CN114290711A - Method for producing continuous fiber bidirectional reinforced resin by one-step method - Google Patents
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- 230000002457 bidirectional effect Effects 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000012545 processing Methods 0.000 claims abstract description 4
- 239000003365 glass fiber Substances 0.000 claims description 92
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- 238000001125 extrusion Methods 0.000 claims description 5
- 229920002748 Basalt fiber Polymers 0.000 claims description 4
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- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
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Abstract
The invention belongs to the technical field of continuous fiber reinforced resin, and particularly relates to a method for producing continuous fiber bidirectional reinforced resin by a one-step method. The invention is innovated in the aspects of formula and process, and a part of continuous fibers are replaced by short fibers in the aspect of formula. Meanwhile, an ultrasonic generator is arranged outside the die, and part of short fibers are forced to be oriented along the Y direction by ultrasonic vibration. As a result, the tensile strength in the X direction is slightly reduced, the tensile strength in the Y direction is greatly improved, and the tensile strength in the X, Y direction can be satisfied, so that a material having high tensile strength in both the X and Y directions can be obtained by one-step processing.
Description
Technical Field
The invention belongs to the technical field of continuous fiber reinforced resin, and particularly relates to a method for producing continuous fiber bidirectional reinforced resin by a one-step method.
Background
The use of fiber reinforced polymers is a common production method in composite materials, in which continuous fibers are used to produce profiled bars by pultrusion, and is more widely used. In the polymer matrix, the continuous fibers are equivalent to a framework, and bear and disperse external force, so that the tensile strength of the material is greatly improved and even higher than the requirement. Taking the continuous glass fiber as an example, the price of the continuous glass fiber is lower than that of a common polymer, the density of the continuous glass fiber is higher than that of the common polymer, and the mass content of the continuous fiber can reach 80 percent at most, so that the tensile strength is improved, and the cost is reduced.
Patent CN202110650353.6 discloses a method for preparing a pultrusion type polyurethane fiber reinforced composite material, which is to fully soak 50-85% by mass of glass fiber and instantly synthesized polyurethane resin to obtain a preformed continuous fiber reinforced composite material.
Patent CN202110609762.1 discloses a pultrusion method of a high-performance thermoplastic composite i-beam, which reasonably calculates the feeding amount of continuous fibers in advance, and amplifies the feeding amount according to a certain method to ensure the flexibility and the degree of automation of the product.
However, the tensile strength of the continuous fiber reinforcement is improved in the continuous fiber direction (i.e., X direction). The tensile strength is not significantly increased in the direction perpendicular to the continuous fibers (i.e., Y direction). The reason is that: in the X direction, the continuous fibers are fully oriented and can bear tension; however, the continuous fibers are not oriented in the Y direction, and cannot withstand external forces. The current solutions are: a continuous fiber reinforced polymer (referred to as L) is formed and the L layers are stacked with a certain angle of rotation between the layers. This results in a material that has no significant orientation and high tensile strength in all directions. However, such a method is a secondary process and is not suitable for use with materials that are too thick.
Patent No. cn202110382091.x discloses a high-performance continuous fiber reinforced thermoplastic resin composite material and a preparation method thereof, wherein a three-dimensional preform structure (50-70% of continuous fiber reinforced resin) is prepared, and then the fibers are oriented at all spatial angles through weaving, so that a good reinforcing effect is achieved. The multilayer stacking and weaving are both performed by secondary processing, so that the production efficiency is reduced to a certain extent.
In summary, it is desirable to obtain a material with higher tensile strength in both the X and Y directions by a single process.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, provides a method for producing the continuous fiber bidirectional reinforced resin by a one-step method, and enables the short fibers to be oriented in the direction vertical to the continuous fibers by ultrasonic vibration, thereby realizing continuous production and bidirectional reinforcement.
In order to solve the technical problems, the following technical scheme is adopted in the invention:
the method for producing the continuous fiber bidirectional reinforced resin by the one-step method is characterized in that when equipment such as pultrusion, extrusion or rolling is adopted to produce the continuous fiber reinforced plastic, the continuous fiber is used as a framework, the reinforced resin and short fibers are premixed, then the continuous fiber is soaked or soaked in the dissolved or molten reinforced premixed resin, then the resin is fixedly formed by a heating mould with a certain shape, and before the fixed forming, ultrasonic treatment is carried out in the direction vertical to the continuous fiber.
Preferably, the reinforced resin, the continuous fibers and the short fibers are 40-80% by mass of the continuous fibers and 5-20% by mass of the short fibers. Corresponding modifiers or auxiliary agents can also be added into the reinforced resin.
Preferably, when the continuous fiber is fixed and formed by the die, an ultrasonic generator is arranged at the position of the die or at the downstream of the die, and the direction of the ultrasonic is perpendicular to the direction of the continuous fiber.
Further, an ultrasonic generator is installed at a single side of the mold. The ultrasonic frequency is 10-200kHz, preferably 20-150 kHz.
Preferably, the resin is a thermosetting resin, a thermoplastic resin, or any combination of the same types thereof.
Preferably, the continuous fibers are one or more of continuous glass fibers, continuous carbon fibers, continuous metal fibers, or continuous basalt fibers.
Preferably, in the product of the bidirectional reinforced resin, the short fibers are one or more of glass fibers, carbon fibers, metal fibers or basalt fibers, and have a length of 0.2 to 5 millimeters.
Preferably, the short fibers are mixed with the reinforced resin or the partially reinforced resin in advance; or added simultaneously with the resin being reinforced in a single process.
Compared with the prior art, the invention has the following beneficial effects:
the invention is innovated in the aspects of formula and process, and a part of continuous fibers are replaced by short fibers in the aspect of formula. Meanwhile, an ultrasonic generator is arranged outside the die, and part of short fibers are forced to be oriented along the Y direction by ultrasonic vibration. The continuous fibers are subjected to a tensile force in the X direction, and thus are difficult to be oriented in the Y direction even under ultrasonic vibration. As a result, the tensile strength in the X direction is slightly reduced, the tensile strength in the Y direction is greatly improved, and the tensile strength in the X, Y direction can be satisfied, so that a material having high tensile strength in both the X and Y directions can be obtained by one-step processing.
Drawings
FIG. 1 is a schematic process diagram of the present invention. In the figure, the long lines in the transverse direction represent continuous glass fibers, and the short lines represent chopped glass fibers. Under the action of the ultrasound, the orientation of the chopped glass fibers in the direction perpendicular to the continuous fibers is increased.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope and application of the present invention are not limited thereto.
The following comparative examples and examples are all in mass percent.
Comparative example 1
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking the glass fiber reinforced polyurethane as an example):
the polyurethane material (A component: polymer polyol; B component: isocyanate; mass ratio of A component to B component is 1: 1): 25%, continuous glass fiber: 75 percent.
Step one, continuous glass fibers pass through a yarn guide frame;
step two, mixing the component A and the component B which are mixed by the metering pump according to the proportion through a static mixer, and then, feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
step three, fully infiltrating a certain amount of mixed resin glue solution and continuous glass fiber bundles in a glue injection box;
step four, the continuous glass fiber soaked by the mixed resin liquid enters a segmented heating mould (front, middle and back), and then is solidified and leaves the mould;
and step five, cutting for later use through a tractor.
And (3) evaluating the longitudinal and transverse tensile and bending properties of the prepared continuous glass fiber reinforced thermosetting resin according to ISO178 and ISO180 standards. The evaluation results are shown in Table 1.
Comparative example 2
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking the glass fiber reinforced polyurethane as an example):
the polyurethane material (A component: polymer polyol; B component: isocyanate; mass ratio of A component to B component is 1: 1): 25%, continuous glass fiber: 65 percent; short glass fiber content: 10 percent. The polyurethane material A component and the short glass fiber are evenly stirred and then are placed in a tank A.
Step one, continuous glass fibers pass through a yarn guide frame;
step two, mixing the component A and the component B which are mixed by the metering pump according to the proportion through a static mixer, and then, feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
step three, fully infiltrating a certain amount of mixed resin glue solution and continuous glass fiber bundles in a glue injection box;
step four, the continuous glass fiber soaked by the mixed resin liquid enters a segmented heating mould (front, middle and back), and then is solidified and leaves the mould;
and step five, cutting for later use through a tractor.
And (3) evaluating the longitudinal and transverse tensile and bending properties of the prepared continuous glass fiber reinforced thermosetting resin according to ISO178 and ISO180 standards. The evaluation results are shown in Table 1.
Comparative example 3
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking the glass fiber reinforced polyurethane as an example):
the polyurethane material (A component: polymer polyol; B component: isocyanate; mass ratio of A component to B component is 1: 1): 25%, continuous glass fiber: 75 percent.
Step one, continuous glass fibers pass through a yarn guide frame;
step two, mixing the component A and the component B which are mixed by the metering pump according to the proportion through a static mixer, and then, feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
step three, fully infiltrating a certain amount of mixed resin glue solution and continuous glass fiber bundles in a glue injection box;
step four, the continuous glass fiber soaked by the mixed resin liquid enters a segmented heating mould (front, middle and back), an ultrasonic generator is arranged on one side of the middle section of the mould, the ultrasonic direction is vertical to the direction of the continuous glass fiber, and then the continuous glass fiber is solidified and leaves the mould;
and step five, cutting for later use through a tractor.
And (3) evaluating the longitudinal and transverse tensile and bending properties of the prepared continuous glass fiber reinforced thermosetting resin according to ISO178 and ISO180 standards. The evaluation results are shown in Table 1.
Comparative example 4
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking the glass fiber reinforced polyurethane as an example):
the polyurethane material (A component: polymer polyol; B component: isocyanate; mass ratio of A component to B component is 1: 1): 25%, continuous glass fiber: 65 percent; short glass fiber content: 10 percent. The polyurethane material A component and the short glass fiber are evenly stirred and then are placed in a tank A.
Step one, continuous glass fibers pass through a yarn guide frame;
step two, mixing the component A and the component B which are mixed by the metering pump according to the proportion through a static mixer, and then, feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
step three, fully infiltrating a certain amount of mixed resin glue solution and continuous glass fiber bundles in a glue injection box;
step four, the continuous glass fiber soaked by the mixed resin liquid enters a segmented heating mould (front, middle and back), an ultrasonic generator is arranged on one side of the middle section of the mould, the ultrasonic direction is vertical to the direction of the continuous glass fiber, and then the continuous glass fiber is solidified and leaves the mould;
and step five, cutting for later use through a tractor.
And (3) evaluating the longitudinal and transverse tensile and bending properties of the prepared continuous glass fiber reinforced thermosetting resin according to ISO178 and ISO180 standards. The evaluation results are shown in Table 1.
Example 1
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking the glass fiber reinforced polyurethane as an example):
the polyurethane material (A component: polymer polyol; B component: isocyanate; mass ratio of A component to B component is 1: 1): 25%, continuous glass fiber: 65 percent; short glass fiber content: 10 percent. The polyurethane material A component and the short glass fiber are evenly stirred and then are placed in a tank A.
Step one, continuous glass fibers pass through a yarn guide frame;
step two, mixing the component A and the component B which are mixed by the metering pump according to the proportion through a static mixer, and then, feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
step three, fully infiltrating a certain amount of mixed resin glue solution and continuous glass fiber bundles;
step four, the continuous glass fiber soaked by the mixed resin liquid enters a segmented heating mould (front, middle and back), an ultrasonic generator is arranged on one side of the middle section of the mould, the ultrasonic direction is vertical to the direction of the continuous glass fiber, and the ultrasonic generator is placed before the product is cured and then is cured and leaves the mould;
and step five, cutting for later use through a tractor.
And (3) evaluating the longitudinal and transverse tensile and bending properties of the prepared continuous glass fiber reinforced thermosetting resin according to ISO178 and ISO180 standards. The evaluation results are shown in Table 1.
Performance data Table 1
Comparative example 5
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking continuous production of a glass fiber reinforced polypropylene plate as an example):
polypropylene particles: 40%, maleic anhydride grafted polypropylene: 10%, continuous glass fiber: 50 percent.
Step one, uniformly stirring polypropylene particles and polypropylene grafted by maleic anhydride, adding the mixture into a double-screw extruder, melting the polypropylene by the extruder, and introducing the melted polypropylene into a heat-preservation glue tank, wherein the temperature in the glue tank is kept at about 220 ℃;
step two, fully dipping the continuous glass fiber subjected to preheating treatment in a high-temperature melt tank at a certain traction speed, and then feeding the glass fiber into a plate die for extrusion and shaping;
and step three, cooling the formed plate into sheets by a compression roller to obtain the long glass fiber reinforced polypropylene plate. (ii) a
The performance test results of the long glass fiber reinforced polypropylene plate are shown in table 2.
Comparative example 6
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking continuous production of a glass fiber reinforced polypropylene plate as an example):
polypropylene particles: 40%, maleic anhydride grafted polypropylene: 10%, continuous glass fiber: 40%, chopped glass fiber: 10 percent.
Step one, uniformly stirring polypropylene particles, chopped glass fibers and maleic anhydride grafted polypropylene, adding the mixture into a double-screw extruder, melting the polypropylene by the extruder, and introducing the melted polypropylene into a heat-preservation glue tank, wherein the temperature in the glue tank is kept at about 220 ℃;
step two, fully dipping the continuous glass fiber subjected to preheating treatment in a high-temperature melt tank at a certain traction speed, and then feeding the glass fiber into a plate die for extrusion and shaping;
and step three, cooling the formed plate into sheets by a compression roller to obtain the long glass fiber reinforced polypropylene plate. (ii) a
The performance test results of the long glass fiber reinforced polypropylene plate are shown in table 2.
Comparative example 7
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking continuous production of a glass fiber reinforced polypropylene plate as an example):
polypropylene particles: 40%, maleic anhydride grafted polypropylene: 10%, continuous glass fiber: 50 percent.
Step one, uniformly stirring polypropylene particles and polypropylene grafted by maleic anhydride, adding the mixture into a double-screw extruder, melting the polypropylene by the extruder, and introducing the melted polypropylene into a heat-preservation glue tank, wherein the temperature in the glue tank is kept at about 220 ℃;
fully soaking the preheated continuous glass fiber in a high-temperature melt tank at a certain traction speed, and placing an ultrasonic generator in a heating area at the front end of the shaping mold in a direction vertical to the continuous glass fiber, wherein the ultrasonic direction is also vertical to the continuous glass fiber;
and step three, cooling the formed plate into sheets by a compression roller to obtain the long glass fiber reinforced polypropylene plate. (ii) a
The performance test results of the long glass fiber reinforced polypropylene plate are shown in table 2.
Comparative example 8
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking continuous production of a glass fiber reinforced polypropylene plate as an example):
polypropylene particles: 40%, maleic anhydride grafted polypropylene: 10%, continuous glass fiber: 40%, chopped glass fiber: 10 percent.
Step one, uniformly stirring polypropylene particles, chopped glass fibers and maleic anhydride grafted polypropylene, adding the mixture into a double-screw extruder, melting the polypropylene by the extruder, and introducing the melted polypropylene into a heat-preservation glue tank, wherein the temperature in the glue tank is kept at about 220 ℃;
fully soaking the preheated continuous glass fiber in a high-temperature melt tank at a certain traction speed, and placing an ultrasonic generator in a heating area at the front end of the shaping mold in a direction vertical to the continuous glass fiber, wherein the ultrasonic direction is also vertical to the continuous glass fiber;
and step three, cooling the formed plate into sheets by a compression roller to obtain the long glass fiber reinforced polypropylene plate. (ii) a
The performance test results of the long glass fiber reinforced polypropylene plate are shown in table 2.
Example 2
The method for producing the continuous fiber bidirectional reinforced resin by the one-step method is a method for producing the continuous fiber bidirectional reinforced thermosetting resin and the continuous fiber bidirectional reinforced thermoplastic resin by the one-step method (taking continuous production of a glass fiber reinforced polypropylene plate as an example):
polypropylene particles: 40%, maleic anhydride grafted polypropylene: 10%, continuous glass fiber: 40%, chopped glass fiber: 10 percent.
Step one, uniformly stirring polypropylene particles, chopped glass fibers and maleic anhydride grafted polypropylene, adding the mixture into a double-screw extruder, melting the polypropylene by the extruder, and introducing the melted polypropylene into a heat-preservation glue tank, wherein the temperature in the glue tank is kept at about 220 ℃;
step two, fully dipping the continuous glass fiber subjected to preheating treatment in a high-temperature melt tank at a certain traction speed, then putting the continuous glass fiber into a plate die for extrusion molding, and placing an ultrasonic generator in a direction of the molding die, which is vertical to the continuous glass fiber, wherein the ultrasonic direction is also vertical to the continuous glass fiber;
and step three, cooling the formed plate into sheets by a compression roller to obtain the long glass fiber reinforced polypropylene plate. (ii) a
The performance test results of the long glass fiber reinforced polypropylene plate are shown in table 2. It is noted that polypropylene is a crystalline resin with a melting point of 150 ℃.
Table 2 of Performance data
From the above test results, it can be seen that: a portion of the continuous fibers is replaced with staple fibers. Meanwhile, an ultrasonic generator is arranged outside the die, and part of short fibers are forced to be oriented along the Y direction by ultrasonic vibration. The continuous fibers are subjected to a tensile force in the X direction, and thus are difficult to be oriented in the Y direction even under ultrasonic vibration. As a result, the tensile strength in the X direction is slightly reduced, the tensile strength in the Y direction is greatly improved, and the tensile strength in the X, Y direction is satisfactory.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A method for producing continuous fiber bidirectional reinforced resin by one-step method is characterized in that: the method comprises the steps of premixing reinforced resin and short fiber by using continuous fiber as a framework, then soaking or impregnating the continuous fiber in the dissolved or molten reinforced premixed resin, then fixing and molding through a mold, and carrying out ultrasonic treatment in a direction vertical to the continuous fiber before fixing and molding.
2. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: the reinforced resin, the continuous fiber and the short fiber, wherein the mass percentage of the continuous fiber is 40-80%, and the mass percentage of the short fiber is 5-20%.
3. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: when the continuous fiber is fixed and formed through the die, an ultrasonic generator is arranged at the position of the die or at the downstream of the die, and the ultrasonic direction is vertical to the continuous fiber direction.
4. The method for producing the continuous fiber bidirectional reinforced resin according to the one-step method of claim 3, wherein: and installing an ultrasonic generator on one side of the die.
5. The method for producing continuous fiber bidirectional reinforced resin according to one step of claim 1 or 3, wherein: the ultrasonic frequency is 10-200 kHz.
6. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: the resin is a thermosetting resin, a thermoplastic resin, or any combination of the same types thereof.
7. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: the continuous fiber is one or more of continuous glass fiber, continuous carbon fiber, continuous metal fiber or continuous basalt fiber.
8. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: in the product of the bidirectional reinforced resin, the short fiber is one or more of glass fiber, carbon fiber, metal fiber or basalt fiber, and the length of the short fiber is 0.2-5 mm.
9. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: the short fibers are mixed with the reinforced resin or the partially reinforced resin in advance; or added simultaneously with the resin being reinforced in a single process.
10. The method for producing the continuous fiber bidirectional reinforced resin according to the claim 1, which is realized by the one-step method, and is characterized in that: the processing mode of pultrusion, extrusion or rolling is adopted.
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