WO2024056562A1 - Système d'imprégnation de fibres pour la production de composites pultrudés de polyuréthane et son procédé d'utilisation - Google Patents

Système d'imprégnation de fibres pour la production de composites pultrudés de polyuréthane et son procédé d'utilisation Download PDF

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Publication number
WO2024056562A1
WO2024056562A1 PCT/EP2023/074825 EP2023074825W WO2024056562A1 WO 2024056562 A1 WO2024056562 A1 WO 2024056562A1 EP 2023074825 W EP2023074825 W EP 2023074825W WO 2024056562 A1 WO2024056562 A1 WO 2024056562A1
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WO
WIPO (PCT)
Prior art keywords
motor vehicle
cavity
inlet
outlet
injection box
Prior art date
Application number
PCT/EP2023/074825
Other languages
English (en)
Inventor
Yongming GU
Pengfei Wu
Zhijiang Li
Original Assignee
Covestro Deutschland Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202211125775.2A external-priority patent/CN117734203A/zh
Priority claimed from EP22205307.6A external-priority patent/EP4364932A1/fr
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2024056562A1 publication Critical patent/WO2024056562A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525—Component parts, details or accessories; Auxiliary operations
    • B29C70/526—Pultrusion dies, e.g. dies with moving or rotating parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material

Definitions

  • the present invention relates to a system for impregnating fibers for producing pultruded composites.
  • the present invention relates to a system for impregnating fibers for producing polyurethane pultruded composites.
  • the present invention also relates to a method for using the system and the polyurethane pultruded composites produced by the system.
  • the one type is the low-pressure injection method.
  • This type of injection box usually has one or more tapers inside, which is/are symmetrical along the central axis of the pultrusion direction, that is, the taper is uniform above/below the central axis, wherein the pultrusion direction is parallel to the horizontal plane.
  • the injection orifices thereof are generally located at the top and bottom of the injection box.
  • the resin is injected into the injection box by the injection machine and then infiltrates the unidirectional fiber yams.
  • This type of injection box is suitable for whole yam pultrusion.
  • the other type is the high-pressure injection method.
  • the injection orifices thereof are generally located at the top and bottom of the injection box.
  • This kind of injection box infiltrates the porous stmcture layers such as tape felts or fabrics at a certain injection pressure.
  • the resin often overflows from the inlet of the injection box, through which the fiber yams are fed, and thus is wasted. If it is controlled so that the resin does not overflow from the inlet of the injection box, the internal fiber infiltration is prone to be poor inside the injection box due to insufficient resin amount.
  • CN106515047A discloses a reaction injection pultrusion equipment including a forming unit for forming resins and fibers, the forming unit including at least four machining sections connected in sequence: a preheating section, a dipping section, a heating section and a cooling section.
  • the present invention relates to a system for impregnating fibers for a polyurethane pultrusion process, the system for impregnating fibers comprising an injection box, the injection box having a cavity for the fiber material to pass through, and the cavity having an inlet and an outlet, wherein the lower wall section of the inner wall of the cavity includes one or more slopes, the lower edge of the inlet of the cavity is not lower than the lower edge of the outlet of the cavity, and the slope closest to the inlet makes the inlet of the cavity sloping down towards the outlet.
  • the fiber material passes through the cavity via the inlet and the outlet thereof.
  • the lower wall section of the inner wall of the cavity has a slope, wherein the corresponding lower wall section and the central axis of the injection box have an included angle a, and the included angle a is in a range of 0-5° .
  • the sectional area of the cavity decreases in the direction from the inlet to the outlet.
  • the sectional area (Tl) of the inlet to the sectional area (T2) of the outlet of the cavity has a ratio (T1/T2) of 2: 1-10: 1 .
  • system of the present invention further comprises a mold, the outlet of the cavity being connected to the mold.
  • a transition section is optionally provided between the outlet and the mold, the cavity and the mold being connected by the transition section.
  • the sectional area of the transition section decreases in the direction from the inlet to the outlet.
  • the present invention also relates to a pultrusion method for producing polyurethane composites, said method using the system of the present invention, and comprising the steps of: providing the polyurethane material, passing the fiber material through the cavity of the injection box, injecting the polyurethane material into the cavity, thereby impregnating the fiber material, curing the impregnated fiber material, thereby obtaining the polyurethane composites.
  • the present invention also relates to a polyurethane composite produced by the method of the present invention.
  • Fig. 1 a) schematic view of the sectional structure, b) and c) schematic view of longitudinal sectional structure of one embodiment of the system for impregnating fibers of the present invention.
  • Fig. 2 schematic view of longitudinal sectional structure of one embodiment of the system for impregnating fibers of the present invention.
  • Fig. 3 schematic view of the method for producing polyurethane pultruded composites.
  • Fig. 4 schematic view of longitudinal sectional structure of a conventional injection box, wherein the inner cavity has a symmetrical taper with respect to the central axis of the pultrusion direction.
  • the terms “about”, “approximately” generally mean that the numerical value of the variable and all numerical values of the variable are within experimental error (for example, within a 95% confidence interval for the mean) or a range of ⁇ 10% of the specified numerical value, or a wider range.
  • the terms "optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes both the occurrence and the non-occurrence of the event or circumstance, and includes further that the content described later is arbitrarily selected. For example, it means that a component can be optionally present, when the content of a certain ingredient is 0%-5% herein, that is, it covers the absence (0%) and the presence (>0-5%).
  • one or more refers to one, two, three, four, five, six, seven, eight, nine or more.
  • the present invention relates to a system for impregnating fibers.
  • the system can be used in the polyurethane pultrusion process.
  • the system for impregnating fibers comprises an injection box.
  • the injection box is provided with a cavity for the fiber material to pass through.
  • the cavity has an inlet and an outlet.
  • the fiber material passes through the cavity via the inlet and the outlet thereof.
  • the inlet and the outlet of the cavity may also be referred to as the inlet of the injection box and the outlet of the injection box, respectively.
  • the lower wall section of the inner wall of the cavity may have one or more slopes.
  • the slope may also be referred to as the inclination. In this context, it refers to the inclination degree of a certain part of the lower wall section of the inner wall of the cavity with respect to the horizontal plane.
  • the slope is set so that the lower wall section of the cavity is inclined up towards the inlet (for example, see Fig. 1 and Fig. 2).
  • the inclination can also be represented by the included angle a between the corresponding lower wall section of the cavity and the central axis of the injection box.
  • the central axis of the injection box is set to be parallel to the horizontal plane, so the included angle a can also refer to the included angle between the lower wall section and the horizontal plane.
  • the included angle a refers to the included angle between the lower wall section of the cavity and the horizontal plane in the longitudinal section. See, for example, Fig. lb and Fig. 1c.
  • the angle formed between the straight line where the lower wall section is located and the horizontal plane (in the longitudinal section of the injection box) is usually is an acute angle.
  • the included angle a is a positive value, such as I °, 5 °, etc.
  • the angle a is negative.
  • the included angle a is 0.
  • the included angle a is advantageously a positive value. The specific description can be found below.
  • the included angle a must be set so that the height of the lower edge of the inlet of the cavity is not lower (preferably higher) than that of the upper and/or lower edge of the outlet, for example, not lower (preferably higher) than that of the lower edge of the outlet.
  • the included angle a should advantageously be greater than or equal to 0°.
  • the polyurethane material may, for example, overflow from the inlet of the cavity.
  • the included angle a is too large, such as more than 5°, the included angle between the lower wall of the cavity and the central axis/horizontal plane will be too large, and the accumulation of polyurethane material occurs easily between the various slopes of the lower wall, or between the lower wall and the inlet of the mold, or between the lower wall and the transition section.
  • the materials may be gelated and even cured, if they cannot be removed as soon as possible, and it may cause peeling on the product or the mold may be even blocked, so that normal pultrusion production cannot be continued.
  • the included angle a is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°, preferably 1° or 1.8°.
  • the lower wall section of the inner wall of the cavity in the injection box of the present application may include one or more slopes, such as a first slope, a second slope, a third slope, and the like.
  • the included angle a corresponding to the slopes can be expressed as included angle al, a2, a3, and so on. It should be understood that the selection of each a is as described above. It should be understood that the expressions "first, second, third, etc.” used herein are only used for distinction, and the indicated parts may be the same or different. When there is only one slope, the included angle a corresponds to the included angle al.
  • the sequence of the signs "first" and "second” refers to the distribution from the inlet to the outlet of the cavity. For example, the slope close to the inlet is the first slope, then the second slope, the third slope, and so on. The later signs are closer to the outlet.
  • each corresponding included angle a should meet the above requirements, when more than one slope is provided in the cavity.
  • the lower wall section of the inner wall of the cavity includes a first slope, and the included angle al is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°, preferably 1° or 1.8°.
  • the lower wall section of the inner wall of the cavity includes further a second slope, and the included angle al is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°. In a preferred embodiment, al>a2.
  • the lower wall section of the inner wall of the cavity includes further a third slope, and the included angle a3 is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°.
  • the multiple slopes are continuous, so that the lower wall of the cavity can form a certain arc, wherein the included angle a corresponding to each slope satisfies the requirements described above.
  • the lower wall section of the inner wall of the cavity has a first slope.
  • the first slope may be distributed from the inlet and may occupy, for example, a major portion of the cavity, such as, 80% or more, 85% or more, 90% or more, 95% or more.
  • the first slope may occupy the entire length of the cavity, such that there is only one slope in the entire cavity. In these cases, the cavity has a substantially flat lower wall.
  • the included angle a (or al) of the first slope is as described above.
  • the lower wall section of the inner wall of the cavity may also have a second slope, which still causes the corresponding lower wall section of the cavity to be inclined up towards the inlet.
  • the included angle a (or a2) of the second slope is as described above.
  • the second slope is different from the first slope, and preferably, the lower wall section corresponding to the second slope is gentler than the lower wall section corresponding to the first slope, that is, al>a2. See, for example, the corresponding part in Fig. 1c.
  • the second slope can be distributed from the outlet and can occupy a minor part of the cavity, such as, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 5% or less.
  • the lower wall section of the inner wall of the cavity may also have a third slope, which still causes the corresponding lower wall section of the cavity to be inclined up towards the inlet.
  • the included angle a (or a3) of the third slope is as described above.
  • the third slope is different from the second slope, and preferably, the lower wall section corresponding to the third slope is gentler than the lower wall section corresponding to the second slope, that is, a2>a3.
  • the lower wall section close to the outlet of the injection box has a nearhorizontal slope (such as the second slope, the third slope, etc.), and the corresponding included angle a is about 0°, for example, 0.1°, 0.2°, etc.
  • a nearhorizontal slope such as the second slope, the third slope, etc.
  • Such setting is beneficial to increasing the stability of the fiber material infiltrated with the polyurethane material at the outlet, and to improving the flatness and uniformity of the obtained composites.
  • the lower wall section and the corresponding upper wall section can form a cavity (as shown in longitudinal section), through which the fiber material passes. Similar to the included angle a between the lower wall section corresponding to the slope and the central axis of the injection box, the corresponding upper wall section and the central axis (horizontal plane) of the injection box can form an included angle , so that the upper wall section has also one or more slopes.
  • the angle P is defined in a similar way to the angle a.
  • the upper wall section corresponding to different slopes may also have different included angles , such as pi, P2, P3, and so on.
  • the included angle P should advantageously be larger than the corresponding included angle a.
  • the difference between the included angle P and the corresponding included angle a is in a range of 1-5°, such as 1°, 1.5°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5° etc.
  • the existence of the included angle P and the setting of the included angle P greater than the corresponding included angle a can make the sectional area of the cavity in the injection box decreasing in the direction from the inlet to the outlet. Therefore, in an embodiment of the present invention, the sectional area of the cavity in the injection box decreases in the direction from the inlet to the outlet.
  • Such setting is conducive to balancing the injection pressure in the cavity of the injection box, so that the injection pressure is more uniform, and is conducive to fully and uniformly infiltrating the fiber material.
  • the sectional area (Tl) of the inlet to the sectional area (T2) of the outlet of the cavity have a ratio (T1/T2) of 2: 1-10: 1, preferably 4: 1-8: 1, such as 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, etc.
  • T1/T2 is too small, it is not conducive to fully infiltrating the fiber material, which may result in insufficient amount of polyurethane in the obtained composites, resulting in the decrease in the performance of the composites.
  • T1/T2 is too large, the polyurethane material in the cavity cannot be easily taken away by the fiber material in time, and the residue of polyurethane material is prone to occur.
  • the mold may be easily blocked due to the gelation and curing of the polyurethane material, which is not conducive to the continuity of the pultrusion process.
  • the shape of the section of the cavity In the system for impregnating fibers of the present invention, there is no special requirement on the shape of the section of the cavity. For example, it can be in a shape of a circle, an ellipse, a rectangle, a rounded rectangle and the like. These shape may be symmetrical in section (see, for example, Fig. la). It can be chosen by those skilled in the art according to actual needs, such as the shape and properties of the polyurethane pultruded composites to be produced and the properties of the polyurethane materials used.
  • the section refers to the section traversing the direction from the inlet to the outlet (and vice versa) .
  • the length of the injection box used in the system for impregnating fibers of the present invention may be 300 mm- 1000 mm, preferably 400-650 mm, such as 600 mm.
  • the length refers to the projected length of the cavity of the injection box on the horizontal axis. When the length is too small, it is not conducive to balancing the injection pressure in the cavity of the injection box, and it is also prone to poor infiltration of the fiber material. When the length is too large, there are higher requirements on the operating time of the resin itself.
  • the injection box of the present invention may further comprise one or more injection orifices.
  • the polyurethane material is injected into the cavity, so that it fully impregnates the fiber material.
  • the injection orifices can be communicated with the inner wall of the cavity for the injection of the polyurethane material.
  • the polyurethane material can also be injected through the inlet of the cavity. In such a case, there is no need to provide an additional injection orifice.
  • the injection box includes a plurality of detachable modules, wherein the cavities inside the plurality of modules are connected successively to form the cavity of the injection box.
  • the plurality of modules can be integrally formed, or can be connected and fixed by positioning devices (for example, positioning pins, concave-convex tables, sliding grooves, etc.). They can also be locked by a quick locking device, so that the modules can be quickly separated after locking.
  • the outlet of the injection box cavity of the present invention can be directly or indirectly connected with the inlet of the mold.
  • the outlet of the injection box cavity can also be indirectly connected to the inlet of the mold in the following way, wherein a transition section can be provided between the inlet of the mold and the outlet of the injection box cavity and used to connect the inlet of the mold and the outlet of the injection box cavity (see, for example, Fig. lb).
  • the section of the transition section can be in a shape of a circle, an ellipse, a rectangle, a rounded rectangle, and the like. It can be chosen by those skilled in the art according to actual needs, such as the shape and properties of the polyurethane pultruded composites to be produced and the properties of the polyurethane materials used.
  • the sectional area of the transition section decreases in the direction from the inlet to the outlet.
  • the sectional area of the transition section outlet is greater than or equal to the sectional area of the inlet of the mold.
  • the ratio of the sectional areas of the inlet to the outlet of the injection box cavity is greater than or equal to the ratio of the inlet to the outlet of the transition section.
  • the length of the transition section can be set as desired.
  • the length of the transition section may be 0. 1-100 mm, preferably 10-100 mm.
  • the length refers to the projected length of the transition segment on the horizontal axis.
  • transition section and parameters thereof helps to improve the infiltration of the fiber material with the polyurethane material, and at the same time increases the flatness of the surface of the fiber material entering the mold, and also helps to prevent the fiber material from breaking due to excessive tension.
  • the whole or part of the injection box may be integrally formed with the mold.
  • the whole or part of the injection box can be integrally formed with the transition section.
  • the whole or part of the injection box can also be integrally formed with the transition section and the mold.
  • the injection box and the mold, or the injection box, the mold and the transition section can be connected and fixed by positioning devices (for example, positioning pins, concave-convex tables, sliding grooves, etc.). They can also be locked by a quick locking device, so that the parts can be quickly separated after locking.
  • positioning devices for example, positioning pins, concave-convex tables, sliding grooves, etc.
  • a sealing device can be provided between the separable structures (for example, between different modules of the injection box, between the injection box and the mold, between the injection box and the transition section, between the transition section and the mold) to ensure sealing.
  • Fig. 1 shows one embodiment of the system for impregnating fibers of the present invention.
  • Fig. la is a schematic view of the sectional structure thereof, showing the section of the injection box (101) and the inlet (102).
  • Fig. lb is a schematic view of the longitudinal sectional structure.
  • the system for impregnating fibers includes an injection box (101), the size of which is related to the profile specification of the composites to be produced.
  • the length of the injection box can be adjusted according to needs, for example, can be about 300-1100 mm; preferably about 400-750 mm.
  • the injection box is provided with a cavity for the fiber material to pass through, the cavity having an inlet (102) and an outlet (103), and the lower inner wall (107) of the cavity having an upward slope with respect to the central axis of the injection box.
  • the lower wall (107) forms an included angle a with the central axis/horizontal plane.
  • the upper wall (106) forms an included angle with the central axis/horizontal plane.
  • the length of the cavity of the injection box can be 300 mm- 1000 mm, preferably 400-650 mm (the length being the projected length of the distance between the inlet and the outlet on the horizontal plane).
  • the sectional area of the cavity decreases in the direction from the inlet to the outlet, and the sectional area of the inlet (102) is larger than the sectional area of the outlet (103).
  • the included angle a is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°, preferably 1° or 1.8°.
  • the system for impregnating fibers may further include a transition section (104).
  • the outlet (103) of the injection box cavity is connected with the inlet of the transition section (104) to form a channel.
  • the injection box is connected to the mold (105) through a transition section.
  • the length of the transition section may be 0.1-100 mm, preferably 10-100 mm.
  • the sectional area of the outlet of the transition section is greater than or equal to the sectional area of the inlet of the mold.
  • the ratio of the sectional areas of the inlet to the outlet of the injection box cavity is greater than or equal to the ratio of the inlet to the outlet of the transition section.
  • the injection box may also include one or more injection orifices (108).
  • Fig. 1c is a schematic longitudinal sectional view of another embodiment, showing the portion from the inlet (102) to the outlet (103) of the cavity.
  • a first slope, a second slope and a third slope are sequentially arranged in the cavity from the inlet to the outlet, corresponding to the included angles al, pi, a2, 2, and a3, 3, respectively.
  • the included angle a corresponding to the slope closest to the outlet (103) is relatively small, and may be about 0°, for example, 0.1°, 0.2°.
  • the second slope and the third slope actually constitute one slope, which can also be called the second slope (corresponding to a2) in this case.
  • the first slope (al) the first slope (al).
  • Fig. 2 is a schematic view of a longitudinal sectional structure of one embodiment of the system for impregnating fibers of the present invention.
  • the system for impregnating fibers includes an injection box, the cavity of the injection box being provided with a slope, and the lower wall of the cavity being inclined downward in the direction from the inlet to the outlet.
  • the included angle a between the lower wall of the cavity and the central axis of the injection box is in a range of 0-5°, such as 0.1°, 0.5°, 1°, 1.5°, 1.8°, 2°, 2.5°, 3°, 3.5°, 4°, 4.5° or 5°, preferably 1° or 1.8°.
  • the sectional area of the injection box cavity decreases in the direction from the inlet to the outlet.
  • the ratio (T1/T2) of the sectional area (Tl) of the inlet to the sectional area (T2) of the outlet (T1/T2) of the injection box cavity is 2: 1-10: 1, preferably 4: 1-8: 1, such as 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, etc.
  • the outlet of the injection box is connected to the inlet of the mold.
  • a transition section (not shown) may also be included between the injection box and the mold.
  • the present invention also relates to a pultrusion method for producing polyurethane pultruded composites, comprising the steps of: providing the polyurethane material, passing the fiber material through the cavity of the injection box, injecting the polyurethane material into the cavity, thereby impregnating the fiber material, curing the impregnated fiber material, thereby obtaining the polyurethane pultruded composites.
  • the polyurethane material of the present invention includes an isocyanate-reactive component and an isocyanate component.
  • the polyurethane material has a gel time of 5-49 minutes at 25°C.
  • the polyurethane material has a curing time of 15-90 seconds at 150-220°C. Having a suitable gel time and curing time is favorable for use in the polyurethane pultrusion process of the present invention, and obtaining composites with good performance.
  • gel time in the present invention refers to the time from when the isocyanate component and the isocyanate-reactive component in the polyurethane material begin to mix until the viscosity reaches a certain value (for example, about 10000 mPa.s).
  • the gel time here can be the time measured by using a gel tester, such as the "Hot Pot” Gel Timer from Gardco (GT-STHP-220).
  • the polyurethane material of the present invention has a relative short curing time and a relative long gel time, and can be better and more flexibly (for example, infiltrating and molding for a longer time) suitable for producing polyurethane pultruded composites, especially large-scale polyurethane pultruded composites.
  • the fiber material can be infiltrated and molded better for a longer time, while at high temperature, such as after entering the mold, it can be cured faster.
  • the isocyanate component of the present invention comprises at least one polyisocyanate.
  • the polyisocyanate can be any aliphatic, cycloaliphatic or aromatic polyisocyanate known to be used in the preparation of polyurethanes. Examples include, but are not limited to: toluene diisocyanate (HTDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate (pMDI), 1,5 -naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), methylcyclohexyl diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p- phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI),
  • the isocyanate-reactive component may contain polyols known to be used for reaction with isocyanate components for preparing polyurethanes. Examples include, but are not limited to, polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, polymer polyols, vegetable oil based polyols, or combinations thereof.
  • polyether polyols can be prepared by known processes, e.g., by reacting olefin oxides with starters in the presence of a catalyst.
  • Polyether carbonate polyols can also be used in the present invention, and can be prepared, for example, by adding carbon dioxide and alkylene oxides onto active hydrogen-containing starters using a double metal cyanide catalyst.
  • polyester polyols may be prepared by reacting dicarboxylic acids or dicarboxylic acid anhydrides with polyols.
  • the polyurethane material of the present invention may also comprise one or more compounds having the structure of formula (I)
  • Ri is selected from hydrogen, methyl or ethyl
  • R2 is selected from alkylene groups having 2- 6 carbon atoms
  • n is an integer selected from 1-6.
  • R2 is selected from ethylene, propylene, butylene, pentylene, 1 -methyl- 1,2-ethylene, 2- methyl-l,2-ethylene, 1 -ethyl- 1,2-ethylene, 2 -ethyl- 1,2-ethylene, l-methyl-l,3-propylene, 2-methyl- 1,3 -propylene, 3-methyl-l,3-propylene, l-ethyl-l,3-propylene, 2-ethyl-l,3-propylene, 3-ethyl-l,3- propylene, 1 -methyl- 1,4-butylene, 2-methyl-l,4-butylene, 3 -methyl- 1,4-butylene and 4-methyl-l,4- butylene, 2,2-propylene-bis(4-phenylene), 1,4-xylylene, 1,3-xylylene, 1,2-xylylene.
  • the compounds of formula (I) is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or combinations thereof.
  • the compounds of formula (I) can be prepared by methods commonly used in the art, for example, by reacting (meth)acrylic anhydride or (meth)acrylic acid, (meth)acryloyl halide and H0-(R20) n -H by esterification. Those skilled in the art are familiar with the preparation method, for example, see CN 104974502A .
  • the polyurethane material may also contain a free radical reaction initiator.
  • the free radical initiator used can be added to the polyol component or the isocyanate component or to both components. Specifically, it may include tert-butylperoxy isopropyl carbonate, tert-butylperoxy- 3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide, and the like.
  • the isocyanate component and the isocyanate-reactive component can adjust the properties and amounts of the isocyanate component and the isocyanate-reactive component as required, such as the molecular weight, functionality, viscosity, hydroxyl value, end-capping, amount used, etc., so that the properties of the prepared polyurethanes can be adjusted, and can make them well matched with the fiber material, thereby obtaining polyurethane pultruded composites with good properties.
  • the reaction between the isocyanate component and the isocyanate-reactive component is namely the addition polymerization of isocyanate groups with hydroxyl groups.
  • the isocyanate groups may include those in the (A) isocyanate component, or may also include those in the intermediates of the reaction of the (A) isocyanate component and the (B) isocyanate-reactive component.
  • the hydroxyl groups may be those contained in the (B) isocyanate-reactive component, or may be those contained in the intermediates of the reaction of the (A) isocyanate component and the (B) isocyanate-reactive component.
  • the polyurethane material of the present invention may also contain additives, which are used to make the preparation process of polyurethanes and the production process of composites have desired properties, such as suitable reaction rate, good infiltration, fluidity, mold release and the like.
  • Additives include, but are not limited to, release agents, initiators, catalysts, cross-linking agents, and the like.
  • Fiber material of the present invention may include, but are not limited to, glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, crystal whiskers, metal fibers or combinations thereof, preferably glass fibers, carbon fibers.
  • the form of the fiber material can be selected according to the requirements, so that the composites have suitable strength and good infiltration effect, examples of which include, but are not limited to: rovings, felts, fabrics, and the like.
  • the fiber material may be partially or fully attached with a peel ply.
  • the peel ply can be attached to the side of the fiber material close to the upper wall of the cavity, or attached to the side of the fiber material close to the lower wall of the cavity, or attached to both sides of the fiber material.
  • the fiber material passes through a preforming frame into the injection box.
  • the fiber material or the fiber material and the attached peel ply
  • the fiber material is drawn to full smoothness by means of a drawing device. It is beneficial to improve the flatness, strength and other properties of composites.
  • the polyurethane material can be injected into the cavity through the injection port, thereby impregnating the fiber material.
  • the components contained in the polyurethane material can be mixed in a certain mixing ratio by a mixing device and then injected into the cavity of the injection box.
  • the components contained in the polyurethane material are pumped continuously to a static mixing head according to a prescribed mixing ratio by an injection machine, and is injected into the cavity of the injection box after being mixed by the mixing head.
  • the injection pressure in the injection box can be controlled within a suitable range to ensure that the fiber material is fully impregnated and, at the same time, the overflowing of the polyurethane material from the inlet of the cavity is prevented.
  • the injection pressure in the injection box may be about 0.1-30 bar, preferably about 0.1-15 bar.
  • the impregnating time of the fiber material should be such that the fiber material is fully infiltrated with the polyurethane material to obtain good infiltration effect. If the impregnating time is too long, the infiltration effect will be poor. If the impregnating time is too long, for example, much longer than the gel time of the polyurethane material, it may cause the residue of polyurethane material in the cavity or even blockage.
  • the system of the present invention may further comprise heating means, cooling means and/or drying means to heat, cool and dry the material as required.
  • the curing process of the impregnated fiber material can take place in a mold.
  • the mold may be provided with heating means.
  • the curing time and temperature should be adjusted according to the polyurethane material and fiber material used, so that the curing is sufficient while the production efficiency is improved.
  • the impregnated fiber material can be continuously drawn through the mold at a certain speed by the drawing device, and the impregnated fiber material is cured during the process of passing through the mold.
  • the drawing device draws the impregnated fiber material at a speed of 0.1-2 m/min, preferably 0.4-1 m/min, for example 0.6 m/min.
  • the curing time is 15-90 s, preferably 20-80 s.
  • the curing temperature is 140-220°C, preferably 150-200°C, more preferably 160-170°C.
  • the composites can be cut by a cutting device according to the requirement on the length thereof.
  • the composites can be wound into rolls for convenience of transportation, storage and use.
  • the humidity of the environment can be controlled.
  • the relative humidity of the environment around the fiber material can be controlled by a dehumidifier within 60% , preferably within 40%, to reduce the impact of moisture on the quality of composites.
  • the production method of the present invention may also optionally include a drying step.
  • Polyurethane pultruded composites can be produced simply and efficiently, and blisters on the surface can be greatly reduced or even eliminated.
  • the drying step can be realized by a drying device, so that the fiber material can be better infiltrated in a relative short time, especially the fiber material with a certain thickness.
  • Polyurethane pultruded composites with excellent quality can be obtained with surface having a certain roughness and with surface having no blisters. Thus, waste can be avoided, resources can be saved, and production efficiency can be improved.
  • Fig. 3 shows a schematic view of the method for producing polyurethane pultruded composites incorporating the system for impregnating fibers of the present invention.
  • the present invention also includes a polyurethane pultruded composite produced by the method of the present invention.
  • the polyurethane pultruded composite includes cable trays, curtain wall frames for doors and windows, ladder frames, tent poles or pipes, anti-glare panels, floors, sucker rods, telegraph poles and cross arms, guardrails, grilles, profiles for buildings, container profiles and plates, bicycle racks, fishing rods, cable cores, insulator mandrels, radomes, single or sandwich continuous plates or plates for producing main beams of turbine blades, motor vehicle fenders, motor vehicle lamp shades, motor vehicle dashboards, motor vehicle hard roofs, motor vehicle doors, motor vehicle skeletons, motor vehicle body shells, motor vehicle radiator grilles, motor vehicle headlight reflectors, motor vehicle front end brackets, motor vehicle floors, motor vehicle seat frames, motor vehicle air deflectors, motor vehicle radiator masks or brackets, motor vehicle guard plates, motor vehicle cross beams, motor vehicle spoilers, motor vehicle sunshades, front and rear bumpers of motor vehicles, motor vehicle engine hoods, motor vehicle trim panels, rear liftgates of motor vehicle
  • the injection box adopts a special design, especially the design of the included angles, which can greatly reduce the overflow of the polyurethane material from the inlet of the injection box cavity.
  • material waste is avoided, and on the other hand, the infiltration of the fibers in the resin can be improved.
  • undesired residue or curing of the polyurethane material in the injection box can be avoided with the design of the system for impregnating fibers of the present invention, so that the flow process and the processing can be realized, and the production efficiency can be greatly improved.
  • test methods without indicated specific conditions are usually carried out in accordance with conventional conditions or in accordance with the conditions suggested by the manufacturer. All percentages and parts are by weight, unless otherwise indicated.
  • Isocyanate component Isocyanate, Desmodur 44CP24 as the trade mark, purchased from Covestro Polymers (China) Co., Ltd.;
  • Isocyanate-reactive component polyol combination, a combination of polyols having the trade mark of Baydur 18BD251 and of Baydur 18BD252 with the weight ratio of Baydur 18BD251 and Baydur 18BD252 of 100:4, all purchased from Covestro Polymers (China) Co., Ltd.;
  • Baydur 18BD252 as the trade mark, purchased from Covestro Polymers (China) Co., Ltd.;
  • Carbon fiber roving TRW 40/50L. A3750 tex as the trade mark, purchased from Mitsubishi Pyrofil TOW;
  • Pultrusion equipment crawler pultrusion machine for composites, purchased from Nanjing Nuoertai Composite Materials Equipment Co., Ltd.;
  • Injection machine Hydraulic Mini Link System, purchased from Magnum Venus Products.
  • the production process of fiber-reinforced polyurethane pultruded sheets is taken as an example for producing a flat plate with a thickness of 5 mm and a width of 105 mm.
  • a certain amount of fiber material 1 is firstly drawn from the creel, passes through the yam guide plate 2, the injection box 4, and the mold 5, and is then drawn forward by the drawing device 6 until the fiber material is all smooth.
  • the heating device of mold 5 is turned on, and the mold temperature is controlled from the inlet to the outlet as follows: 80°C, 170°C, 160°C. After the temperature is stable, the injection machine is turned on.
  • the isocyanate component and the polyol combination (100 parts of Baydur 18BD251 and 4 parts of Baydur 18BD252) are continuously pumped to the static mixing head according to the specified mixing ratio. After being mixed by the mixing head, it is injected into the injection box 4 through the injection orifice.
  • the polyurethane material is controlled not to overflow from the inlet, while the fiber material 1 can be fully impregnated.
  • the injection pressure in the injection box 4 is controlled at 0.1-15 bar.
  • the fiber material 1 fully impregnated in the injection box 4 is continuously drawn through the mold 5 by the drawing device 6 at a speed of 0.6 m/min, and then cut off after exiting the mold, so that a composite plate of a certain length (specification: thickness of 5 mm, width of 105 mm) is obtained.
  • the surface thereof is smooth without dry yam and without blister. Then, it is wound into rolls for later use.
  • the comparative example 1 was obtained with reference to the production method described above.
  • the fiber material 1 was glass fiber yam
  • the injection box 4 was a conventional injection box as shown in Fig. 4.
  • the cavity of the injection box had a symmetrical taper with respect to the central axis of the pultrusion direction, i.e. there were taper angles both upward and downward.
  • the comparative example 2 was obtained with reference to the production method described above.
  • the fiber material 1 was carbon fiber yam
  • the injection box 4 was a conventional injection box as shown in Fig. 4.
  • the example 1 was obtained with reference to the production method described above.
  • the fiber material 1 was glass fiber yam
  • the injection box 4 was the injection box of the present invention shown in Fig. 1.
  • the length of the injection box was 600 mm
  • the inclination degree (a) was 1.8°
  • Example 2 The example 2 was obtained with reference to the production method described above.
  • the fiber material 1 was carbon fiber yam, and the setting of the injection box 4 referred to that in Example 1.
  • Example 1-2 During the production process of Example 1-2, the polyurethane material did not or almost did not overflow from the inlet of the injection box cavity, thereby realizing the continuous pultrusion. Moreover, there was no residue of polyurethane material in the cavity of the injection box. The infiltration effect on the fiber material was good. A polyurethane composite plate with good infiltration was obtained.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un système d'imprégnation de fibres pour un procédé de pultrusion de polyuréthane, le système d'imprégnation de fibres comprenant une boîte d'injection (101), la boîte d'injection (101) ayant une cavité pour le passage du matériau fibreux, et la cavité ayant une entrée (102) et une sortie (103), la section de paroi inférieure (107) de la paroi interne de la cavité comprenant une ou plusieurs pentes, le bord inférieur de l'entrée de la cavité n'étant pas inférieur au bord inférieur de la sortie (103) de la cavité, et la pente la plus proche de l'entrée amenant l'entrée (102) de la cavité à s'incliner vers le bas vers la sortie (103).
PCT/EP2023/074825 2022-09-15 2023-09-11 Système d'imprégnation de fibres pour la production de composites pultrudés de polyuréthane et son procédé d'utilisation WO2024056562A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202211125775.2 2022-09-15
CN202211125775.2A CN117734203A (zh) 2022-09-15 2022-09-15 用于生产聚氨酯拉挤复合材料的纤维浸渍系统及其使用方法
EP22205307.6A EP4364932A1 (fr) 2022-11-03 2022-11-03 Système d'imprégnation de fibres pour la production de composites pultrudés en polyuréthane, son procédé d'utilisation et composite pultrudé en polyuréthane
EP22205307.6 2022-11-03

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336738A2 (fr) * 1988-04-06 1989-10-11 BICC Public Limited Company Fabrication d'un tube flexible, avec circonférence rigide pour un câble optique
EP0384063A2 (fr) * 1989-01-30 1990-08-29 Edison Polymer Innovation Corporation ( Epic) Procédé de fabrication de matériaux composites
EP0513927A1 (fr) * 1991-05-16 1992-11-19 Shell Internationale Researchmaatschappij B.V. Imprégnation de fibres avec de la résine
CN104974502A (zh) 2014-04-10 2015-10-14 拜耳材料科技(中国)有限公司 聚氨酯复合材料及其制备方法
CN106515047A (zh) 2016-11-02 2017-03-22 北京化工大学 一种反应注射拉挤成型设备及反应注射拉挤成型方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336738A2 (fr) * 1988-04-06 1989-10-11 BICC Public Limited Company Fabrication d'un tube flexible, avec circonférence rigide pour un câble optique
EP0384063A2 (fr) * 1989-01-30 1990-08-29 Edison Polymer Innovation Corporation ( Epic) Procédé de fabrication de matériaux composites
EP0513927A1 (fr) * 1991-05-16 1992-11-19 Shell Internationale Researchmaatschappij B.V. Imprégnation de fibres avec de la résine
CN104974502A (zh) 2014-04-10 2015-10-14 拜耳材料科技(中国)有限公司 聚氨酯复合材料及其制备方法
CN106515047A (zh) 2016-11-02 2017-03-22 北京化工大学 一种反应注射拉挤成型设备及反应注射拉挤成型方法

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