CN112940257A - Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof - Google Patents
Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses eugenol epoxy double-splint type cage-like silsesquioxane as well as a preparation method and application thereof. The structural formula of the eugenol epoxy double-splint type cage-like silsesquioxane is shown as the following formula (I); the product is bio-based cage type silsesquioxane, has excellent thermal stability and water resistance, and can be independently used for preparing bio-based epoxy resin; the modified carbon-based epoxy resin composite material has good compatibility with carbon-based materials, can realize high uniform dispersion of nano-scale when used as a modifier in an epoxy resin system, effectively improves the performances of the resin in the aspects of hydrophobicity, heat resistance, impact resistance and the like, and has wide application prospect in the fields of preparation and application of high-performance hybrid or composite materials.
Description
Technical Field
The invention relates to the technical field of silsesquioxane, in particular to eugenol epoxy double-splint type cage type silsesquioxane, a preparation method thereof and application thereof in preparation of bio-based epoxy resin nano hybrid materials.
Background
The organic-inorganic nano composite material has the characteristics of various organic matters, light weight, easy modification and the like and the advantages of inorganic matters such as heat resistance, ageing resistance and the like, and is widely applied to the fields of aerospace, machinery, traffic, buildings, electronic and electric appliances, medical products and the like. Inorganic components commonly used in composite materials include ceramics, metals, layered metal compounds, zeolites, glass fibers, carbon fibers, mica, calcium carbonate, kaolin, nano-silicates, cellulose nanocrystals, carbon nanotubes, hexagonal boron nitride, graphene and the like, and before the composite materials are prepared, inorganic particles are usually required to be properly treated, the preparation process is usually complicated, and the problem of particle agglomeration in the composite process is usually difficult to avoid. The dispersion state of the inorganic component in the organic material is the key to determine whether the performance of the composite material is excellent, and the focus of the researchers is how to prepare the composite material which is more uniformly dispersed on the nanometer scale.
The three-dimensional size of the cage type oligomeric silsesquioxane (POSS for short) is on the nanometer scale, the cage type oligomeric silsesquioxane is considered as an 'isometric' nano particle, and the functionalized POSS is used as a unique nano building block, can be used for manufacturing various hybrid or composite materials needing to accurately control the nano structure and performance, provides possibility for modifying polymers on the molecular level, and has great potential in the preparation field of advanced functional nano materials. The properties of POSS depend to a large extent on the organic functional groups in their structures, and different functional groups of POSS are often synthesized in order to meet the performance requirements of various types of materials. However, the synthesis of the POSS monomer has many influencing factors, long reaction period, complex separation and purification, low yield and high cost. And the existing POSS is still very limited in variety, very few and expensive POSS entering commercialization are difficult to meet the requirements of material preparation, and the development of POSS is restricted.
In addition, most of the epoxy resins are prepared from petrochemical products with limited resources, wherein more than 80% of epoxy resin prepolymers are prepared by reacting bisphenol A with epichlorohydrin, and cured products of the epoxy resins can dissolve out bisphenol A through hydrolysis and contact with human bodies. Bisphenol a has been classified as carcinogenic mutagenic and reproductive toxic and is considered an endocrine disrupter and is severely limited in its use. Currently, the academia and industry are highly concerned about the substitution of bisphenol a and other raw materials, many biobased resources have been tried as possible substitution of bisphenol a for more than ten years, and more biobased epoxy is mainly researched from cardanol, eugenol, vanillin, tannic acid, gallic acid and the like (Wan et al, 2020). Since 2019, some bio-based epoxy monomers, prepolymers, curing agents and flame retardants with new structures have been reported to be mainly derived from vanillin (Huang et al,2019, Memon et al,2020, Liu et al,2020), garcinol (Noe et al,2019), resveratrol (Tian et al,2020), magnolol (Qi et al,2020), protocatechualdehyde (Xie et al,2020), genistein (Dai et al,2019), daidzein (Ma and Li,2019) and salicylaldehyde (Li and Cai,2020), and the like. Unfortunately, these bio-based epoxy monomers are mainly of small molecule linear or branched structures, and the modification effect is often relatively single, and studies on bio-based epoxy functionalized POSS are rarely reported.
Chinese patent publication No. CN103204872A discloses a dihydroxy cage-type silsesquioxane monomer in which a cassetter catalyst is used for the preparation thereof and the final reaction solution is simply subjected to distillation under reduced pressure, and a method for preparing the same. The selection of the catalyst and the post-treatment process are not suitable for the synthesis of the double-splint cage-type silsesquioxane with higher boiling point and larger steric effect of the functional monomer.
Disclosure of Invention
The invention aims at the problems and provides eugenol epoxy double-splint type cage-like silsesquioxane. The bio-based POSS has excellent thermal stability and better compatibility with carbon-based materials, can be directly used as a base material to prepare bio-based epoxy resin, can also be used as a bio-based modifier to be compounded to other epoxy resin systems, can realize highly uniform dispersion of molecular scale with other epoxy resin matrixes, and effectively improves the performances of the resin in various aspects such as water resistance, heat resistance, impact resistance and the like.
The specific technical scheme is as follows:
a eugenol epoxy double-splint type cage-like silsesquioxane has a structural formula shown as the following formula (I):
the eugenol epoxy double-splint type cage-like silsesquioxane has the melting point of 131.9 ℃, and has better processing performance advantage compared with common same type silsesquioxane such as 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane (marked as 2H-DDSQ, the melting point is 278.6 ℃).
Initial thermal decomposition temperature (T) under nitrogen atmosphere-5％) The carbon residue is 381 ℃, the carbon residue is up to 61.0 percent at 800 ℃, and the carbon residue is obviously superior to common silsesquioxane of the same type.
The eugenol epoxy double-splint type cage-like silsesquioxane disclosed by the invention is novel in structure, the melting temperature of the body-type structure bio-based monomer is low, and the processing is easy; the resin has excellent thermal stability, high initial thermal decomposition temperature and high carbon residue, can be independently used as a base material to prepare bio-based epoxy resin, and has excellent performances of high temperature resistance, water resistance and high impact resistance; and the compatibility with carbon-based materials is good, an epoxy resin cross-linked network can be introduced in a co-curing mode, and the epoxy resin cross-linked network is highly and uniformly dispersed in other resin matrixes through characterization, so that the high-temperature resistance, water resistance and impact resistance of the epoxy resin cross-linked network are fully exerted.
The invention also discloses a preparation method of the eugenol epoxy double-splint type cage-like silsesquioxane, which comprises the following steps:
(a) mixing 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane, eugenol epoxy monomer, solvent and catalyst in an inert atmosphere to perform hydrosilylation reaction until the reaction is complete;
(b) separating and purifying the reaction mother liquor obtained in the step (a) to obtain the eugenol epoxy double-splint type cage-like silsesquioxane;
the separation and purification method comprises the following steps: removing catalyst from mother liquid by column chromatography, rotary distilling to remove low-boiling-point substance, adding petroleum ether into crude product, stirring and washing several times, and vacuum drying.
In step (a):
the inert atmosphere is a gas conventional in the art, such as nitrogen, argon, and the like.
The 3, 13-dihydro octaphenyl double-splint type cage silsesquioxane reference (Macromolecules, Vol.39, No.10,2006) reports a method for preparing the silsesquioxane.
The eugenol epoxy monomer reference (ACS sustatin chem. eng.2018,6,8856-.
The molar charge ratio of the 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane to the eugenol epoxy monomer is 1: 2-10; preferably 1: 3 to 7.
The solvent is selected from one or more of toluene, tetrahydrofuran and isopropanol; further preferred is toluene.
The solvent is 5-15 times of the eugenol epoxy monomer by mass.
The solvent is required to be dried before use.
The catalyst is selected from platinum catalysts, preferably chloroplatinic acid and/or platinum dioxide. Tests show that the platinum catalyst with larger volume has poorer catalytic effect on the system, such as a common Kanster catalyst for hydrosilylation.
The content of platinum in the catalyst is 50-300 ppm calculated by the mole number of the reaction functional group.
The temperature of the hydrosilylation reaction is 60-100 ℃.
The separation and purification process in the step (b) is the key for obtaining the eugenol epoxy double-splint type cage-like silsesquioxane with high yield, and the key is the purification by adopting petroleum ether.
Tests show that the crude product shows excellent separation effect in petroleum ether, and other common separation and purification reagents, such as diethyl ether, cyclohexane, n-hexane, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, dichloromethane, acetone, chloroform, toluene and the like, are difficult to purify or have poor purification effect.
Preferably, the washing is carried out under heating.
The invention also discloses application of the eugenol epoxy double-splint type cage-like silsesquioxane in preparation of epoxy resin.
The method specifically comprises the following steps:
the eugenol epoxy double-splint type cage-like silsesquioxane and other epoxy resin which can be selectively added are taken as raw materials, and the biological epoxy resin nano hybrid material is prepared after curing.
The eugenol epoxy double-splint type cage-like silsesquioxane and the epoxy resin can realize uniform dispersion in a nanometer scale, so that the eugenol epoxy double-splint type cage-like silsesquioxane and the epoxy resin have no special requirements on the using amounts of the eugenol epoxy double-splint type cage-like silsesquioxane and can be mixed in any proportion.
The eugenol epoxy double-splint type cage-like silsesquioxane can be independently used as a raw material, and a biological epoxy resin material is prepared by curing. The resin material has excellent high temperature resistance, water resistance and impact resistance.
The eugenol epoxy double-splint type cage-like silsesquioxane can also be blended with epoxy resin commonly used in the field and then cured to prepare the bio-based epoxy resin nano hybrid material. The characterization of the interior of the prepared bio-based epoxy resin hybrid material shows that the eugenol epoxy double-splint type cage-like silsesquioxane is completely and uniformly distributed in a nanoscale, so that the high-temperature resistance, the water resistance and the shock resistance of the material can be fully exerted.
The epoxy resin is selected from the group common in the art, including bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin, and the like.
The curing agent used for the curing is not particularly required and is selected from the common categories in the field, such as polyamine type, anhydride type, phenolic type and the like.
Compared with the prior art, the invention has the following gain effects:
1. the invention discloses eugenol epoxy double-splint type cage-like silsesquioxane, wherein the bio-based with a body structure has excellent thermal stability and water resistance, and the bio-based epoxy resin prepared by curing the bio-based with the eugenol epoxy double-splint type cage-like silsesquioxane has excellent high-temperature resistance, water resistance and impact resistance.
2. The eugenol epoxy double-splint type cage-like silsesquioxane disclosed by the invention also has better compatibility with carbon-based materials, can be used as a biological epoxy resin modifier, can introduce an epoxy resin crosslinking network in a co-curing mode, can be highly and uniformly dispersed in other resin matrixes, can be mixed in any proportion, and effectively improves the comprehensive performance of the resin.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of eugenol epoxy double-splint type cage-like silsesquioxane;
FIG. 2 is a nuclear magnetic carbon spectrum of eugenol epoxy double-splint type cage-like silsesquioxane;
FIG. 3 is a nuclear magnetic silicon spectrum of eugenol epoxy double-splint type cage-like silsesquioxane;
FIG. 4 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of eugenol epoxy double-splint type cage silsesquioxane;
FIG. 5 is a comparison graph of thermogravimetric curves of eugenol epoxy double-splint type cage-like silsesquioxane and 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane in a nitrogen atmosphere;
FIG. 6 is a transmission electron microscope image of the interior of the epoxy nanocomposite;
FIG. 7 is an atomic force microscope phase diagram of the interior of an epoxy nanocomposite.
Detailed Description
Example 1
Preparing a high-purity eugenol epoxy monomer: adding clove into a flask provided with a magnetic stirrer, a serpentine condenser and a thermometer under the nitrogen atmospherePhenol (82.1g, 0.5mol), epichlorohydrin (46g,0.5mol) and benzyltriethylammonium chloride (2.27g, 0.01 mol). The temperature is reduced to 60 ℃ after the system is refluxed for 3h, NaOH aqueous solution (20 wt.%, 102g) is slowly added dropwise, and the reaction temperature is maintained for continuous reaction for 5 h. Filtering the reaction solution to remove NaCl and unreacted NaOH, washing with saturated NaCl water solution for several times to remove sodium salt in organic phase, and using small amount of CH2Cl2A small amount of product in the extracted aqueous wash was combined back into the organic phase. Removing the solvent and excessive raw materials by rotary evaporation, adding 15 g of methanol into the obtained liquid, cooling and crystallizing at 0 ℃, and carrying out suction filtration after 5h to obtain white needle-shaped crystals, namely the high-purity epoxidized eugenol, with the yield of 88%.1H NMR(400MHz,Chloroform-d)δ6.89–6.78(m,1H),6.74–6.60(m,2H),5.92(ddt,J＝16.8,10.1,6.7Hz,1H),5.10–5.00(m,2H),4.17(dd,J＝11.4,3.4Hz,1H),4.00–3.90(m,1H),3.81(s,3H),3.36–3.24(m,3H),2.81(m,1H),2.67(dd,J＝5.0,2.6Hz,1H).13C NMR(101MHz,Chloroform-d)δ149.60,146.36,137.57,133.84,120.52,115.70,114.45,112.47,70.48,55.85,50.25,44.84,39.81.
Preparation of octaphenyltetrasilanol sodium salt: in a 500mL flask equipped with a magnetic stirrer and reflux condenser, deionized water (5.0g, 278mmol), isopropanol (240mL), phenyltrimethoxysilane (48.0g, 242mmol), sodium hydroxide (6.4g, 160mmol) were added. The system is placed under the atmosphere of high-purity nitrogen, stirred and refluxed vigorously for 4 hours, cooled to room temperature and then stirred continuously for 15 hours. The precipitate was collected by filtration and washed with isopropanol. The product was dried under vacuum at 70 ℃ for 5 hours to give a white fluffy powder (yield 99%).
Preparation of 3, 13-dihydrooctaphenyl double-splint type cage silsesquioxane: sodium octaphenyltetrasilanol salt (11.6g, 10.0mmol), purified triethylamine (6.1g, 60mmol) and dry tetrahydrofuran (200mL) were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere, and the system was placed in an environment at 0 ℃ to be mixed uniformly. Diluting methyldichlorosilane (6.9g, 60mmol) into a proper amount of dry tetrahydrofuran, dropwise adding the mixture into the mixed solution, reacting the system at 0 ℃ for 2 hours, and continuing to react at 5-10 ℃ for 15 hours. After the reaction is finished, removing solid precipitate, collecting liquid phase part, removing solvent and other low-boiling-point substances by rotary evaporation, and obtaining crude productThe material was dissolved in dichloromethane, precipitated with methanol, washed and dried in vacuo (50 ℃ C., 24h) to give a yield of 47%.1H NMR(400MHz,CDCl3,δ):0.28(d,6H,-SiCH3,J＝1.5Hz),4.91(d,2H,-SiH,J＝1.5Hz),7.02～7.61(m,40H,-Ph).29Si NMR(500MHz,CDCl3,δ):-32.69(s,-SiCH3),-77.73(s,-Si(Ph)OSi(CH3)-),-79.22(t,PhSiO3/2(PhSiO3/2)3)).MALDI-TOF-MS(DHB matrix):calc.[M+H]+m/z＝1153.08,found 1152.96.
Preparing eugenol epoxy double-splint type cage type silsesquioxane: to a flask equipped with a magnetic stirrer and a reflux condenser, 3, 13-dihydrooctaphenyl double-sandwich type cage silsesquioxane (7.85g, 6.80mmol), eugenol epoxy (9.0g, 41mmol), dry toluene (150mL) and chloroplatinic acid catalyst (platinum content 200ppm) were added under a nitrogen atmosphere. The system is stirred for more than 24 hours at 85 ℃ until the hydrosilylation reaction is completely finished. Removing the catalyst from the mixed solution by fast column chromatography, removing the solvent by rotary evaporation, adding petroleum ether into the crude product, stirring and washing for a plurality of times at 60 ℃, and drying in vacuum at 60 ℃ until the weight is constant to obtain white powder, namely eugenol epoxy double-splint type cage-like silsesquioxane with the yield of 89%.
The melting point of the eugenol epoxy double-splint type cage-like silsesquioxane is 131.9 ℃, and the structural characterization results are shown in the nuclear magnetic hydrogen spectrum, the carbon spectrum, the silicon spectrum and the matrix-assisted laser desorption ionization time-of-flight mass spectrum of figures 1-4.
Example 2
The preparation method of the high-purity eugenol epoxy monomer and the 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane is the same as that of the example 1.
To a flask equipped with a magnetic stirrer and a reflux condenser, 3, 13-dihydrooctaphenyl double-sandwich type cage silsesquioxane (7.85g, 6.80mmol), eugenol epoxy (6.0g, 27.2mmol), dry toluene (150mL) and chloroplatinic acid catalyst (platinum content 100ppm) were added under a nitrogen atmosphere. The system is stirred for more than 24 hours at 85 ℃ until the hydrosilylation reaction is completely finished. The mixed solution is subjected to fast column chromatography to remove the catalyst, the solvent is removed by rotary evaporation, the crude product petroleum ether is washed to remove unreacted eugenol epoxy, and the crude product petroleum ether is dried in vacuum at 60 ℃ to constant weight to obtain white powder, namely eugenol epoxy double-splint type cage-like silsesquioxane with the yield of 85 percent.
Comparative example 1
The preparation method of the high-purity eugenol epoxy monomer and the 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane is the same as that of the example 1.
To a flask equipped with a magnetic stirrer and a reflux condenser, 3, 13-dihydrooctaphenyl double-sandwich type cage silsesquioxane (7.85g, 6.80mmol), eugenol epoxy (9.0g, 41mmol), dry toluene (150mL) and a Kanst catalyst (platinum content 200ppm) were added under a nitrogen atmosphere. The system was stirred at 100 ℃ for 24 h. Removing the solvent by rotary evaporation, and washing and purifying by petroleum ether. The yield was 0%.
This comparative example was prepared by a procedure substantially identical to that of example 1 except that a casite catalyst was used in the preparation of eugenol epoxy-based double-sandwich type cage-type silsesquioxane. The test shows that the yield of the eugenol epoxy double-splint type cage-like silsesquioxane is 0.
Comparative examples 2 to 6
The preparation processes of the high-purity eugenol epoxy monomer, the 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane and the eugenol epoxy double-splint type cage-like silsesquioxane are completely the same as those in the example 1, and the difference is only that other organic solvents are adopted to replace petroleum ether in the separation and purification stage. The specific solvent types and the final isolation and purification are shown in Table 1 below.
TABLE 1
| Kind of solvent | Methanol | Ethanol | Cyclohexane | Methylene dichloride | Ether (A) |
| Purification situation | The yield is low and is less than 20 percent | Difficulty in | Difficulty in | Can not be separated | Difficulty in |
Thermal stability test
FIG. 5 is a comparison graph of the thermogravimetric curves of eugenol epoxy double-splint type cage-like silsesquioxane and 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane in a nitrogen atmosphere. The result shows that the eugenol epoxy functionalized cage-type silsesquioxane has excellent thermal stability, the initial thermal decomposition temperature reaches 381 ℃, the carbon residue at 800 ℃ is as high as 61 percent, and the thermal decomposition temperature is far higher than that of 3, 13-dihydro octaphenyl double-splint type cage-type silsesquioxane.
Application example
The preparation method of the bio-based epoxy resin nano hybrid material comprises the following specific steps: mixing eugenol epoxy double-splint type cage-like silsesquioxane and bisphenol A epoxy resin (DGEBA) according to a mass ratio of 1:4, dissolving in acetone, violently stirring and ultrasonically dispersing, adding a curing agent 3,3' -diaminodiphenyl sulfone according to a stoichiometric ratio [ N-H/epoxy (mol) ═ 1/1] of reaction groups and the like after heating and volatilizing the acetone, heating to 110 ℃, and violently stirring until the system is uniform and transparent. Removing gas in vacuum (100-110 ℃), pouring into a preheated polytetrafluoroethylene mould for curing (140 ℃,2 hours, 160 ℃,2 hours, 180 ℃,2 hours).
The impact strength test is based on GB/T1043.1-2008 standard
The measurement is finished on a pendulum bob impactor, and a sample (120 multiplied by 10 multiplied by 4 mm) is measured by adopting a simple beam mode3) The notched impact strength of each sample was averaged over five specimens.
The thermal stability, hydrophobicity and impact resistance data of the epoxy resin nano hybrid material are shown in table 2.
The transmission electron microscope picture and the internal atomic force microscope phase picture of the internal distribution condition of the cage-type silsesquioxane modifier in the bisphenol A epoxy resin matrix are respectively shown in fig. 6 and fig. 7, and the observation of the two pictures can determine that the eugenol epoxy double-splint type cage-type silsesquioxane can be highly uniformly dispersed in the bisphenol A epoxy resin matrix in a nanoscale.
Comparative application
Bisphenol A epoxy resin (DGEBA) and curing agent 3,3' -diaminodiphenyl sulfone are mixed according to the stoichiometric ratio of reactive groups and the like [ N-H/epoxy group (mol) ═ 1/1], and the mixture is heated to 110 ℃ and stirred vigorously until the system is uniform and transparent. Removing gas in vacuum (100-110 ℃), pouring into a preheated polytetrafluoroethylene mould for curing (140 ℃,2 hours, 160 ℃,2 hours, 180 ℃,2 hours). The resin thermal stability, hydrophobicity and impact performance data are shown in table 2.
TABLE 2
The eugenol epoxy double-splint type cage-like silsesquioxane provided by the invention and the preparation method and application thereof are described in the embodiment. The principles, embodiments and applications of the present invention have been described herein using specific examples, which are provided only to assist in understanding the methods and key points of the present invention. This summary should not be construed to limit the present invention.
Claims (9)
1. A eugenol epoxy double-splint type cage-like silsesquioxane is characterized in that the structural formula is shown as the following formula (I):
2. the eugenol epoxy double-splint type cage-like silsesquioxane according to claim 1, wherein the melting point is 131.9 ℃, the initial thermal decomposition temperature under nitrogen atmosphere is 381 ℃, and the residual carbon content at 800 ℃ is 61.0%.
3. A method for preparing eugenol epoxy double-splint type cage-like silsesquioxane according to claim 1 or 2, comprising the steps of:
(a) mixing 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane, eugenol epoxy monomer, solvent and catalyst in an inert atmosphere to perform hydrosilylation reaction until the reaction is complete;
(b) separating and purifying the reaction mother liquor obtained in the step (a) to obtain the eugenol epoxy double-splint type cage-like silsesquioxane;
the separation and purification method comprises the following steps: removing catalyst from mother liquid by column chromatography, rotary distilling to remove low-boiling-point substance, adding petroleum ether into crude product, stirring and washing several times, and vacuum drying.
4. The method for preparing eugenol epoxy double-splint type cage-like silsesquioxane according to claim 3, wherein in the step (a), the molar charge ratio of the 3, 13-dihydro octaphenyl double-splint type cage-like silsesquioxane to the eugenol epoxy monomer is 1: 2 to 10.
5. The method for preparing eugenol epoxy double-splint type cage-like silsesquioxane according to claim 3, wherein in the step (a), the solvent is one or more selected from toluene, tetrahydrofuran and isopropanol;
according to the mass, the solvent is 5-15 times of the mass of the eugenol epoxy monomer.
6. The method for preparing eugenol epoxy double-splint type cage-like silsesquioxane as claimed in claim 3, wherein in the step (a), the catalyst is selected from platinum-based catalysts;
the content of platinum in the catalyst is 50-300 ppm calculated by the mole number of the reaction functional group.
7. The method for preparing eugenol epoxy double-splint type cage-like silsesquioxane according to claim 3, wherein the temperature of the hydrosilylation reaction in step (a) is 60-100 ℃.
8. Use of the eugenol epoxy double-splint type cage-like silsesquioxane disclosed by claim 1 or 2 in preparation of bio-based epoxy resin nano hybrid materials.
9. The application of the eugenol epoxy double-splint type cage-like silsesquioxane in the preparation of the bio-based epoxy resin nano hybrid material as claimed in claim 8, wherein the eugenol epoxy double-splint type cage-like silsesquioxane and other epoxy resins which can be selectively added are taken as raw materials, and the bio-based epoxy resin nano hybrid material is prepared after curing.
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| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114369215A (en) * | 2021-12-09 | 2022-04-19 | 西北工业大学 | Hybrid phenolic resin, synthetic method thereof and fiber/hybrid phenolic resin composite material |
| CN114573816A (en) * | 2022-03-08 | 2022-06-03 | 浙江大学 | Epoxy MQ silicon resin and preparation method and application thereof |
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