CN112876683A - Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof - Google Patents
Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN112876683A CN112876683A CN202110156551.7A CN202110156551A CN112876683A CN 112876683 A CN112876683 A CN 112876683A CN 202110156551 A CN202110156551 A CN 202110156551A CN 112876683 A CN112876683 A CN 112876683A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- octaeugenol
- type silsesquioxane
- cage type
- silsesquioxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses octaeugenol epoxy group liquid cage type silsesquioxane as well as a preparation method and application thereof. The structural formula of the octaeugenol epoxy group liquid cage type silsesquioxane is shown as the following formula (I); the product is bio-based cage type silsesquioxane which is liquid at room temperature, 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 octaeugenol epoxy group liquid cage type silsesquioxane, a preparation method thereof and application thereof in preparation of a bio-based epoxy resin nano hybrid material.
Background
The epoxy resin is one of three thermosetting resins, has excellent bonding, mechanical and electrical properties, and is 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. At present, the modification research of epoxy resin mainly focuses on the aspects of performance improvement, environmental protection substitution and the like, and the adopted approaches can be summarized into the following two categories: (1) the resin body is modified by adopting the functional modifier/filler so as to improve the performances of the resin in the aspects of processing, mechanics, weather resistance, corrosion resistance, flame retardance and the like and expand the application range and the field of the resin; (2) the high-performance environment-friendly epoxy resin is prepared by using the bio-based raw materials to replace the traditional petroleum-based raw materials (such as bisphenol A and the like). For filler modification, the problem of dispersion of particles in an epoxy resin matrix is to be overcome; in addition, many of the conventional bio-based epoxies are mainly linear or branched aliphatic and aromatic small molecules, which are disadvantageous in many aspects such as thermal stability and flame retardancy, and the effect of the modified epoxy resins is often relatively single.
Polyhedral Oligomeric silsesquioxane (POSS) is used as a unique nanoscale organic-inorganic hybrid material and has outstanding heat resistance, oxidation resistance, hydrophobicity, low dielectric constant and mechanical properties. Thanks to the designability of the molecular structure, POSS can be used in hybrid or composite materials requiring precise control of the nanostructure and performance, realizing modification of polymers at the molecular level, and having great potential in the field of advanced functional nanomaterial preparation. By combining POSS and epoxy resin, the brittleness 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, polysiloxane materials such as POSS have poor compatibility with epoxy matrices, resulting in less than ideal properties of the final composite.
For example, chinese patent publication No. CN 111116869 a reports an allyl glycidyl ether grafted POSS modified epoxy resin and a preparation method thereof, which improves the compatibility of POSS and epoxy matrix and improves the resin performance. However, the side chain of the POSS is an aliphatic long chain, the thermal stability is general, the compatibility with an epoxy body needs to be further improved, and the modified resin has low high-temperature carbon residue and is difficult to meet the requirement of a high-temperature resistant application environment.
Disclosure of Invention
Aiming at the problems, the invention provides octaeugenol epoxy group liquid cage type silsesquioxane, the bio-based POSS 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 bio-based epoxy resin, can also be used as a bio-based modifier to be compounded into 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, shock resistance and the like.
The specific technical scheme is as follows:
an octaeugenol epoxy group liquid cage type silsesquioxane, the structural formula is shown as the following formula (I):
the glass transition temperature of the octaeugenol epoxy group liquid cage type silsesquioxane is-11.9 ℃, and the initial thermal decomposition temperature (T) is in a nitrogen atmosphere-5%) The residual carbon content was 47.0% at 454 ℃ and 800 ℃. The heat resistance of the material is obviously superior to that of cage type octa (glycidyl ether oxypropyl dimethyl siloxy) silsesquioxane (marked as 8 AGE-POSS).
The octaeugenol epoxy group liquid cage type silsesquioxane disclosed by the invention is novel in structure, and the body type structure bio-based monomer is in a liquid state at room temperature; the thermal stability is particularly excellent, the initial thermal decomposition temperature is up to 454 ℃, the residual carbon content is high, the resin can be independently used as a base material to prepare bio-based epoxy resin, and the resin 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 octaeugenol epoxy group liquid cage type silsesquioxane, which comprises the following steps:
(a) under inert atmosphere, mixing cage octa-poly (dimethylsiloxy) silsesquioxane (8H-POSS) 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 octaeugenol epoxy group liquid cage type silsesquioxane.
In step (a):
the inert atmosphere is a gas conventional in the art, such as nitrogen, argon, and the like.
The cage octapoly (dimethylsiloxy) silsesquioxane reference (Macromolecules,2003,36(15): 5666-5682).
The eugenol epoxy monomer reference (ACS sustatin chem. eng.2018,6,8856-.
Molar mass, cage octapoly (dimethylsiloxy) silsesquioxane: eugenol epoxy monomer ═ 1: 8-40; preferably 1: 15 to 25.
The solvent is selected from one or more of toluene, tetrahydrofuran and isopropanol; toluene is preferred.
The solvent is 5-30 times of the eugenol epoxy monomer by mass; preferably 8 to 15 times.
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 concentration of the catalyst is 10-300 ppm by mole of the reaction functional group; the catalyst concentration is calculated by the content of platinum in the catalyst; preferably 150 to 300 ppm.
The temperature of the hydrosilylation reaction is 70-120 ℃.
In the step (b), the separation and purification method comprises the following steps:
distilling the reaction mother liquor to remove low-boiling-point substances, adding petroleum ether into the crude product, stirring and washing for several times, and then drying in vacuum.
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, ethanol, isopropanol, n-butanol, dichloromethane, acetone, chloroform, toluene and the like, are difficult to purify or have unsatisfactory purification effect.
The invention also discloses application of the octaeugenol epoxy group liquid cage type silsesquioxane in preparation of a bio-based epoxy resin nano hybrid material.
The method specifically comprises the following steps:
the octaeugenol epoxy group liquid cage type silsesquioxane and other epoxy resin which can be selectively added are taken as raw materials, and the biological epoxy resin nanometer hybrid material is prepared after curing.
The octaeugenol epoxy group liquid 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 octaeugenol epoxy group liquid cage type silsesquioxane and the epoxy resin, and the octaeugenol epoxy group liquid cage type silsesquioxane and the epoxy resin can be mixed in any proportion.
The octaeugenol epoxy group liquid 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 octaeugenol epoxy group liquid cage type silsesquioxane can also be mixed with common epoxy resin 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 octaeugenol epoxy group liquid cage type silsesquioxane is completely and uniformly distributed in a nanoscale, so that the high temperature resistance, the water resistance and the shock resistance of the octaeugenol epoxy group liquid cage type 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 octaeugenol epoxy group liquid cage type silsesquioxane, wherein a body structure bio-based monomer is liquid at room temperature and has excellent thermal stability and water resistance, and bio-based epoxy resin prepared by curing the monomer serving as a base material has excellent high temperature resistance, water resistance and impact resistance.
2. The octaeugenol epoxy group liquid 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 octaeugenol epoxy group liquid cage type silsesquioxane;
FIG. 2 is a nuclear magnetic silicon spectrum of octaeugenol epoxy group liquid cage type silsesquioxane;
FIG. 3 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of octaeugenol epoxy group liquid cage silsesquioxane;
FIG. 4 is a comparison graph of the thermal weight loss curves of octaeugenol epoxy group liquid cage-type silsesquioxane and allyl glycerol ether grafted cage-type silsesquioxane in a nitrogen atmosphere;
FIG. 5 is a transmission electron microscope image of the interior of the epoxy resin composite material;
FIG. 6 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 a reflux condenser, under a nitrogen atmosphere, was added cage octapoly (dimethylsiloxy) silsesquioxane (1.25g, 1.23mmol), excess eugenol epoxy (5.42g, 24.6mmol), dry toluene (43g) and a Kanst catalyst (platinum content 300 ppm). The system was reacted at 110 ℃ for 36 h. Removing the catalyst from the mixed solution by flash column chromatography, removing the solvent by rotary evaporation, adding petroleum ether into the crude product, stirring and washing for several times at 60 ℃, and drying to obtain viscous liquid, namely the octaeugenol epoxy cage type silsesquioxane (8EUEP-POSS, the yield is 90%).
FIGS. 1 to 3 show nuclear magnetic hydrogen spectra, silicon spectra and mass spectra of the octaeugenol epoxy group liquid 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
To a flask equipped with a magnetic stirrer and a reflux condenser, under a nitrogen atmosphere, was added cage octapoly (dimethylsiloxy) silsesquioxane (1.25g, 1.23mmol), excess eugenol (6.78g, 30.75mmol), dry toluene (101.7g), and chloroplatinic acid catalyst (platinum content 100 ppm). The system was reacted at 90 ℃ for 36 h. The mixed solution is subjected to flash column chromatography to remove the catalyst, solvent is removed by rotary evaporation, methanol is washed, and viscous liquid is the octaeugenol epoxy cage type silsesquioxane (the yield is 80 percent).
Comparative example 1
To a flask equipped with a magnetic stirrer and condenser, under nitrogen, were added 8H-POSS (1.06g, 1.04mmol), excess allyl glycidyl ether (4.75g, 41.6mmol), dry toluene (43g) and Kansted catalyst (Pt mole content 100 ppm). The system is reacted for more than 24 hours at 100 ℃. 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
FIG. 4 shows a comparison of the thermal weight loss curves of octaeugenol epoxy cage silsesquioxane (8EUEP-POSS) and allyl glycerol ether grafted cage silsesquioxane (8AGE-POSS) under nitrogen. The result shows that the eugenol epoxy functionalized cage-type silsesquioxane has excellent thermal stability, the initial thermal decomposition temperature is up to 454 ℃, the carbon residue at 800 ℃ is up to 47 percent, and the thermal stability is far higher than that of the allyl glycidyl ether grafted cage-type silsesquioxane.
TABLE 1
Initial thermal decomposition temperature (N)2,T-5%,℃) | Residual carbon content (wt%, 800 ℃ C.) | |
8EUEP-POSS | 454 | 47.0 |
8AGE-POSS | 219 | 25.2 |
Application example
The preparation method of the bio-based epoxy resin nano hybrid material comprises the following specific steps: mixing octaeugenol epoxy group 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 [ N-H/epoxy group (mol) ═ 1/1] of reaction groups and the like after heating and volatilizing the acetone, and heating to 115 ℃ 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 standardThe 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 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 figures 5 and 6, and the observation of the two pictures can determine that the octaeugenol epoxy group liquid 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' -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 115 ℃ 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 (10)
2. the octaeugenol epoxy liquid cage silsesquioxane of claim 1 wherein the glass transition temperature is-11.9 ℃, the initial thermal decomposition temperature under nitrogen atmosphere is 454 ℃ and the residual carbon content at 800 ℃ is 47.0%.
3. A method for preparing the octaeugenol epoxy based liquid cage type silsesquioxane as defined in claim 1 or 2, comprising the steps of:
(a) under inert atmosphere, mixing cage octa-poly (dimethylsiloxy) 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 octaeugenol epoxy group liquid cage type silsesquioxane.
4. The method for preparing octaeugenol epoxy liquid cage type silsesquioxane as claimed in claim 3, wherein in step (a), the molar mass of cage type octapoly (dimethylsiloxy) silsesquioxane: eugenol epoxy monomer ═ 1: 8-40.
5. The method for preparing octaeugenol epoxy liquid cage type silsesquioxane as defined in claim 3, wherein in step (a), the solvent is selected from one or more of toluene, tetrahydrofuran, isopropanol;
the solvent is 5-30 times of the eugenol epoxy monomer by mass.
6. The method for preparing octaeugenol epoxy based liquid cage type silsesquioxane as claimed in claim 3, wherein in step (a), said catalyst is selected from platinum based catalysts;
the catalyst concentration is 10-300 ppm based on the mole number of the reaction functional group.
7. The method for preparing octaeugenol epoxy liquid cage type silsesquioxane according to claim 3, wherein the temperature of the hydrosilylation reaction in step (a) is 70-120 ℃.
8. The method for preparing octaeugenol epoxy liquid cage type silsesquioxane as defined in claim 3, wherein in the step (b), the separation and purification method comprises the following steps:
distilling the reaction mother liquor to remove low-boiling-point substances, adding petroleum ether into the crude product, stirring and washing for several times, and then drying in vacuum.
9. Use of the octaeugenol epoxy based liquid cage type silsesquioxane as defined in claim 1 or 2 in preparation of bio-based epoxy resin nano hybrid material.
10. The application of the octaeugenol epoxy group liquid cage-type silsesquioxane in preparing the bio-based epoxy resin nano hybrid material as claimed in claim 9, wherein the octaeugenol epoxy group liquid cage-type silsesquioxane and other epoxy resins which can be selectively added are used as raw materials, and the bio-based epoxy resin nano hybrid material is prepared after curing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110156551.7A CN112876683B (en) | 2021-02-04 | 2021-02-04 | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110156551.7A CN112876683B (en) | 2021-02-04 | 2021-02-04 | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112876683A true CN112876683A (en) | 2021-06-01 |
CN112876683B CN112876683B (en) | 2022-04-22 |
Family
ID=76057256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110156551.7A Active CN112876683B (en) | 2021-02-04 | 2021-02-04 | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112876683B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114573816A (en) * | 2022-03-08 | 2022-06-03 | 浙江大学 | Epoxy MQ silicon resin and preparation method and application thereof |
CN114836034A (en) * | 2022-06-01 | 2022-08-02 | 江南大学 | Bismaleimide resin composition and application thereof |
CN115304922A (en) * | 2022-09-06 | 2022-11-08 | 哈尔滨工业大学 | Preparation method of bio-based POSS/epoxy hybrid material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101503420A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-epoxy cage type sesquialter siloxane and preparation thereof |
CN101665562A (en) * | 2009-08-07 | 2010-03-10 | 厦门大学 | Preparation method of POSS-epoxy hybrid material with controllable phase structure |
CN102492116A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method |
CN103214510A (en) * | 2013-04-10 | 2013-07-24 | 吉林大学 | Octohydroxy cage-like silsesquioxane monomer and preparation method thereof |
US20130287714A1 (en) * | 2010-11-12 | 2013-10-31 | Sven Gohla | Cosmetic and/or dermatological preparations containing snow algae extract |
CN111116869A (en) * | 2019-05-28 | 2020-05-08 | 杭州师范大学 | Liquid epoxy group functionalized POSS modified epoxy resin and preparation method thereof |
-
2021
- 2021-02-04 CN CN202110156551.7A patent/CN112876683B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101503420A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-epoxy cage type sesquialter siloxane and preparation thereof |
CN101665562A (en) * | 2009-08-07 | 2010-03-10 | 厦门大学 | Preparation method of POSS-epoxy hybrid material with controllable phase structure |
US20130287714A1 (en) * | 2010-11-12 | 2013-10-31 | Sven Gohla | Cosmetic and/or dermatological preparations containing snow algae extract |
CN102492116A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method |
CN103214510A (en) * | 2013-04-10 | 2013-07-24 | 吉林大学 | Octohydroxy cage-like silsesquioxane monomer and preparation method thereof |
CN111116869A (en) * | 2019-05-28 | 2020-05-08 | 杭州师范大学 | Liquid epoxy group functionalized POSS modified epoxy resin and preparation method thereof |
Non-Patent Citations (5)
Title |
---|
CHENG LI等: "Biobased Epoxy Resin with Low Electrical Permissivity and Flame Retardancy: From Environmental Friendly High-Throughput Synthesis to Properties", 《ACS SUSTAINABLE CHEM. ENG》 * |
PERIYASAMY THIRUKUMARAN: "Synthesis of Eugenol-Based Polybenzoxazine–POSS Nanocomposites for Low Dielectric Applications", 《POLYMER COMPOSITES》 * |
张先伟: "功能化笼型低聚倍半硅氧烷的制备和性能研究及其在杂化材料中的应用", 《中国优秀博士学位论文全文数据库工程科技I辑》 * |
谭慧民: "《固体推进剂化学与技术》", 30 September 2015 * |
陈祥宝: "《先进复合材料技术导论》", 30 September 2017 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114573816A (en) * | 2022-03-08 | 2022-06-03 | 浙江大学 | Epoxy MQ silicon resin and preparation method and application thereof |
CN114836034A (en) * | 2022-06-01 | 2022-08-02 | 江南大学 | Bismaleimide resin composition and application thereof |
CN114836034B (en) * | 2022-06-01 | 2023-02-17 | 江南大学 | Bismaleimide resin composition and application thereof |
CN115304922A (en) * | 2022-09-06 | 2022-11-08 | 哈尔滨工业大学 | Preparation method of bio-based POSS/epoxy hybrid material |
Also Published As
Publication number | Publication date |
---|---|
CN112876683B (en) | 2022-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112876683B (en) | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof | |
CN112795015B (en) | Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof | |
US5902863A (en) | Dendrimer-based networks containing lyophilic organosilicon and hydrophilic polyamidoamine nanoscopic domains | |
CN112940257B (en) | Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof | |
CN112876685B (en) | Tetraepoxy group liquid cage type silsesquioxane as well as preparation method and application thereof | |
US8507618B2 (en) | Siloxane mixtures containing epoxide resins and method for the preparation thereof and use thereof | |
Luo et al. | Low-k and recyclable high-performance POSS/polyamide composites based on Diels–Alder reaction | |
Nazir et al. | The influence of temperature and interface strength on the microstructure and performance of sol–gel silica–epoxy nanocomposites | |
Govindaraj et al. | Microwave‐assisted synthesis of nanocomposites from polyimides chemically cross‐linked with functionalized carbon nanotubes for aerospace applications | |
CN105254828A (en) | Cage-shaped oligomerization silsesquioxane hybridized phenolic resin with eight phenolic hydroxyl groups and preparation method thereof | |
Devaraju et al. | Hyperbranched polysiloxane‐based diglycidyl ether of bisphenol a epoxy composite for low k dielectric application | |
Chang et al. | Preparation and comparative properties of membranes based on PANI and three inorganic fillers. | |
Ahn et al. | Nanocomposite membranes consisting of poly (vinyl chloride) graft copolymer and surface-modified silica nanoparticles | |
CN110229338B (en) | Hyperbranched polysiloxane and preparation method and application thereof | |
CN111777801A (en) | Silicone rubber composite material for insulated cable and preparation method thereof | |
Gunasekaran et al. | Siloxane core dianhydride modified ether linked cyclohexyl diamine based multi-walled carbon nanotube reinforced polyimide (MWCNT/PI) nanocomposites | |
CN111892820A (en) | High-conductivity silicone rubber and preparation method and application thereof | |
Chen et al. | Surface modification of calcium sulfate whisker using thiol‐ene click reaction and its application in reinforced silicone rubber | |
CN111100332B (en) | Preparation method and application of dumbbell type fluorine-containing polyphosphazene modified halloysite nanotube | |
Zhao et al. | Hybridization of polyhedral oligomeric silsesquioxane and boron nitride for epoxy composites with improved dielectric, thermal and tensile properties | |
CN115960464B (en) | Liquid vinyl cage polysilsesquioxane modified addition type liquid silicone rubber and preparation method thereof | |
Gowri et al. | Novel copolymer for SiO2 nanoparticles dispersion | |
Fang et al. | Cyclotriphophazene-centered six-arm eugenol-linked low-dielectric materials with high thermostability and transparency | |
Pan et al. | Dielectric and thermal properties of epoxy resin nanocomposites containing polyhedral oligomeric silsesquioxane | |
Peng et al. | Preparation of benzocyclobutene-functionalized organic–inorganic hybrid microspheres and their reduction of permittivity to DVSBCB resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |