WO2022223467A1 - Procédé de préparation d'un composite de polyuréthane pultrudé - Google Patents

Procédé de préparation d'un composite de polyuréthane pultrudé Download PDF

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Publication number
WO2022223467A1
WO2022223467A1 PCT/EP2022/060120 EP2022060120W WO2022223467A1 WO 2022223467 A1 WO2022223467 A1 WO 2022223467A1 EP 2022060120 W EP2022060120 W EP 2022060120W WO 2022223467 A1 WO2022223467 A1 WO 2022223467A1
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WO
WIPO (PCT)
Prior art keywords
liquid level
resin
level information
fiber
infiltration box
Prior art date
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PCT/EP2022/060120
Other languages
English (en)
Inventor
Yongming GU
Zhijiang Li
Hao Cheng
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 CN202110438963.XA external-priority patent/CN115230197A/zh
Priority claimed from EP21182668.0A external-priority patent/EP4112262A1/fr
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2022223467A1 publication Critical patent/WO2022223467A1/fr

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Classifications

    • 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
    • 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
    • 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 the field of the polyurethane pultrusion process. Specifically, the present invention relates to a process and an apparatus for preparing a pultruded polyurethane composite with an automatic control method.
  • the traditional pultrusion process mainly adopts an open-bath, namely, fibers, fabrics or felts pass through a resin-bath with a compression roller or a compression bar, the fibers with resin are stepwisely extruded by a preformed plate and then enter a heated mold, and are finally solidified and shaped.
  • an open-bath namely, fibers, fabrics or felts pass through a resin-bath with a compression roller or a compression bar
  • the fibers with resin are stepwisely extruded by a preformed plate and then enter a heated mold, and are finally solidified and shaped.
  • There are some problems for the traditional open-bath process for example, a high VOC volatilization, a higher resin waste rate, and a high porosity content of the finished product, and the resin system with a short gelation time is not applicable to this process too.
  • the time required for the shutdown and the product specification replacement is relatively long and the cost is relatively high.
  • One process is based on a low-pressure resin-injection mode, there are usually one or more tapering degrees inside this resin-injection box, its resin-injection holes are generally located on the upper and lower of the injection box.
  • the resin is injected into the - injection box by means of an injection machine to infiltrate the unidirectional rovings.
  • This type of the injection box is suitable for the all rovings pultrusion.
  • the other process is based on a high-pressure injection box, its injection holes are generally located on the upper and lower of the injection box, and this type of the injection box is suitable for plies with porous structures such as felt or fabric.
  • the amount of the resin in the above-mentioned infiltration device is generally controlled by manually observing whether the resin is leaking at the inlet of the injection box.
  • the problems of the continuous resin exposure to waste the resin or the poor infiltration due to too little resin in the injection box often occur.
  • the pultrusion production speed may change in real time. If the process parameter is not adjusted in time, it is very easy to cause the resin waste or the poor infiltration, thereby affecting the production.
  • CN109986810A discloses a centralized feeding device and a composite pultrusion apparatus comprising the same.
  • the centralized feeding device comprises at least one group of centralized feeding assembly, each group of the centralized feeding assembly is used for providing a material for a pultrusion traction device, and each group of the centralized feeding assembly comprises a material storage barrel used for storing materials to be transported; a temporary storage barrel that is connected with the material storage barrel through transportation pipelines and used for temporarily storing materials to be injected; a material injection assembly and the like.
  • the automatic production apparatus comprises a fiber yarn storage device, which is used for storing the fiber yarn; a fiber yarn guiding device, which is used for guiding the fiber yarns guided out by the fiber yarn storage device; a pultrusion mold device, which is used for achieving the heating and shaping of the sectional material; an injection device, which is used for injecting materials into the injection material box and/or the pultrusion mold; a clamping traction device, which is used for realizing the clamping traction of the sectional material; a dust collection and cutting device, which is used for achieving the dust collection and the cutting of the sectional material; and a central control device, which is used for realizing the automatic control of the aforementioned devices.
  • WO 2012/139582 discloses a pultrusion apparatus comprising a controller for collecting data related to the amount of resin within an injection box, at least one pump capable of adjusting the amount of resin supplied to said injection box, and thereby facilitating that the at least one pump is configured to be controlled on the basis of said data from said controller, thereby adjusting the supply of resin to said injection box accordingly. Acquisition of information on the amount of resin within the injection box takes place at a single position.
  • CN 109605781 discloses an open bath pultrusion process for epoxy resin based wind power blades.
  • One aspect of the present invention is to provide an automatic control method for preparing a pultruded polyurethane composite, comprising: Injecting a polyurethane composition into an infiltration box (5) with a resin-injection system (30) to form a liquid level;
  • said liquid level information comprises the liquid level information at two or more than two different acquiring positions.
  • the infiltration box is a closed infiltration box.
  • a closed infiltration box is a box with a bottom part connected to a top part such that the majority of the box’ interior is closed, i.e., roofed over by the top part.
  • the interior of a closed infiltration box is thus not available for visual inspection, in contrast to an open bath which is used in an open bath pultrusion process.
  • Said process parameter preferably comprises resin-injection velocity, resin-injection amount, formula, temperature and the like, preferably resin-injection velocity or resin-injection amount.
  • Said resin-injection velocity refers to a velocity at which the polyurethane composition is injected, for example, 30 grams per minute (g/min).
  • Said resin-injection amount refers to the amount of the polyurethane composition injected, for example, in volume or in weight.
  • the liquid level information at two or more than two different positions is acquired simultaneously.
  • the positions for acquiring said liquid level information are the acquiring position 1 (2) and the acquiring position 2 (4).
  • said infiltration box (5) comprises an inlet (5a) and an outlet (5b), the straight-line distance between said acquiring position 1 (2) and said inlet (5a) is 0-100 mm, the straight-line distance between said acquiring position 2 (4) and said inlet (5a) is 110-300 mm, preferably 120- 250 mm, more preferably 130-200 mm.
  • the method also comprises: pre-storing a plurality of correspondences between historical liquid level information and historical process parameter, and adjusting the process parameter according to the acquired liquid level information and said correspondence between historical liquid level information and historical process parameter.
  • the length of said infiltration box (5) is 300-800 mm, preferably 350-700 mm, more preferably 400-650 mm.
  • said liquid level information is acquired from at least one sensor, preferably acquired from two sensors.
  • said sensor is selected from a contact sensor, an infrared sensor, an ultrasonic sensor or a combination thereof.
  • a process for preparing the pultruded polyurethane composite comprising said automatic control method for preparing the pultruded polyurethane composite, compared to a process for preparing the pultruded polyurethane composite not comprising said automatic control method for preparing the pultruded polyurethane composite, has a reduction of >1%, preferably>2%, more preferably>3% in the used amount of the polyurethane composition.
  • the inlet (5a) and the outlet (5b) of said infiltration box (5) both comprise cross sections
  • the cross section area ratio of the inlet (5a) to the outlet (5b) of said infiltration box (5) is 2: 1-8:1, preferably 3: 1-8:1.
  • Ai:Ao is 2: 1-8: 1 , preferably 3 : 1 -8 : 1.
  • the method also comprises acquiring the temperature information in the infiltration box (5), and transmitting said temperature information to a resin-injection system (30) and/or a control system (40), and the resin-injection system (30) and/or the control system (40) adjusting the process parameter, preferably a resin-injection temperature, according to said temperature information.
  • the method also comprises:
  • said at least one peel ply (2a, 2b) is two pieces of the peel ply (2a, 2b), said two pieces of the peel ply (2a, 2b) are placed on two opposite inner sides (5i, 5j) of the infiltration box (5) respectively, and said fiber-reinforced material (1) is located between the two pieces of the peel ply (2a, 2b).
  • Said peel ply does not completely cover the fiber-reinforced material, but only partly covers the fiber-reinforced material.
  • the polyurethane composition contacts with the fiber-reinforced material through the part that is not covered by the peel ply, and infiltrates the fiber-reinforced material.
  • said at least one peel ply (2a, 2b) is two pieces of the peel ply (2a, 2b), said two pieces of the peel ply (2a, 2b) are placed on two opposite inner sides (5i, 5j) of the infiltration box (5) respectively, said fiber-reinforced material (1) is located between the two pieces of the peel ply (2a, 2b), said resin-injection system (30) comprises at least two resin- injection ports (4a, 4b), and said two resin-injection ports (4a, 4b) are located on two opposite sides (5m, 5n) of the infiltration box (5) where no peel ply is placed.
  • the method also comprises mixing the polyurethane composition by using an autometering and mixing device.
  • said polyurethane composition comprises the following components:
  • Component A comprising one or more organic polyisocyanates
  • Component B comprising:
  • Bl one or more organic polyols, wherein the content of said polyol is 21-60wt%, preferably 21- 40wt%, based on 100wt% of the total weight of said polyurethane composition;
  • Ri is selected from hydrogen, methyl or ethyl
  • R2 is selected from an alkylene group having 2-6 carbon atoms, 2,2-bis(4-phenylene)-propane, 1 ,4-bis(methylene)benzene, 1,3- bis(methylene)benzene, l,2-bis(methylene)benzene
  • n is an integral number selected from 1-6
  • Component C a free -radical initiator.
  • the organic polyol has a functionality of 1.7-6, preferably 1.9-4.5 and a hydroxyl value of 150-1100 mg KOH/g, preferably 150-550 mg KOH/g.
  • the component B2) is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or a combination thereof.
  • said polyurethane composition has the gelation time at 25 °C of 10-40 minutes, preferably 15-30 minutes, more preferably 16-28 minutes.
  • fiber-reinforced material means a fibrous material which is suitable for reinforcing another material such as a polyurethane.
  • said fiber-reinforced material (1) is selected from glass fiber, carbon fiber, polyester fiber, natural fiber, aromatic polyamide fiber, nylon fiber, basalt fiber, boron fiber, silicon carbide fiber, asbestos fiber, metal fiber or a combination thereof.
  • the method also comprises pulling the infiltrated fiber-reinforced material (1) through a mold (7), the velocity of said fiber-reinforced material (1) passing through the mold (7) is 0.2-2 m/min, preferably 0.2- 1.5 m/min, and said polyurethane composition is injected from a resin- injection system (30) into said infiltration box (5) at a velocity of 30-2000 g/min, preferably 40- 1500 g/min, more preferably 60-1200 g/min.
  • the step of acquiring liquid level information of the polyurethane composition in the infiltration box is performed two or more times, such as 6 to 180 times or 12 to 120 times, preferably at a frequency of up to 500 Hz.
  • the automatic control method for preparing the pultruded polyurethane composite of the present invention simply, efficiently and objectively realizes the collection, treatment and application of the process information such as the liquid level information, the temperature information and the like of a pultrusion production line, can ensure the good infiltration of a fiber-reinforced material, and simultaneously does not waste a polyurethane composition raw material, and is economical and environment-friendly.
  • the process for preparing the pultruded polyurethane composite of the present invention uses a continuous pultrusion process, in which the peel ply and the fiber-reinforced material are pulled to pass through the infiltration box at a certain velocity, the polyurethane composition is injected into the infiltration box through the resin-injection device to infiltrate said fiber-reinforced material, preferably, a polyurethane composition is injected via a part of the fiber-reinforced material (1) not covered by the peel ply and infiltrates said fiber-reinforced material (1).
  • the method of the present invention which includes the characteristics such as the peel ply, the proper resin-injection position, the infiltration method, the traction velocity, and the velocity of injecting the polyurethane composition, not only provides a high quality pultruded polyurethane composite having a satisfactory surface, but also improves the production efficiency and saves the cost.
  • Another aspect of the present invention is to provide a device for the automatic control method for preparing the pultruded polyurethane composite, comprising:
  • said at least one information-acquiring device (2, 4) is at least two information acquiring devices (2, 4), an information-acquiring device 1 (2) is placed above the infiltration box (5) and at a position having a straight-line distance from the inlet (5a) of said infiltration box (5) of 0-100 mm, and an information-acquiring device 2 (4) is placed above the infiltration box (5) and at a position having a straight-line distance from the inlet (5a) of said infiltration box (5) of 110-300 mm, preferably 120-250 mm, more preferably 130-200 mm.
  • it also comprises at least one temperature information acquiring device (6).
  • control system for receiving the information, processing the information and adjusting the process parameter.
  • said resin-injection system (30) comprises at least two resin-injection ports (4a, 4b) located at two opposite sides (5m, 5n, 5i, 5j) of the infiltration box (5).
  • said infiltration box (5) is a cuboid, and said resin-injection ports (4a, 4b) are located at two sides (5m, 5n) perpendicular to the travelling direction of the fiber-reinforced material (1).
  • the infiltration box is a closed infiltration box.
  • a closed infiltration box is a box with a bottom part connected to a top part such that the majority of the box’ interior is closed, i.e., roofed over by the top part.
  • the interior of a closed infiltration box is thus not available for visual inspection, in contrast to an open bath which is used in an open bath pultrusion process.
  • a process for preparing the pultruded polyurethane composite comprising the automatic control method for preparing the pultruded polyurethane composite as aforementioned in the present invention.
  • Said automatic control method for preparing the pultruded polyurethane composite comprises:
  • said liquid level information comprises the liquid level information at two or more than two different positions.
  • the positions for acquiring said liquid level information are the acquiring position 1 (2) and the acquiring position 2 (4), respectively.
  • said infiltration box (5) comprises an inlet (5a), the straight-line distance between said acquiring position 1 (2) and said inlet (5a) is 0-100 mm, the straight-line distance between said acquiring position 2 (4) and said inlet (5a) is 110-300 mm, preferably 120-250 mm, more preferably 130-200 mm.
  • said automatic control method also comprises: pre-storing a plurality of correspondences between historical liquid level information and historical process parameter, and adjusting the process parameter according to the acquired liquid level information and said correspondence between historical liquid level information and historical process parameter.
  • said process for preparing a pultruded polyurethane composite comprising the automatic control method compared to the process for preparing the pultruded polyurethane composite not comprising the automatic control method, has a reduction of > 1%, preferably> 2%, more preferably> 3% in the used amount of the polyurethane composition.
  • Said automatic control method is the automatic control method for preparing the pultruded polyurethane composite of the present invention.
  • a polyurethane product comprising the polyurethane composite of the present invention.
  • the polyurethane product is selected from: cable trays, frames of doors, windows and curtain walls, frames of ladders, tent poles or pipes, anti-glare shields, floors, sucker rods, telegraph poles and cross arms, guardrails, gratings, architectural sectional materials, container sectional materials and plates, bike racks, fishing rods, cable cores, insulator core rods, antenna housings, single-layer or sandwiched continuous plates or sheet materials for producing main spars of the turbine fan blade.
  • the process for preparing the pultruded polyurethane composite including the automatic control method of the present invention can economically, simply and efficiently prepare the pultruded polyurethane composite with the non-smooth or rough surface that has the satisfactory quality and meets the requirements.
  • the process of the present invention can realize good infiltration and simultaneously can prepare the pultruded polyurethane composite with satisfactory surface properties. It can also save raw materials and economize manpower and material resources, thereby being more economic and environment-friendly.
  • the process for preparing the polyurethane composite by the polyurethane pultrusion process of the present invention adopts the above-mentioned polyurethane composition, and skillfully designs the resin-injection device and the infiltration box which are applicable thereto. With the appropriate method, not only the pultruded polyurethane composite with excellent quality is prepared, but also the surface condition of the pultruded polyurethane composite is improved, raw materials, manpower and material resources are saved, the production efficiency is enhanced, and the cost is saved.
  • the polyurethane composition of the present invention has a longer gelation time, so that a better polyurethane pultrusion can be achieved.
  • the polyurethane composite of the present invention has good physical properties and a high glass fiber content.
  • the polyurethane composition of the present invention has a shorter curing time and a longer gelation time, and can be suitable for preparing a pultruded polyurethane composite, in particular a large-scale pultruded polyurethane composite, for example, a sectional material of spar cap of the wind blade, in a more flexible manner and in a better way (for example, can be infiltrated and shaped for a longer time).
  • the fibre- reinforced material can be infiltrated and shaped for a longer time and in a better way at an ordinary temperature, for example before entering the mold, and can be more rapidly cured at a higher temperature, for example after entering the mold.
  • the automatic control method for preparing the pultruded polyurethane composite comprises:
  • said liquid level information comprises the liquid level information at two or more than two different positions.
  • the liquid level information at two or more than two different positions is acquired simultaneously.
  • the positions for acquiring said liquid level information are the acquiring position 1 (2) and the acquiring position 2 (4), respectively.
  • said infiltration box (5) comprises an inlet (5a), the straight-line distance between said acquiring position 1 (2) and said inlet (5a) is 0-100 mm, the straight-line distance between said acquiring position 2 (4) and said inlet (5a) is 110-300 mm, preferably 120-250 mm, more preferably 130-200 mm.
  • the method also comprises: pre-storing a plurality of correspondences between historical liquid level information and historical process parameter, and adjusting the process parameter according to the acquired liquid level information and said correspondence between historical liquid level information and historical process parameter.
  • the length of said infiltration box (5) is 300-800 mm, preferably 350-700 mm, more preferably 400-650 mm.
  • said liquid level information is acquired from at least one sensor, preferably acquired from two sensors.
  • said sensor is selected from a contact sensor, an infrared sensor or an ultrasonic sensor or a combination thereof.
  • the automatic control method of the present invention comprises the steps of: the liquid level information in the infiltration box is measured in step Sll.
  • step S12 it is determined whether the liquid level information conforms to the requirements based on a conversion relationship, which is formed based on the historical data of the liquid level information and the process parameter.
  • step SI 3 a process parameter is adjusted according to the obtained liquid level information.
  • step Sll for example, the liquid level information of at least two different positions in the infiltration box is first measured, and for example, specifically the liquid level information and the temperature information at a designated position can be measured by using a sensor.
  • the resin-injection system 30 includes one or more sensors 301, a computing unit 302, and a transmitting unit 303, wherein the one or more sensors 301 are configured to measure information such as the liquid level information and the temperature information on the polyurethane composite production line, for example, the sensor 301 can be specifically utilized to measure the liquid level information and/or the temperature information at one or more positions in the infiltration box.
  • the control system 40 further specifically includes a receiving unit 401 and an adjusting unit 402, wherein the receiving unit 401 is configured to receive the liquid level information, and the adjusting unit 402 is configured to adjust the parameters of the control system 40 according to the liquid level information.
  • the receiving unit 401 can receive the liquid level information reported from the resin-injection system 30 and send it to the adjusting unit 402, and then the adjusting unit 402 adjusts the parameters of the control system 40 according to the liquid level information.
  • the adjusting unit 402 may send an instruction to adjust the parameters of the control system 40 according to the difference between the measured liquid level information and the required liquid level information, the instructions are sent to various execution components (not shown) of the control system 40, so that the measured liquid level information approaches or even equals to the required liquid level information. For example, if the measured liquid level information cannot reach the production requirement, now the adjusting unit 402 may send instructions to adjust the parameters of the control system 40.
  • the parameters that can be adjusted include the formula parameter and the process parameter.
  • the formula parameter comprises the raw material proportion, specifically the amounts of the components of the polyurethane composition
  • the process parameter comprises one or more of the temperature of the resin/composition, the resin- injection velocity, the resin-injection amount and the feeding velocity of the fiber-reinforced material.
  • the adjusting unit 402 may send an instruction to a precision pump (e.g., a piston pump, a gear pump) to adjust the composition, the injection amount of the resin, or may send an instruction to a conveyor motor to adjust the feeding velocity of the fiber-reinforced material.
  • said polyurethane composition comprises the following components:
  • Component A comprising one or more organic polyisocyanates
  • Component B comprising:
  • Bl one or more organic polyols, wherein the content of said polyol is 21-60wt%, preferably 21- 40wt%, based on 100wt% of the total weight of said polyurethane composition;
  • R1 is selected from hydrogen, methyl or ethyl
  • R2 is selected from an alkylene group having 2-6 carbon atoms, 2,2-bis(4-phenylene)-propane, 1 ,4-bis(methylene)benzene, 1,3- bis(methylene)benzene, l,2-bis(methylene)benzene
  • n is an integral number selected from 1-6;
  • Component C a free -radical initiator.
  • the shape and the size of the fiber-reinforced material is not limited and for example it may be a continuous fiber, a fiber web formed by bonding, or a fiber fabric.
  • the fiber-reinforced material is selected from glass fiber, carbon fiber, polyester fiber, natural fiber, aromatic polyamide fiber, nylon fiber, basalt fiber, boron fiber, silicon carbide fiber, asbestos fiber, crystal whisker, metal fiber or a combination thereof.
  • the organic polyisocyanate may be any aliphatic, alicyclic, or aromatic isocyanate known to be used in the preparation of polyurethanes.
  • the isocyanate that can be used in the present invention has the functionality of preferably 2.0-3.5, particularly preferably 2.1-2.9.
  • the isocyanate has a viscosity of preferably 5-700 mPa-s, particularly preferably 10-300 mPa-s measured at 25 °C according to DIN53019-1-3.
  • the organic polyisocyanate comprises isocyanate dimer, trimer, tetramer, pentamer or a combination thereof.
  • the isocyanate component A) is selected from diphenylmethane diisocyanate (MDI), polypheny lmethane polyisocyanate (pMDI), and their polymers, prepolymers or a combination thereof.
  • MDI diphenylmethane diisocyanate
  • pMDI polypheny lmethane polyisocyanate
  • Blocked-isocyanate may be also used as isocyanate component A), which may be prepared from the reaction of an excessive amount of an organic polyisocyanate or a mixture of organic polyisocyanates with a polyol compound. Those of ordinary skill in the art are familiar with these compounds and their preparation methods.
  • the polyurethane composition of the present invention contains one or more organic polyols Bl).
  • the content of the organic polyol is 21-60wt%, based on 100wt% of the total weight of said polyurethane composition.
  • the organic polyol can be an organic polyol conventionally used in the art for preparing a polyurethane, which comprises, but is not limited to a polyether polyol, a polyether carbonate polyol, a polyester polyol, a polycarbonate diol, a polymer polyol, a vegetable oil-based polyol or a combination thereof.
  • the polyether polyol can be prepared by known processes, for example, obtained by reacting an olefin oxide with a starter in the presence of a catalyst.
  • the polyether carbonate polyol may also be used in the present invention.
  • the polyether carbonate polyol can be prepared by adding carbon dioxide and alkylene oxide on an active hydrogen- containing starter by using a double metal cyanide catalyst.
  • Said polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyol.
  • the functionality and the hydroxyl value of the organic polyol refer to the average functionality and the average hydroxyl value.
  • the polyurethane composition of the present invention further contains one or more compounds B2) having the structure of formula (I)
  • Ri is selected from hydrogen, methyl or ethyl
  • R is selected from an alkylene group having 2-6 carbon atoms
  • n is an integral number selected from 1-6.
  • R is selected from ethylene, propylene, butylene, pentylene, 1 -methyl- 1,2-ethylene, 2-methyl- 1,2-ethylene, 1 -ethyl- 1,2-ethylene, 2-ethyl-
  • said Bl) is selected from an organic polyol, wherein the organic polyol is selected from those having the functionality of 1.7-6, preferably 1.9-4.5, and the hydroxyl value of 150-1100 mg KOH/g, preferably 150-550 mg KOH/g.
  • the component B2) is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or a combination thereof.
  • the compound of formula (I) may be prepared by conventional methods in the art, for example may be prepared by the esterification reaction of (meth)acrylic anhydride or (meth)acrylic acid, (meth)acryloyl halide compounds and HO-(R 2 0) n H.
  • Those skilled in the art are familiar with these preparation methods, for example, as explained in "Manual of Polyurethane Raw Materials and Additives” (Liu Yijun, published on 1st April 2005), Chapter III, and “Polyurethane Elastomer” (Liu Houjun, published in August 2012), Chapter II, and CN104974502A. The entire contents of these documents are incorporated herein by reference.
  • the polyurethane composition of the present invention further contains C) free radical reaction initiator.
  • the free radical initiator that is used in the present invention may be added to the polyol component or an isocyanate component, or can be added to both components. It specifically can include tert-butyl peroxy isopropyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, methylethyl ketone peroxide, cumene hydroperoxide and the like.
  • the content of the free radical reaction initiator of the present invention is 0.1-8wt%, based on 100wt% of the total weight of the polyurethane composition of the present invention.
  • an accelerator such as a cobalt compound or an amine compound, may be present.
  • the polyurethane composition may also contain a catalyst for catalyzing the reaction of an isocyanate group (NCO) and a hydroxyl group (OH).
  • An appropriate catalyst for the polyurethane reaction is preferably, but not limited to an amine catalyst, an organometallic catalyst, or a mixture thereof.
  • the used amount of the catalyst is 0.001-10wt%, based on 100wt% of the total weight of the polyurethane composition of the present invention.
  • the isocyanate group in the addition polymerization reaction of an isocyanate group with a hydroxyl group, can be an isocyanate group contained in the organic polyisocyanate (component A), or an isocyanate group contained in the intermediate product of the reaction of the organic polyisocyanate (component A) and the organic polyol (Bl) component) or B2) component
  • the hydroxy group can be a hydroxy group contained in the organic polyol (Bl) component) or B2) component, or a hydroxy group contained in the intermediate product of the reaction of the organic polyisocyanate (component A) and the organic polyol (Bl) component) or B2) component.
  • the free radical polymerization reaction is an addition polymerization reaction of olefinic bonds, wherein the olefinic bonds may be an olefinic bond contained in B2) component or an olefinic bond contained in the intermediate product of the reaction of B2) component and the organic polyisocyanate.
  • the polyurethane addition polymerization reaction i.e., an addition polymerization reaction of the isocyanate group and the hydroxyl group
  • the free radical polymerization reaction is simultaneously performed with the free radical polymerization reaction.
  • suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are performed successively, however the polyurethane matrix thus prepared has a different structure than the polyurethane resin matrix prepared where the polyurethane addition polymerization reaction and the free radical polymerization reaction are performed simultaneously; and thereby the prepared polyurethane composites have different mechanical properties and manufacturabilities.
  • the above-mentioned polyurethane composition can also contain auxiliaries or additives.
  • the internal release agent that can be used in the present invention comprises any conventional release agent used for producing polyurethanes, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearic amide, fatty acid esters, metal salts of long-chain carboxylic acids, such as zinc stearate, or polysiloxanes.
  • long-chain carboxylic acids particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearic amide, fatty acid esters, metal salts of long-chain carboxylic acids, such as zinc stearate, or polysiloxanes.
  • flame retardants examples include triaryl phosphates, trialkyl phosphates, triaryl phosphates or trialkyl phosphates with halogen, melamine, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.
  • adjuvants that can be used in the present invention include water-removing agents such as molecular sieves; defoamers such as poly dimethyl siloxane; coupling agents such as monoethylene oxide or organic amine functionalized trialkoxysilane or combinations thereof. Coupling agents are particularly preferably for improving the adhesion of the resin matrix to the fiber-reinforced material. Fine particle fillers, such as clay and fumed silica, are commonly used as thixotropic agent.
  • the free radical reaction suppressant that can be used in the present invention comprises a polymerization inhibitor and a polymerization retarder, and the like, for example, some phenols, quinone compounds or hindered amine compounds. Examples thereof include methyl hydroquinone, p-methoxyphenol, benzoquinone, polymethyl pyridine derivatives, low-valent copper ions, and the like.
  • the process for preparing the pultruded polyurethane composite of the present invention can simply and efficiently control the production process, so that the pultruded polyurethane composite with the required rough surface and the satisfactory quality can be prepared in a better way.
  • the resin-injection device and the infiltration box with special design that are applicable to the method of the present invention can infiltrate the fiber-reinforced material, especially the fiber material with certain thickness, in a shorter time and in a better way.
  • the polyurethane composition of the present invention has a shorter curing time and a longer gelation time, and can be suitable for preparing a pultruded polyurethane composite, in particular a large-scale pultruded polyurethane composite in a more flexible manner and in a better way (for example, can be infiltrated and shaped for a longer time).
  • the fiber-reinforced material can be infiltrated and shaped for a longer time and in a better way at an ordinary temperature, for example before entering the mold, and can be more rapidly cured at a higher temperature, for example after entering the mold.
  • Fig. 1 represents a mold and process flow schematic view represented by the process for preparing the pultruded polyurethane composite with the pultrusion process according to the preferred embodiment of the present invention, wherein: 1 -fiber-reinforced material, 2-1# liquid level sensor or information acquiring position 1, 3-yarn guide plate, 4-2# liquid level sensor or information acquiring position 2, 5 -infiltration box, 6-temperature sensor, 7-mold, 8-sectional material/pultruded polyurethane composite, 9-holding device.
  • Fig. 2 is a relative position diagram of the preferred infiltration box and resin-injection device/and peel ply of the present invention, wherein: 2a, 2b-peel ply (in order to avoid the figure being too complicated, the fiber-reinforced material which should be arranged between the two pieces of peel ply is not shown), 30-resin-injection apparatus/system, 4a, 4b-resin-injection port, 5 represents the infiltration box, 5a represents the inlet of the infiltration box, 5b represents the outlet of the infiltration box, 5m, 5n represent two opposite sides of the infiltration box (5) (5i and 5j are two up and down opposite sides, as shown in Fig. 3), and X represents the vertical distance between said resin-injection system (30) and the inlet (5a) of the infiltration box in the pultrusion direction.
  • Fig. 3 represents the front view of the preferred infiltration box of the present invention, wherein 5i and 5j respectively represent two up and down opposite sides of the infiltration box.
  • Fig. 4 is the cross-sectional view of the preferred infiltration box of the present invention, wherein 5 represents the infiltration box, 5a represents the inlet of the infiltration box, and 5b represents the outlet of the infiltration box.
  • Fig. 5 is an automatic control flowchart 200 of the preferred embodiment of the present invention, in which 22 represents a resin-injection machine, 201 represents-resin-injection (I), 202 represents + resin-injection ( ⁇ ), 203 represents resin-injection at the fixed frequency, 1# represents the sensor 1, 2# represents the sensor 2, Y represents Yes, and N represents No.
  • 22 represents a resin-injection machine
  • 201 represents-resin-injection (I)
  • 202 represents + resin-injection ( ⁇ )
  • 203 represents resin-injection at the fixed frequency
  • 1# represents the sensor 1
  • 2# represents the sensor 2#
  • Y represents Yes
  • N No.
  • Fig. 6 illustrates the steps of the automatic control method according to the preferred embodiment of the present invention.
  • Fig. 7 shows a resin-injection system according to the preferred embodiment of the present invention.
  • Fig. 8 shows a control system according to the preferred embodiment of the present invention.
  • Isocyanate index refers to the numerical value calculated by the following formula:
  • Isocyanate index (%) the mole number of isocyanate groups (NCO groups) in Component A/the mole number of isocyanate group-reactive groups in Component Bxl00%.
  • NCO content refers to the content of the NCO groups in the system, and is measured according to GB/T12009.4-2016.
  • the pultrusion rate/velocity i.e. the speed at which the fiber-reinforced material is pulled through the mold, refers to the length of the pultruded fiber-reinforced material per minute through the mold, i.e. the length per minute at which the pultruded article is produced; its specific test method is as follows: the length of the pultruded fiber-reinforced material measured using a speed sensor or a stopwatch plus a ruler is divided by the time used to obtain the length through the mold per unit time, i.e. the pultrusion rate/velocity.
  • the curing time refers to the time period starting from mixing component A and component B of the reaction system until the curing.
  • the gelation time refers to the time period starting from mixing component A and component B of the reaction system until the viscosity reach a certain value (for example about 10000 mPa ⁇ s).
  • the gelation time of the present invention is tested by using a gelation tester.
  • the specific test method is as follows: mixing component A and component B uniformly, placing the mixture into the gelation tester, and recording the time period from pressing the turn-on button until the gelation tester stops working as the gelation time.
  • the gelation tester used in the present invention is selected from Shanghai SINO-LAB Instrument Co. Ltd. (Type GT-STHP-220). Source and description of raw materials
  • the production of 3 mm * 100 mm flat sheet was taken as an example to describe the production process of the glass fiber-reinforced polyurethane pultruded sectional material/sheet material with peel ply.
  • the cross-sectional area ratio of the inlet to the outlet of the infiltration box was 7:1; the vertical distance between the resin-injection system (30) and the inlet (5a) of the infiltration box in the pultrusion direction was 50 mm; the width of the resin-injection flow channel was 10 mm, the diameter of the hole of the flow channel was 2 mm, the length of the hole of the flow channel was 200 mm, and the gap length was 50 mm.
  • the resin-injection system (30), the infiltration box (5) and the mold (7) were assembled and fixed on the pultrusion platform.
  • the 1# liquid level sensor (2) was installed at a position having a distance of 20 mm from the inlet of the infiltration box (5), and simultaneously the 2# liquid level sensor (4) was installed at a position having a distance of 150 mm from the inlet of the infiltration box(5), then the infiltration box (5) and the mold were assembled according to the drawings, and fixed on the pultrusion platform.
  • a resin-injection machine was started after the temperature became stable.
  • component A Desmodurl511L
  • component B 100 parts of Baydurl8BD209: 4 parts of Baydurl8BD101
  • a temperature sensor (6) might be installed on the infiltration box (5).
  • the temperature sensor real-time recorded the temperature of the material at the outlet of the infiltration box (5), and a signal was simultaneously sent to the resin-injection system (30)/control system (40) to guarantee the product quality:
  • the sensor informed the resin-injection machine to turn on the resin cooling device so as to reduce the material temperature, and simultaneously informed the pultrusion line to increase the speed and reduce the resin retention;
  • the sensor informed the resin- injection machine to turn on the resin heating device so as to reduce the resin viscosity and improve the resin wettability.
  • the resin was injected into the resin-injection flow channel from the resin-injection ports (4a, 4b) at two sides (5m, 5n) of the infiltration box (5), the resin was uniformly injected into the infiltration box through a plurality of the flow channel holes on the resin flow channel and completely filled the infiltration box (the average resin-injection velocity was 110 g/min), so that the glass fiber (1) and the peel ply (2a, 2b) were fully infiltrated, and the resin-injection pressure in the infiltration box (5) was controlled to 0.1-15 bar.
  • the glass fiber (1) and the peel ply (2a, 2b) infiltrated in the infiltration box (5) were continuously pulled through the mold (7) by the traction device 8 at the speed of 0.5 m/min, after being taken out of the mold, the sheet material was smooth without dry yarns, and when the obtained pultruded polyurethane composite/sectional material was knocked with metal at a position of 1 meter away from the mold, the sound was clear and crisp, indicating good infiltration and curing.
  • the peel ply was removed, namely, the pultruded polyurethane composite/sectional material with a satisfactory surface condition could be obtained.
  • Example 2 Except that no automatic control method was used, the same procedure and steps as those in Example 1 were used to obtain a pultruded polyurethane composite having the same density and the same size of 100 meters * 3 millimeters * 100 millimeters. It was recorded that the amount of the consumed polyurethane composition was 13.5kg.
  • the automatic control method of the present invention was very suitable for the pultrusion process, and could accurately and objectively control the injection time and velocity of the raw materials in the pultrusion production process, and produce the pultruded polyurethane composite with good infiltration and curing, and at the same time, it could also save raw materials, economize manpower and material resources, and reduce the cost, and therefore it is conducive to the commercialization of related products.
  • Example 1 It can also be seen from Example 1 that the inventive method comprising acquiring liquid level information which comprises the liquid level information at two or more than two different positions reduces the amount of polyurethane composition spent because a single liquid level sensor (2) would have increased the resin-injection velocity in step 2) of the liquid level sensor operation of Example 1 whereas it was sufficient to stabilize the resin injection velocity instead of increasing it.
  • the polyurethane composition of the present invention had a shorter curing time and a longer gelation time, and could be suitable for preparing a polyurethane product, in particular a large-scale polyurethane product in a more flexible manner and in a better way (for example, could be infiltrated and shaped for a longer time).

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un procédé de commande automatique et un appareil pour préparer le composite de polyuréthane pultrudé avec la pultrusion de polyuréthane.
PCT/EP2022/060120 2021-04-22 2022-04-14 Procédé de préparation d'un composite de polyuréthane pultrudé WO2022223467A1 (fr)

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CN202110438963.X 2021-04-22
CN202110438963.XA CN115230197A (zh) 2021-04-22 2021-04-22 一种制备聚氨酯拉挤复合材料的方法
EP21182668.0A EP4112262A1 (fr) 2021-06-30 2021-06-30 Procédé de préparation d'un composite de polyuréthane pultrudé
EP21182668.0 2021-06-30

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CN109986810A (zh) 2017-12-29 2019-07-09 江苏源盛复合材料技术股份有限公司 一种集中供料装置及包括该装置的复合材料拉挤成型设备
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