CN112876685B - Tetraepoxy group liquid cage type silsesquioxane as well as preparation method and application thereof - Google Patents
Tetraepoxy group liquid cage type silsesquioxane as well as preparation method and application thereof Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 4
- 150000001721 carbon Chemical class 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- -1 siloxane chain Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a tetracycloxy liquid cage type silsesquioxane, and a preparation method and application thereof. The structural formula of the tetracycloxy liquid cage type silsesquioxane is shown as the following formula (I); the product is the four-functional-group body type cage type silsesquioxane, has a smooth molecular chain structure and excellent thermal stability and water resistance, and can be independently used for preparing 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 tetracycloxy liquid cage type silsesquioxane, a preparation method thereof and application thereof in preparation of epoxy resin nano hybrid materials.
Background
The epoxy resin has excellent adhesive property, mechanical property and electrical property, and can be widely applied to the fields of adhesives, structural composite materials, electronic semiconductor packaging and the like. But also has the defects of high crosslinking density, brittleness, insufficient temperature resistance grade, poor impact resistance and the like after curing.
The organic silicon is a compound which takes a siloxane chain segment as a main chain and is connected with an organic functional group on a silicon atom, and has the characteristics of low surface energy, weather resistance, heat resistance, hydrophobicity, smoothness of a molecular chain and the like. By combining the organic silicon and the epoxy resin, the flexibility of the resin can be improved, and the performances of the resin in the aspects of water resistance, heat resistance, weather resistance and the like can be improved. However, the organosilicon material has poor compatibility with epoxy resin, and a phase-separated structure is easily formed after compounding, and the size and stability of the phase domain size have important influence on the final performance of the epoxy product.
In recent years, cage-type silsesquioxane (POSS) synthesized from silane as a starting material has been favored by researchers because of its rigid ordered cubic structure, multiple functionality, and flexibility in designing its molecular structure. As a unique nanoscale organic-inorganic hybrid material, POSS can be used in hybrid or composite materials where precise control of nanostructure and properties is required. However, the improvement of the matrix performance is mainly influenced by the dispersion performance, and in order to improve the dispersion state of the POSS in the resin matrix, the type and functionality of the functional group of the POSS generally need to be adjusted to improve the compatibility of the POSS and the resin matrix and the final comprehensive performance of the product.
Chinese patent publication No. CN 111116869 a discloses a liquid epoxy-based functionalized POSS modified epoxy resin and a preparation method thereof, wherein the liquid epoxy-based functionalized POSS has eight functionalities, and although a good effect is obtained in the modification application of epoxy resin. However, since the epoxy resin has high crosslinking density and strong brittleness, if POSS with a multi-functional group and a rigid structure is introduced, the toughening effect of the POSS on the epoxy resin is still limited. Moreover, its compatibility with the epoxy resin matrix is still limited, and the addition amount is not more than 10% of the mass of the epoxy resin matrix, which further limits its modification effect on the epoxy resin.
Disclosure of Invention
Aiming at the problems, the invention provides the tetracycloxy cage-type silsesquioxane, which has a flexible molecular chain, is liquid at room temperature, has excellent thermal stability and better compatibility with carbon-based materials, can be directly used as a base material to prepare epoxy resin, can also be used as a modifier to be compounded into 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, shock resistance and the like.
The specific technical scheme is as follows:
a tetracycloxy cage type silsesquioxane has a structural formula shown as the following formula (I):
the glass transition temperature of the tetracyclooxy cage-type silsesquioxane is-23.1 ℃, and the initial thermal decomposition temperature (T) is in a nitrogen atmosphere-5％) The residual carbon content was 29.6% at 340 ℃ and 800 ℃. The heat resistance is obviously better than that of the cage type octa (glycidyl ether oxypropyl dimethyl siloxy) silsesquioxane.
The tetracycloxy cage-type silsesquioxane disclosed by the invention is novel in structure, and the molecular chain of the bio-based monomer with the body type structure is flexible and is liquid at room temperature; the resin has better thermal stability, high initial thermal decomposition temperature and high residual carbon content, 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 tetracycloxy cage type silsesquioxane, which comprises the following steps:
(a) under inert atmosphere, mixing tetrafunctional hydrosilation functionalized cage-type silsesquioxane with a structural formula shown as the following formula (II), allyl glycidyl ether, a solvent and a catalyst to perform a 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 tetrafunctional hydrosilyl functionalized cage-type silsesquioxane reference (chem. commun.,2017,53,10370) was prepared.
The tetrafunctional hydrosilation functionalized cage type silsesquioxane comprises the following components in molar mass: allyl glycidyl ether ═ 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 4-30 times of the allyl glycidyl ether 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 10-300 ppm calculated by the mole number of the reaction functional group, and the catalyst concentration is calculated by the content of platinum; preferably 100 to 150 ppm.
The temperature of the hydrosilylation reaction is 60-120 ℃.
In the step (b), the separation and purification method comprises the following steps: removing low-boiling-point substances from the reaction mother liquor by rotary evaporation, adding the crude product into an organic solvent, stirring and washing for a plurality of times, and then drying in vacuum;
the organic solvent is one or more selected from diethyl ether, cyclohexane, n-hexane, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, dichloromethane, acetone, chloroform, toluene, and petroleum ether.
Preferably, the washing is carried out under heating.
The invention also discloses application of the tetracycloxy liquid polyhedral oligomeric silsesquioxane in preparation of an epoxy resin nano hybrid material.
The method specifically comprises the following steps:
the epoxy resin nano hybrid material is prepared by curing the four epoxy group liquid cage type silsesquioxane and other epoxy resin which can be selectively added as raw materials.
The tetracycloxy liquid cage type silsesquioxane and the epoxy resin can realize uniform dispersion in a nanoscale, so that the tetracycloxy liquid cage type silsesquioxane and the epoxy resin have no special requirements on the using amounts of the tetracycloxy liquid cage type silsesquioxane and the epoxy resin, and can be mixed in any proportion.
The tetracyclooxy liquid polyhedral oligomeric silsesquioxane can be independently used as a raw material, and an epoxy resin material is prepared by curing. The resin material has excellent high temperature resistance, water resistance and impact resistance.
The tetracycloxy liquid cage type silsesquioxane can also be mixed with epoxy resin commonly used in the field and then cured to prepare the epoxy resin nano hybrid material. The interior of the prepared epoxy resin hybrid material is characterized, and the fact that the tetracycloxy liquid polyhedral oligomeric silsesquioxane is completely and uniformly distributed in a nanoscale can be found, so that the high-temperature resistance, the water resistance and the shock resistance of the tetracycloxy liquid polyhedral oligomeric silsesquioxane 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 a tetracycloxy liquid cage type silsesquioxane, wherein a POSS monomer molecular chain with a body structure is flexible, is liquid at room temperature, has excellent thermal stability and water resistance, and an epoxy resin prepared by curing the POSS monomer molecular chain serving as a base material has excellent high-temperature resistance, water resistance and impact resistance.
2. The tetracycloxy liquid polyhedral oligomeric silsesquioxane disclosed by the invention has better compatibility with carbon-based materials, can be used as an epoxy resin modifier, can introduce an epoxy resin cross-linked 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 tetracycloxy liquid cage type silsesquioxane;
FIG. 2 is a nuclear magnetic silicon spectrum of a tetracycloxy liquid cage silsesquioxane;
FIG. 3 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of a tetracycloxy liquid polyhedral oligomeric silsesquioxane;
FIG. 4 is a transmission electron microscope image of the interior of the epoxy resin composite material;
FIG. 5 is an atomic force microscope phase diagram of the interior of an epoxy nanocomposite.
Detailed Description
Example 1
To a flask equipped with a magnetic stirrer and reflux condenser, under a nitrogen atmosphere, was added tetrafunctional hydrosilyl-functionalized cage silsesquioxane (1.21g, 0.929mmol), excess allyl glycidyl ether (2.12g, 18.6mmol), dry toluene (45g) and a Kanst catalyst (platinum content 200 ppm). The reaction was carried out at 95 ℃ for 24 hours or more. The mixed solution is subjected to rotary evaporation to remove low-boiling-point substances, washed and purified by petroleum ether, and dried in vacuum. The yield was 94%.
FIGS. 1 to 3 show nuclear magnetic hydrogen spectra, silicon spectra and mass spectra of the tetracycloxy liquid polyhedral oligomeric silsesquioxane prepared by the invention, and the characterization can confirm that the prepared product conforms to the structure of the formula (I).
Example 2
To a flask equipped with a magnetic stirrer and a reflux condenser, under a nitrogen atmosphere, was added tetrafunctional hydrosilyl-functionalized cage-type silsesquioxane (1.21g, 0.929mmol), allyl glycidyl ether (0.424g, 3.716mmol), dry toluene (12.6g), and chloroplatinic acid (platinum content 200 ppm). The system is reacted for more than 24 hours at 85 ℃. The mixed solution is subjected to rotary evaporation to remove low-boiling-point substances, washed and purified by petroleum ether, and dried in vacuum. The yield was 90%.
Comparative example 1
To a flask equipped with a magnetic stirrer and condenser, under a nitrogen atmosphere, was added 8H-POSS (1.06g, 1.04mmol), excess allyl glycidyl ether (4.75g, 41.6mmol), dry toluene (43g) and Kansted catalyst (platinum content 100 ppm). The reaction system is reacted at 100 ℃ for more than 24 ℃. The mixed solution is subjected to flash column chromatography to remove the catalyst, and the solvent and low-boiling-point substances are removed under reduced pressure to prepare the allyl glyceryl ether grafted cage-type silsesquioxane, namely cage-type octa (glycidyl ether oxypropyl dimethyl siloxy) silsesquioxane (8AGE-POSS, the yield is 95%).
Thermal stability test
Thermal stability data for the tetracyclooxy liquid cage silsesquioxane and the cage octa (glycidoxypropyldimethylsiloxy) silsesquioxane are set forth in Table 1 below.
TABLE 1
Application example
The preparation method of the epoxy resin nano hybrid material comprises the following specific steps: mixing the tetracycloxy liquid cage type silsesquioxane and bisphenol A epoxy resin (DGEBA) according to the mass ratio of 1:4, dissolving in acetone, violently stirring and ultrasonically dispersing, adding a curing agent 3,3' -diaminodiphenyl sulfone according to the stoichiometric ratio of reaction groups and the like [ N-H/epoxy (mol) ═ 1/1] after heating and volatilizing the acetone, and heating to 105 ℃ 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 performance data of the epoxy nanohybrid are shown in table 2 below.
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 shown in figures 4 and 5, and the observation of the two pictures can determine that the four-functionality eugenol epoxy functionalized cage-type silsesquioxane can be highly uniformly dispersed in the bisphenol A epoxy resin matrix in a nano 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 present invention.
Claims (1)
1. The application of the tetracycloxy liquid cage-type silsesquioxane in preparing the epoxy resin nano hybrid material is characterized in that the tetracycloxy liquid cage-type silsesquioxane and other epoxy resins which can be selectively added are taken as raw materials, and the epoxy resin nano hybrid material is prepared after curing;
the structural formula of the tetracycloxy liquid cage type silsesquioxane is shown as the following formula (I):
the glass transition temperature of the tetracycloxy liquid cage type silsesquioxane is-23.1 ℃, the initial thermal decomposition temperature under the nitrogen atmosphere is 340 ℃, and the residual carbon content at 800 ℃ is 29.6%;
the preparation method of the tetracycloxy liquid cage type silsesquioxane comprises the following steps:
1.21g, 0.929mmol of tetrafunctional hydrosilyl-functionalized cage-type silsesquioxane, 2.12g, 18.6mmol of excess allyl glycidyl ether, 45g of dry toluene and a Kaster catalyst with a platinum content of 200ppm were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere; the system reacts for more than 24 hours at 95 ℃; removing low-boiling-point substances from the mixed solution by rotary evaporation, washing and purifying by petroleum ether, and drying in vacuum;
the structural formula of the tetrafunctional hydrosilation functionalized cage-type silsesquioxane is shown as the following formula (II);
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