CN115304922A - Preparation method of bio-based POSS/epoxy hybrid material - Google Patents
Preparation method of bio-based POSS/epoxy hybrid material Download PDFInfo
- Publication number
- CN115304922A CN115304922A CN202211086147.8A CN202211086147A CN115304922A CN 115304922 A CN115304922 A CN 115304922A CN 202211086147 A CN202211086147 A CN 202211086147A CN 115304922 A CN115304922 A CN 115304922A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- bio
- preparation
- based poss
- steps
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
- Silicon Polymers (AREA)
Abstract
A preparation method of a bio-based POSS/epoxy hybrid material relates to the field of high polymer materials and aims to solve the problem of high dielectric constant of the existing epoxy resin material. The method comprises the following steps: firstly, the method comprises the following steps: mixing a single-end double-bond phenolic compound, epichlorohydrin and sodium hydroxide, adding tetramethylammonium bromide to react, washing with water, distilling and recrystallizing to obtain single-end double-bond epoxy; II, secondly: adding polyhedral oligomeric silsesquioxane with octahydro functional groups into a solvent, and mixing single-end double-bond epoxy, a catalyst and the solvent; and dropwise adding the mixture into polyhedral oligomeric silsesquioxane with octahydro functional groups, stirring for reaction, adding activated carbon, filtering, and performing rotary evaporation to obtain the bio-based POSS/epoxy hybrid resin. After being cured, the bio-based POSS/epoxy hybrid resin prepared by the method has excellent low dielectric property, thermal stability and hydrophobicity. The invention is used for preparing epoxy resin materials.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a preparation method of a bio-based POSS/epoxy hybrid material.
Background
Due to the low dielectric material having a low dielectric constantThe material has the advantages of high water absorption, low dielectric loss, high heat resistance and the like, is widely applied to portable and low-power microelectronic systems, but provides higher requirements for low dielectric materials in special fields. With the further development of the microelectronics industry, D with low dielectric constant is developed k Dielectric loss D f The copper-clad plate formula system with characteristics becomes the latest and hottest research subject. Because the polymer material has the advantages of low water absorption, molecular design, good processability and the like, the polymer material is widely concerned in the research and application of low dielectric materials. The current rapid development of 5G has resulted in faster transmission speeds, which require lower dielectric constants and dielectric losses for the propagation medium material.
Epoxy polymer is an important thermosetting resin, and is widely applied to the fields of aviation, aerospace, microelectronics, electronic packaging, printed circuit boards, building, rail transportation and the like due to excellent mechanical properties, bonding properties, dimensional stability, heat resistance, insulativity and chemical resistance. However, epoxy resin also has the disadvantages of high dielectric constant and large dielectric loss due to the generation of a large number of hydroxyl groups after curing, which greatly limits the potential application potential of epoxy resin in the future internet of things and 5G technology. Expensive resin systems such as polytetrafluoroethylene, polyphenylene oxide and hydrocarbon resin have to be used, so that the cost of the high-frequency printed circuit board base material is always in a high state, and a new low-dielectric technical scheme based on epoxy resin is urgently needed. The siliconized epoxy resin is generally obtained by polycondensation of a siliconized bisphenol compound and epichlorohydrin, and has low surface tension, friction factor and refractive index due to silicon atoms closely arranged around a main chain of the resin, and excellent hydrophobicity, corrosion resistance, wear resistance, moisture resistance, heat resistance, dielectricity, durability and the like. Therefore, the organosilicon epoxy taking the double bond epoxy resin as the matrix material has excellent comprehensive performance and strong adhesive capacity to various matrixes.
The hollow glass microspheres are hollow thin-wall microspheres made of sodium borosilicate glass with water resistance and chemical stability, and have high fluidity, low density and excellent mechanical and electrical insulation properties. Therefore, it can be used as a filler in low to ultra-low dielectric electronic component materials, such as copper-clad laminates, electrical connectors, and radomes. However, phase separation between the polymer and the filler is a critical issue for the reduction of mechanical properties. In recent years, several strategies to reduce phase separation have been reported. Compatibility can be significantly improved by modifying the filler with reactive groups (e.g., amino and hydroxyl groups) or synthesizing a filler containing reactive groups. In addition, the strategy to reduce the dielectric constant and dielectric loss of epoxy polymers is, in theory, to reduce the polarity of the epoxy matrix. An effective method is to select an anhydride compound as a curing agent to avoid hydroxyl formation during the curing process. This system is commonly used in electrical insulation materials.
The siloxane has low polarity, excellent electrical insulation, a dielectric constant of 3, and a dielectric loss tangent of about 0.001. In particular, polyhedral Polysiloxanes (POSS) are hollow cage-like rigid frameworks formed from silicon atoms and oxygen atoms, combined with siloxane and "nanobubbles", and have a low dielectric constant (2.1-2.8). The POSS modified epoxy resin also attracts wide attention, and the POSS is an ideal modified body in epoxy polymer and can effectively reduce dielectric constant, but when the POSS is introduced in a large amount, the occurrence of aggregation and phase separation phenomena can often reduce the mechanical property. At present, the key technical problem is how to improve the compatibility of POSS and epoxy and avoid the occurrence of aggregation and phase separation. In general, chemical covalent attachment of POSS to epoxy backbones or networks is an effective means.
Disclosure of Invention
The invention aims to solve the problem of high dielectric constant of the existing epoxy resin material, and provides a preparation method of a bio-based POSS/epoxy hybrid material.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a bio-based POSS/epoxy hybrid material comprises the following steps:
the method comprises the following steps: generating single-end double-bond epoxy by the ring-opening reaction of phenolic hydroxyl of the single-end double-bond phenolic compound and epichlorohydrin;
step two: the double bond of the single-end double bond epoxy and the silicon hydrogen of the polyhedral oligomeric silsesquioxane with the octa-silicon hydrogen functional group are subjected to addition reaction under the action of a Karster catalyst to obtain the bio-based POSS/epoxy hybrid resin;
step three: preparing silane modified glass beads;
step four: and sequentially adding a curing agent and silane modified glass beads into the bio-based POSS/epoxy hybrid resin, and curing for 6-10 hours at 105-200 ℃ to obtain the bio-based POSS/epoxy hybrid material.
Further, the method comprises the following steps:
the method comprises the following steps: mixing a single-end double-bond phenolic compound, epoxy chloropropane and sodium hydroxide, stirring at room temperature for 15-60 min, adding tetramethylammonium bromide, heating to 60-80 ℃, reacting for 2-3 h, washing with water, distilling, and recrystallizing to obtain single-end double-bond epoxy; wherein the molar ratio of the single-end double-bond phenolic compound to the epichlorohydrin to the sodium hydroxide to the tetramethylammonium bromide is 1:4 to 15:1.5 to 5:0.01 to 0.3;
step two: adding polyhedral oligomeric silsesquioxane with octahydro functional groups into a solvent with the mass 5 times that of the polyhedral oligomeric silsesquioxane, and mixing single-terminal double-bond epoxy, a catalyst and the solvent with the mass 5 times that of the polyhedral oligomeric silsesquioxane to obtain a mixture; dropwise adding the mixture into a polyhedral oligomeric silsesquioxane solution containing octahydro functional groups at 90-110 ℃, completing dropwise addition within 30-60min, stirring for reaction for 24-48 h, adding activated carbon to remove a catalyst, filtering, and performing rotary evaporation to obtain the bio-based POSS/epoxy hybrid resin; wherein the molar ratio of the single-end double-bond epoxy to the octahydro-octahydro functional group polyhedral oligomeric silsesquioxane is 1-1.2: 1, the dosage of the catalyst is 10-20ppm of the total mass of the polyhedral oligomeric silsesquioxane with single-ended double bond epoxy and octahydro functional groups;
step three: adding 10-20 g of glass beads into 0.3 mol/L300-600 mL of aqueous solution, reacting at 60-80 ℃ for 1-2 h, washing with deionized water to be neutral, and drying for later use; 20-50 g of absolute ethyl alcohol, 15-30 g of water, 0.3-0.5g of silane coupling agent and 5-10 g of the obtained glass microspheres are quickly stirred for 3-5 min, after suction filtration, the glass microspheres are put into a 100 ℃ oven for 5-10 min and then taken out, added with 30-50 mL of absolute ethyl alcohol, subjected to ultrasonic treatment for 10-30 min, then subjected to suction filtration, dried and sieved;
step four: and sequentially adding a curing agent and silane modified glass beads into the bio-based POSS/epoxy hybrid resin, stirring to obtain a stable resin mixture, and curing at 105-200 ℃ for 6-10 hours to obtain the bio-based POSS/epoxy hybrid material. The adding amount of the silane modified glass beads is 10%,20%,30% and 40% of the resin amount respectively, wherein the using amount of the curing agent is the using amount of the curing agent commonly used in the field.
Further, in the first step, the phenolic compound with single-end double bond is any one or combination of several of eugenol, methyl eugenol, 2-methoxy-4-vinylphenol, 3 '-propenyl-4' -hydroxyacetophenone, 4- (3-methyl-2-en-1-yl) phenol, trans-4-hydroxystilbene and 4-vinylphenol.
Further, in the second step, the catalyst is a Castript catalyst or chloroplatinic acid H 2 PtCl 6 ·6H 2 O; the solvent is one of tetrahydrofuran, toluene or xylene.
Further, in the second step, the mass of the solvent in the mixture is 5 times of the total mass of the single-ended double-bond epoxy and the catalyst.
The use amount of the solvent is too small to facilitate thermal diffusion, so that the temperature of a reaction system is increased suddenly; the use amount is too much, which causes a certain waste of the solvent. The solvent with 5 times of mass does not cause solvent waste, and is beneficial to the heat dissipation of a reaction system.
Further, in the third step, the glass bead is one of S60, S60HS, K1, K15, K20 or S4630.
Further, in the third step, the silane coupling agent is one of KH550, KH560, KBM602 or KBM 603.
Further, in the first step, the curing agent is an amine curing agent or an anhydride curing agent; the amine curing agent is one or the combination of two of diamino diphenyl sulfone and diamino diphenyl methane, and the anhydride curing agent is one or the combination of any more of methyl tetrahydrophthalic anhydride, methyl nadic anhydride and methyl hexahydrophthalic anhydride; when the acid anhydride curing agent is used, an accelerator 2,4, 6-tri (dimethylaminomethyl) phenol or N, N-dimethylbenzylamine is also added.
Further, the mass of the accelerator is 0.5-1.0% of that of the anhydride curing agent.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a preparation method of a bio-based POSS/epoxy hybrid resin with excellent performance based on the characteristics of low polarity, high dissociation energy, large molecular volume and the like of a siloxane chain segment, and the bio-based POSS/epoxy hybrid resin prepared by the method has excellent low dielectric property and thermal stability after being cured, the dielectric constant can reach 2.56, the temperature of 5 percent weight loss can reach more than 408 ℃, and the temperature of the maximum weight loss is 462-475 ℃. The cured bio-based POSS/epoxy hybrid resin also has hydrophobicity, the contact angle can reach 110 +/-2 degrees, and the cured bio-based POSS/epoxy hybrid resin has high mechanical property. In addition, the preparation method is simple and convenient, low in price and low in cost. The method has the advantages of high reaction rate, short preparation period and no pollution.
Drawings
FIG. 1 is an infrared spectrum of the bio-based POSS/epoxy hybrid resin prepared in example 1.
FIG. 2 is a drawing of the bio-based POSS/epoxy hybrid resin prepared in example 1 1 H-NMR chart.
FIG. 3 is a graph of the dielectric frequency of the bio-based POSS/epoxy hybrid material of example 1.
FIG. 4 is a graph of the thermal weight loss of the bio-based POSS/epoxy hybrid material of example 1.
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples. The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The principle of the invention is as follows: the phenolic hydroxyl of the single-end double-bond phenolic compound and epoxy chloropropane generate ring-opening reaction to generate single-end double-bond epoxy, and the double bond of the single-end double-bond epoxy and the silicon hydrogen of the polyhedral oligomeric silsesquioxane with an octa-silicon hydrogen functional group generate addition reaction under the action of a Karster catalyst.
Example 1:
a preparation method of a degradable low-dielectric-constant bio-based POSS/epoxy hybrid material comprises the following steps:
1. adding 40g of eugenol, 35g of sodium hydroxide and 228g of epoxy chloropropane into a 500ml three-necked bottle, stirring at room temperature for 20min, adding 0.7g of tetramethylammonium bromide, heating to 68 ℃, reacting for 150min, washing with water, distilling, and recrystallizing with methanol to obtain high-purity eugenol epoxy (EUEP);
2. adding 11.5g of octahydro-functional polyhedral oligomeric silsesquioxane and 5 times the mass of toluene into a 250ml single-neck flask, and mixing 20g of eugenol epoxy, 0.158g of a castpt catalyst and 5 times the mass of toluene to obtain a mixture; and then dropwise adding the mixture into octahydro-functional polyhedral oligomeric silsesquioxane at 110 ℃, completing dropwise addition within 30min, reacting for 24 hours, adding activated carbon to remove the catalyst, and filtering to remove the solvent to obtain the bio-based POSS/epoxy hybrid resin. The infrared and nuclear magnetic spectra of the reaction products are shown in fig. 1 and fig. 2, respectively, which illustrate the successful synthesis of silicone/epoxy hybrid resins (SHEP). The mass of the mixture toluene was 5 times the total mass of the eugenol epoxy and the castpt catalyst.
The catalyst is directly added into polyhedral oligomeric silsesquioxane with an octahydro functional group, and the gelation phenomenon can occur, so the method adopts the mode of mixing the catalyst and eugenol epoxy together, toluene is a good solvent, the addition of toluene can ensure that epoxy resin and the catalyst are better and uniformly mixed, and the dropwise addition mode is adopted to ensure that the reaction of the catalyst and the epoxy resin is more sufficient, and the influence of steric hindrance can be reduced along with the reaction.
3. Adding 3.87g of methylhexahydrophthalic anhydride and 0.1g of N, N-dimethylbenzylamine BDMA into 10g of organosilicon/epoxy hybrid resin (SHEP), uniformly stirring to obtain a resin mixture, pouring the resin mixture into a mold after bubbles are removed, reacting at 105 ℃ for 5 hours, then reacting at 160 ℃ for 4 hours, and finally reacting at 200 ℃ for 1 hour to obtain the bio-based POSS/epoxy hybrid material (SHEP-MHHPA).
Example 2:
a preparation method of a degradable low-dielectric-constant bio-based POSS/epoxy hybrid material comprises the following steps:
1. adding 40g of eugenol, 35g of sodium hydroxide and 228g of epoxy chloropropane into a 500ml three-necked bottle, stirring at room temperature for 20min, adding 0.7g of tetramethylammonium bromide, heating to 68 ℃, reacting for 150min, washing with water, distilling, and recrystallizing with methanol to obtain high-purity eugenol epoxy (EUEP);
2. adding 11.5g of octahydro-functional polyhedral oligomeric silsesquioxane and 5 times of toluene by mass into a 250ml single-neck flask, and mixing 20g of eugenol epoxy, 0.158g of a castpt catalyst and a certain amount of toluene to obtain a mixture; and then dropwise adding the mixture into octahydro-functional polyhedral oligomeric silsesquioxane at 110 ℃, completing dropwise addition within 30min, reacting for 24 hours, adding activated carbon to remove the catalyst, and filtering to remove the solvent to obtain the bio-based POSS/epoxy hybrid resin. The infrared and nuclear magnetic spectra of the reaction products are shown in fig. 1 and fig. 2, respectively, which illustrate the successful synthesis of silicone/epoxy hybrid resins (SHEP). The mass of the mixture toluene was 5 times the total mass of the eugenol epoxy and the castpt catalyst.
Adding 10g of glass beads into 0.3mol/L aqueous solution, reacting for 1h at 80 ℃, washing with deionized water to be neutral, and drying for later use; 30g of absolute ethyl alcohol, 20g of water, 0.5g of silane coupling agent and a proper amount of the obtained glass beads are quickly stirred for 3-5 min, the obtained glass beads are put into a 100 ℃ oven to be dried for 5-10 min after being filtered, then the obtained glass beads are taken out, added with a proper amount of absolute ethyl alcohol to be subjected to ultrasonic treatment for 10-30 min, filtered, dried and sieved.
The catalyst is directly added into polyhedral oligomeric silsesquioxane with an octahydro functional group, and the gelation phenomenon can occur, so the method adopts the mode of mixing the catalyst and eugenol epoxy together, toluene is a good solvent, the addition of toluene can ensure that epoxy resin and the catalyst are better and uniformly mixed, and the dropwise addition mode is adopted to ensure that the reaction of the catalyst and the epoxy resin is more sufficient, and the influence of steric hindrance can be reduced along with the reaction.
3. Adding 10/20/30/40g of silane modified glass microsphere, 3.87g of methylhexahydrophthalic anhydride and 0.1g of N, N-dimethylbenzylamine BDMA into 10g of organosilicon/epoxy hybrid resin (SHEP), uniformly stirring to obtain a resin mixture, pouring the resin mixture into a mold after removing bubbles, reacting at 105 ℃ for 5 hours, then reacting at 160 ℃ for 4 hours, and finally reacting at 200 ℃ for 1 hour to obtain the bio-based POSS/epoxy hybrid material (x% S4630-KBM603@ SHEP-MHHPA).
The following tests were carried out on the bio-based POSS/epoxy hybrid material obtained after curing by the above method:
dielectric property test
Through Agilent 4294A instrument, for 20X 1mm 3 The dielectric properties of the sample were measured to obtain a dielectric constant of the material at 25 ℃ and 10MHz, and the results are shown in FIG. 3.
(II) thermal stability test
The thermal weight loss graph of the bio-based POSS/epoxy hybrid material of this example is shown in fig. 4. As can be seen from fig. 4, the material has good thermal stability, and is relatively high in heat resistance among silicone epoxy materials.
(III) hydrophobicity test
And (3) testing the contact angle of the bio-based POSS/epoxy hybrid material obtained after curing by using a droplet morphology analyzer, placing the sample on a contact angle testing platform, adopting polar liquid-ultrapure water, carrying out parallel experiments for 10 times on each sample, and taking the average value of five experiments with the error within 5%. The contact angle test result is shown in table 1, and the bio-based POSS/epoxy hybrid material prepared by the invention has better hydrophobicity.
TABLE 1
| Sample (I) | Contact angle |
| SHEP-MHHPA | 110±4° |
| 10％S4630-KBM603@SHEP-MHHPA | 106±2° |
| 20％S4630-KBM603@SHEP-MHHPA | 103±3° |
| 30％S4630-KBM603@SHEP-MHHPA | 99±2° |
| 40％S4630-KBM603@SHEP-MHHPA | 97±2° |
In conclusion, the bio-based POSS/epoxy hybrid material has excellent comprehensive performance.
Claims (9)
1. A preparation method of a bio-based POSS/epoxy hybrid material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: the phenolic hydroxyl of the single-end double-bond phenolic compound and epichlorohydrin are subjected to ring-opening reaction to generate single-end double-bond epoxy;
step two: the double bonds of the single-end double bond epoxy and the silicon hydrogen of the polyhedral oligomeric silsesquioxane with the octa-silicon hydrogen functional group are subjected to addition reaction under the action of a Karster catalyst to obtain the bio-based POSS/epoxy hybrid resin;
step three: preparing silane modified glass beads;
step four: and sequentially adding a curing agent and silane modified glass beads into the bio-based POSS/epoxy hybrid resin, and curing for 6-10 hours at 105-200 ℃ to obtain the bio-based POSS/epoxy hybrid material.
2. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
the method comprises the following steps: mixing a single-end double-bond phenolic compound, epoxy chloropropane and sodium hydroxide, stirring at room temperature for 15-60 min, then adding tetramethyl ammonium bromide, heating to 60-80 ℃, reacting for 2-3 h, washing with water, distilling, and recrystallizing to obtain single-end double-bond epoxy; wherein the molar ratio of the single-end double-bond phenolic compound to the epichlorohydrin to the sodium hydroxide to the tetramethylammonium bromide is 1:4 to 15:1.5 to 5:0.01 to 0.3;
step two: adding octahydro-functional polyhedral oligomeric silsesquioxane into 5 times of a solvent by mass, and mixing single-end double-bond epoxy, a catalyst and the 5 times of the solvent by mass to obtain a mixture; dropwise adding the mixture into a solution of polyhedral oligomeric silsesquioxane containing an octahydro functional group at 90-110 ℃, stirring to react for 24-48 h, adding activated carbon to remove the catalyst, filtering, and performing rotary evaporation to obtain the bio-based POSS/epoxy hybrid resin; wherein the molar ratio of the single-end double-bond epoxy to the octahydro-octahydro functional polyhedral oligomeric silsesquioxane is 1-1.2: 1, the dosage of the catalyst is 10-20ppm of the total mass of the polyhedral oligomeric silsesquioxane with single-ended double bond epoxy and octahydro functional groups;
step three: adding 10-20 g of glass beads into 0.3mol/L of 300-600 mL of aqueous solution, reacting for 1-2 h at 60-80 ℃, washing with deionized water to be neutral, and drying for later use; 20-50 g of absolute ethyl alcohol, 15-30 g of water, 0.3-0.5g of silane coupling agent and 5-10 g of the obtained glass microspheres are quickly stirred for 3-5 min, are put into a 100 ℃ oven for 5-10 min after being subjected to suction filtration, are taken out, are added with 30-50 mL of absolute ethyl alcohol, are subjected to ultrasonic filtration for 10-30 min, are dried and are sieved;
step four: and sequentially adding a curing agent and silane modified glass beads into the bio-based POSS/epoxy hybrid resin, stirring to obtain a stable resin mixture, and curing at 105-200 ℃ for 6-10 hours to obtain the bio-based POSS/epoxy hybrid material.
3. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the first step, the single-end double-bond phenol compound is any one or a combination of several of eugenol, methyl eugenol, 2-methoxy-4-vinylphenol, 3 '-propenyl-4' -hydroxyacetophenone, 4- (3-methyl-2-en-1-yl) phenol, trans-4-hydroxystilbene and 4-vinylphenol.
4. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the second step, the catalyst is a Castlpt catalyst or chloroplatinic acid H 2 PtCl 6 ·6H 2 O; the solvent is one of tetrahydrofuran, toluene or xylene.
5. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the second step, the mass of the solvent in the mixture is 5 times of the total mass of the single-end double bond epoxy and the catalyst.
6. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the third step, the glass bead is one of S60, S60HS, K1, K15, K20 or S4630.
7. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the third step, the silane coupling agent is one of KH550, KH560, KBM602 or KBM 603.
8. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: in the first step, the curing agent is an amine curing agent or an anhydride curing agent; the amine curing agent is one or the combination of two of diamino diphenyl sulfone and diamino diphenyl methane, and the anhydride curing agent is one or the combination of any more of methyl tetrahydrophthalic anhydride, methyl nadic anhydride and methyl hexahydrophthalic anhydride; when the acid anhydride curing agent is used, an accelerator 2,4, 6-tri (dimethylaminomethyl) phenol or N, N-dimethylbenzylamine is also added.
9. The preparation method of the bio-based POSS/epoxy hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: the mass of the accelerator is 0.5-1.0% of that of the anhydride curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211086147.8A CN115304922A (en) | 2022-09-06 | 2022-09-06 | Preparation method of bio-based POSS/epoxy hybrid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211086147.8A CN115304922A (en) | 2022-09-06 | 2022-09-06 | Preparation method of bio-based POSS/epoxy hybrid material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115304922A true CN115304922A (en) | 2022-11-08 |
Family
ID=83867015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211086147.8A Pending CN115304922A (en) | 2022-09-06 | 2022-09-06 | Preparation method of bio-based POSS/epoxy hybrid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115304922A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937165A (en) * | 2014-02-13 | 2014-07-23 | 甘肃康博丝特新材料有限责任公司 | Deep sea-using solid buoyancy material with semi-interpenetrating polymer network structure and preparation method thereof |
| CN111393828A (en) * | 2020-04-07 | 2020-07-10 | 广东圆融新材料有限公司 | Low dielectric constant polyphenyl ether composition and preparation method thereof |
| CN112876683A (en) * | 2021-02-04 | 2021-06-01 | 浙江大学 | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof |
| CN113402850A (en) * | 2021-07-13 | 2021-09-17 | 深圳先进电子材料国际创新研究院 | Low-dielectric-constant and low-warpage epoxy plastic packaging material composition, preparation and application |
| CN114716682A (en) * | 2022-05-25 | 2022-07-08 | 哈尔滨工业大学 | Preparation method and application of degradable low-dielectric bio-based epoxy/organic silicon hybrid resin |
-
2022
- 2022-09-06 CN CN202211086147.8A patent/CN115304922A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937165A (en) * | 2014-02-13 | 2014-07-23 | 甘肃康博丝特新材料有限责任公司 | Deep sea-using solid buoyancy material with semi-interpenetrating polymer network structure and preparation method thereof |
| CN111393828A (en) * | 2020-04-07 | 2020-07-10 | 广东圆融新材料有限公司 | Low dielectric constant polyphenyl ether composition and preparation method thereof |
| CN112876683A (en) * | 2021-02-04 | 2021-06-01 | 浙江大学 | Oceugenol epoxy group liquid cage type silsesquioxane as well as preparation method and application thereof |
| CN113402850A (en) * | 2021-07-13 | 2021-09-17 | 深圳先进电子材料国际创新研究院 | Low-dielectric-constant and low-warpage epoxy plastic packaging material composition, preparation and application |
| CN114716682A (en) * | 2022-05-25 | 2022-07-08 | 哈尔滨工业大学 | Preparation method and application of degradable low-dielectric bio-based epoxy/organic silicon hybrid resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
| CN116572603B (en) * | 2023-07-13 | 2023-09-22 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111234752A (en) | High-thermal-conductivity electrical insulation packaging material and preparation method thereof | |
| US20200283575A1 (en) | Silicone-modified polyphenylene ether resin, preparation method therefor, and use thereof | |
| CN105315454B (en) | The application of the organic-silicon-modified method for preparing siliceous double hydroxyl polyphenylene oxide and product | |
| CN115304922A (en) | Preparation method of bio-based POSS/epoxy hybrid material | |
| US20040147715A1 (en) | Epoxy resin curing agent, curable epoxy resin composition and cured product | |
| WO2017170551A1 (en) | Maleimide resin, curable resin composition and cured product of same | |
| CN101638517A (en) | Organosilicon resin composition | |
| Zhou et al. | Synchronously improved wave-transparent performance and mechanical properties of cyanate ester resins via introducing fluorine-containing linear random copolymer | |
| CN115232589A (en) | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof | |
| Hou et al. | Recent Advance in Low‐Dielectric‐Constant Organosilicon Polymers | |
| Qu et al. | Preparation and dielectric properties research of a novel kind of intrinsic silane-containing polyimide | |
| CN114716682A (en) | Preparation method and application of degradable low-dielectric bio-based epoxy/organic silicon hybrid resin | |
| CN109825231B (en) | Flame-retardant ultraviolet-resistant epoxy encapsulating adhesive and preparation method thereof | |
| JP6254475B2 (en) | Epoxy resin curing agent, production method, composition, cured product and use thereof | |
| CN111777541B (en) | high-Tg low-dielectric active ester curing agent, preparation method and application | |
| CN116162407B (en) | Polyimide insulating paint material resistant to high voltage and corona and preparation method thereof | |
| TW200409799A (en) | Halogen-free, phosphorus-free flame-retardant advanced epoxy resin and an epoxy composition containing the same | |
| CN112409397A (en) | Bio-based epoxy resin containing silicon phenylene structure, composition and preparation method thereof | |
| CN114437657B (en) | Preparation method of high-strength metal epoxy AB glue | |
| CN115772264B (en) | Alkoxy-terminated polysiloxane with self-adhesive property, and preparation method and application thereof | |
| CN112409396B (en) | Bio-based epoxy resin containing silicon phenylene structure, composition and preparation method thereof | |
| JP4374756B2 (en) | Imide oligomers having acid anhydride groups at the ends and curable resin compositions | |
| CN101362859B (en) | Stable nanometer oxidate dispersion solution, preparation method and application thereof | |
| Pan et al. | Synthesis and application of cyclotetrasiloxane modified with epoxy resins | |
| EP4053214A1 (en) | Composition, curable composition, and cured product |
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 |