CN112852143B - Graphene polyurethane composite material and preparation method thereof - Google Patents
Graphene polyurethane composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112852143B CN112852143B CN202110066595.0A CN202110066595A CN112852143B CN 112852143 B CN112852143 B CN 112852143B CN 202110066595 A CN202110066595 A CN 202110066595A CN 112852143 B CN112852143 B CN 112852143B
- Authority
- CN
- China
- Prior art keywords
- graphene
- glass fiber
- composite material
- polyurethane
- parts
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K7/06—Elements
-
- 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
-
- 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
- C08K7/14—Glass
Abstract
The invention discloses a graphene polyurethane composite material and a preparation method thereof. According to the graphene polyurethane composite material and the preparation method thereof provided by the invention, a small amount of graphene nano material is added into a double-component polyurethane raw material, the graphene nano material is fully and uniformly mixed and then compounded with a fiber reinforced material, and after pultrusion and curing molding, the obtained graphene polyurethane composite material greatly improves the mechanical properties vertical to the fiber direction while maintaining the mechanical properties such as the bending strength or modulus of the material parallel to the fiber direction and the like, so that the defect of insufficient transverse properties of the polyurethane composite material generated in the pultrusion process of the polyurethane composite material is overcome.
Description
Technical Field
The invention relates to a polyurethane composite material and a preparation method thereof, in particular to a graphene polyurethane composite material and an improvement of the preparation method thereof.
Background
At present, many of the used composite materials are organic high polymer materials as a matrix, and inorganic or organic fiber reinforced materials which are compounded as a reinforcement comprise carbon fibers, glass fibers, aramid fibers and the like, and are formed by pultrusion. The principle is to weave and bind the fiber reinforced material which is generally arranged in parallel through the organic high polymer material. Thus, typical composite materials exhibit anisotropic physical properties, with high strength in the lengthwise, i.e. longitudinal, direction of the parallel aligned fiber reinforcement, generally good mechanical properties, and weak strength in the perpendicular, i.e. transverse, direction, which is poor mechanical properties. In a typical pultrusion process, transverse strength can be generally improved by adding fiber mats or fiber cloths, but in this case, the improvement of transverse strength is limited, and the strength in the longitudinal direction is reduced.
Polyurethane resins generally have very good adhesion to the surface of the fiber-reinforced material because of their excellent elasticity, at the same time, the strength of the body is higher, so the composite material is a good choice for the matrix material in the composite material, but when the fiber reinforced material is compounded by using pure polyurethane resin, because the mechanical properties such as the material strength or modulus of the polyurethane resin are still far lower than those of most fiber reinforced materials in the fiber length direction, especially the inorganic fiber reinforced materials such as glass fiber or carbon fiber reinforced materials, the difference between the mechanical properties such as the material strength or modulus of the generated composite material in the fiber length direction and the fiber length direction is still very large, so that the composite material is easily torn along the fiber direction in the composite material in practical application, and the application range of the polyurethane composite material is greatly influenced.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a graphene polyurethane composite material and a preparation method thereof, so that the mechanical properties of the produced graphene polyurethane composite material, such as material strength or modulus, in the direction perpendicular to the fiber direction are greatly improved, and the defect of insufficient transverse properties of the material formed by the existing pultrusion process is overcome.
The present application includes the following:
a. passing the fiber-reinforced material through a pre-form plate into a closed injection box;
b. adding the polyol liquid and the isocyanate liquid which are fully mixed with the graphene nano material into a static mixer according to the weight ratio of 1.2:1 to 1.4:1, and fully mixing to form liquid polyurethane resin;
c. injecting the liquid polyurethane resin into the injection cartridge under pressure;
d. the fiber reinforced material is fully soaked in the liquid polyurethane resin in the injection box and then enters a mold, and the fiber reinforced material is heated, cured and molded;
e. continuously pulling out the molded product from the mold and cutting the molded product according to the required length;
wherein, the order of the step a and the step b can be interchanged.
Embodiment 8. the method of preparing a graphene polyurethane composite according to embodiment 7, wherein the graphene nanomaterial is added and mixed well in the polyol liquid.
Embodiment 9. the method of preparing a graphene polyurethane composite material according to embodiment 8, wherein the pressure for pressure injection in step c is not greater than 10MPa, and the temperature for heating in step d is 80 to 220 ℃.
The technical scheme of the invention is as follows:
a graphene polyurethane composite material is formed by compounding polyurethane resin with a fiber reinforced material through pultrusion, wherein the polyurethane resin is also mixed with a graphene nano material;
the graphene polyurethane composite material comprises, by weight, 65-80 parts of a fiber reinforced material, 20-35 parts of a polyurethane resin and 0.00002-0.04 part of a graphene nano material;
the graphene polyurethane composite material is characterized in that the fiber reinforced material comprises glass fibers, carbon fibers, aramid fibers and basalt fibers;
the graphene polyurethane composite material, wherein the fiber reinforcement material is glass fiber and comprises glass fiber roving;
the graphene polyurethane composite material comprises, by weight, 50-80 parts of glass fiber roving, 10-20 parts of glass fiber felt and 10-30 parts of glass fiber cloth, wherein the glass fiber further comprises glass fiber felt and/or glass fiber cloth;
the graphene polyurethane composite material is characterized in that the polyurethane resin is synthesized by two-component polyurethane raw materials, and comprises the following components: isocyanate and polyol are synthesized according to the weight ratio of 1.2:1 to 1.4: 1;
a preparation method of any one of the graphene polyurethane composite materials comprises the following steps:
a. passing the fiber-reinforced material through a pre-form plate into a closed injection box;
b. adding the polyol liquid and the isocyanate liquid which are fully mixed with the graphene nano material into a static mixer according to the weight ratio of 1.2:1 to 1.4:1, and fully mixing to form liquid polyurethane resin;
c. injecting the liquid polyurethane resin into the injection cartridge under pressure;
d. the fiber reinforced material is fully soaked in the liquid polyurethane resin in the injection box and then enters a mold, and the fiber reinforced material is heated, cured and molded;
e. continuously pulling out the molded product from the mold and cutting the molded product according to the required length;
wherein the order of the step a and the step b can be interchanged;
the preparation method of the graphene polyurethane composite material comprises the following steps of adding and fully mixing the graphene nano material into the polyol liquid;
the preparation method of the graphene polyurethane composite material comprises the following steps of c, wherein the pressure of pressurized injection in the step c is not more than 10MPa, and the heating temperature in the step d is 80-220 ℃.
According to the graphene polyurethane composite material and the preparation method thereof provided by the invention, a small amount of graphene nano material is added into a double-component polyurethane raw material, the graphene nano material is fully and uniformly mixed and then compounded with a fiber reinforced material, and after pultrusion and curing molding, the obtained graphene polyurethane composite material greatly improves the mechanical properties vertical to the fiber direction while maintaining the mechanical properties such as the bending strength and modulus of the material parallel to the fiber direction, so that the defect of insufficient transverse properties of the polyurethane composite material generated in the pultrusion process of the polyurethane composite material is overcome.
Drawings
Fig. 1 is a schematic view of the microstructure of the graphene polyurethane composite material of the present invention.
Fig. 2 is a flow chart of a preparation process of the graphene polyurethane composite material of the present invention.
Fig. 3 is a schematic structural diagram of a preparation process of the graphene polyurethane composite material.
In the figure, 1 fiber reinforced material, 2 polyurethane resin and 3 graphene nano material
4 injection box 5 static mixer 6 mould 7 terminal section bar
Detailed Description
The invention provides a graphene polyurethane composite material and a preparation method thereof, and in order to make the purposes, technical schemes and effects of the invention clearer and clearer, the invention is further described in detail below by referring to the attached drawings and taking examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Graphene is a crystal in which carbon atoms are hybridized into bonds through an SP2 orbital and then arranged into a hexagonal planar honeycomb shape, and the thickness of the graphene is only a single layer or a plurality of layers of atoms. The material has a plurality of excellent physical properties including large surface area, high strength, higher thermal conductivity and electrical conductivity, excellent mechanical properties such as material strength and modulus, and extremely high toughness and hardness.
In a preferred embodiment of the present invention, a schematic microstructure of the graphene polyurethane composite material is shown in fig. 1, and the graphene nano-material 3 is uniformly dispersed in the polyurethane resin 2, so as to be uniformly distributed on or around the fibers of the fiber reinforced material 1 which are approximately distributed in parallel. In the production process of the graphene polyurethane composite finished product, fibers of the fiber reinforced material 1 are soaked in the liquid polyurethane resin 2 input from a static mixer 5 through a sealed injection box 4. When passing through the opening of the injection box 4, the fiber reinforced structure is formed after being distributed and arranged in an approximately parallel mode under the restriction of the size of the opening.
When the polyurethane resin 2 is manufactured, a proper amount of graphene nano-materials 3 are added into raw materials, generally a polyol liquid, and are uniformly dispersed, so that the polyol liquid is selected instead of an isocyanate liquid because the isocyanate is active in chemical properties. When the polyol liquid is mixed with the isocyanate liquid and polyurethane resin 2 is generated, the graphene nanomaterial 3 is uniformly dispersed in the liquid polyurethane resin 2, so that in a finished product of the graphene polyurethane composite material, the graphene nanomaterial 3 is uniformly dispersed around the fiber reinforced material 1 which is approximately distributed in parallel, and the graphene has the characteristic of large surface area, so that the graphene has large adhesive force to the attached fiber reinforced material 1, and the fiber reinforced material 1 can be greatly bound by the toughness, hardness and strength of the graphene, so that the transverse short bonding force of the composite material is greatly compensated while the longitudinal mechanical property of the generated composite material is not reduced.
The fiber reinforced material 1 may be made of organic or inorganic fiber materials with better strength and toughness, such as glass fiber, carbon fiber, aramid fiber, basalt fiber, and the like, preferably glass fiber materials, especially glass fiber roving.
In a preferred embodiment of the present invention, the content of the fiber reinforced material 1 is 65 to 80 parts, the content of the polyurethane resin is 20 to 35 parts, and the graphene nanomaterial 3 is preferably 0.00002 to 0.04 part by weight. More preferably, when the fiber reinforced material 1 is made of glass fiber, the content of the glass fiber is 75-80 parts, and the content of the polyurethane resin is 20-25 parts. More preferably, the content of the glass fiber is 78-80 parts, and the content of the polyurethane resin is 20-22 parts.
In the embodiment of the present invention, the glass fiber may be only glass fiber roving, and the diameter of the glass fiber roving can be determined according to actual needs. In a preferred embodiment of the present invention, the glass fiber may further include a glass fiber mat, or/and a glass fiber cloth, and the specific ratio may be 50 to 80 parts by weight of the glass fiber roving, 10 to 20 parts by weight of the glass fiber mat, and 10 to 30 parts by weight of the glass fiber cloth. The advantage of adding glass fiber felt and/or glass fiber cloth is that the mechanical properties of the polyurethane composite material in different directions can be further strengthened.
In a preferred embodiment of the present invention, the polyurethane resin 2 is synthesized from two-component polyurethane raw materials, including but not limited to: the isocyanate and the polyol are synthesized in a weight ratio of 1.2:1 to 1.4: 1.
Referring to the flow chart of the preparation process in fig. 2 and the schematic diagram of the preparation process in fig. 3, the preparation process of the graphene polyurethane composite material is preferably as follows:
firstly, adding the dried graphene nano-material 3 into the liquid of the polyhydric alcohol according to the required mass and proportion, and fully and uniformly mixing by a method such as centrifugal shearing. In a preferred embodiment, the graphene nanomaterial 3 preferably has a mass of: when the polyurethane resin accounts for 20-35 parts by weight, the graphene nano-material 3 accounts for 0.00002-0.04 part by weight. For example, in one embodiment, 3.6g of graphene is added to 5kg of polyurethane polyol Rimline SK14001 and mixed thoroughly under high shear of 2000 revolutions for 2 hours to obtain a polyol with graphene uniformly dispersed.
Then, the polyurethane two-component raw material fully mixed with the graphene nanomaterial 3 is preferably mixed with the following raw materials in proportion, for example: after mixing the isocyanate and the polyol in a weight ratio of 1.2:1 to 1.4:1, for example, 5kg of the above polyurethane polyol, together with 7kg of the isocyanate, are charged into different material tanks of a two-component injection molding machine and stirred and mixed in a static mixer 5 thereof to form a liquid polyurethane resin 2 containing the graphene nanomaterial 3.
Simultaneously with the above steps, or both, the fiber-reinforced material 1 is fed into a closed injection box 4, and the injection box 4 is soaked with the liquid urethane resin 2 fed from the static mixer 5 after being mixed. The opening of the injection box 4 is used to constrain the arrangement of the fibers inside the fiber-reinforced material 1, and as shown in the figure, when the fiber bundles of the fiber-reinforced material pass through the opening of the injection box 4, because the opening is smaller, the fibers inside the fiber-reinforced material will be constrained to keep approximately parallel distribution, and a fiber-reinforced structure of the final composite material product is formed.
The temperature of the interior of the injection box 4 is kept at 10-25 ℃, the pressure is higher than the atmospheric pressure, the liquid polyurethane resin 2 containing uniformly distributed graphene nano materials 3 generated in the previous step is injected into the injection box through pressurizing at 0-10MPa, the fiber reinforced structure is soaked by the liquid polyurethane resin 2, a composite material model with the reinforced fiber material 1 wrapped by the polyurethane resin 2 is formed, then the composite material model enters a mold 6 and is heated to 80-220 ℃, after curing and forming, a formed product is continuously extruded from the mold 6 through a traction machine, and the final terminal section 7 of the graphene polyurethane composite material, which comprises a plate or pipe structure, is obtained, and then the terminal section is cut off according to needs.
The plate structure of the graphene polyurethane composite material disclosed by the invention has the following test results:
in 2017, 8, 1, the report was completed by the Owens CORNING Asia Pacific Science & Technology Center.
Sample information:
glass fiber, Owens Corning PS4100, Tex4400, weight portion: 80 portions
Resin: the polyurethane resin comprises the following components in parts by weight: 20 portions of
Additive: graphene particles (weight part: 0.03 part)
And (3) testing results: as shown in tables 1 and 2.
Table 1: 0 degree bending property
Table 2: 90 DEG bending property
From the test results it can be seen that:
1. after the graphene nano material is added into the polyurethane resin, the bending strength in the 0 degree (longitudinal) direction is maintained at 1400-1500MPa without obvious change, and the modulus is improved by about 9 percent from 51.6Gpa to 56.4 Gpa.
2. In the 90 DEG (transverse) direction, the average bending strength is improved from 112MPa to 157MPa by about 40 percent, and the transverse bending modulus is improved from about 14GPa to 28GPa by 100 percent.
Namely, the graphene polyurethane composite material greatly enhances the mechanical property in the direction perpendicular to the fiber direction (transverse direction) while keeping the mechanical property in the direction parallel to the fiber length direction (longitudinal direction) unchanged.
According to the graphene polyurethane composite material and the preparation method thereof provided by the invention, a small amount of graphene nano material is added into a double-component polyurethane raw material, the two components are fully and uniformly mixed, then a fiber reinforced material is compounded, the composite material is cured and molded in a mold, and the graphene polyurethane composite material obtained through pultrusion is greatly improved in transverse mechanical property while the longitudinal mechanical property is kept unchanged by utilizing the special layered structure of graphene, so that the defect of insufficient transverse property in the pultrusion process of the polyurethane composite material is solved, and the graphene polyurethane composite material does not contain volatile solvents such as styrene and the like, does not contain amines or acid anhydride strong corrosive chemicals, is friendly to ecological environment and has wide market prospect.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations are possible to those skilled in the art in light of the above teachings, and that, for example, all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (8)
1. A graphene polyurethane composite material is formed by pultrusion of polyurethane resin compounded with a fiber reinforced material,
the fiber reinforced material is glass fiber, the polyurethane resin is also mixed with graphene nano material, and the graphene nano material is uniformly dispersed in the polyurethane resin so as to be uniformly distributed around the fiber reinforced material which is approximately distributed in parallel;
the glass fiber content is 75-80 parts, the polyurethane resin content is 20-25 parts, and the graphene nano material content is 0.00002-0.04 part by weight.
2. The graphene polyurethane composite material according to claim 1, wherein the glass fiber content is 78-80 parts, and the polyurethane resin content is 20-22 parts.
3. The graphene polyurethane composite of claim 1 or 2, wherein the glass fiber comprises a glass fiber roving.
4. The graphene polyurethane composite material according to claim 3, wherein the glass fiber further comprises 50-80 parts of glass fiber roving, 10-20 parts of glass fiber felt and 10-30 parts of glass fiber cloth, calculated by weight.
5. The graphene polyurethane composite material according to claim 1 or 2, wherein the polyurethane resin is synthesized from a two-component polyurethane raw material comprising: the isocyanate and the polyol are synthesized in a weight ratio of 1.2:1 to 1.4: 1.
6. A method for preparing the graphene polyurethane composite material of any one of claims 1 to 5, comprising the steps of:
a. passing the glass fiber through a pre-forming plate into a closed injection box;
b. adding the polyol liquid and the isocyanate liquid which are fully mixed with the graphene nano material into a static mixer according to the weight ratio of 1.2:1 to 1.4:1 of isocyanate to polyol, and fully mixing to form liquid polyurethane resin;
c. injecting the liquid polyurethane resin into the injection cartridge under pressure;
d. the glass fiber is fully soaked in the liquid polyurethane resin in the injection box and then enters a mold, and the glass fiber is heated, cured and molded;
e. continuously pulling out the molded product from the mold and cutting the molded product according to the required length;
wherein the order of the step a and the step b can be interchanged,
calculated by weight parts, the glass fiber content is 75-80 parts, the polyurethane resin content is 20-25 parts, and the graphene nano material content is 0.00002-0.04 part.
7. The method for preparing the graphene polyurethane composite material according to claim 6, wherein the graphene nanomaterial is added and sufficiently mixed in the polyol liquid.
8. The method for preparing the graphene polyurethane composite material according to claim 7, wherein the pressure for pressurized injection in the step c is not more than 10MPa, and the temperature for heating in the step d is 80-220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110066595.0A CN112852143B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710849978.9A CN107523038B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
| CN202110066595.0A CN112852143B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710849978.9A Division CN107523038B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112852143A CN112852143A (en) | 2021-05-28 |
| CN112852143B true CN112852143B (en) | 2022-03-25 |
Family
ID=60737047
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710849978.9A Active CN107523038B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
| CN202110066595.0A Active CN112852143B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710849978.9A Active CN107523038B (en) | 2017-09-20 | 2017-09-20 | Graphene polyurethane composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN107523038B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285517B (en) * | 2018-02-12 | 2021-08-20 | 化州市联合民生轮业有限公司 | Graphene/ester ether copolymerization type thermosetting polyurethane composite material and preparation method thereof |
| CN108329681A (en) * | 2018-03-02 | 2018-07-27 | 山西凝固力新型材料有限公司 | A kind of polyurethane pultruded panels of two-way enhancing and preparation method thereof |
| CN109575567A (en) * | 2018-10-26 | 2019-04-05 | 河北纳格新材料科技有限公司 | A kind of abrasion resistant polyurethane resin composite materials and preparation method thereof |
| CN111169034A (en) * | 2018-11-10 | 2020-05-19 | 浙江盛迪新材料股份有限公司 | Preparation method of polyurethane section |
| CN110219695A (en) * | 2019-05-30 | 2019-09-10 | 上海高铁电气科技有限公司 | A kind of tunnel compound polyurethane material conduit and application method |
| CN113115589A (en) * | 2019-11-13 | 2021-07-13 | 远景能源有限公司 | Method and equipment for manufacturing graphene modified fiber reinforced material |
| CN111534082A (en) * | 2020-06-12 | 2020-08-14 | 江苏省建筑科学研究院有限公司 | Transverse reinforced glass fiber reinforced polyurethane pultrusion profile and preparation method thereof |
| CN113863013A (en) * | 2021-10-15 | 2021-12-31 | 南京宁镁碳中和科技研究院有限公司 | Graphene oxide-carbon fiber composite material 3D printing wire with high-strength corrosion-resistant performance and manufacturing process |
| CN113999515B (en) * | 2021-12-10 | 2023-04-07 | 南京经略复合材料有限公司 | Glass fiber reinforced polyurethane material, supporting beam and preparation process of supporting beam |
| CN115093540B (en) * | 2022-05-24 | 2023-03-17 | 烟台瑞特橡塑有限公司 | High-hardness polyurethane tire and preparation method thereof |
| CN116355388A (en) * | 2023-04-10 | 2023-06-30 | 江西龙正科技发展有限公司 | Polyurethane anticorrosion composite material bracket |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447832A (en) * | 2000-08-18 | 2003-10-08 | 亨茨曼国际有限公司 | One component thermose polyurethane system |
| CN102504523A (en) * | 2011-11-03 | 2012-06-20 | 中国电力科学研究院 | High-toughness polyurethane composite insulator core rod and preparation method thereof |
| CN102731989A (en) * | 2012-07-17 | 2012-10-17 | 上海珀理玫化学科技有限公司 | Composite material for pultrusion polyurethane resin and preparation method thereof |
| CN104788960A (en) * | 2015-04-27 | 2015-07-22 | 中国科学院重庆绿色智能技术研究院 | Method for enhancing properties of carbon fiber-high polymer composite material and product thereof |
| CN105131571A (en) * | 2015-09-18 | 2015-12-09 | 江苏众成复合材料有限责任公司 | Polyurethane composite solar photovoltaic module frame and preparation method thereof |
| CN106280287A (en) * | 2016-08-30 | 2017-01-04 | 山东圣泉新材料股份有限公司 | A kind of resin combination, composite and its preparation method and application |
| CN106519650A (en) * | 2016-11-15 | 2017-03-22 | 王世伟 | Polymer composite and bearing bush made of same |
| CN106751636A (en) * | 2016-12-23 | 2017-05-31 | 中国铁道科学研究院铁道建筑研究所 | Graphene/Fiber Reinforced Composite Materials and its application |
| CN107033580A (en) * | 2017-04-14 | 2017-08-11 | 郑州大学 | Thermoplastic polyurethane fibers composite and its preparation method and application |
| CN107099117A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-polymer composites and preparation method thereof |
-
2017
- 2017-09-20 CN CN201710849978.9A patent/CN107523038B/en active Active
- 2017-09-20 CN CN202110066595.0A patent/CN112852143B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447832A (en) * | 2000-08-18 | 2003-10-08 | 亨茨曼国际有限公司 | One component thermose polyurethane system |
| CN102504523A (en) * | 2011-11-03 | 2012-06-20 | 中国电力科学研究院 | High-toughness polyurethane composite insulator core rod and preparation method thereof |
| CN102731989A (en) * | 2012-07-17 | 2012-10-17 | 上海珀理玫化学科技有限公司 | Composite material for pultrusion polyurethane resin and preparation method thereof |
| CN104788960A (en) * | 2015-04-27 | 2015-07-22 | 中国科学院重庆绿色智能技术研究院 | Method for enhancing properties of carbon fiber-high polymer composite material and product thereof |
| CN105131571A (en) * | 2015-09-18 | 2015-12-09 | 江苏众成复合材料有限责任公司 | Polyurethane composite solar photovoltaic module frame and preparation method thereof |
| CN107099117A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-polymer composites and preparation method thereof |
| CN106280287A (en) * | 2016-08-30 | 2017-01-04 | 山东圣泉新材料股份有限公司 | A kind of resin combination, composite and its preparation method and application |
| CN106519650A (en) * | 2016-11-15 | 2017-03-22 | 王世伟 | Polymer composite and bearing bush made of same |
| CN106751636A (en) * | 2016-12-23 | 2017-05-31 | 中国铁道科学研究院铁道建筑研究所 | Graphene/Fiber Reinforced Composite Materials and its application |
| CN107033580A (en) * | 2017-04-14 | 2017-08-11 | 郑州大学 | Thermoplastic polyurethane fibers composite and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Mechanical and thermal properties of cationic ring-opening o-cresol formaldehyde epoxy/polyurethane acrylate composites enhanced by reducing graphene oxide;Hongzhe Han etc.;《Polym.Bull》;20160831;第73卷(第8期);第2227-2244页 * |
| 连续玻璃纤维增强聚氨酯复合材料的力学性能;卢军凯等;《工程塑料应用》;20170331;第45卷(第3期);第31-35页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112852143A (en) | 2021-05-28 |
| CN107523038B (en) | 2021-03-16 |
| CN107523038A (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112852143B (en) | Graphene polyurethane composite material and preparation method thereof | |
| Jamir et al. | Natural lightweight hybrid composites for aircraft structural applications | |
| Justo et al. | Characterization of 3D printed long fibre reinforced composites | |
| Arshad et al. | Effect of coir fiber and TiC nanoparticles on basalt fiber reinforced epoxy hybrid composites: physico–mechanical characteristics | |
| Jose et al. | Advances in polymer composites: macro‐and microcomposites–state of the art, new challenges, and opportunities | |
| Asadi et al. | Basalt fibers as a sustainable and cost-effective alternative to glass fibers in sheet molding compound (SMC) | |
| Wei et al. | Mechanical properties of carbon fiber paper reinforced thermoplastics using mixed discontinuous recycled carbon fibers | |
| Zhang et al. | Recent progress of 3D printed continuous fiber reinforced polymer composites based on fused deposition modeling: a review | |
| EP3395530B1 (en) | Methods for producing structure | |
| CN109867916B (en) | Plant fiber reinforced resin matrix composite material and preparation method thereof | |
| CN103180134A (en) | Overmolded polyamide composite structures and processes for their preparation | |
| Ramamoorthy et al. | Mechanical performance of biofibers and their corresponding composites | |
| CN111393800A (en) | Epoxy resin suitable for pultrusion process and carbon fiber composite material thereof | |
| KR20130028561A (en) | Large tow carbon fiber composite with improved flexural property and surface property | |
| CN102101942B (en) | Reinforced polyurethane rigid foam material and manufacturing method thereof | |
| Chaudhari et al. | CHARACTERIZATION OFHIGH PRESSURE RTM PROCESSES FOR MANUFACTURINGOFHIGH PERFORMANCE COMPOSITES | |
| CN103881297A (en) | Thermosetting resin-based composite material and preparation method thereof | |
| David et al. | CFRP laminates with recycled carbon fiber: resin infusion and mechanical characterisation | |
| CN115023329B (en) | Cold press molded article comprising carbon fiber and glass fiber, and method for producing same | |
| Mubashir et al. | Carbon fibre composites: Outlook for the automobile sector | |
| McCrary-Dennis et al. | Development of the displaced foam dispersion technique for the manufacture of multiscale composites | |
| Sharma et al. | Fabrication and characterization of Glass Fiber/SiC reinforced polymer composite | |
| Hassanin et al. | Date palm fiber composite fabrication techniques | |
| Terwadkar et al. | Mechanical Properties of Banana Fabric and Kenaf Fiber Reinforced Epoxy Composites: Effect of Treatment and Hybridization | |
| Sakil et al. | Comprehensive review on plant fiber-reinforced polymeric biocomposites |
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 |