CN112795015B - Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof - Google Patents
Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The invention discloses a four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and a preparation method and application thereof. The structural formula of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane is shown as the following formula (I); the product is bio-based cage type silsesquioxane, has a flexible molecular chain structure and 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 a four-functionality eugenol epoxy functionalized cage type silsesquioxane, a preparation method thereof and application thereof in preparation of a bio-based epoxy resin nano hybrid material.
Background
Silsequioxanes (silsequioxanes) are a class of silsequioxanes having (RSiO)3/2)nThe empirical T-type organosilicon materials can be classified into random, trapezoidal, cage-shaped, and macrocyclic structures, depending on the structure. Among them, Polyhedral Oligomeric Silsesquioxane (POSS for short) is a class of nanoscale body-type molecules with precise configuration, and is also a class of Silsesquioxane which is researched more at present. Structurally, POSS is composed ofThe Si-O-Si inorganic cage core skeleton and organic substituent covered on the periphery. The size of POSS is usually 1-3 nm, the Si-O-Si cage-shaped inner core in the structure can endow the POSS with advantages in the aspects of heat and mechanics, organic substituent groups connected with the inner core can enable the POSS to be compatible with organic matters, biological systems or surfaces, and the substituent groups can be functionalized and derivatized accurately and quantitatively. The unique inorganic-organic structure of POSS makes its molecular structure easy to design, and has outstanding heat-resisting, oxidation-resisting, hydrophobic, low dielectric and mechanical properties, these characteristics make POSS become a kind of very promising nanometer structure unit, have a great potential in the preparation field of advanced functional nano-materials. However, the existing POSS has very limited varieties and is difficult to meet the requirements of material preparation, thereby restricting the development of POSS.
Epoxy resins have been developed into a large class of thermosetting resins because of their excellent mechanical and electrical properties, and are widely used in the fields of adhesives, structural composites, electronic semiconductor packaging, and the like. But the toughness is poor and the performance is greatly influenced by the epoxy resin matrix. At present, most of epoxy resins are prepared from petrochemical products with limited resources, wherein most of epoxy resin prepolymers are prepared by reacting bisphenol A with epichlorohydrin. However, bisphenol a has been classified as carcinogenic mutagenic and reproductive toxic and is considered an endocrine disrupter and is severely limited in its use. In addition, the price of bisphenol A is greatly fluctuated by the international crude oil price and is not reproducible; the cured product has poor flame retardancy and electrical properties, and is limited in application in high-tech fields. Therefore, bisphenol a epoxy resins have been banned from use in related fields in contact with food and human bodies in many countries of the world, and it is of great significance to develop environmentally friendly epoxy resins that can replace bisphenol a epoxy resins.
Currently, many bio-based epoxies are used for the modification of epoxy resins, mainly derived from cardanol, eugenol, vanillin, tannic acid, gallic acid, etc. (Wan et al,2020), and vanillin (Huang et al,2019, Memon et al,2020, Liu et al,2020), gamboge (Noe et al,2019), resveratrol (Tian et al,2020), magnolol (Qi et al,2020), protocatechuic aldehyde (Xie et al,2020), genistein (Dai et al,2019), daidzein (Ma and Li,2019) and salicylaldehyde (Li and Cai,2020), among others. The bio-based epoxy resin mainly comprises linear or branched aliphatic and aromatic micromolecules, has no advantages in many aspects such as thermal stability, flame retardance and the like, and is often single in effect. In addition, the poor compatibility of POSS and carbon-based materials leads to the unsatisfactory combination property of the composite materials, and is also one of the problems to be solved.
Disclosure of Invention
The invention aims at the problems and provides a four-functionality eugenol epoxy functionalized cage-type silsesquioxane. The bio-based POSS is viscous and liquid at normal temperature, 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 nanoscale highly uniform dispersion 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 tetrafunctional eugenol epoxy functionalized cage type silsesquioxane has a structural formula shown as the following formula (I):
the glass transition temperature of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane is 10.7 ℃, and the initial thermal decomposition temperature (T) is in a nitrogen atmosphere-5％) The temperature was 375 ℃ and the residual carbon content at 800 ℃ was 46.0%. Obviously superior to other prior four-functionality POSS, such as four-functionality hydrosilicon functionalized cage type silsesquioxane (marked as DDSQ-4H) or four-functionality vinyl functionalized cage type silsesquioxane (marked as DDSQ-4Vi)
The invention discloses a tetrafunctional eugenol epoxy functionalized cage type silsesquioxane which has a novel structure, and a biological-based monomer molecular chain with the body type structure is soft and smooth and is in a viscous liquid state at normal temperature; 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 four-functionality eugenol epoxy functionalized cage type silsesquioxane, which comprises the following steps:
(a) under inert atmosphere, mixing four-functionality-degree hydrosilation functionalized cage-type silsesquioxane with a structural formula shown as a formula (II), eugenol epoxy monomer, solvent and catalyst to perform hydrosilylation reaction until the reaction is complete;
(b) separating and purifying the reaction mother liquor in the step (a) to obtain the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane.
In step (a):
the inert atmosphere is a gas conventional in the art, such as nitrogen, argon, and the like.
The DDSQ-4H reference reports (chem. commun.,2017,53,10370) preparation.
The preparation reference of the eugenol epoxy monomer reports (ACS Sustainable chem. Eng.2018,6,8856-8867) preparation, and the purity of the eugenol epoxy monomer is more than 98 percent.
A tetrafunctional hydrosilyl functionalized cage-type silsesquioxane, based on molar mass: eugenol epoxy monomer ═ 1: 4-20, preferably 1: 6 to 10.
The solvent is selected from one or more of toluene, tetrahydrofuran and isopropanol; toluene is preferred.
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 one or more of a Karster catalyst, chloroplatinic acid and platinum dioxide.
The catalyst concentration is 10-200 ppm calculated by the mole number of the reaction functional group, and the catalyst concentration is calculated by the content of platinum in the catalyst; preferably 100 to 150 ppm.
The temperature of the hydrosilylation reaction is 80-120 ℃.
In the step (b), the separation and purification method comprises the following steps: the reaction mother liquor is subject to rotary evaporation to remove low-boiling-point substances, the crude product is added with petroleum ether, stirred and washed for several times, and then vacuum drying is carried out.
Preferably, the washing is carried out under heating.
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.
The invention also discloses application of the tetrafunctional eugenol epoxy functionalized cage type silsesquioxane in preparation of epoxy resin.
The method specifically comprises the following steps:
the biological epoxy resin nanometer hybrid material is prepared by taking the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and other epoxy resin which can be selectively added as raw materials and curing the raw materials.
The four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin can realize uniform dispersion in a nanometer scale, so that no special requirement is imposed on the dosage of the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin, and the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin can be mixed in any proportion.
The tetrafunctional eugenol epoxy functionalized cage type 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 tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane can be blended with epoxy resin commonly used in the field and then cured to prepare a bio-based epoxy resin nano hybrid material. The interior of the prepared bio-based epoxy resin hybrid material is characterized, and the fact that the four-functionality eugenol epoxy functionalized cage-type silsesquioxane is completely and uniformly distributed in a nanoscale manner can be found, so that the high-temperature resistance, the water resistance and the shock resistance of the cage-type silsesquioxane are 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 a four-functionality eugenol epoxy functionalized cage-type silsesquioxane, wherein a biological-based monomer molecular chain with a body structure is flexible, is liquid at room temperature, has excellent thermal stability and water resistance, and is cured to prepare a biological-based epoxy resin with the biological-based monomer molecular chain as a base material, which has excellent high-temperature resistance, water resistance and impact resistance.
2. The four-functionality eugenol epoxy functionalized cage-type 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 cross-linking 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 a tetrafunctional eugenol epoxy functionalized cage type silsesquioxane;
FIG. 2 is a nuclear magnetic silicon spectrum of a tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane;
FIG. 3 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of a tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane;
FIG. 4 is a graph comparing thermogravimetric curves of tetrafunctional eugenol epoxy functionalized cage silsesquioxane (DDSQ-4EUEP), tetrafunctional hydrosilation functionalized cage silsesquioxane (DDSQ-4H), and or tetrafunctional vinyl functionalized cage silsesquioxane (DDSQ-4Vi) in a nitrogen atmosphere;
FIG. 5 is a transmission electron microscope image of the interior of the epoxy resin composite material;
FIG. 6 is a graph of the nano-IR intensity distribution of Si-O groups inside the epoxy resin composite.
Detailed Description
Example 1
DDSQ-4H (3.0g, 2.3mmol), excess high purity eugenol epoxy (6.1g, 28mmol), dry toluene (43g) and Kansted catalyst (platinum content 150ppm) were added to a flask equipped with a magnetic stirrer and reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24h at 100 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 60 ℃, and drying the crude product in vacuum to obtain liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 95 percent.
FIGS. 1 to 3 show nuclear magnetic hydrogen spectra, silicon spectra and mass spectra of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane prepared by the invention, and the characterization can confirm that the prepared product conforms to the structure of the formula (I).
Example 2
DDSQ-4H (3.0g, 2.3mmol), high purity eugenol epoxy (2.0g, 9.2mmol), dry toluene (10g) and platinum dioxide (platinum content 100ppm) were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24h at 100 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 50 ℃, and drying the crude product in vacuum to obtain liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 88 percent.
Example 3
DDSQ-4H (3.0g, 2.3mmol), excess high purity eugenol epoxy (10.0g, 46mmol), dry toluene (150g) and chloroplatinic acid (platinum content 100ppm) were added to a flask equipped with a magnetic stirrer and reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24 hours at 90 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 60 ℃, and drying the crude product in vacuum to obtain the liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 93 percent.
Thermal stability test
FIG. 4 shows a comparison of thermal weight loss curves of tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane, tetrafunctional hydrosilation functionalized cage-type silsesquioxane and tetrafunctional vinyl functionalized cage-type silsesquioxane under nitrogen atmosphere, and the related thermal stability data are shown in Table 1 below. It can be seen that the eugenol epoxy functionalized cage-like silsesquioxane has excellent thermal stability, the initial thermal decomposition temperature reaches 375 ℃, the carbon residue at 800 ℃ is as high as 46 percent, and is far higher than the other two.
The tetrafunctional vinyl functionalized cage type silsesquioxane in table 1 is synthesized by itself by the following preparation process: 4Na-DDSQ (10.0g, 8.64mmol), purified triethylamine (10.49g, 103.7mmol) and dry THF (200mL) were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere, and the system was placed at 0 ℃ and mixed uniformly. The mixed solution is slowly injected with vinyl dimethylchlorosilane (12.5g, 103.6mmol) through a syringe, the system reacts for 2h at 0 ℃, and the reaction continues for 20h at 10 ℃. After the reaction is finished, solid precipitates are separated and removed, a liquid phase part is collected, the solvent and other low-boiling substances are removed by rotary evaporation, the crude product is dissolved in dichloromethane and precipitated by methanol (repeated once), the methanol is leached for three times, and the crude product is dried in vacuum (60 ℃,20 h).
TABLE 1
Application example
The preparation method of the bio-based epoxy resin nano hybrid material comprises the following specific steps: mixing four-functionality eugenol epoxy functionalized cage-type silsesquioxane and bisphenol A epoxy resin (DGEBA) according to a mass ratio of 1:4, dissolving in acetone, vigorously 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, and raising the temperature to 105 ℃ and vigorously 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 bio-based epoxy resin nano-hybrid material are shown in the following table 2.
The transmission electron microscope picture and the Si-O group nanometer infrared intensity distribution picture of the internal distribution condition of the cage-type silsesquioxane modifier in the bisphenol A epoxy resin matrix are respectively shown in fig. 5 and fig. 6, and the observation of the picture in fig. 5 and fig. 6 can determine that the four-functionality eugenol epoxy functionalized cage-type silsesquioxane can be highly and uniformly dispersed in the bisphenol A epoxy resin matrix in a nanometer scale.
Comparative application
Bisphenol A epoxy resin (DGEBA) and curing agent 3,3' -diamino diphenyl 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 105 ℃ 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 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 invention.
Claims (7)
1. The application of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane in preparing a bio-based epoxy resin nano hybrid material is characterized in that the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane has a structural formula shown as the following formula (I):
the glass transition temperature of the four-functionality eugenol epoxy functionalized cage-type silsesquioxane is 10.7 ℃, and the four-functionality eugenol epoxy functionalized cage-type silsesquioxane can realize high uniform dispersion with an epoxy resin matrix in a nano scale; the initial thermal decomposition temperature under the nitrogen atmosphere is 375 ℃, and the residual carbon content at 800 ℃ is 46.0 percent;
the preparation method of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane comprises the following steps:
(a) under the inert atmosphere, mixing tetrafunctional hydrosilation functionalized cage-type silsesquioxane with a structural formula shown as the following formula (II), eugenol epoxy monomer, solvent and catalyst to perform hydrosilylation reaction until the reaction is complete;
(b) separating and purifying the reaction mother liquor in the step (a) to obtain the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane.
2. The use of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane for preparing bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein in step (a), the tetrafunctional hydrosilation functionalized cage-type silsesquioxane is prepared by the following steps of (a): eugenol epoxy monomer ═ 1:4 to 20.
3. The use of the tetrafunctional eugenol epoxy functionalized cage-like silsesquioxane in the preparation of bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein in step (a), the solvent is selected from one or more of toluene, tetrahydrofuran and isopropanol;
the solvent is 5-15 times of the eugenol epoxy monomer by mass.
4. The use of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane for preparing bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein in step (a), the catalyst is selected from platinum group catalysts;
the catalyst concentration is 10-200 ppm based on the mole number of the reaction functional group.
5. The application of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane in the preparation of bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein the temperature of the hydrosilylation reaction in step (a) is 80-120 ℃.
6. The use of the tetrafunctional eugenol epoxy functionalized cage-like silsesquioxane in the preparation of bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein in step (b), the method for separation and purification is as follows: the reaction mother liquor is subject to rotary evaporation to remove low-boiling-point substances, the crude product is added with petroleum ether, stirred and washed for several times, and then vacuum drying is carried out.
7. The application of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane in preparing a bio-based epoxy resin nano hybrid material as claimed in claim 1, wherein the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane and other epoxy resins which can be selectively added are used as raw materials, and the raw materials are cured to prepare the bio-based epoxy resin nano hybrid material.
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