CN112940441A - Hydrocarbon resin and silicon oxide composite material and preparation method thereof - Google Patents
Hydrocarbon resin and silicon oxide composite material and preparation method thereof Download PDFInfo
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- CN112940441A CN112940441A CN202110116474.2A CN202110116474A CN112940441A CN 112940441 A CN112940441 A CN 112940441A CN 202110116474 A CN202110116474 A CN 202110116474A CN 112940441 A CN112940441 A CN 112940441A
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- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a hydrocarbon resin and silicon oxide composite material and a preparation method thereof. The invention utilizes the thermoplasticity of hydrocarbon resin, completes the hybridization compounding with silicon dioxide short fiber and silicon dioxide ball, has low cost and simple process, and the prepared composite material has higher mechanical strength and plasticity, low dielectric constant and smaller dielectric loss, and provides a high-quality manufacturing material for the production of high-speed high-frequency circuit boards.
Description
Technical Field
The invention relates to the technical field of hybrid composite material synthesis, and particularly provides a hydrocarbon resin and silicon oxide composite material and a preparation method thereof.
Background
The organic-inorganic nano hybrid material is a material obtained by combining organic and inorganic materials on a microscopic scale, is a novel material which is started to rise in the eighties of the twentieth century, and is used for compounding the inorganic and organic materials on a macroscopic scale so as to overcome the defect of a single material. Such composite materials on a microscopic level have unique properties not found in conventional organic and inorganic materials, as well as in conventional macro-scale composites. In the synthesis of organic-inorganic hybrid materials, sol-gel methods, intercalation composite techniques, surface modification of inorganic ions, electrochemical synthesis methods, assembly methods, and the like are the mainstream at present.
The hydrocarbon resin refers to a resin having a total hydrocarbon component, i.e., a resin having a molecular structure containing only C, H elements and a molecular structure containing no polar groups, and thus having excellent dielectric properties. The resin is a matrix resin for a high-frequency and high-speed copper-clad plate emerging in recent years, but the resin has low glass transition temperature and poor heat resistance. Hydrocarbon resins with good dielectric properties have long been studied by those skilled in the art.
Patent WO97/38564 discloses a circuit board made of a nonpolar tetrapolymer of styrene, butadiene and divinylbenzene, wherein a magnesium aluminosilicate filler is added, and glass fiber cloth is used as a reinforcing material, although the circuit board has excellent dielectric properties, the heat resistance of the circuit board is poor, the glass transition temperature is only about 100 ℃, and the requirement of a lead-free process (above 240 ℃) in a PCB manufacturing process is difficult to meet.
U.S. Pat. No. 5,571609, which is a circuit board made of a low molecular weight 1, 2-polybutadiene or polyisobutylene diene having a molecular weight less than 5000, and a high molecular weight copolymer of butadiene and styrene, and a large amount of silica powder is added as a filler, and glass fiber cloth is used as a reinforcing material, although the dielectric properties are excellent, the process properties in the process of making a prepreg are deteriorated because the prepreg is improved by using high molecular weight components, and the sheet made therefrom has poor rigidity and low bending strength because the proportion of rigid structure benzene rings in the resin molecules of the whole resin system is small and the chain segments after crosslinking are mostly made of methylene having low rigidity.
The Chinese patent CN101544841B uses hydrocarbon resin with the molecular weight of 11000 and the vinyl content of more than 60 percent as a main body, adopts allyl modified phenolic resin to improve the sticky characteristic of a prepreg, and improves the peel strength to a certain extent, but the heat resistance of the cured system is low, and the risk of delamination failure of a copper clad laminate in the PCB processing process is higher.
Disclosure of Invention
The technical task of the invention is to provide a hydrocarbon resin and silicon oxide composite material and a preparation method thereof aiming at the problems.
A preparation method of a hydrocarbon resin and silicon oxide composite material comprises the steps of heating and softening the hydrocarbon resin, and mixing the softened hydrocarbon resin with short silicon dioxide fibers and silicon dioxide spheres to prepare an inorganic-organic double-nano hybrid material.
After the high polymer is added with a small amount of layered inorganic matter and intercalation compounding is realized, the mechanical property of a nano composite system can be greatly improved, the heat resistance is also obviously enhanced, and the mechanical property of the material can be greatly improved by optimizing the clay content, the interface action and the dispersion state, so that the structural material with better performance is obtained.
The silicon dioxide spheres are nano spherical silicon dioxide, have the characteristics of small particle size, true spherical shape, large specific surface area, strong ultraviolet, visible light and infrared reflection capability and the like, have good compatibility with organic polymer materials, and the compactness, toughness and smoothness of the materials are greatly improved by utilizing the nano spherical SiO2 to manufacture the composite material.
The silicon dioxide short fiber used as a reinforcing material has the advantages of high tensile strength, large elastic modulus, strong aging resistance and chemical corrosion resistance, good heat resistance, sufficient raw materials, low price and the like, the rigidity of the silicon dioxide short fiber is organically combined with the flexibility of hydrocarbon resin, and the composite material has the characteristics of high modulus, high strength, tear resistance, swelling resistance, dynamic fatigue resistance and the like, load is transferred to the fiber from a resin matrix in a certain mode, and the fiber generally has higher tensile strength and modulus than the resin, so that the tensile strength and modulus of the composite material can be effectively improved.
The mixing mass ratio of the hydrocarbon resin, the silicon dioxide short fibers and the silicon dioxide balls is as follows: 55-70 to 20-30 to 10-15, preferably 60 to 25 to 12.
The method is realized by the following steps:
1) heating and softening hydrocarbon resin;
2) mixing the heated and softened hydrocarbon resin with the silica short fibers and the silica balls;
3) and pressing and cooling the mixed material to prepare a flat plate structure.
The heating temperature in the step 1) is 70-80 ℃.
The thickness of the flat plate structure in the step 3) is 0.5-2 mm.
The diameter of the silica spheres is 1 to 15 μm, and more preferably, the diameter of the silica spheres is 5 to 10 μm.
The size of the silica short fiber is 1 to 10 μm, and more preferably, the size of the silica short fiber is 3 to 5 μm.
The heating mode in the step 1) is water bath heating.
And pressing the mixed material into a flat plate structure by a dry pressing method or a rolling method.
Preferably, the silica short fibers are silica hollow short fibers.
The hollow nanometer material is a material group with a special shape, and the particle size is from nanometer to micron. Because it has not only outer surface but also inner surface, its specific surface area is much larger than that of common nano material, and at the same time it also has the opportunity of making different modifications to its inner and outer surfaces so as to make their inner and outer surfaces have different properties. Compared with the solid material with the same size, the hollow material has the obvious advantages of low density and material saving. More importantly, the hollow structure inside the hollow nano material enables the hollow nano material to have unique mechanical, acoustic, magnetic, optical and catalytic properties. The addition of the hollow fiber material obviously increases the tensile strength, the bending strength and the impact strength of the composite material, improves the glass transition point and obviously improves the dielectric property of the composite material.
Preferably, the silica spheres are silica hollow spheres.
The hollow microsphere is a multi-scale multi-layer nano structure which is composed of nano particles, has the size ranging from nano to micron and is provided with a hollow cavity. Compared with the corresponding block material, the material has larger specific surface area, smaller density, special mechanical, optical, electrical and other physical properties and application values, and can further improve the dielectric property of the material.
A hydrocarbon resin and silicon oxide composite material is prepared by any one of the methods.
Compared with the prior art, the novel hydrocarbon resin and silicon oxide hybrid composite material and the preparation method thereof have the following outstanding beneficial effects:
the method of the invention completes hybrid compounding by utilizing the thermoplasticity of hydrocarbon resin, silicon dioxide short fiber and silicon dioxide ball, has low cost and simple process, and the prepared composite material has higher mechanical strength and plasticity, low dielectric constant and smaller dielectric loss, and provides a high-quality manufacturing material for the production of high-speed high-frequency circuit boards.
Drawings
FIG. 1 is an electron microscope image of a silica hollow short fiber;
FIG. 2 is an electron micrograph of a silica hollow sphere.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A hydrocarbon resin and silicon oxide composite material and a preparation method thereof comprise the following steps:
(1) hybrid composite of hydrocarbon resin, silicon dioxide short fiber and silicon dioxide ball
Heating 10 g of hydrocarbon resin powder to 80 ℃ in water bath, and stirring until the resin is completely softened;
5 g of short silica fibers of 3 to 5 microns and 1.75 g of silica spheres of 5 to 10 microns in diameter are added to the hydrocarbon resin, heated in a water bath and stirred until completely and uniformly mixed.
(2) Film formation by dry pressing
Preparing the mixture of the softened hydrocarbon resin, the short silicon dioxide fibers and the silicon dioxide balls into a flat plate with the thickness of 1mm by using a uniaxial dry pressing method, and cooling and hardening to obtain the hybrid composite material of the hydrocarbon resin and the silicon oxide with low dielectric loss and capable of being used for the PCD plate substrate.
Example 2
(1) Hybrid composite of hydrocarbon resin, silicon dioxide hollow short fiber and silicon dioxide hollow sphere
Heating 14 g of hydrocarbon resin powder to 70 ℃ in water bath, and stirring until the resin is completely softened;
6 g of hollow short silica fiber of 1-3 microns in diameter, as shown in FIG. 1, and 3 g of hollow silica spheres of 1-5 microns in diameter, as shown in FIG. 2, were added to the hydrocarbon resin and heated in a water bath with stirring until thoroughly mixed.
(2) Film formation by dry pressing
The mixture of the softened hydrocarbon resin, the hollow short silicon dioxide fibers and the hollow silicon dioxide spheres is prepared into a flat plate with the thickness of 2mm by a uniaxial dry pressing method, and the flat plate is cooled and hardened to obtain the hybrid composite material of the hydrocarbon resin and the silicon oxide with low dielectric loss and capable of being used for the PCD plate substrate.
Example 3
(1) Hybrid composite of hydrocarbon resin, silicon dioxide short fiber and silicon dioxide hollow sphere
Heating 11 g of hydrocarbon resin powder to 75 ℃ in water bath, and stirring until the resin is completely softened;
adding 4 g of 5-10 micron short silica fiber and 2 g of 10-15 micron diameter hollow silica spheres into the hydrocarbon resin, heating in a water bath, and stirring until the mixture is completely and uniformly mixed.
(2) Film formation by dry pressing
Preparing the mixture of the softened hydrocarbon resin, the short silicon dioxide fibers and the hollow silicon dioxide spheres into a flat plate with the thickness of 0.5mm by using a uniaxial calendering method, and cooling and hardening to obtain the hybrid composite material of the hydrocarbon resin and the silicon oxide with low dielectric loss, which can be used for the PCD plate substrate.
Example 4
(1) Hybrid composite of hydrocarbon resin, silicon dioxide hollow short fiber and silicon dioxide ball
Heating 12 g of hydrocarbon resin powder to 75 ℃ in water bath, and stirring until the resin is completely softened;
5 g of 5-10 micron hollow silica short fiber and 2.5 g of 10-15 micron diameter silica ball are added into hydrocarbon resin, and the mixture is heated and stirred in a water bath until the mixture is completely and uniformly mixed.
(2) Film formation by dry pressing
Preparing a mixture of softened hydrocarbon resin, hollow short silicon dioxide fibers and silicon dioxide spheres into a flat plate with the thickness of 1.5mm by using a uniaxial rolling method, and cooling and hardening to obtain the hybrid composite material of the hydrocarbon resin and silicon oxide with low dielectric loss and capable of being used for the PCD plate substrate.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a hydrocarbon resin and silicon oxide composite material is characterized in that the hydrocarbon resin is heated and softened and then mixed with short silicon dioxide fibers and silicon dioxide spheres to prepare the inorganic-organic double-nano hybrid material.
2. The preparation method of the hydrocarbon resin and silicon oxide composite material as claimed in claim 1, wherein the mixing mass ratio of the hydrocarbon resin, the silicon dioxide short fibers and the silicon dioxide balls is as follows: 55-70 to 20-30 to 10-15.
3. The preparation method of the hydrocarbon resin and silicon oxide composite material as claimed in claim 1, wherein the method is realized by the following steps:
1) heating and softening hydrocarbon resin;
2) mixing the heated and softened hydrocarbon resin with the silica short fibers and the silica balls;
3) and pressing and cooling the mixed material to prepare a flat plate structure.
4. The method for preparing a hydrocarbon resin and silicon oxide composite material as claimed in claim 3, wherein the heating temperature in the step 1) is 70-80 ℃.
5. The method for preparing a hydrocarbon resin and silicon oxide composite material according to claim 3, wherein the thickness of the flat plate structure in the step 3) is 0.5-2 mm.
6. The method for preparing a hydrocarbon resin and silicon oxide composite material as claimed in claim 3, wherein the diameter of the silica spheres is 1-15 μm.
7. The method for preparing a hydrocarbon resin and silicon oxide composite material as claimed in claim 3, wherein the size of the short silica fiber is 1-10 μm.
8. The method as claimed in claim 1, wherein the short silica fibers are hollow short silica fibers.
9. The method for preparing a hydrocarbon resin and silicon oxide composite material as claimed in claim 1 or 8, wherein the silica spheres are silica hollow spheres.
10. A hydrocarbon resin and silica composite material, characterised in that the composite material is prepared by a method as claimed in any preceding claim.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110116474.2A CN112940441A (en) | 2021-01-28 | 2021-01-28 | Hydrocarbon resin and silicon oxide composite material and preparation method thereof |
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| CN202110116474.2A CN112940441A (en) | 2021-01-28 | 2021-01-28 | Hydrocarbon resin and silicon oxide composite material and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992022422A1 (en) * | 1991-06-19 | 1992-12-23 | Rogers Corporation | Shape retaining flexible electrical circuit |
| CN101544841A (en) * | 2009-04-10 | 2009-09-30 | 广东生益科技股份有限公司 | Composite material and high frequency circuit substrate made of the same |
| CN104479294A (en) * | 2014-12-05 | 2015-04-01 | 中国科学院过程工程研究所 | Electrical insulating epoxy resin composition and preparation method thereof |
| CN111154197A (en) * | 2020-01-15 | 2020-05-15 | 上海材料研究所 | Hydrocarbon resin composition and preparation method and application thereof |
| CN111622016A (en) * | 2020-04-30 | 2020-09-04 | 南京珈时新材料科技有限公司 | Pressure-resistant heat-insulating paper containing hollow porous silica microspheres and preparation method thereof |
| CN111718581A (en) * | 2020-05-20 | 2020-09-29 | 中广核俊尔(浙江)新材料有限公司 | Low-dielectric-constant low-dielectric-loss reinforced polyphenylene sulfide composite material special for 5G antenna oscillator and preparation method and application thereof |
-
2021
- 2021-01-28 CN CN202110116474.2A patent/CN112940441A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992022422A1 (en) * | 1991-06-19 | 1992-12-23 | Rogers Corporation | Shape retaining flexible electrical circuit |
| CN101544841A (en) * | 2009-04-10 | 2009-09-30 | 广东生益科技股份有限公司 | Composite material and high frequency circuit substrate made of the same |
| CN104479294A (en) * | 2014-12-05 | 2015-04-01 | 中国科学院过程工程研究所 | Electrical insulating epoxy resin composition and preparation method thereof |
| CN111154197A (en) * | 2020-01-15 | 2020-05-15 | 上海材料研究所 | Hydrocarbon resin composition and preparation method and application thereof |
| CN111622016A (en) * | 2020-04-30 | 2020-09-04 | 南京珈时新材料科技有限公司 | Pressure-resistant heat-insulating paper containing hollow porous silica microspheres and preparation method thereof |
| CN111718581A (en) * | 2020-05-20 | 2020-09-29 | 中广核俊尔(浙江)新材料有限公司 | Low-dielectric-constant low-dielectric-loss reinforced polyphenylene sulfide composite material special for 5G antenna oscillator and preparation method and application thereof |
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