• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    POLYURETHANE COMPOSITES PRODUCED BY A VACUUM INFUSION PROCESS. The present invention relates to a polyurethane forming system with a viscosity at 25 ° C of less than 600 mPas for at least 30 minutes, a gel time at room temperature of more than 60 minutes and a water content of less 0.06% by weight, based on the total weight of the system, which is used to produce composites by a vacuum infusion process. This system makes it possible to produce large composites, such as wind turbine blades, with excellent physical properties.
    公开号:BR112013024040B1
    申请号:R112013024040-7
    申请日:2012-03-20
    公开日:2020-08-25
    发明作者:Usama E. Younes
    申请人:Bayer Materialscience Llc；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to a polyurethane forming system for the production of polyurethane composites reinforced by a vacuum infusion process and to composites produced with this system. The processing characteristics of this system and the physical properties of the composites produced with this system of the present invention are particularly advantageous for the production of large articles. The composites of the present invention are particularly suitable for applications such as wind turbine blades.
    [0002] [002] Reinforced composites are being used for numerous applications where strength and light weight are important physical properties. Examples of applications for which reinforced composites are employed include automotive components and building materials.
    [0003] [003] Until now, the applications for which fiber-reinforced composites have been used were limited by the processability of the polymer forming system and the properties of the polymeric material used to produce the composite. More specifically, the production of larger composite articles requires a liquid reactive system with a viscosity that is low enough to fully penetrate the reinforcement material and a reactivity sufficiently slow to not completely harden before the shape or mold has been completely filled, but not so slow that the production of a single molded composite article requires a period of time so extremely long that it becomes uneconomical to produce a composite article with that material.
    [0004] [004] A method for increasing the speed with which a reactive system is introduced into the reinforcement material is a vacuum infusion molding process. In a vacuum infusion molding process, the reinforcement material is positioned inside a vacuum chamber. The pressure inside that vacuum chamber is then reduced. The pressure differential between the bag in which the pressure was reduced and the atmospheric pressure on the reaction mixture to be fed into the bag pushes the reaction mixture into the bag and into the reinforcement material. This technique is not, however, without problems. Localized areas of the produced composite may exhibit less than optimal physical properties due to poor fiber volume control, less fiber volume and excess resin.
    [0005] [005] Attempts to resolve the problems encountered with the vacuum infusion process included the use of a specially designed mold (US 2008/0237909), use of a double-chamber resin infusion device (US 2008/0220112) , use of multiple flow injection points, introduction of a thermoplastic material in two separate stages (US 2010/0062238) and production of smaller segments of the desired article with subsequent union of these segments (US 2007/0183888).
    [0006] [006] However, these techniques require specially designed equipment and / or multiple process steps.
    [0007] [007] Until now, the modification of the polymer-forming reaction mixture, particularly a polyurethane-forming reaction mixture, has not been an approach that has been successfully implemented in a vacuum infusion process for the production of large composite articles, like wind turbines.
    [0008] [008] Consequently, it would be advantageous to develop a polyurethane forming system with a viscosity that is low enough to be successfully infused into a reinforcement material before the polyurethane forming reaction has been completed and a reactivity that is not as that production of the composite becomes economically impractical. SUMMARY OF THE INVENTION
    [0009] [009] It is an objective of the present invention to present a polyurethane forming system for the production of large composite articles.
    [0010] [0010] It is also an objective of the present invention to present a polyurethane forming system that can be effectively infused into a reinforcement material by a vacuum infusion process.
    [0011] [0011] It is an additional object of the present invention to present a composite article produced with the polyurethane forming system of the present invention.
    [0012] [0012] It is another objective of the present invention to present a polyurethane forming system for the production of a composite wind turbine blade.
    [0013] [0013] It is also an object of the present invention to present a process for vacuum infusion of a reinforcement material with the polyurethane forming system of the present invention.
    [0014] [0014] It is an additional objective of the present invention to present composites produced by a vacuum infusion process that have sufficient mechanical strength in green to be molded in 6 hours or less.
    [0015] [0015] These and other objectives that will become clear to those skilled in the art are achieved with the polyurethane forming system with a viscosity at 25 ° C of less than 600 mPas for at least 30 minutes, a gel time of more than 60 minutes and a water content of less than 0.06% by weight which is more fully described below. BRIEF DESCRIPTION OF THE DRAWINGS
    [0016] [0016] The Figure graphically illustrates the elastic fatigue data for composite panels produced with the polyurethane forming system of Example 2, an epoxy resin and a vinyl ester resin. DETAILED DESCRIPTION OF THE PRESENT INVENTION
    [0017] [0017] The present invention relates to a polyurethane forming system with a viscosity at 25 ° C of less than 600 mPas for at least 30 minutes, preferably less than 400 mPas, more preferably 250 to 300 mPas, a gel time of more than 60 minutes, preferably greater than 180 minutes, and a water content of less than 0.06% by weight, based on the total weight of the polyurethane forming system.
    [0018] [0018] The system of the present invention includes an isocyanate component and an isocyanate reactive component.
    [0019] The isocyanate component of the system of the present invention must have a viscosity at 25 ° C of about 20 to about 300 mPas, preferably from about 20 to about 300 mPas, more preferably less than 100 mPas , most preferably from about 40 to about 80 mPas. This isocyanate component includes at least one diisocyanate or polyisocyanate.
    [0020] The isocyanate-reactive component of the system of the present invention includes: (i) one or more polyols with a viscosity (s) at 25 ° C of 20 to 850 mPas, preferably from about 30 to about 750 mPas, more preferably from about 40 to about 700 mPas, most preferably from about 50 to about 650 mPas, and an OH number from about 200 to about 800 mg KOH / g, preferably from about 300 to about 700 mg KOH / g, more preferably about 400 to about 600, most preferably about 350 to about 520 mg KOH / g; (ii) up to about 6% by weight, based on the reactive component with total isocyanate, preferably up to about 4% by weight, most preferably up to about 3% by weight, of a flow additive, and (iii) from about 2 to about 6% by weight, based on the reactive component with total isocyanate, preferably from about 2 to about 4% by weight, most preferably from about 2 to about 3% by weight of a drying agent, with the sum of weight percentages for all components of the isocyanate-reactive component being equal to 100% by weight.
    [0021] [0021] The isocyanate-reactive component of the present invention will generally have an average functionality of about 2 to about 6, preferably about 2 to about 4, most preferably about 2 to about 3.
    [0022] [0022] Optionally, up to 1% by weight of additives that do not cause foaming can also be included in the system of the present invention, preferably in the isocyanate-reactive component.
    [0023] [0023] The isocyanate component and the isocyanate reactive component are reacted in sufficient quantities for the NCO Index (ie, the ratio of the total number of reactive isocyanate groups present to the total number of isocyanate reactive groups that can react with the isocyanate under the conditions employed in the process multiplied by 100) is 99 to 110, preferably about 100 to about 105, most preferably about 102.
    [0024] [0024] Any of the known diisocyanates or polyisocyanates with a viscosity of maximum 300 mPas at 25 ° C or which, when combined with other diisocyanates or polyisocyanates, results in an average viscosity of a maximum of 300 mPas at 25 ° C can be included in the polyisocyanate component of the system of the present invention. It is noted, however, that only one diisocyanate or polyisocyanate is included in the isocyanate component of the present invention. Diphenylmethane diisocyanate (MDI) and polymeric MDI are particularly preferred. An example of a particularly preferred polyisocyanate is one that is commercially available from Bayer MaterialScience LLC under the names Mondur CD, Mondur MRS-4 and Mondur MRS-5.
    [0025] Any of the known polyols with a viscosity at 25 ° C of less than 850 mPas and an OH number of about 200 to about 800 would be a suitable polyol component of the system of the present invention. Suitable polyols include polyether polyols and polyester polyols. Preferred polyols are polyether polyols with a viscosity at 25 ° C of less than 850 mPas and an OH number of about 200 to about 800. Examples of the preferred polyols are those polyether polyols that are commercially available under the names Multranol 9168, Multranol 9138, Multranol 4012, Multranol, 4035, Multranol 9158, Multranol 9198, Multranol 9170, Arcol PPG425, Arcol 700 and Arcol LHT 240.
    [0026] [0026] Any of the known flow additives can be included in the isocyanate-reactive component of the system of the present invention. Examples of preferred flow additives include those that are commercially available under the names Byk 1790, Byk 9076, Foamex N, BYK A530, BYK 515, BYK-A 560, BYK C-8000, BYK 054, BYK 067A, BYK 088 and Momentive L1920.
    [0027] [0027] Any of the known drying agents can be included in the isocyanate-reactive component of the system of the present invention. Examples of suitable drying agents include: those that are commercially available under the name Incozol, p-toluenesulfonyl isocyanate available from the OMG Group, powder sieves and calcium hydride.
    [0028] [0028] The reaction mixture can optionally contain a catalyst for one or more of the polyisocyanate polymer formation reactions. The catalyst (s), when used, is preferably introduced into the reaction mixture by pre-mixing with the isocyanate-reactive component. Catalysts for organic polyisocyanate polymer formation reactions are well known to those skilled in the art. Preferred catalysts include, but are not limited to, tertiary amines, tertiary amine acid salts, organic metal salts, covalently bonded organometallic compounds and combinations thereof. The levels of preferred catalysts required to achieve the required reactivity profile will vary with the composition of the formulation and have to be optimized for each reaction system (formulation). Such optimization would be well understood by those skilled in the art. The catalysts preferably have at least some degree of solubility in the used isocyanate-reactive component and are, most preferably, completely soluble in that component at the required usage levels.
    [0029] [0029] The formulation of the invention may contain other optional additives, if desired. Examples of additional optional additives include fillers in short particles or fibers, internal mold release agents, fire retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, small amounts of inert viscosity reducing diluents, combinations of these and any other additives known in the art. In some embodiments of the present invention, the additives or parts thereof can be applied to the fibers, such as by coating the fibers with the additive.
    [0030] [0030] Other optional additives include moisture removers, such as molecular sieves; anti-foam agents, such as poly-dimethylsiloxanes; coupling agents, such as the functional mono-oxirane or organo-amine trialcoxysilanes; combinations of these and others. Fire retardants are sometimes desirable as additives in composites. Examples of preferred types of fire retardants include, but are not limited to, triaryl phosphates; trialkyl phosphates, particularly those with halogens; melamine (as a filler); melamine resins (in small quantities); halogenated paraffins and their combinations.
    [0031] [0031] The present invention also relates to reinforced composites produced with the system of the present invention. Such reinforced composites are produced by infusing the system of the present invention into a reinforcing material and subsequently curing the infused reinforced material.
    [0032] [0032] Reinforcement materials suitable for the production of these composites include: any fibrous material or materials that can provide long fibers capable of being at least partially wetted by the polyurethane formulation during impregnation. The fibrous reinforcement material can be insulated yarns, braided yarns, woven or non-woven mat structures and combinations thereof. Long fiber mats or veils can be used in single-layer or multi-layer structures. Suitable fibrous materials are known. Examples of suitable fibrous materials include: glass fibers, glass mats, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers and combinations thereof. Long glass fibers are particularly preferred in the present invention. Reinforcement fibers can optionally be pretreated with sizing agents or adhesion promoters known to those skilled in the art.
    [0033] [0033] The weight percentage of the reinforcement of long fibers in the composites of the present invention can vary considerably, depending on the type of fiber used and the end use application desired for the composite articles. The reinforcement charges can be from 30 to 80% by weight of glass, preferably from 40 to 75% by weight of the final composite, more preferably from 50 to 72% by weight, and most preferably from 55 to 70% by weight , based on the weight of the final composite. The long fiber reinforcement can be present in the composites of the present invention in an amount varying between any combination of these values, including the mentioned values.
    [0034] [0034] The composites of the present invention are characterized by tensile strengths with fatigue (determined according to ASTM E647-05) that are at least twice the fatigue strengths of reinforced epoxy composites. The composites of the present invention also have interlaminar fracture strength values (determined in accordance with ASTM D5528) that are at least twice the interlaminar strength of a fiber reinforced epoxy composite. These characteristics make the composites of the present invention particularly useful for applications such as wind turbine blades.
    [0035] [0035] The composites of the present invention are preferably prepared by a vacuum infusion process. Vacuum infusion processes are known to those skilled in the art.
    [0036] [0036] More specifically, in the production of a composite with the system of the present invention by vacuum infusion, the isocyanate and isocyanate reactive components are degassed and combined to form the reaction mixture. The reinforcement material is placed in a vacuum chamber (typically one or more bags). The pressure inside that vacuum chamber is then reduced. The pressure differential between the vacuum chamber in which the pressure has been reduced and the atmospheric pressure over the reaction mixture pushes the reaction mixture into the vacuum chamber and into the reinforcement material. The reaction mixture is cured, and the composite thus formed is removed from the vacuum chamber.
    [0037] [0037] A more detailed description of a vacuum infusion process can be found in U.S. Patent Applications Published 2008/0220112 and 2008/0237909.
    [0038] [0038] Having thus described the invention, the following Examples are given as illustrative of it. All parts and percentages presented in these Examples are parts by weight or percentages by weight, unless otherwise indicated. EXAMPLES
    [0039] [0039] The materials used in the Examples that follow were:
    [0040] [0040] POLYOL A: A polyether polyol with a viscosity at 25 ° C of approximately 315 mPas, a functionality of 3 and an OH number of approximately 350 mg KOH / g which is commercially available from Bayer MaterialScience LLC under the name Multranol 9170 .
    [0041] [0041] POLIOL B: A polypropylene oxide based diol with a viscosity at 25 ° C of approximately 73 mPas and an OH number of approximately 263 mg KOH / g which is commercially available from Bayer MaterialScience LLC under the name Arcol PPG 425.
    [0042] [0042] POLIOL C: A polyether polyol with a viscosity at 25 ° C of approximately 650 mPas, a functionality of 3 and an OH number of approximately 370 mg KOH / g which is commercially available from Bayer MaterialScience LLC under the name Multranol 4012 .
    [0043] [0043] POLIOL D: A polypropylene oxide based diol with a viscosity at 25 ° C of approximately 55 mPas and an OH number of approximately 515 mg KOH / g which is commercially available from Bayer MaterialScience LLC under the name Multranol 9198 .
    [0044] [0044] POLIOL E: A polyether polyol with a viscosity at 25 ° C of approximately 450 mPas, a functionality of 3 and an OH number of approximately 470 mg KOH / g which is commercially available from Bayer MaterialScience LLC under the name Multranol 9158 .
    [0045] [0045] DRYING AGENT A: Incozol 2 which is commercially available from Incozel Inc.
    [0046] [0046] DRYING AGENT B: Powdered Zeolite which is commercially available under the name Baylith.
    [0047] [0047] DRYING AGENT C: P-toluenesulfonyl isocyanate which is commercially available from the OMG Group.
    [0048] [0048] CATALYST A: Delayed-acting amine catalyst that is commercially available from Momentive under the name Niax A577.
    [0049] [0049] CATALYST B: Delayed-acting amine catalyst that is commercially available from Momentive under the name Niax A575.
    [0050] [0050] FLOW ADDITIVE A: Silicone-free material commercially available from BYK under the designation BYK-A 560.
    [0051] [0051] FLOW ADDITIVE B: Silicone-free material commercially available from BYK under the designation BYK-A 1790.
    [0052] [0052] ISOCIANATE A: polymeric MDI with a viscosity at 25 ° C of 40 mPas which is commercially available from Bayer Materi-alScience LLC under the name Mondur CD.
    [0053] [0053] ISOCIANATE B: polymeric MDI with a viscosity at 25 ° C of 40 mPas which is commercially available from Bayer MaterialScience LLC under the name Mondur MRS-4.
    [0054] [0054] ISOCIANATE C: polymeric MDI with a viscosity at 25 ° C of 40 mPas which is commercially available from Bayer Materi-alScience LLC under the name Mondur MRS-5.
    [0055] [0055] General procedure used to produce panels for tests in the Examples
    [0056] [0056] Panels measuring 61 cm (24 inches) by 61 cm (24 inches) were produced with the materials listed above in the combination (s) indicated in the table below and a fiberglass mat for a vacuum-assisted resin transfer molding (RTM) process. The panels were prepared by infusing the perimeter with the vacuum pulling through the center. After the glass surface on a table was thoroughly cleaned, sealing tape was applied to the full edge of the glass surface for the outer pouch, while the inner edge of the tape outlined the used fiberglass mats. A mold release agent was applied to the inner area of the tape twice, with excess mold release agent being rubbed between the edges of the tape. After the mold release agent was rubbed onto the table and air dried, the fiberglass mat was placed inside the edge.
    [0057] [0057] After a coiled polyethylene tube was heated to remove unwanted rolled parts, a T-joint was connected to one end of the tube. The tube was then placed around the entire perimeter of the fiberglass mat with small pieces of 1.27 cm (half inch) of the same sealing tape to form an edge and finally connect the tube to the other end of the T joint A polyethylene sheet, used as a release film, was cut to fit inside the rim of the resin release tube with a 1.27 cm (half inch) square cut in the center of the sheet. A small rectangle of air passage cloth was cut and placed under the resin connector in the middle of the fiberglass mat. The piece of cloth covered the square and advanced a few inches so that, when the resin connector was slightly off center, any resin that reached the center would not be sucked into the tube too quickly, causing bubbles in the piece being produced.
    [0058] [0058] The first vacuum bag was then cut. Sealing tape was placed on the edge of the resin connector and around the base of the T-joint. The vacuum bag was placed over the entire mat, with three to five centimeters of excess on all sides of the first edge of the sealing tape. A hole was drilled for the T joint to pass through, and a circle was cut, so that the resin connector could also pass through. The vacuum bag was attached side by side to the sealing tape using pleats when necessary to keep the bag as flat and wrinkle-free as possible on the part.
    [0059] [0059] After the inner bag was completely sealed, the outer vacuum bag was cut from the roll. The same procedure was repeated to open a hole for the T joint and cut a hole for the resin connector in the external vacuum bag after the vacuum bag was placed over the entire panel. Sealing tape was again placed on the edges of the T joint and the resin connector. The vacuum bag was attached to both of these parts and, again, began to be sealed side by side using pleats when necessary, leaving an open side where the vacuum tube of the external bag would be inserted.
    [0060] [0060] The air passage cloth and the pressure sensitive tape were placed at the end of the vacuum tube, and then sealing tape was wrapped around the area that would touch the edge of the sealing tape (about 10.2 cm) (four inches) to 12.7 cm (five inches) inside the panel).
    [0061] [0061] After the external vacuum line was in place, the last side could be sealed. The previously heated polyethylene tube was then cut to the appropriate size, so that the tube passed through the central resin connector that connected to another T joint used to connect the main vacuum line with the other external tube to the secondary bag. .
    [0062] [0062] Another tube was then cut and used to connect the T infusion joint with the empty resin jar. This line was secured with a clamp to seal the entire panel. The vacuum was then turned on and all air was allowed to be drawn from the part. The vacuum was pulled while eliminating as many wrinkles on the piece as possible. After no more leaks could be heard, a vacuum leak detector was used to check micro leaks around the entire panel. After all the leaks had been located and eliminated, the part was ready to be infused.
    [0063] [0063] The amounts of polyol and isocyanate shown in Table 1 were measured and mixed for 30 seconds to one minute. The resin tube was then passed through a hole in the lid of the resin jar, and the resin jar was screwed to the cap while the tube was still attached with a clamp. Once the resin jar was in place and lower than the panel, resting on a bucket or bench, the clamp was released. The line was completely open. The resin jar must be placed lower than the infusion surface to control the resin flow pressure to help control the resin flow rate. The piece began to fill up from the perimeter. The progress of the flow was plotted, and the time recorded while infusing. After the part had completely filled or was no longer moving, the primary vacuum line was closed (usually after an hour to two hours, depending on the complexity of the fiberglass). The resin line was then closed and finally the direct vacuum line was closed to close the entire system.
    [0064] [0064] The tube leading to the vacuum was then cut below the part with the clamp, and the end was covered with sealing tape. This tube was then cut below the resin line clamp to allow the resin to drain from the tube. The tube was then cut above that cut and capped with sealing tape to prevent the piece from leaking. In this way, the piece was infused and could be left to cure at room temperature or put in an oven to increase the curing time.
    [0065] [0065] The composites were produced using 6 VectorPly E-BX-2400 biaxial glass woven panels, 800 g / m, +/- 45 E, with the polyurethane forming composition of Example 2, and with epoxy resins and of vinyl ester commercially available for comparison. The epoxy resin used was EpiKote 135i mixed with Hexion EpiCure 1366 curing agent which is commercially available from Hexi-on. The vinyl ester resin used was DION® IMPACT 9102-75 which is commercially available from Reichhold. The strength characteristics of these panels were then compared. This comparison is graphically illustrated in the Figure.
    [0066] [0066] It is readily clear from the Figure that the elastic fatigue of the composite produced in accordance with the present invention is greater than that of panels produced with the known epoxy or vinyl ester resins.
    [0067] [0067] G1C interlaminar fracture resistance tests were conducted according to ASTM D5528 on the VectorPly E-BX-2400 glass biaxial fabric composite panels, 800 g / m, +/- 45 E with the polyurethane forming composition of Example 2, and with commercially available epoxy and vinyl ester resins for comparison. The epoxy resin used was EpiKote 135i mixed with Hexion EpiCure 1366 curing agent which is commercially available from Hexion. The vinyl ester resin used was the one sold under the name DION® IMPACT 9102-75 which is commercially available from Reichhold. The results of these strength tests are shown in Table 2. It is clear from the results shown in Table 2 that the polyurethane system of the present invention was at least twice as strong as panels prepared with epoxy and vinyl resins.
    [0068] [0068] A key feature of the compositions of the present invention is the ability of the polyurethane forming system to remain liquid at low viscosity for long periods of time (i.e., at least 30 minutes, preferably at least 40 minutes, most preferably at least 50 minutes) at room temperatures, to allow the infusion of large parts.
    [0069] [0069] TABLE 3 compares the viscosity rise with time of a typical commercially available polyurethane forming system (Baydur RTM 902 which is commercially available from BMS LLC) with the polyurethane forming system of the present invention of Example 2.
    [0070] [0070] Although the invention has been described in detail in the preceding part for purposes of illustration, it should be understood that these details are for that purpose only, and that variations can be made by those skilled in the art without departing from the spirit and scope of the invention, except as may be limited by the claims.
    权利要求:
    Claims (11)
    [0001]
    Process for producing a fiber-reinforced polyurethane composite from a polyurethane forming system with a viscosity at 25 ° C below 600 mPas for at least 30 minutes, a gel time at room temperature greater than 60 minutes and a water content of less than 0.06% by weight, based on the total weight of the system, and comprising: (a) an isocyanate component with a viscosity at 25 ° C of 20 to 300 mPas comprising a diisocyanate or a polyisocyanate; and (b) an isocyanate-reactive component, comprising: (i) one or more polyols with a viscosity at 25 ° C of 20 to 850 mPas and an OH number of 200 to 600, (ii) up to 6% by weight, based on the total reactive isocyanate component, of a flow additive, and (iii) from 2 to 6% by weight, based on the total reactive isocyanate component, of a drying agent; with the sum of the weight percentage of all components of the isocyanate-reactive component equal to 100% by weight; and (c) optionally, up to 1% by weight of non-foaming additives; components (a) and (b) are reacted in such quantities that the NCO Index is 99 to 110 to form a polyurethane with sufficient green strength to be molded at room temperature in no more than 6 hours, by vacuum infusion, said process being characterized by the fact that it comprises: (1) degassing each of the components (a) and (b), (2) combining the degassed components (a) and (b) to obtain a polyurethane-forming reaction mixture, (3) apply vacuum pressure to a dry fiber reinforcement material so that the fiber reinforcement material is infused with the polyurethane forming reaction mixture.
    [0002]
    Process according to claim 1, characterized by the fact that the polyurethane forming system has a viscosity at 25 ° C below 400 mPas, or 250 to 300 mPas.
    [0003]
    Process according to claim 1 or 2, characterized in that (b) (i) comprises at least one polyether polyol, or two or more polyether polyols.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the isocyanate component has a viscosity at 25 ° C below 100 mPas.
    [0005]
    Process according to claim 1, characterized by the fact that the isocyanate component comprises diphenylmethane diisocyanate (MDI) or polymeric MDI.
    [0006]
    Process according to any one of claims 1 to 5, characterized by the fact that (b) (i) has a viscosity at 25 ° C of 600 to 700 mPas.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that (b) (i) includes a polyol with a viscosity at 25 ° C of 50 to 75 mPas.
    [0008]
    Process according to any one of claims 1 to 7, characterized by the fact that the isocyanate-reactive component (b) has an average functionality of 2 to 3.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the components (a) and (b) are reacted in quantities such that the NCO index is 102.
    [0010]
    Process according to claim 1, characterized by the fact that the fiber reinforcing material comprises: glass fibers, carbon fibers, aramid fibers and / or basalt fibers.
    [0011]
    Fiber-reinforced polyurethane composite, characterized by the fact that it is produced by the process, as defined in claim 1, and which is in the form of a wind turbine blade.
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-06-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-08-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-01-11| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/071,810|US9580598B2|2011-03-25|2011-03-25|Polyurethane composites produced by a vacuum infusion process|
    US13/071,810|2011-03-25|
    PCT/US2012/029758|WO2012134878A2|2011-03-25|2012-03-20|Polyurethane composites produced by a vacuum infusion process|
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