CN114474484A

CN114474484A - Method and equipment for manufacturing resin in-situ coated fiber precursor and application thereof

Info

Publication number: CN114474484A
Application number: CN202210101040.XA
Authority: CN
Inventors: 胡海东
Original assignee: Individual
Current assignee: Individual
Priority date: 2022-01-27
Filing date: 2022-01-27
Publication date: 2022-05-13

Abstract

The invention discloses a manufacturing method, equipment and application of resin in-situ coated fiber strands, wherein the manufacturing method comprises the following steps: s1: attaching resin to a plurality of fiber monofilament protofilaments and compounding the resin into presoaked protofilaments; s2: the presoaked protofilaments are gathered into presoaked yarn bundles at a certain temperature and/or under a certain pressure; s3: the prepreg yarn bundles are wound into prepreg yarn rolls. The invention leads the resin with different forms to be attached on the fiber protofilament to form the preimpregnated protofilament, then the preimpregnated protofilament is gathered into the preimpregnated yarn bundle, and the preimpregnated yarn bundle is wound into the preimpregnated yarn roll, thereby reducing the filament breakage rate of the resin in the prior art, realizing good matching between the resin infiltration coating speed and the filament drawing speed, avoiding the water spraying cooling and drying process in the fiber production, saving the energy, leading the protofilament to be fully coated by the resin, being protected to the utmost extent, avoiding the damage in the fiber storage and use process, and maintaining the strength and the isotropic performance of the fiber to the utmost extent.

Description

Method and equipment for manufacturing resin in-situ coated fiber precursor and application thereof

Technical Field

The invention particularly relates to a manufacturing method, equipment and application of resin in-situ coated fiber precursor.

Background

Fibers, particularly glass fibers and basalt fibers, are formed by drawing and cooling a liquid material at high temperature through a perforated plate at high speed into monofilaments, generally, coating a sizing agent containing a lubricant, a coupling agent, a film-forming agent, and the like by an oiling roller to repair/prevent surface damage of the monofilaments, then bundling the monofilaments into yarns, winding the yarns into balls, and finally, commonly, drying the yarns into yarn rolls.

The fiber yarn is the first-grade product of fiber reinforced composite material, and in order to meet the requirements of various composite material processes, the fiber yarn is further made into fiber products such as fiber mats, fabrics, 3D products and the like, and also made into semi-finished products such as prepreg/bulk molding compound/sheet molding compound or even wire rods or granules and the like directly and/or through the fiber products and thermosetting resin/thermoplastic resin, and of course, the composite material products can also be directly made through processes such as pultrusion, spraying, winding and the like.

In the process in which fibers are used for the manufacture of composite materials, in particular for the manufacture of thermoplastic composite semi-finished or finished products, two basic stages of impregnation and shaping are experienced, wherein the quality of the impregnation plays a crucial role in the performance of the composite material. The fiber yarn is supplied in the form of bundles of a plurality of fibers, and in the impregnation stage, the resin is required to sufficiently fill not only the spaces between the fiber bundles but also the spaces between the monofilaments within the fiber bundles. Since the filaments of the fibers have a small diameter, a large specific surface area, a small gap between filaments, and are entangled with each other, it is extremely difficult to obtain a desired state of filling the gaps between filaments, particularly for thermoplastic resins having a large melt viscosity. In view of the above, many efforts in composite material technology have focused on how to improve the impregnation quality of fibers, especially thermoplastic resin impregnated fibers, wherein the ideal or dream is to impregnate monofilaments with resin, and if the ideal impregnation coating of resin can be achieved in the fiber drawing stage, the impregnation problem in the formation of finished or semi-finished composite materials is solved.

However, no one has achieved this ideal in the industry to date. The reason is mainly that: (1) in-situ compounding of wire drawing, because the change of the viscosity of the resin causes the change of wire drawing tension, when the wire drawing tension exceeds the strength of the glass melt, wire breaking occurs, and the wire drawing production is forced to be stopped due to the wire breaking; (2) the drawing in-situ compounding requires that the coating speed is required to be consistent with the drawing speed, the drawing speed is very high and reaches 2000 m/min, the coating speed is limited by the viscosity of resin and the infiltration speed, and the existing resin suitable for serving as a base material has high viscosity and low infiltration speed and is difficult to match with the drawing speed.

Taking glass fiber as an example, as shown in fig. 1 and 2, the prior wire drawing technology is shown, glass is molten glass at a high temperature of 1100-1300 ℃, the glass is loaded in a molten glass crucible 1, a crucible bushing 2 is arranged at the bottom of the crucible, 400-3000 wire holes 21 are formed in the crucible bushing, the molten glass leaks out of the wire holes to form wire roots, the wire roots are adhered to a wire drawing rod to be drawn downwards, the molten glass is drawn and cooled to 30-70 ℃ to form 400-3000 single raw wires 3, then a wetting agent is coated on the glass winding roller 4, then yarns are gathered by a bunching roller 5 to form a yarn roll, the rotating line speed and the traction tension of the winding roller form the traction speed and the traction force of the raw wires, and when the traction force is disturbed to exceed the force at the wire roots, the raw wires are broken; generally, the winding system is composed of a plurality of winding rollers connected to a winding conversion shaft and synchronously rotates, when one winding roller works, other winding rollers become standby winding rollers, the precursor is twisted and wound on the winding rollers firstly during wiredrawing, the winding rollers rotate at high speed to pull the precursor to become a yarn bundle through an oiling roller and a collecting roller to be continuously wound on the winding rollers, one winding roller is fully wound, or when the yarn bundle needs to be withdrawn from a working position to be pushed out, the winding roller conversion shaft rotates to enable the standby winding roller to be changed to the working position of the winding roller, and the yarn bundle continues to be wound on the winding roller at the working position. Because the impregnating compound is an aqueous solution containing a coupling agent, a lubricating agent and a film-forming agent, the yarn roll is wet and needs to be baked at about 80 ℃ for 4-24 hours to remove water to form a finished product, and the film-forming agent can be transferred to the yarn bundle on the outer layer of the yarn roll and even to the protofilaments on the outer layer of the whole yarn bundle in the baking process. In a word, the strands of the finished glass fiber are distributed with thin film forming agents, the film forming agents are polymers of polyester, starch, epoxy and polyurethane, but the film forming agents are discontinuous, and the quality of resin-impregnated fiber is reduced by excessively thick film forming agents. Glass fiber yarns are the first grade products of glass fibers.

It can be seen from this technique that it is not feasible to simply replace the sizing with resin. Firstly, the drawing speed is very high and reaches 500-3000 m/min, monofilaments need to be bundled into fiber yarns in a very short time and wound on a winding roller to form a yarn roll, and if resin is not cured, the yarn bundles are adhered and tangled and cannot be unwound for use. And if the resin viscosity is high, the oiling roller generates transverse traction force perpendicular to the traction direction of the precursor when rotating, and the transverse traction force not only increases the traction force of the precursor, but also generates disturbance of the traction force, so that the filament is easy to break.

The existing coating mode can not solve the problem of filament breakage caused by the traction disturbance of the filament, such as: the disclosure in patent publication No. CN1880255A "a general apparatus for coating the surface of nascent glass fibers with matrix resin is: roll-to-roll coaters, nozzle-to-nozzle coaters, open-cup coaters, pressure-cup coaters, fluidized-bed coaters, duck-nozzle hot-melt pump-pressure coaters, and the like ".

Disclosure of Invention

In order to solve the technical problems, the invention provides a manufacturing method, equipment and application of a resin in-situ coated fiber precursor, and the technical scheme is as follows in order to achieve the purpose:

on one hand, the invention discloses a method for manufacturing resin in-situ coated fiber precursor, which comprises the following steps:

s1: attaching resin to a plurality of fiber monofilament protofilaments and compounding the resin into presoaked protofilaments;

in S1, the resin is attached to a plurality of fiber monofilament strands by adopting any one mode or a combination of a plurality of modes from T1 to T5 to form prepreg strands;

t1: fusing one or more of resin film, resin fiber and resin fabric made of resin with the precursor to composite into pre-impregnated precursor;

t2: transferring the resin onto the protofilaments through the isolation material, and compounding the resin and the protofilaments into presoaked protofilaments;

t3: coating the resin on the surface of the protofilament through an oiling roller or a glue applying roller, and compounding the resin and the protofilament into presoaked protofilament;

t4: the protofilaments pass through a fluidized bed containing resin powder, so that the resin powder is adsorbed on the surfaces of the protofilaments and compounded or fused with the protofilaments to form presoaked protofilaments;

t5: the resin is sprayed to the protofilament and compounded or fused with the protofilament to form pre-impregnated protofilament;

s2: the presoaked protofilaments are gathered into presoaked yarn bundles at a certain temperature and/or under a certain pressure;

s3: winding the prepreg yarn bundle into a prepreg yarn roll;

in S1, the resin is in the form of one or more of liquid bulk, solution, emulsion, powder suspension, melt, powder, film, fiber, and fabric.

On the basis of the technical scheme, the following improvements can be made:

preferably, the method further comprises the following steps before S1:

s0: charging the protofilament; or, the resin is charged with a charge opposite to the surface charge of the filaments at the same time as the filaments are charged.

By adopting the preferable scheme, the resin can be quickly and sufficiently adhered to the surface of the precursor.

Preferably, the resin and the release material are bundled together in S2 to form a prepreg yarn bundle to prevent the prepreg yarn bundle from being entangled in a yarn package.

By adopting the preferable scheme, the prepreg yarn bundles in the prepreg yarn roll are prevented from being mutually adhered and tangled.

Preferably, when the resin is in the form of one or more of a melt, a powder, a film, a fiber, and a woven fabric, the temperature of the strands is 0 to 40 ℃ or higher than the melting point of the resin in S1, and the resin is melted and adhered to the surfaces of the strands on the surfaces of the strands.

By adopting the preferable scheme, the temperature is proper, and the resin can be smoothly melted and adhered to the surface of the protofilament.

Preferably, S1 is performed under an inert gas-containing protective environment, and when the resin is in the form of one or more of a film, a fiber, and a woven fabric, the back surface of the contact surface of the resin with the filaments is cooled, thereby preventing premature melt fracture of one or more of the resin film, the resin fiber, and the resin woven fabric.

With the above preferred scheme, one or more of the resin film, the resin fiber and the resin fabric are prevented from being melted and broken prematurely.

Preferably, S1 is performed under an inert gas atmosphere.

With the above preferred arrangement, the use of a protective environment with inert gas can avoid degradation or burning of the resin at high temperatures. Inert gases include, but are not limited to, carbon dioxide, nitrogen, helium, argon, and the like.

Preferably, the predetermined temperature in S2 is 0 to 40 ℃ higher than the melting point of the resin.

Preferably, S2 further includes the following steps: and extruding the bundled prepreg yarn bundles to accelerate the infiltration of the resin in the prepreg yarn bundles into the protofilaments, and removing air bubbles in the prepreg yarn bundles and/or extruding redundant resin to adjust the resin content in the prepreg yarn bundles.

With the above preferred scheme, the resin content in the prepreg bundles is adjusted.

Preferably, the following steps are further included between S1 and S2: and heating and/or curing the prepreg strands to melt, dry and cure the resin on the prepreg strands.

With the above preferred embodiments, the heating and/or curing means includes, but is not limited to, hot air, infrared, microwave, ultrasonic, laser, ultraviolet light, and combinations thereof.

Preferably, the following steps are further included between S2 and S3:

and (3) carrying out one or more of the following operations on the bundled prepreg yarns: heating, curing and semi-curing the prepreg yarn bundles, removing water in the prepreg yarn bundles or partially or completely curing resin in the prepreg yarn bundles, and preventing the prepreg yarn bundles in the prepreg yarn roll from being mutually adhered and entangled.

Preferably, the following steps are further included between S2 and S3: and cooling the collected prepreg yarn bundles to prevent the prepreg yarn bundles from being adhered and tangled in yarn rolls.

With the above preferred embodiments, the cooling methods include, but are not limited to, natural cooling, air/cold air, water spray/water application, cold roll contact cooling, and combinations thereof.

Preferably, the resin contains one or more of a curing agent, a lubricant, a colorant, a filler, a flame retardant, an antistatic agent, and an ionic auxiliary agent.

With the preferred embodiment described above, a suitable auxiliary is added to the resin.

On the other hand, the invention also discloses a manufacturing device of the resin in-situ coated fiber precursor, which is prepared by any one of the manufacturing methods, and specifically comprises the following steps:

the preimpregnation protofilament composite device is used for attaching resin to a plurality of monofilament protofilaments and compositing the resin into preimpregnated protofilaments, and the preimpregnation protofilament composite device comprises: conveying rollers and/or oiling rollers and/or sizing rollers and/or fluidized beds and/or heating devices and/or cooling devices, wherein the conveying rollers are used for conveying one or more of resin films, resin fibers, resin fabrics and isolating materials;

the presoaking protofilament bunching device is used for enabling the presoaking protofilaments to be gathered into presoaking protofilament bundles at a certain temperature and/or under a certain pressure;

and the fiber winding device is used for winding the prepreg yarn bundle into a prepreg yarn roll.

Preferably, the prepreg strand composite apparatus further includes: and a static electricity generating device for electrostatically charging the resin.

Preferably, the prepreg strand composite device comprises one or more pairs of oiling rollers which are relatively horizontally arranged or relatively staggered, and the relative positions of the oiling rollers are fixed or can be opened and closed.

With the preferred solution described above, one or more pairs of oiling rollers, arranged horizontally or staggered with respect to each other, are used to balance the lateral disturbances of the traction force generated by the resin-bound strands. Preferably, the prepreg strand composite apparatus further includes: a powder coating device;

the powder coating device includes: the device comprises a compressed air conveying pipeline, an air pressure adjusting device, a resin powder conveying device and one or more nozzles, wherein the nozzles blow and spray resin powder from bottom to top in an inclined mode towards the traction direction of the protofilament.

By adopting the preferable scheme, the resin is obliquely blown and sprayed on the surface of the protofilament from bottom to top, and the blowing and spraying pressure is controlled by the air pressure adjusting device to dynamically keep the resin powder at a certain height.

Preferably, the nozzles are one or more pairs of oppositely disposed nozzles, the filaments passing between the oppositely disposed nozzles.

With the above preferred embodiment, the resin is blown obliquely upward from the front and back surfaces of the yarn.

Preferably, a powder collecting device is provided on the opposite surface of the nozzle, and the powder collecting device is configured to collect excess resin powder.

With the above preferred scheme, the powder collecting device can collect the redundant resin powder for recycling, and the collecting method includes but is not limited to natural sedimentation, negative pressure adsorption and electrostatic adsorption.

Preferably, the prepreg strand composite apparatus includes: a vertically-leaky fluidized bed, the fluidized bed comprising: the upper edge of the inner container is lower than the outer shell, and a dust collecting interlayer is formed between the outer shell and the inner container.

By adopting the preferable scheme, the dust collecting interlayer is used for collecting the resin powder blown from the bottom by sedimentation, so that the resin powder is convenient to be recycled subsequently.

Preferably, the manufacturing apparatus further includes: the first heating and curing device is used for heating and/or curing the prepreg protofilament so as to realize one or more of melting, drying and curing of the resin on the prepreg protofilament.

With the above preferred aspect, the first heating and curing device is used to heat and/or cure the prepreg filaments.

Preferably, the cooling device is used for cooling the back surface of the contact surface of the resin film, the resin fiber, the resin fabric or the isolation material and the protofilament and/or the collected prepreg yarn bundles, so as to prevent the resin film, the resin fiber, the resin fabric or the isolation material from being prematurely broken in the process of compounding the resin film, the resin fiber, the resin fabric or the isolation material with the protofilament to form the prepreg protofilament and/or prevent the prepreg yarn bundles from being adhered and tangled in the yarn roll after being collected into the prepreg yarn bundle and wound into the prepreg yarn roll.

Preferably, the manufacturing apparatus further includes: a second heating and curing device, wherein the second heating and curing device is used for carrying out one or more of the following operations on the collected prepreg yarn bundles: heating, curing and semi-curing to form a film, and removing moisture in the prepreg yarn bundles or partially or completely curing resin in the prepreg yarn bundles to prevent the prepreg yarn bundles in the prepreg yarn roll from being mutually adhered and tangled.

Preferably, the manufacturing apparatus further includes: and the isolating material conveying equipment is used for conveying the isolating material and the prepreg protofilaments together to the bundling equipment for bundling together, so that the prepreg strands are prevented from being adhered and tangled in yarn rolls.

With the preferred scheme, the prepreg yarn bundles are prevented from being adhered and tangled in yarn rolls.

Preferably, the manufacturing apparatus further includes: and the extrusion equipment is used for extruding the prepreg yarn bundles in the bundles, accelerating the infiltration of the resin in the prepreg yarn bundles to the protofilaments, eliminating air bubbles in the prepreg yarn bundles and/or extruding redundant resin to adjust the resin content in the prepreg yarn bundles.

With the preferred arrangement described above, the resin content in the prepreg tows is adjusted by removing air bubbles from the prepreg tows and/or squeezing out excess resin. Preferably, the bundling device is a bundling roller, the pressing device is a pressing roller pressed on the bundling roller, and the gap between the pressing roller and the bundling roller can be adjusted.

In addition, the invention also discloses a fiber prepreg yarn, a plurality of fiber protofilaments are impregnated in situ by resin and then are bundled into a prepreg yarn bundle, and the prepreg yarn bundle is manufactured by any one of the manufacturing methods and/or any one of the manufacturing devices. In addition, the invention also discloses a composite material prepreg or product, which is manufactured by directly adopting the fiber prepreg yarns or is manufactured by the fiber prepreg yarns.

In addition, the invention also discloses a 3D printing additive which is prepared by preparing a prepreg yarn bundle by coating a plurality of fiber protofilaments in situ with resin, wherein the prepreg yarn bundle is prepared by any one of the preparation methods and/or any one of the preparation devices.

The invention skillfully solves the long-standing problem of the composite material industry, the manufacturing method and the equipment disclosed by the invention are used for attaching the resin with different forms to the fiber protofilament, even the resin with different forms is attached to the fiber protofilament by utilizing the waste heat in the wire drawing process in the process from the liquid state to the protofilament forming process of the fiber to form the pre-impregnated protofilament, then the pre-impregnated protofilament is gathered into the pre-impregnated yarn bundle, and the pre-impregnated yarn bundle is wound into the pre-impregnated yarn roll, thereby reducing the yarn breakage rate of the resin in the prior art, realizing good matching between the resin infiltration coating speed and the wire drawing speed, avoiding the water spraying cooling and drying process in the fiber production, saving energy, further fully coating the protofilament by the resin, protecting the protofilament to the maximum extent, avoiding the damage in the fiber storage and use processes generally, and further maintaining the strength and various performances of the fiber to the maximum extent, finally, the production cost of the fiber is reduced, the performance of the composite material can be greatly improved, and the economic, technical and environmental protection properties are comprehensively improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

Fig. 1 is a schematic view of a drawing apparatus according to the prior art.

FIG. 2 is a front view of a bushing tip plate according to the prior art.

Fig. 3 is a front view of a manufacturing apparatus according to a first embodiment of the present invention.

Fig. 4 is a side view of a manufacturing apparatus according to an embodiment of the present invention.

Fig. 5 is a front view of a manufacturing apparatus according to a second embodiment of the present invention.

Fig. 6 is a side view of a manufacturing apparatus according to a second embodiment of the present invention.

Fig. 7 is a front view of a manufacturing apparatus according to a third embodiment of the present invention.

Fig. 8 is a side view of a manufacturing apparatus provided in a third embodiment of the present invention.

Fig. 9 is a front view of a manufacturing apparatus according to a fourth embodiment of the present invention.

Fig. 10 is a side view of a manufacturing apparatus according to a fourth embodiment of the present invention.

Fig. 11 is a front view of a manufacturing apparatus according to a fifth embodiment of the present invention.

Fig. 12 is a side view of a manufacturing apparatus according to a fifth embodiment of the present invention.

Fig. 13 is a front view of a manufacturing apparatus according to a sixth embodiment of the present invention.

Fig. 14 is a side view of a manufacturing apparatus according to a sixth embodiment of the present invention.

Fig. 15 is a front view of a manufacturing apparatus according to a seventh embodiment of the present invention.

Fig. 16 is a side view of a manufacturing apparatus according to a seventh embodiment of the present invention.

Fig. 17 is a front view of a manufacturing apparatus according to an eighth embodiment of the present invention.

Fig. 18 is a side view of a manufacturing apparatus according to an eighth embodiment of the present invention.

Fig. 19 is a front view of a manufacturing apparatus according to a tenth embodiment of the present invention.

Fig. 20 is a side view of a manufacturing apparatus provided in the tenth embodiment of the present invention.

Fig. 21 is a side view of a manufacturing apparatus according to a twelfth embodiment of the present invention.

Fig. 22 is a side view of a manufacturing apparatus provided in a fourteenth embodiment of the present invention.

Wherein: 1-a molten glass crucible, 2-a crucible bushing, 21-a filament hole, 3-a raw filament, 4-an oiling roller, 5-a bundling roller, 51-a groove, 6-a winding roller, 7-a conveying roller, 8-a resin film, 9-a pre-impregnated raw filament, 10-a pre-impregnated yarn bundle, 11-a blowing device, 12-an extruding roller, 13-a cooling device, 14-an isolation material, 15-a heating device, 16-an oiling box, 17-a powder fluidized bed, 18-a vertical fluidized bed, 19-a glue moving roller, 20-a scraper, 22-a drying warmer, 23-a liftable fluidized bed, 24-a glue applying roller, 25-a glue applying roller and 26-a glue amount control roller.

Detailed Description

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The expression "comprising" an element is an "open" expression which merely means that a corresponding component or step is present and should not be interpreted as excluding additional components or steps.

In order to achieve the purpose of the invention, in some embodiments of a manufacturing method, a manufacturing device and an application thereof of resin in-situ coated fiber strands, the manufacturing method comprises the following steps:

s3: winding the prepreg yarn bundle into a prepreg yarn roll;

In order to further optimize the implementation effect of the present invention, in other embodiments, the remaining features are the same, except that the following steps are further included before S1:

In order to further optimize the working effect of the invention, in other embodiments, the rest of the characteristic techniques are the same, except that the resin and the isolation material are bundled together into the prepreg yarn bundle in S2, and the prepreg yarn bundle is prevented from being adhered and tangled in the yarn roll.

By adopting the preferable scheme, the prepreg yarn bundles in the prepreg yarn roll are prevented from being mutually adhered and tangled. The release material includes, but is not limited to, polypropylene, polyethylene, release coated cellophane or other paper or polyester film, polyvinyl chloride, polytetrafluoroethylene, nylon, polyetheretherketone, polyimide, polyphenylene sulfide, coated fabric, silicone rubber, or combinations of one or more thereof; preferably, the isolation material has a release function or the surface of the isolation material is coated with a release agent; preferably, the spacer material is transparent or light transmissive.

In order to further optimize the effect of the present invention, in other embodiments, the same features and techniques are used, except that when the resin is in the form of one or more of melt, powder, film, fiber, and fabric, the temperature of the strand is 0 to 40 ℃ higher than the melting point of the resin in S1, and the resin is melted and adhered to the surface of the strand on the surface of the strand.

By adopting the preferable scheme, the temperature is proper, and the resin can be smoothly melted and adhered to the surface of the protofilament. Meanwhile, the composite process can be realized in the temperature range of the precursor by using the self waste heat of the precursor in the wire drawing process, thereby reducing the time and energy consumption for cooling and saving the working procedure and energy consumption for heating the precursor

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the characteristic techniques are the same, except that S1 is performed under a protective environment with inert gas, when the resin is in the form of one or more of film, fiber and fabric, the back of the contact surface of the resin and the precursor is cooled, and one or more of resin film, resin fiber and resin fabric is prevented from being melted and broken prematurely.

With the preferred scheme, one or more of the resin film, the resin fiber and the resin fabric are prevented from being melted and broken prematurely.

In order to further optimize the practical effect of the present invention, in other embodiments, the rest of the features are the same, except that S1 is performed in an environment protected by inert gas.

With the above preferred scheme, the use of a protective environment with inert gas can avoid degradation or burning of the resin at high temperatures. Inert gases include, but are not limited to, carbon dioxide, nitrogen, helium, argon, and the like. Preferably, nitrogen is used for protection because it is heavier than air, deposits easily, does not diffuse easily, and does not affect the carbon dioxide content of air.

In order to further optimize the implementation effect of the present invention, in other embodiments, the other features are the same, except that in S2, the certain temperature is 0 to 40 ℃ higher than the melting point of the resin.

By adopting the preferable scheme, the temperature is proper, and the resin can be fully melted and adhered to the surface of the protofilament.

In order to further optimize the implementation effect of the present invention, in other embodiments, the remaining features are the same, except that S2 further includes the following steps: and extruding the bundled prepreg yarn bundles to accelerate the infiltration of the resin in the prepreg yarn bundles into the protofilaments, and removing air bubbles in the prepreg yarn bundles and/or extruding redundant resin to adjust the resin content in the prepreg yarn bundles.

In order to further optimize the implementation effect of the present invention, in other embodiments, the remaining features are the same, except that the following steps are further included between S1 and S2: and heating and/or curing the prepreg strands to melt, dry and cure the resin on the prepreg strands.

With the above preferred embodiments, the heating and/or curing means includes, but is not limited to, hot air, infrared, microwave, ultrasonic, laser, ultraviolet light, and combinations thereof. The embodiments are particularly directed to the resin being a liquid bulk, solution, emulsion, powder suspension, for which the temperature of the resin and the filament composite in S1 is between 20 and 80 ℃.

In order to further optimize the implementation effect of the present invention, in other embodiments, the remaining features are the same, except that the following steps are further included between S2 and S3:

In order to further optimize the implementation effect of the present invention, in other embodiments, the remaining features are the same, except that the following steps are further included between S2 and S3: and cooling the collected prepreg yarn bundles to prevent the prepreg yarn bundles from being adhered and tangled in yarn rolls.

In order to further optimize the performance of the present invention, in other embodiments, the remaining features are the same, except that one or more combinations of curing agents, lubricants, colorants, fillers, flame retardants, antistatic agents, and ionic aids are contained in the resin.

By adopting the preferable scheme, a proper auxiliary agent is added into the resin to adapt to the requirements of different processes or applications.

On the other hand, the embodiment of the invention also discloses a manufacturing device of the resin in-situ coated fiber precursor, which is prepared by using the manufacturing method disclosed by any one of the embodiments, and the manufacturing method specifically comprises the following steps:

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the characteristics are the same, except that the prepreg strand composite device further comprises: and a static electricity generating device for electrostatically charging the resin.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest features are the same, except that the prepreg strand composite device comprises one or more pairs of oiling rollers which are relatively horizontally arranged or relatively staggered, and the relative positions of the oiling rollers are fixed or can be opened and closed.

With the preferred solution described above, one or more pairs of oiling rollers, arranged horizontally or staggered with respect to each other, are used to balance the lateral disturbances of the traction force generated by the resin-bound strands.

Optionally, a groove for passing the filaments is provided on the oiling roller, and the filaments are coated with the resin deposited in the groove. Furthermore, the oiling roller can adopt a magnetic suspension bearing or a liquid bearing or the rotating linear speed is synchronous with the traction speed of the protofilament so as to reduce the torque, reduce the traction resistance on the protofilament and prevent filament breakage.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest features are the same, except that the prepreg strand composite device further comprises: a powder coating device;

In order to further optimize the working effect of the invention, in other embodiments, the remaining features are technically the same, except that the nozzles are arranged in one or more pairs opposite to each other, and the filaments pass between the nozzles arranged opposite to each other.

With the above preferred embodiment, the strands are sufficiently coated with the resin by blowing the resin obliquely upward from the front and back surfaces of the strands.

In order to further optimize the effect of the present invention, other embodiments have the same features except that a powder collecting device for collecting excess resin powder is provided on the opposite surface of the nozzle.

In order to further optimize the implementation of the invention, in other embodiments, the remaining features are the same, except that the prepreg strand composite device comprises: a vertically-leaky fluidized bed, the fluidized bed comprising: the outer shell and the inner container arranged in the outer shell, wherein the upper edge of the inner container is lower than the outer shell, and a dust collecting interlayer is formed between the outer shell and the inner container.

By adopting the preferable scheme, the dust collecting interlayer is used for collecting the resin powder which is settled and blown from the bottom, so that the resin powder is convenient to recycle and the dust is prevented from flying.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the features are the same, except that the manufacturing equipment further comprises: the first heating and curing device is used for heating and/or curing the prepreg protofilament so as to realize one or more of melting, drying and curing of the resin on the prepreg protofilament.

With the above preferred aspect, the first heating and curing device is used to heat and/or cure the prepreg filaments. The device is particularly suitable for use when the resin is in the form of a liquid body, solution, emulsion, powder suspension, or the like.

In order to further optimize the implementation effect of the invention, in other embodiments, the other features are the same, except that the cooling device is used for cooling the back surface of the contact surface of the resin film, the resin fiber, the resin fabric or the isolation material and the precursor and/or the collected prepreg yarn bundle, so as to prevent the resin film, the resin fiber, the resin fabric or the isolation material from being broken prematurely in the process of forming the prepreg precursor by compounding with the precursor and/or prevent the prepreg yarn bundle from being adhered and tangled in the yarn roll after the prepreg yarn bundle is collected and wound into a prepreg yarn roll.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the features are the same, except that the manufacturing equipment further comprises: a second heating and curing device, wherein the second heating and curing device is used for carrying out one or more of the following operations on the collected prepreg yarn bundles: heating, curing and semi-curing to form a film, and removing moisture in the prepreg yarn bundles or partially or completely curing resin in the prepreg yarn bundles to prevent the prepreg yarn bundles in the prepreg yarn roll from being mutually adhered and tangled.

By adopting the preferable scheme, the prepreg yarns in the prepreg yarn roll are prevented from being mutually adhered and tangled.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the features are the same, except that the manufacturing equipment further comprises: and the isolating material conveying equipment is used for conveying the isolating material and the prepreg protofilaments together to the bundling equipment for bundling together, so that the prepreg strands are prevented from being adhered and tangled in yarn rolls.

In order to further optimize the implementation effect of the invention, in other embodiments, the rest of the features are the same, except that the manufacturing equipment further comprises: and the extrusion equipment is used for extruding the prepreg yarn bundles in the bundles, accelerating the infiltration of the resin in the prepreg yarn bundles into the protofilaments, eliminating air bubbles in the prepreg yarn bundles and/or extruding redundant resin to adjust the resin content in the prepreg yarn bundles.

With the preferred arrangement described above, the resin content in the prepreg tows is adjusted by removing air bubbles from the prepreg tows and/or squeezing out excess resin. Preferably, the bundling device is a bundling roller, the extrusion device is an extrusion roller pressed against the bundling roller, and the gap between the extrusion roller and the bundling roller can be adjusted.

In addition, the embodiment of the invention also discloses a fiber prepreg yarn, a plurality of fiber protofilaments are impregnated in situ by resin and then are bundled into a prepreg yarn bundle, and the prepreg yarn bundle is manufactured by adopting any one of the manufacturing methods and/or any one of the manufacturing devices. In addition, the invention also discloses a composite material prepreg or product, which is manufactured by directly adopting the fiber prepreg yarns or is manufactured by the fiber prepreg yarns.

In addition, the embodiment of the invention also discloses a 3D printing additive, which is prepared by coating a plurality of fiber precursors with resin in situ to prepare a prepreg yarn bundle, wherein the prepreg yarn bundle is prepared by adopting any one of the preparation methods and/or any one of the preparation devices.

The 3D printing additive disclosed by the invention contains fiber reinforcement, the strength is far higher than that of a common additive, the fiber content is adjustable, the prepreg yarn additive can be ultrafine, the precise printing is realized, and the 3D printing additive can also be formed by bundling a plurality of prepreg yarns, so that the rapid printing of large-size products is realized.

The various embodiments above may be implemented in cross-parallel.

In order to provide a thorough understanding of the present invention, a number of embodiments are described below.

The first embodiment is as follows: as shown in fig. 3 and 4, the prepreg filament compounding device includes a feed roller 7, the bundling device includes a bundling roller 5, the winding device includes a winding roller 6, and the state of the resin is a fiber bundle, fabric or film made of the resin. Hereinafter, taking the resin film 8 as an example, the resin content in the prepreg yarn bundle 10 can be controlled by controlling the thickness of the resin film 8 by drawing the glass fiber roots into the yarn 3, then combining the yarn with the resin film 8 conveyed by the conveying roller 7 to form the prepreg yarn 9, then bundling the yarn together with the yarn into the prepreg yarn bundle 10 by the bundling roller 5, and then winding the yarn onto the winding roller 6 to form a prepreg yarn roll.

Preferably, the resin is charged or a charged cationic coupling agent is added to the resin in order to improve the adhesion of the resin to the filaments. Preferably, the precursor 3 is compounded with the resin film 8 on the conveying roller 7 at 0 to 40 ℃ above the melting point of the resin, so that the resin film 8 is fused and attached to the precursor 3. Preferably, the conveying roller 7 conveys the resin film 8 at the same linear speed as the drawing speed of the strands by using a liquid or magnetic suspension bearing or by using a counter roller to reduce the drawing resistance to the strands. Preferably, the back of the face of the resin film 8 in contact with the filaments is cooled or lubricated to avoid premature melting and fracture of the resin film 8, by means including but not limited to blowing/cold air/water mist; alternatively, water or an aqueous solution is dip-coated on the rotating conveying roller 7 or the conveying roller 7 is directly cooled to cool and/or lubricate the back surface of the resin film 8 passing through the conveying roller 7, without causing the resin film 8 to melt and adhere to the conveying roller 7 during the process of being combined with the strands to generate a lateral disturbance to the traction force of the strands. Preferably, the bundling roller 5 is provided with a groove 51, and the shape of the groove 51 is a V-shaped or U-shaped groove with a wide opening and a narrow bottom, so that the prepreg protofilaments can be easily gathered into prepreg yarn bundles. Preferably, the bundling roller 5 is heated to 0 to 40 ℃ above the melting point of the resin, so that the resin on the pre-impregnated filaments passing through the bundling roller 5 is sufficiently melted and wets the filaments. Optionally, the bundling roller 5 is one or more. Alternatively, a scraper is provided against the collecting roller 5 to scrape off excess resin melt adhering to the surface of the collecting roller 5 for reuse. Preferably, the prepreg strands are heat-dried to remove moisture adhering to the resin film 8 before passing through the bundling roller 5, and the heat-drying means includes, but is not limited to, one or a combination of infrared, microwave, and hot air heating means. Preferably, the prepreg yarn bundles are cooled and/or lubricated prior to entering the wind-up roll, and the cooling and/or lubricating means include, but are not limited to, a natural air-drying zone, a blowing/cooling air, a water spray device, a cooled or water lubricated cooling roll contact cooling/lubricating device. Optionally, the winding system is composed of 2 or more than 2 winding rollers 6 circumferentially arranged on the winding conversion shaft, the self-transmission speeds of the winding rollers are synchronous, the winding roller on the working position leaves the working position every time the winding conversion shaft rotates once, and the adjacent standby winding rollers enter the working position and sequentially circulate; when the machine is started or stopped to restart drawing, firstly, fibers are pulled from filament roots to form protofilaments, the protofilaments are twisted with resin films and collected by the bundling roller 5 and then wound on the winding roller 6 rotating at high speed, after one winding roller 6 is fully wound, the winding conversion shaft is rotated to enable a new winding roller to be in a winding working position, the original winding roller is withdrawn from the working position, and the prepreg yarn bundles are cut off, so that the prepreg yarn bundles can be stably wound on the new winding roller to form prepreg yarn rolls.

Such fiber prepreg reels, which will become the primary product for the production of composite prepregs or semi-finished or finished products, may be used in a variety of composite processes, downstream processing including, but not limited to, fiber prepreg manufacturing processes and direct molding processes for composite finished products, including, but not limited to, one-dimensional, two-dimensional, three-dimensional: thermoplastic/thermosetting prepreg felt/cloth/tape, prepreg filament, fiber reinforced pellet, bulk molding compound, sheet molding compound, three-dimensional woven body, and the forming process of the fiber prepreg includes but is not limited to weaving, laying, spray deposition/bonding, and three-dimensional forming in one or more combinations; the composite material direct forming process comprises but is not limited to the combination of one or more of pultrusion, winding, rolling, spraying/laying bag pressing/laminating/molding and injection molding, and is characterized in that: the resin infiltration link is removed from the direct molding process of the composite material, the composite material is molded under certain pressure and temperature conditions after the presoaking yarns are directly preformed, and the full infiltration of the resin on the fiber protofilaments is realized, so that the resin impregnation link is omitted, the composite material with few gaps can be realized only by removing the air among the presoaking yarns in the molding process, the performance of the composite material can be greatly improved, the quality control points in the production are greatly reduced, the production management is greatly simplified, and the quality stability of the product can be greatly improved; and moreover, because the resin is semi-cured or cured and fully coats the precursor, resin volatile matters and fibers are rarely scattered in the production place of the composite material, and the composite material is clean and environment-friendly.

The fiber prepreg yarn bundle can be made into superfine 3D printing additive or large prepreg yarn bundles by bundling a plurality of strands and is respectively used for making precise 3D printing composite material products or large-size 3D printing composite material products.

In the first embodiment, the resin film 8 is used for coating the precursor in situ, so that the transverse disturbance to the traction force of the precursor in the process of coating the precursor with the resin can be reduced, the risk of filament breakage can be avoided, and the infiltration quality of the precursor coated with the resin can be ensured.

Example two, as shown in fig. 5 and 6, example two is a modification of example one, and it is possible to further prevent a lateral disturbance to the filament pulling force when the resin coats the filaments.

The difference between the first embodiment and the second embodiment is that the strands 3 are not combined with the resin film 8 on the conveying roller 7, but combined with the resin film 8 in the air before the strands 3 enter the bundling roller, so that the risk of transverse disturbance of the traction force of the strands due to the adhesion of the molten resin on the conveying roller 7 is completely eliminated.

The specific implementation scheme is as follows: one or a pair of rotating conveying rollers 7 is/are used for conveying the resin film 8 to one side or two opposite sides of the path of the precursor fiber 3 entering the bundling roller 5, and the precursor fiber 3 is clamped and fused and compounded into a prepreg yarn bundle 10 through the bundling roller 5. Preferably, the resin film 8 is blown to the precursor fibers 3 by an air blower 11 on the path before entering the bundling roller 5, wherein the temperature of the precursor fibers 3 is 0-40 ℃ higher than the melting point of the resin, and the resin film 8 has longer time to fuse and coat the precursor fibers. More preferably, a pressing roller 12 is provided to press the prepreg yarn 10 passing through the collecting roller 5, which helps to remove air bubbles from the prepreg yarn and improve the wetting quality of the resin-coated strands, and at the same time, the resin content in the prepreg yarn 10 can be adjusted by adjusting the gap between the pressing roller and the collecting roller, and a scraper can be used to scrape off excess resin on the surfaces of the pressing roller 12 and the collecting roller 5.

In the operation, the squeezing roller 12 is separated from the bundling roller 5 when the operation is started, the cooling device 13 arranged between the bundling roller and the winding roller is started, the protofilament 3 and the resin film 8 are twisted together, and then the protofilament 3 and the resin film 8 are wound on the winding roller after passing through the bundling roller 5 together with the resin film to start simultaneously drawing the protofilament 3 and the resin film 8 until the drawing is stable, the squeezing roller is closed, when the operation is normal, the air blowing device 11 on the back of the resin film is started to enable the resin film to be attached to the protofilament before entering the bundling roller for fusion and compounding, then the resin film is melted into the pre-impregnated yarn bundle 10 in the groove 51 of the bundling roller 5, and the pre-impregnated yarn bundle is wound on the winding roller 6 after being blown with air/cold air/water mist for cooling/lubricating the pre-impregnated yarn bundle and before being wound on the winding roller to form the pre-impregnated yarn winding.

Example three, as shown in fig. 7 and 8, is a modification of the process shown in example one, and can further prevent a lateral disturbance to the filament pulling force when the resin coats the filaments.

The other embodiment is different from the first embodiment in that a pair of oppositely rotating conveying rollers 7 are adopted to convey the resin film 8 to enter the bundling roller 5 through the raw filaments 3 to be bundled into a prepreg yarn bundle 10, and then the prepreg yarn bundle is wound on a winding roller to be a prepreg yarn roll.

During specific operation, the conveying rollers 7 are firstly separated, the precursor 3 and the resin film 8 are twisted together and then wound on the winding roller 6 through the bundling roller 5, the conveying rollers 7 are folded, the resin film 8 and the precursor are fused together to enter the bundling roller 5 when the temperature of the precursor 3 is 0-40 ℃ higher than the melting point of the resin, and after the precursor 3 is normally pulled, the converting shaft of the winding roller 6 is rotated to enable a new winding roller to enter a working position to normally produce the prepreg yarn roll.

Example four, as shown in fig. 9 and 10, shows a variation of the first to third processes of examples, and can be applied to various forms of resins. The method comprises the steps of attaching resin in a certain form to a spacer material 14, compounding the spacer material 14 with protofilaments 3 from one side or two sides through a spacer material conveying roller 7 to transfer the resin to the protofilaments and coat the protofilaments to form pre-impregnated protofilaments 9, winding the pre-impregnated protofilaments 9 and the spacer material 14 on a winding roller through a bundling roller 5 to form a pre-impregnated yarn roll, and directly entering the next process for use or applying the pre-impregnated yarn roll to a production process of semi-finished products and finished products of composite materials after drying and/or curing, wherein the resin form comprises but is not limited to melt, film, fiber, fabric, powder suspension, emulsion, bulk liquid and solution.

Preferably, barrier material 14 is wound onto take-up roll 6, by means of gathering roll 5, gripping the filaments 3 from opposite sides thereof. Preferably, there is a means for heating and/or curing the prepreg filaments before the gathering roller 5, the heating and/or curing means including, but not limited to, one or a combination of more of heating, infrared, microwave, laser, ultrasonic, UV curing means; preferably, the prepreg yarn bundles are cooled and/or lubricated prior to entering the wind-up roll, and the cooling and/or lubricating means include, but are not limited to, a natural air-drying zone, air/cold air, water spray means, cooled or water lubricated chill roll contact cooling/lubricating means. Preferably, a squeeze roll 12 is provided to squeeze out bubbles and aid in wetting of the prepreg strands on the gathering roll, and the resin content within the prepreg strands is adjusted by adjusting the gap between the squeeze roll and the gathering roll to squeeze out excess resin. Preferably, the bundling roller 5 is provided with a groove, and the preferable shape is a V-shaped or U-shaped groove with a wide opening and a narrow bottom, so that the prepreg protofilaments can be easily gathered into the prepreg yarn bundles, and the resin content in the prepreg yarn bundles can be fixedly adjusted through the shape and the cross section of the groove when the pressing roller presses the prepreg yarn bundles. Preferably, the bundling roller 5 is heated to 0-40 ℃ above the melting point of the resin, so that the resin on the pre-impregnated protofilaments passing through the bundling roller 5 is fully melted and infiltrated into the protofilaments; optionally, the bundling roller is one or more.

The release material 14 includes, but is not limited to, a combination of one or more of polypropylene, polyethylene, release coated cellophane or other paper or polyester film, polyvinyl chloride, polytetrafluoroethylene, nylon, polyetheretherketone, polyimide, polyphenylene sulfide, coated fabric, silicone rubber; preferably, the release material 14 has a release function or its surface is coated with a release agent; preferably, the isolation material 14 is transparent or light transmissive.

The advantages of using this process are: 1) the speed of the isolation material is the same as that of the precursor, and the disturbance of the adhesive force of the resin to the traction force of the precursor is avoided; 2) the release material gives the resin sufficient time to wet the resin during winding; 3) the problem that the drying and/or curing speed of the resin is not matched with the traction speed is solved, and the prepreg yarn roll can be dried and/or cured off line; 4) the prepreg yarns are isolated by an isolating material, and are not adhered and tangled; 5) with the isolation of the isolation material, the prepreg yarn bundles in the prepreg yarn roll can be cured or dried after being rolled, and the curing time is not limited by the traction speed of the protofilament.

As shown in fig. 9 and 10, a specific method for carrying out the resin in the form of a film/high-viscosity resin body or a resin in a melt or powder state: the prepreg strand compounding device is a pair of openable and closable separating material conveying rollers 7, one separating material conveying roller 7 and a squeezing roller 12 are separated when the separating material is started, the protofilament 3 and the separating material 14 are drawn to be twisted so that the separating material 14 is wound on a winding roller 6 from the double-sided sandwiched protofilament 3 through a bundling roller 5, then the separating material conveying roller 7 and the squeezing roller 12 are closed, the separating material 14 is coated or coated with the resin in the form, the protofilament is coated on the separating material to form prepreg strands before the resin enters the bundling roller and/or after the resin is wound, and the prepared prepreg strands can directly enter the process of the next link or be wound again to remove stub bars and/or the separating material or be wound again after being heated and/or semi-cured. Preferably, before passing through the bundling roller and on the bundling roller, the resin is coated with the precursor fibers to be compounded into pre-impregnated precursor fibers when the temperature of the precursor fibers is 0-40 ℃ higher than the melting point of the resin, and the melting point of the isolation material is higher than the melting point of the resin, so that the film can not be melted and broken; preferably, the resin powder is charged to prevent the powder from scattering by electrostatic adsorption on the insulation material or the insulation material made of fabric coated with a release agent facilitates separation of the prepreg yarn bundle from the insulation material.

In the fifth embodiment, as shown in fig. 11 and 12, as another embodiment of the fourth embodiment, an embodiment in which the resin is in the form of a liquid having a low viscosity such as a liquid bulk, a solution, an emulsion, a powder suspension, or a solution is shown. Other like current wire drawing technique, preimpregnation silk set composite includes fat liquoring box 16, and the difference lies in: 1) changing the impregnating compound into low-viscosity resin in a liquid state, coating the resin on the surface of the protofilament by an oiling roller 4 through an oiling box 16, wherein the coating temperature of the protofilament is 20-80 ℃; 2) the conveying roller 7 conveys the isolation material 14, and the isolation material 14 is lined on one side or two sides or clamps the protofilaments 3 and is compounded with the protofilaments by the method of the fourth embodiment and is wound on the winding roller 6 by the bundling roller 5 to form a prepreg yarn roll.

Preferably, spacer material 14 is sandwiched between prepreg strands 9 by squeeze roll 12 and gathering roll 5 to form prepreg yarn bundles spaced apart from each other. Preferably, the coated prepreg filaments are heated/cured by a heating device 15 to dehydrate and/or semi-cure/cure the resin on the filaments into a film. More preferably, the gathering roll and/or the release material delivery roll heat to remove water and/or accelerate the reaction of the resin reaction precursor. The resin contains a curing agent which can be fully cured or semi-cured under suitable curing conditions into a polymer matrix of linear or branched structure, the curing agent includes but is not limited to a combination of one or more of thermal initiators, photoinitiators, latent curing agents, and release materials 14 are preferably release coated papers, fabrics, and films. The prepreg yarns produced by this process can be run directly to the next process or can be baked to remove water and/or cured and then unwound from the separator material 14 as a package for further processing.

In specific implementation, the extrusion roller 12 is started to be opened, the precursor is drawn and wound on the bundling roller and the isolation material wound on the extrusion roller together to be twisted and wound on the winding roller 6, and the extrusion roller is abutted after the wiredrawing is stable.

Example six, as shown in fig. 13 and 14, example six is a modification of example five. The other embodiment is as the fifth embodiment, except that the oiling box 16 is replaced by the powder fluidized bed 17 in the prepreg filament compounding device, resin powder is absorbed by the oiling roller 4 and transferred onto the filaments passing through the oiling roller 4 to form prepreg filaments, then the prepreg filaments are clamped by the isolation material 14 to enter the gap between the bundling roller 5 and the extrusion roller 12, and the filaments between the isolation material 14 are fully infiltrated under certain temperature and pressure and certain gap, air bubbles in the filament bundle are extruded, and the content of the resin/resin reaction precursor mixture in the filament bundle is adjusted.

Preferably, the resin is charged or an ionic auxiliary agent is added, so that resin powder is easily adsorbed on the protofilament; preferably, the resin is contacted with the oiling roller 4 at the temperature of the protofilament which is 0-40 ℃ higher than the melting point of the resin, and the oiling roller 4 is cooled or coated with water to prevent the resin from being adhered to the oiling roller to cause transverse disturbance to the traction force of the protofilament; more preferably, the bundling roller and/or the diaphragm conveying roller are/is heated to 0-40 ℃ above the melting point of the resin to melt the resin powder to coat the protofilament; preferably, the insulation material 14 is made of a high temperature resistant film including, but not limited to, cellophane or other paper or a combination of one or more of polytetrafluoroethylene, polyetheretherketone, polyimide, polyphenylene sulfide, coated fabric, silicone rubber, such that the insulation material is resistant to the high temperature of the resin melt; more preferably, an inert compressed gas is used as the bubbling gas for the fluidized bed to prevent deterioration and even burning of the resin powder at high temperatures.

Example seven example a vertical fluidized bed process for coating filaments in situ with a barrier material, as shown in figures 15 and 16. The pre-preg filament compounding device comprises a vertical fluidized bed 18, and specifically comprises: a vertical fluidized bed 18 with upper and lower open spaces and circumferentially closed is arranged below the crucible bushing 2, an operation door on one side of the fluidized bed 18 facing an operator is movably opened and closed, a blowing nozzle which blows and sprays raw filaments in an upward direction is arranged at the bottom of the fluidized bed 18, and the bundling roller 5 is positioned right below the vertical fluidized bed 18.

Preferably, the temperature of the filaments 3 passing vertically through the fluidized bed 18 is not lower than the melting point of the resin; preferably, the blowing nozzles are arranged on the front and back sides of the strands, and a squeezing roller 12 is preferably arranged to enable the isolating material to double-side clamp the strands 3 and wind the strands on a winding roller 6 through a bundling roller 5. During specific operation, an operation door of a vertical fluidized bed 18 is opened, an extrusion roller 12 is opened, an operator pulls a precursor twist and an isolation material to be wound on a winding roller rotating at a high speed through a bundling roller to start continuous traction of precursors, after normal traction is performed, the operation door is closed, the extrusion roller 12 is pressed, a blowing nozzle blows and sprays resin powder to the precursors at constant pressure, the resin powder is melted and coated on the precursors, and redundant resin powder can fall on the isolation material on the extrusion roller and the bundling roller; preferably, at least one of the pressing roller and the bundling roller is heated to 0-40 ℃ above the melting point of the resin, so that the prepreg strands are bundled and then further bubble removal and sufficient infiltration are performed, and the bundled prepreg strands are wound on the winding roller 6 to form prepreg strands to enter the next process or are directly used for manufacturing the composite material. Preferably, the resin is charged or is added with an ionic auxiliary agent, so that the resin is easier to adsorb on the protofilament; preferably, a dust collecting device is arranged opposite to the blowing nozzle and used for collecting the resin powder blown out by the blowing nozzle for recycling, and the collecting method comprises but is not limited to natural sedimentation, negative pressure and electrostatic adsorption; preferably, an inner container with an upper opening and a lower opening is arranged on the inner wall of the vertical fluidized bed 18, the height of the inner container is lower than that of the fluidized bed, the inner container and the fluidized bed 18 form a dust collecting interlayer, and the resin powder and the inert gas are blown to the upper edge of the dust collecting inner container and then naturally sink into the dust collecting interlayer for recycling after collection; more preferably, vertical fluidized bed 18 is the frustum type of narrow down wide from top to bottom, and the inner bag is the cylinder type, by transparent material preparation, and integrated inner bag is like this and leaks hopper-shaped narrow down for wide from top to bottom, and the fluidized bed inner wall is the cylindricality, and the fluidized bed of formation is even stable, can make the precursor fuse with the contact of resin powder uniformly, and the dust collection is gone up the wide pressure decline that makes things convenient for the dust to subside on making the dust blow, and transparent material can make things convenient for operating personnel to observe fluidized bed state, precursor cladding condition and the broken silk condition. Preferably, the compressed gas used to deliver the resin powder and blow is an inert gas, including but not limited to carbon dioxide, nitrogen, argon, etc., to prevent degradation or combustion of the resin at high temperatures.

Example eight, as shown in fig. 17 and 18, the example is a modification of example seven. The other is as in example seven, except that: the insulation material is removed, accordingly, the bundling roller is placed right below the vertical fluidized bed to enable the falling resin powder to fall onto the bundling roller, the bundling roller is heated to 0-40 ℃ above the melting point of the resin, the facility extrusion roller is preferred to remove air bubbles in the prepreg yarn bundles and assist in wetting, the rubber transfer roller 19 and the scraper blade 20 are preferred to remove excess resin on the bundling roller 5 and the extrusion roller 12, the prepreg yarn bundles are preferably cooled and/or lubricated by cooling measures including but not limited to air/cold air/water mist/cold roller contact, and the cooling and/or lubricating measures are preferred to prevent the prepreg yarn bundles from being adhered and tangled in the prepreg yarn roll.

The ninth embodiment is a modification of the seventh embodiment, and is different from the seventh embodiment in that: the isolating material is removed, and a cooling device is arranged between the bundling roller 5 and the winding roller 6, so that the process is simplified.

Example ten, as shown in fig. 19 and 20, example ten is a solution to the problem of filament breakage and yarn bundle blocking using a resin powder suspension and a heated cluster roll. The impregnating compound in an oiling box in the prior art is replaced by resin powder suspension, an oiling roller 4 is moved up to a position where the temperature of protofilaments is 0-40 ℃ higher than the melting point of resin, a bundling roller 5 is heated to the temperature of 0-40 ℃ higher than the melting point of the resin, the protofilaments are drawn, twisted to form prepreg protofilaments through the oiling roller 4, then the prepreg protofilaments are bundled by the bundling roller 5 to form prepreg yarns, and the prepreg yarns are wound on a winding roller rotating at high speed to form prepreg yarn windings. Preferably, the pre-impregnated filaments are heated by a drying and heating device 22, including but not limited to hot air, infrared, microwave, laser, ultrasonic, etc., before passing through the gathering roll 5, drying it and promoting the melting of the resin to coat the filaments. Preferably, the prepreg yarn bundles are cooled and/or lubricated prior to entering the wind-up roll using cooling means including, but not limited to, air/chilled air/water mist/chilled roll contact. Since the powder suspension is also not higher in viscosity than the aqueous solution, the transverse disturbance to the traction force of the precursor is small, and the cooling and/or lubricating measures ensure that the prepreg yarn bundles cannot be adhered and tangled in the prepreg yarn roll.

Example eleven, example eleven shows a solution to the problem of filament breakage and yarn bundle blocking using a resin emulsion and a heating and/or curing device. Example eleven is similar to example eleven except that the size in the prior art oiling box is replaced with a resin emulsion, and preferably the resin contains a curing agent, wherein the curing agent includes, but is not limited to, one or more of a latent curing agent, a heat-sensitive curing agent and an ultraviolet initiator; the method comprises the steps of drawing protofilaments, twisting the protofilaments into pre-impregnated protofilaments through an oiling roller 4, bundling the pre-impregnated protofilaments through a bundling roller 5 to form pre-impregnated protofilaments, winding the pre-impregnated protofilaments to a winding roller 6 rotating at a high speed to form a pre-impregnated protofilament roll, heating and/or curing the pre-impregnated protofilaments before the pre-impregnated protofilaments pass through the bundling roller 5, drying resin emulsion on the pre-impregnated protofilaments and promoting resin film formation or reaction film formation to coat the protofilaments, wherein the heating measures include but are not limited to hot air, infrared, microwave, laser, ultrasonic, UV (ultraviolet) curing and the like, and the curing measures include but are not limited to infrared, microwave, laser, ultrasonic, UV (ultraviolet) curing and the like. The resin emulsion has viscosity not higher than that of water solution, so that the transverse disturbance to the traction force of the precursor is small, and the film-formed resin can prevent the prepreg yarn bundles from being adhered and tangled in the prepreg yarn roll. Of course, this process is only feasible for resin emulsions that can be rapidly dried and/or cured into films.

Example twelve, as shown in fig. 21, example twelve illustrates an in situ filament coating process using resin from an elevating fluidized bed 23 and oiling roller 4. The prepreg filament compounding device includes: a liftable fluidized bed and/or an oiling roller, a bundling area of the bundling roller is higher than the bottom of the oiling roller, a liftable fluidized bed is arranged right below the bushing, resin powder is loaded, and preferably, the gas for blowing the resin powder is inert gas, the inert gas includes but is not limited to carbon dioxide, nitrogen, argon and the like, meanwhile, the oiling roller is cooled to prevent the resin from melting on the oiling roller to form melt which disturbs the traction force of the precursor, the temperature of the precursor in the region where the oiling roller 4 is located is 0-40 ℃ higher than the melting point of the resin, heating the bundling roller to 0-40 ℃ above the melting point of the resin, horizontally arranging the bundling roller and the oiling roller, enabling the high point of the bundling roller to be higher than the low point of the oiling roller, and enabling the bundling roller 5 and the oiling roller 4 to rotate at the same linear speed as the traction speed of the precursor wires synchronously by adopting a liquid bearing or a magnetic suspension bearing so as to reduce disturbance on the traction speed of the precursor wires; preferably, the oiling roller and/or the bundling roller are provided with a scraper 20 which can scrape off the surface of the resin, a cooling device 13 is arranged between the bundling roller 5 and the winding roller 6, and the cooling device 13 adopts cooling measures including but not limited to air/cold air/water mist/cold roller contact and the like to cool and/or lubricate the prepreg yarn bundles. When the device is started, the fluidized bed descends to expose the oiling roller, the drawn protofilaments are twisted, pass through the oiling roller 4, then horizontally bypass the bundling roller 5 to form a yarn bundle, and then are wound on the winding roller rotating at a high speed, the fluidized bed is lifted after the drawn protofilaments are stabilized, the protofilaments are immersed in resin powder, are fused with the resin powder through the fluidized bed 23 to form pre-impregnated protofilaments, and are further fused and bundled into pre-impregnated yarn bundles through the grooves in the bundling roller 5, and then are cooled and/or lubricated by the cooling device 13 and then are wound on the winding roller to form pre-impregnated yarn rolls, so that the infiltration of the resin powder on the protofilaments is better ensured.

The thirteenth embodiment is a modification of the tenth embodiment, and is otherwise the same as the tenth embodiment except that the prepreg filament compounding device comprises two oiling rollers 4 which are oppositely arranged, so that the transverse disturbance of the resin on the oiling rollers 4 to the traction of the strands can be balanced, and the device and the method can be suitable for the resin with slightly high viscosity.

In a fourteenth embodiment, as shown in fig. 22, the fourteenth embodiment is a modification of the eleventh embodiment, and is different from the eleventh embodiment in that: the pre-dipping silk compounding device comprises an applicator roll 24, the applicator roll 24 is arranged up and down relative to the bundling roll 5 in a mode that the applicator roll 24 coats the resin melt with protofilament instead of a fluidized bed to coat resin powder with protofilament, the applicator roll 24 and the bundling roll are heated to 0-40 ℃ above the melting point of resin, and the applicator roll 24 is arranged at a position where the temperature of the protofilament is 0-40 ℃ above the melting point of the resin. The sizing roller 25 is arranged outside the sizing roller 24, and the sizing roller 25 applies the resin melt to the surface of the sizing roller 24 and controls the thickness of the resin melt on the surface of the sizing roller. Preferably, the squeeze rollers are positioned to help remove air bubbles from the prepreg tows on the gathering rollers and to help wet out, which balances the lateral disturbance of the resin melt to the filament draw. Preferably, a glue amount control roller 26 is installed outside the bundling roller 5, and the glue amount control roller 26 controls the thickness of the glue layer on the surface of the bundling roller 5.

While there have been shown and described what are at present considered to be the fundamental principles of the invention and its essential features and advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.

Claims

1. The method for manufacturing the resin in-situ coated fiber strand is characterized by comprising the following steps of:

s3: winding the prepreg yarn bundle into a prepreg yarn roll; in S1, the resin is in the form of one or more of liquid bulk, solution, emulsion, powder suspension, melt, powder, film, fiber, and fabric.

2. The manufacturing method according to claim 1, further comprising, before S1, the steps of:

3. The method of claim 1, wherein the resin and the release material are bundled together into the prepreg yarn bundle at S2 to prevent the prepreg yarn bundle from being entangled by adhesion in a yarn package.

4. The method according to claim 1, wherein when the resin is in the form of one or more of a melt, a powder, a film, a fiber, and a woven fabric, the temperature of the filaments is 0 to 40 ℃ or higher than the melting point of the resin in S1, and the resin is melted and adhered to the surfaces of the filaments on the surfaces of the filaments.

5. The method according to claim 4, wherein when the resin is in the form of one or more of a film, a fiber, and a woven fabric, the back surface of the contact surface of the resin with the filaments is cooled to prevent premature melt fracture of one or more of the resin film, the resin fiber, and the woven fabric.

6. The manufacturing method according to claim 1, wherein S1 is performed in an environment with an inert gas blanket.

7. The method according to claim 1, wherein the predetermined temperature in S2 is 0 to 40 ℃ above the melting point of the resin.

8. The manufacturing method according to claim 1, wherein S2 further includes the steps of: and extruding the bundled presoaked yarn bundles to accelerate the infiltration of the resin in the presoaked yarn bundles to the protofilaments, and removing air bubbles in the presoaked yarn bundles and/or extruding redundant resin to adjust the resin content in the presoaked yarn bundles.

9. The manufacturing method according to claim 1, further comprising the steps between S1 and S2:

and heating and/or curing the prepreg strands to melt, dry and cure the resin on the prepreg strands.

10. The manufacturing method according to claim 1, further comprising the steps between S2 and S3:

11. The manufacturing method according to claim 1, further comprising the steps between S2 and S3: and cooling the collected prepreg yarn bundles to prevent the prepreg yarn bundles from being adhered and tangled in yarn rolls.

12. The method according to claim 1, wherein the resin contains one or more of a curing agent, a lubricant, a colorant, a filler, a flame retardant, an antistatic agent, and an ionic auxiliary agent in combination.

13. The manufacturing equipment of the resin in-situ coated fiber strand is characterized by being prepared by the manufacturing method of any one of claims 1 to 12, and specifically comprising the following steps:

the preimpregnation protofilament composite device is used for attaching resin to a plurality of fiber monofilament protofilaments to be composited into preimpregnated protofilaments, and comprises: conveying rollers and/or oiling rollers and/or applicator rollers and/or fluidized beds and/or heating devices and/or cooling devices, wherein the conveying rollers are used for conveying one or more of resin films, resin fibers, resin fabrics and isolating materials;

14. The manufacturing apparatus of claim 13, wherein the prepreg strand compounding device further comprises: a static electricity generating device for electrostatically charging the resin.

15. The manufacturing equipment as claimed in claim 13, wherein the prepreg strand composite device comprises one or more pairs of oiling rollers which are relatively horizontally arranged or relatively staggered, and the oiling rollers are relatively fixed in position or can be opened and closed.

16. The manufacturing apparatus as claimed in claim 13, wherein the prepreg strand composite device further comprises: a powder coating device;

the powder coating device includes: the device comprises a compressed air conveying pipeline, an air pressure adjusting device, a resin powder conveying device and one or more nozzles, wherein the nozzles blow and spray resin powder from bottom to top obliquely towards the traction direction of the protofilament.

17. The manufacturing apparatus of claim 16, wherein the nozzles are one or more pairs arranged in opposition, the filaments passing between the oppositely disposed nozzles.

18. The manufacturing apparatus according to claim 16, wherein a powder collecting device for collecting excess resin powder is provided on an opposite surface of the nozzle.

19. The manufacturing apparatus of claim 18, wherein the prepreg strand compounding device comprises: a vertically-hollowed fluidized bed, said fluidized bed comprising: the upper edge of the inner container is lower than the outer shell, and a dust collecting interlayer is formed between the outer shell and the inner container.

20. The manufacturing apparatus of any one of claims 13-19, further comprising: the first heating and curing device is used for heating and/or curing the prepreg protofilament so as to realize one or more of melting, drying and curing of the resin on the prepreg protofilament.

21. The manufacturing equipment according to any one of claims 13 to 19, wherein the cooling device is used for cooling the back surface of the contact surface of the resin film, the resin fiber, the resin fabric or the isolation material and the precursor fiber and/or the collected prepreg yarn bundle, so as to prevent the resin film, the resin fiber, the resin fabric or the isolation material from being prematurely broken during the process of compounding with the precursor fiber to form the prepreg precursor fiber and/or prevent the prepreg yarn bundle from being adhered and tangled in the yarn roll after the prepreg yarn bundle is collected and wound into a prepreg yarn roll.

22. The manufacturing apparatus of any one of claims 13-19, further comprising: a second thermal curing device for performing one or more of the following operations on the collected prepreg yarn bundles: heating, curing and semi-curing to form a film, and removing moisture in the prepreg yarn bundles or partially or completely curing resin in the prepreg yarn bundles to prevent the prepreg yarn bundles in the prepreg yarn roll from being mutually adhered and tangled.

23. The manufacturing apparatus of any one of claims 13-19, further comprising: and the isolating material conveying equipment is used for conveying the isolating material and the prepreg strands together to the bundling equipment for bundling together, so that the prepreg strands are prevented from being adhered and tangled in yarn rolls.

24. The manufacturing apparatus of any one of claims 13-19, further comprising: and the extrusion equipment is used for extruding the prepreg yarn bundles in the bundles, accelerating the infiltration of the resin in the prepreg yarn bundles into the protofilaments, eliminating air bubbles in the prepreg yarn bundles and/or extruding redundant resin to adjust the resin content in the prepreg yarn bundles.

25. Fibrous prepreg manufactured by a manufacturing method according to any one of claims 1 to 13 and/or by a manufacturing apparatus according to any one of claims 13 to 24, wherein a plurality of fiber strands are impregnated with a resin in situ and then bundled into a prepreg strand.

26. A composite prepreg or article manufactured directly from the fibrous prepreg of claim 25 or manufactured from the fibrous prepreg of claim 25.

A 3D printing additive, wherein the additive is made by in-situ coating a plurality of fiber strands with a resin to make a prepreg strand, wherein the prepreg strand is made by the manufacturing method of any one of claims 1-13 and/or by the manufacturing apparatus of any one of claims 13-24.