mol, and standing for 3 h. Filtering to obtain a product, washing with clear water, recrystallizing with tetrahydrofuran, purifying, and vacuum drying at 50 deg.C for 5 hr to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.8mol of epichlorohydrin was added to the flask at room temperature, heated to 70 ℃ and a 20% by mass NaOH solution, having a NaOH content of 0.8mol, was slowly added over 30min, and the reaction mixture was held at this temperature for 30 min. The reaction mixture was kept at this temperature for 30 min. After cooling to room temperature, the product is obtained by filtration, washed three times with xylene and then dried in vacuum at 30 ℃ for 8h to obtain the benzophenone epoxy monomer.
Finally stirring benzophenone epoxy monomer for 8min at 30 ℃, adding curing agent DDS (ratio is 1:3), stirring for 3min, pouring into a preheated mold, and stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
Example 9:
(1) a round-bottomed flask with a condenser was charged with 0.12mol of vanillic acid, 0.12mol of resorcinol and 0.6mol of boron trifluoride etherate, heated to 90 ℃ and the mixture was kept at this temperature for 70 min. After cooling to room temperature, pouring 20% sodium acetate buffer solution by mass fraction, wherein the sodium acetate is 3.6mol, and standing for 5 h. Filtering to obtain a product, washing with clear water, recrystallizing with methanol for purification, and vacuum drying at 60 deg.C for 6h to obtain product DA.
(2) 0.08mol of the product is added into a round-bottom flask with a condenser and placed in N 2 And (4) under the environment. 0.8mol of epichlorohydrin was added to the flask at room temperature, heated to 90 ℃ and a 20% by mass NaOH solution, having a NaOH content of 0.8mol, was slowly added over 70min, and the reaction mixture was held at this temperature for 50 min. After cooling to room temperature, filtering to obtain a product, washing with ethanol for three times, and then drying in vacuum at 70 ℃ for 9 hours to obtain the benzophenone epoxy monomer.
Finally, stirring benzophenone epoxy monomer for 20min at 50 ℃, adding curing agent DDS (ratio of 1:4), stirring for 5min, pouring into a preheated mold, and carrying out stirring at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h. The carbon residue of the obtained epoxy resin can reach 35 percent, which is shown in figure 5.
Claims (10)
1. A flame-retarding epoxy resin with biological basic characteristics is prepared through catalytic Friedel-crafts acylation of vanillic acid and resorcinol, substitution reaction of vanillic acid with epichlorhydrin to obtain benzophenone epoxy monomer, and heating to mix it with solidifying agent DDS for solidification.
2. The method for preparing a bio-based characteristic type flame retardant epoxy resin according to claim 1, wherein the vanillic acid and the resorcinol are subjected to Friedel-crafts acylation reaction under the catalysis condition, and then are subjected to substitution reaction with the epichlorohydrin to obtain a benzophenone epoxy monomer, and the benzophenone epoxy monomer is mixed with the curing agent DDS under the heating condition for curing to obtain the bio-based characteristic type flame retardant epoxy resin.
3. The method for preparing the biological basic characteristic type flame retardant epoxy resin as claimed in claim 2, wherein the benzophenone epoxy monomer is synthesized by the following steps:
(1) preparation of product DA: heating vanillic acid, resorcinol and boron trifluoride diethyl etherate for full reaction, cooling to room temperature, pouring sodium acetate buffer solution, standing, filtering to obtain a product, cleaning, recrystallizing for purification, and vacuum drying to obtain a product DA, wherein the reaction process is shown as formula (a):
(2) preparing a benzophenone epoxy monomer: product DA is placed in N 2 Under the environment, epichlorohydrin is added into a flask at room temperature, heating and reacting are carried out, NaOH solution is slowly added, the reaction mixture is subjected to heat preservation reaction at the temperature, the reaction mixture is cooled to room temperature, filtering is carried out to obtain a product, the product is washed by a solvent, and then vacuum drying is carried out to obtain the benzophenone epoxy monomer, wherein the reaction process is shown as a formula (d):
4. the preparation method of the biological basic characteristic type flame retardant epoxy resin as claimed in claim 3, wherein the molar ratio of vanillic acid to resorcinol is 0.7-1.5: 1, the molar ratio of vanillic acid to boron trifluoride diethyl etherate is 1: 3-8, the molar ratio of vanillic acid to sodium acetate is 1: 20-50, and the mass fraction of the sodium acetate buffer solution is 5-25%.
5. The method for preparing a bio-basic feature type flame retardant epoxy resin according to claim 3, wherein the recrystallization solvent is one of tetrahydrofuran, acetone, methanol and dichloromethane.
6. The method for preparing the bio-basic characteristic type flame-retardant epoxy resin according to claim 3, wherein the molar ratio of epichlorohydrin to DA is 3-11: 1, the molar ratio of NaOH to DA is 3-12: 1, and the mass fraction of NaOH solution is 10-40%.
7. The method for preparing the bio-basic feature type flame retardant epoxy resin as claimed in claim 3, wherein the cleaning solvent is one of xylene, ethanol, butanone and dichloromethane.
8. The method for preparing the flame-retardant epoxy resin with the biological basic characteristics according to claim 3, wherein the temperature of the heating reaction in the first step is 70-120 ℃, and the temperature of the heating reaction in the second step is 70-130 ℃.
9. The method for preparing the biological basic characteristic type flame retardant epoxy resin as claimed in claim 2, wherein the benzophenone epoxy monomer is obtained by stirring at 30-80 ℃ for 8-30 min, adding the curing agent DDS, stirring for 3-8 min, pouring into a preheated mold, and reacting at 120 ℃ for 2h, 150 ℃ for 2h,180 ℃ for 2h and 200 ℃ for 1 h.
10. The method for preparing the biological basic characteristic type flame retardant epoxy resin as claimed in claim 2, wherein the mass ratio of the benzophenone epoxy monomer to the curing agent DDS is 1: 3-6.
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| CN112876509B (en) * | 2021-04-13 | 2021-10-22 | 南京工业大学 | Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin |
| CN114349085B (en) * | 2021-12-13 | 2023-10-03 | 山东省煤炭科学研究院有限公司 | High-concentration high-salt water thickening treatment agent, and preparation method and application method thereof |
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