PU composite resin

Abstract

The present invention relates to a fiber composite material comprising: (a) a polyurethane obtained or obtainable by reaction of at least the following components: (i) a polyisocyanate composition, (ii) a polyol composition comprising at least 15% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups (ii.1), and (b) fibers at least partially embedded in the high-density polyurethane, wherein the polyisocyanate composition (i) and the polyol composition (ii) are used in a ratio such that the isocyanate index is between 99 and 400. The present invention further relates to a process for the production of the fiber composite material, to the fiber composite material obtained or obtainable by this process, and to a process for using the fiber composite material for the production of pipes, in particular conical pipes, pipe connectors, pressure vessels, storage tanks, shielding, masts, strips, rollers, torsion shafts, profiles, pieces of sporting goods, molded parts, covers, automotive exterior parts, ropes, cables, isogrid structures, or semi-finished fiber products.

Description

[Technical Field]

[0001] The present invention relates to a polyurethane obtained or obtainable by reaction of the components: (a) at least component (i) a polyisocyanate composition, (ii) a polyol composition comprising at least 15% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, and (b) at least in part compact and a fiber composite material comprising fibers embedded in polyurethane.

[0002] The invention further relates to a method for the production of a fiber composite material, to the fiber composite material obtained or obtainable by this method, and to the use of the fiber composite material for the production of pipes, in particular conical pipes, pipe connectors, pressure vessels, storage tanks, insulators, masts, strips, rollers, torsion shafts, profiles, pieces of sporting goods, moulded parts, covers, automotive exterior parts, ropes, cables, isogrid structures or semi-finished textile products. [Background technology]

[0003] Filament winding is a manufacturing method for creating rotationally symmetrical parts. In filament winding, fibers are typically drawn from one or more spools as rovings, soaked in resin, and wound around a rotating core. Rovings are bundles, strands, or multifilament yarns made of parallel filaments (continuous fibers). They are primarily used to create fiber-composite or fiber-reinforced plastics, a subgroup of composite materials. In principle, in addition to rovings, two-dimensional fiber materials such as nonwovens, woven fabrics, or knitted fabrics can also be used. After winding onto the rotating core, the laminate is cured in an oven. By varying the fiber type, winding angle, and layer thickness, a wide range of laminates can be produced, making them useful in a variety of applications.

[0004] Standard requirements for formulations for filament winding include a long open time, typically greater than 30 minutes, and preferably greater than 45 minutes. The reaction mixture must not gel in the open bath where the continuous fibers are impregnated with the respective resin. Furthermore, it is essential that bubbles do not form on the surface due to the inclusion of air during the winding process, especially due to the reaction of atmospheric moisture / wet fibers with isocyanates. This leads to conventional polyurethane (PU) formulations for such resin baths using less reactive polyols or catalysts, typically polyols capped with propylene oxide, i.e., secondary alcohols. Due to its reactivity and hydrophilicity, propylene oxide (PO) is clearly preferred over ethylene oxide (EO).

[0005] WO 2016 / 183073 A1 discloses a method for producing composite elements by fiber winding, in which an amine-initiated polyol is used, but its exact composition is not disclosed. WO 03 / 085022 A1 describes a reactive system for use in filament winding, which uses an organic multifunctional resin exhibiting hydrogen-containing reactive groups, and the polyol used is almost entirely PO-based.

[0006] The use of ethylene oxide-capped polyols is usually avoided because the open time of the polyol component is short, and the reactive resin gels after a short time in an open impregnation bath, making such reactive resins unprocessable by conventional processing techniques. However, shorter cure times are desirable from an economic standpoint, and one aim is to minimize sensitivity to moisture. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2016 / 183073(A1) Brochure [Patent Document 2] International Publication No. 03 / 085022(A1) Brochure Summary of the Invention [Problem to be solved by the invention]

[0008] The aim of the present invention was to produce a PU fibre composite which allows for a shorter open time in production and in which the resin component exhibits a lower sensitivity to moisture, also allowing for a shorter cure time. [Means for solving the problem]

[0009] The purpose is to have the following ingredients: a) At least the ingredients: i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups; Polyurethanes obtained or obtainable by the reaction of b) At least partially compact Fibers embedded in polyurethane This was achieved by fiber composite materials, including [Effects of the Invention]

[0010] Surprisingly, it has been found that the use of at least 15% by weight of at least trifunctional alcohols (ii.1) presenting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, i.e., polyols presenting reactive primary hydroxyl groups, leads to significantly better results in terms of avoiding unwanted bubble formation during thread winding (in a winding test). Thus, polyurethanes based on at least 15% by weight of at least trifunctional alcohols (ii.1) presenting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, showed no or at most very little bubble formation during thread winding, despite atmospheric humidities as high as 85%, while the use of less than 15% by weight of at least trifunctional alcohols (ii.1) presenting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, led to foaming, i.e., the formation of unwanted bubbles on the component surface. For almost all of the mechanical properties investigated, advantages were found when using at least trifunctional alcohols (ii.1) presenting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, in particular for impact strength. DETAILED DESCRIPTION OF THE INVENTION

[0011] The polyurethanes according to (a) exhibit a density of 850 g / l or more, preferably in the range of 1000 to 1500 g / l (L.J. Gibson and M.F.A. Shby, Cellular Solids, Cambridge Press, 2nd edition, 1997, pp. 54-56), more preferably in the range of 1000 to 1300 g / l. compact Polyurethane, the density is determined using the buoyancy method in accordance with DIN EN ISO 1183-1 (September 2019). compactAll information regarding the density of polyurethanes always refers to the pure polyurethane resin, without taking into account the filler. When fillers are used in accordance with the following explanation for (ii.1.4) below, the specified density of the polyurethanes according to the invention will vary depending on the amount and density of the filler used.

[0012] In the context of the present invention, small amounts of blowing agent, such as water, which are contained in the polyol as a result of the production process are not to be understood here as constituting an addition of blowing agent. compact The reaction mixture for the production of polyurethane preferably contains less than 0.2% by weight, particularly preferably less than 0.1% by weight, in particular less than 0.05% by weight, of water.

[0013] The at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, is preferably selected from the group consisting of trimethylolpropane (TMP), butane-1,2-4-triol, pentane-1,3,5-triol, 3-(hydroxymethyl)pentane-1,2,5-triol, heptane-1,4,7-triol, a phenol derivative and at least two equivalents of formaldehyde, glycerol, pentaerythritol, sorbitol, mannitol, erythrol, erythrulose, ribulol, ribulose, xylulol, xylulose, fructose, sorbose, tagatose, psicose, and ethoxylated polyethers. more preferably, from the group consisting of reaction products of a phenol derivative with at least two equivalents of formaldehyde, and an ethoxylated polyether polyol; more preferably, from the group consisting of trimethylolpropane (TMP), butane-1,2-4-triol, pentane-1,3,5-triol, 3-(hydroxymethyl)pentane-1,2,5-triol, heptane-1,4,7-triol, a reaction product of a phenol derivative with at least two equivalents of formaldehyde, and an ethoxylated polyether polyol; more preferably, from the group consisting of trimethylolpropane (TMP), butane-1,2-4-triol, pentane-1,3,5-triol, 3-(hydroxymethyl)pentane-1,2,5-triol, heptane-1,4,7-triol, and an ethoxylated polyether polyol.

[0014] According to the present invention, a polyisocyanate composition is used according to (i). The di- or polyisocyanate (i) used can consist of any aliphatic, cycloaliphatic, or aromatic isocyanate known for producing polyurethanes, and also any mixtures thereof. The polyisocyanate composition here comprises at least one polyisocyanate. According to the present invention, the polyisocyanate composition can also comprise two or more polyisocyanates. The at least one polyisocyanate is preferably at least one diisocyanate, more preferably selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, and aromatic diisocyanates, and mixtures of two or more of these diisocyanates. In particular, for example, the following aromatic diisocyanates: toluene-2,4-diisocyanate, mixtures of toluene-2,4- and -2,6-diisocyanate, diphenylmethane-4,4'-, -2,4'- and / or -2,2'-diisocyanate (MDI), mixtures of diphenylmethane-2,4'- and -4,4'-diisocyanate, liquid urethane-, carbodiimide- or uretonimine-modified diphenylmethane-4,4'- and / or Mention may also be made of -2,4-diisocyanate, 4,4'-diisocyanatodiphenylethane, mixtures of monomeric methanediphenyl diisocyanate and homologues of methanediphenyl diisocyanate with multiple rings (polymeric MDI), naphthylene-(1,2)- and -1,5-diisocyanate, or prepolymers of these isocyanates and polyols, or isocyanates and isocyanate-reactive components.As aliphatic diisocyanates, use is made of the customary aliphatic and / or cycloaliphatic diisocyanates, such as tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-dicyclohexylmethane diisocyanate, or oligomers or prepolymers of these isocyanates. Isocyanate compositions containing MDI are preferred.

[0015] The di- or polyisocyanates (i) preferably consist of isocyanates based on diphenylmethane diisocyanate, for example 2,4'-MDI, 4,4'-MDI, or mixtures of these components, optionally together with MDI homologues having multiple rings. The di- and polyisocyanates (a) preferably have a functionality of 2.0 to 2.9, particularly preferably 2.0 to 2.8.

[0016] The di- and polyisocyanates of the polyisocyanate composition (i) can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting the above-described polyisocyanate (i) in excess with a compound having at least two groups reactive with isocyanates at temperatures of, for example, 30 to 100°C, preferably around 80°C, to give a prepolymer. The NCO content of the polyisocyanate prepolymers according to the invention is preferably 15% to 33% by weight, particularly preferably 25% to 30% by weight. The viscosity at 25°C of the di- or polyisocyanates or polyisocyanate prepolymers (i) according to DIN 53019-1-3 is preferably between 5 and 1000 mPa·s, more preferably between 5 and 700 mPa·s, and particularly preferably between 10 and 400 mPa·s. The di- and / or polyisocyanates (i) particularly preferably exhibit at least 50 mol %, more preferably at least 70 mol %, of isocyanates with a functionality of 2.

[0017] In one embodiment, the fiber composite material comprises the following components: a) At least the ingredients: i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups; Polyurethanes obtained or obtainable by the reaction of b) At least partially compact Fibers embedded in polyurethane Including, The at least trifunctional alcohol (ii.1) is an alkoxylated polyether polyol in which at least one terminal alkoxy group is based on ethylene oxide.

[0018] Alkoxylated polyether polyols in which at least one terminal alkoxy group is based on ethylene oxide are those having the terminal structural unit -[-O-CH2-CH2] p It means a polyether polyol containing the terminal structural unit -[-O-CHR-CH2], where p is an integer ranging from 1 to 6. Preferably, an alkoxylated polyether polyol in which at least one terminal alkoxy group is based on ethylene oxide is a polyether polyol containing the terminal structural unit -[-O-CHR-CH2] p’ -[-O-CH2-CH2] p -OH, where p is an integer ranging from 1 to 6, p' is zero or an integer ranging from 1 to 6, and R is independently selected for each p' repeat unit from a methyl group and an ethyl group.

[0019] In one embodiment, the fiber composite material comprises the following components: a) At least the ingredients: i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1). Polyurethanes obtained or obtainable by the reaction of b) At least partially compact Fibers embedded in polyurethane Includes.

[0020] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) is ii.1.1) Polyol initiators with a functionality of 3 to 6, preferably 3 or 4 and, ii.1.2) with ethylene oxide, In the presence of an alkoxylation catalyst (ii.1.3), ii.1.4) optionally in the presence of further auxiliaries and / or additives Obtained or obtainable by reaction.

[0021] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) exhibits an equivalent molecular weight of less than 200 g / mol, preferably in the range of 50 to 140 g / mol, more preferably in the range of 55 to 135 g / mol, more preferably in the range of 60 to 130 g / mol.

[0022] "Polyols with a functionality of 3 to 6" are understood to mean polyols exhibiting an average of 2.8 to 3.0 hydroxyl groups per molecule, or 3.8 to 4.0 hydroxyl groups per molecule, or 4.8 to 5.0 hydroxyl groups per molecule, or 5.8 to 6.0 hydroxyl groups per molecule. Similarly, "polyols with a functionality of 3 or 4" are understood to mean polyols exhibiting an average of 2.8 to 3.0 hydroxyl groups per molecule, or 3.8 to 4.0 hydroxyl groups per molecule. In practice, deviations from the nominal functionality occur because various side reactions during polyol synthesis can result in functionality that may actually be lower than that nominally assumed (M. Ionescu, Chemistry and Technology of Polyols, Rapra, 2005, pp. 67-75). In the equivalent molecular weight range below 200 g / mol, functionality is expected to be very close to 3, 4, 5, or 6, preferably very close to 3 or 4. The equivalent molecular weight (EMW) is the ratio of the molecular weight of the polyether polyol (M(polyether polyol)) to the functionality (F) of the polyether polyol: EMW = M (polyether polyol) / F [g] is defined as:

[0023] Alkoxylation catalysts (ii.1.3) are known to those skilled in the art. Basic catalysts, such as alkali metal salts such as sodium methoxide, sodium hydroxide, potassium hydroxide and / or cesium hydroxide, amines such as imidazole derivatives, or Lewis acid catalysts, such as boron-based fluorine-containing Lewis acid catalysts, such as BF or trispentafluorophenylborane, are used.

[0024] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) exhibits a hydroxyl number of more than 300 mg KOH / g, preferably more than 450 mg KOH / g, more preferably in the range of 300 to 1400 mg KOH / g, more preferably in the range of 450 to 1300 mg KOH / g, more preferably in the range of 450 to 1260 mg KOH / g.

[0025] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) is used in an amount of 15% to 100% by weight, preferably 20% to 100% by weight, more preferably 25% to 75% by weight, more preferably 30% to 50% by weight, relative to 100% by weight of the total weight of the polyol composition (ii).

[0026] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) exhibits no propylene oxide-based and / or butylene oxide-based end groups, and the ethoxylated polyether polyol (ii.1) preferably exhibits exclusively ethylene oxide-based end groups. In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) exhibits exclusively ethylene oxide-based groups and does not contain propylene oxide-based and / or butylene oxide-based groups.

[0027] In one embodiment of the fiber composite, the polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) is a triol having a functionality of 3, preferably of formula (I): [ka] wherein l, m, n, and o are each, independently of one another, an integer ranging from 1 to 6. Preferably, l, m, n, and o of at least one triol (ii.1.1) of formula (I) are each, independently of one another, an integer ranging from 1 to 3, and more preferably l, m, n, and o are all 1.

[0028] The triol (ii.1.1) preferably exhibits a hydroxyl number in the range of 200 to 2000 mg KOH / g, preferably in the range of 250 to 1850 mg KOH / g, more preferably in the range of 300 to 1850 mg KOH / g.

[0029] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without further alkylene oxide.

[0030] In one embodiment of the fiber composite, the polyol initiator (ii.1.1.), in particular the ethoxylated polyether polyol (ii.1) formed by reacting the triol of formula (I) with ethylene oxide (ii.1.2), is used in combination with one or more triols having at least two primary hydroxyl groups. The triols used in this context are the at least trifunctional alcohols (ii.1) described above, excluding the ethoxylated polyether polyols, which have at least two primary hydroxyl groups, preferably three primary hydroxyl groups.

[0031] In one embodiment of the fiber composite material, the ethoxylated polyether polyol (ii.1) is produced solely by reacting a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of any additional initiator, in particular an amine initiator. The term "amine initiator" includes compounds containing one or more primary, secondary, and / or tertiary amine groups. This includes primary amine compounds such as ethanolamine, secondary amine compounds such as diethanolamine, oligoamines with primary amine groups such as isophoronediamine, diaminotoluene, diaminohexane, diaminodiphenylmethane, diaminodicyclohexylmethane, or ethylenediamine, tertiary amine compounds such as triethanolamine or triethylamine, or polyamines with primary amine groups.

[0032] In one embodiment of the fiber composite, the ethoxylated polyether polyol (ii.1) is based on a triol, preferably on the triol (ii.1.1) of formula (I) described above, preferably on the formula (II): [ka] [In the formula, l, m, n, and o are each independently an integer ranging from 1 to 6, and more preferably l, m, n, and o are all 1; p, q, and r are each independently zero or an integer ranging from 1 to 6; X 1 , X 2 , and X 3 are each a -CH2-CH2-O- group] It presents.

[0033] Preferably, the polyol composition (ii) does not include a polyol based on an amine initiator.

[0034] In one embodiment of the fiber composite material, polyurethane (a) can be obtained or is obtained without the use of polyols based on amine initiators.

[0035] In one embodiment of the fiber composite, the polyol composition (ii) comprises less than 10% by weight of polyols exhibiting propylene oxide and / or butylene oxide end groups.

[0036] The polyol composition according to (ii) preferably comprises, in addition to the at least one ethoxylated polyether polyol (ii.1), one or more further polyols, which further polyols are selected from the group of polyester polyols, more preferably aromatic polyester polyols or oleochemical polyols. The at least one polyester polyol, preferably aromatic polyester polyol or oleochemical polyol, preferably exhibits a functionality in the range from 2 to 3, more preferably in the range from 2.4 to 3.

[0037] Polyesterols are produced, for example, by polycondensation of aliphatic or aromatic dicarboxylic acid derivatives with polyhydric alcohols, polythioether polyols, polyesteramides, hydroxyl-containing polyacetals, and / or hydroxyl-containing aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Further possibilities include ring-opening polymerization of cyclic esters (e.g., ε-caprolactone or hydroxycarboxylic acids, such as ω-hydroxycaproic acid) or carbonates, and also transesterification of polyesterols with polyhydric alcohols. Further possible polyols are cited, for example, in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics Handbook, Volume 7, Polyurethanes], Carl Hanser Verlag, 3rd Edition, 1993, Chapter 3.1.

[0038] Preferably, a polyfunctional alcohol, preferably a diol having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, is reacted with a polyfunctional carboxylic acid having 2 to 12 carbon atoms, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, maleic acid, fumaric acid, preferably phthalic acid, isophthalic acid, terephthalic acid, and a mixture of naphthalenedicarboxylic acid isomers. The dicarboxylic acids can be used individually or in admixture with each other. Polycondensation can be carried out in the presence of a fatty acid, such as oleic acid or ricinoleic acid. Examples of dihydric or polyhydric alcohols include ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4- or 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, and trimethylolpropane.

[0039] The polyesterols preferably have a functionality between 1.8 and 4, preferably 2-3, and a number average molecular weight of 3480-3000, preferably 480-3000 g / mol.

[0040] They also exhibit an acid number of less than 10, preferably less than 2.

[0041] To produce polyester polyols, organic polycarboxylic acids and / or derivatives and polyhydric alcohols can be polycondensed without a catalyst or, preferably, in the presence of an esterification catalyst, advantageously in an inert gas atmosphere, such as nitrogen, carbon monoxide, helium, or argon, in the melt at temperatures of 150 to 250°C, preferably 180 to 220°C, optionally under reduced pressure, to the desired acid number, preferably less than 10, particularly preferably less than 2. In a preferred embodiment, the esterification mixture is polycondensed at the aforementioned temperatures under standard pressure and subsequently at a pressure of less than 500 mbar, preferably 50 to 150 mbar, to an acid number of 80 to 30, preferably 40 to 30. Iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin catalysts, for example in the form of metals, metal oxides, or metal salts, are suitable as esterification catalysts. However, the polycondensation can also be carried out in the liquid phase in the presence of a diluent and / or entrainer, such as benzene, toluene, xylene or chlorobenzene, for removing the water of condensation by azeotropic distillation.To produce the polyester polyols, the organic polycarboxylic acids and / or derivatives and the polyhydric alcohols are advantageously polycondensed in a molar ratio of 1:1 to 1:8, preferably 1:1.05 to 1.2.

[0042] The preferred polyesterols used are aromatic polyesterols and oleochemical polyesterols. Examples of oleochemical polyols are described, inter alia, in M. Ionescu, Chemistry and Technology of Polyols, Rapra, 2005, Chapter 17.1. Hydroxyl-functionalized oleochemical compounds, i.e., oleochemical polyols, are preferably used. There are several hydroxyl-functionalized oleochemical compounds that can be used. Examples include castor oil, hydroxyl-modified oils such as grapeseed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio kernel oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil, hemp oil, safflower oil, walnut oil, myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, thymnodonic acid, clupanodonic acid, or cervonic acid-based hydroxyl-modified fatty acid esters. In one embodiment of the oleochemical polyol, castor oil (triglyceride mixture) and its derivatives are used. Preferred derivatives are reaction products with alkylene oxide or ketone-formaldehyde resins. The latter compound is sold, for example, by Covestro AG under the designation Desmophen® 1150. A further preferred group of oleochemical polyols used can be obtained by ring-opening of epoxidized fatty acid esters with simultaneous reaction with alcohols, optionally followed by further transesterification. The incorporation of hydroxyl groups into fats and oils is primarily achieved by epoxidation of the olefinic double bonds contained in these products, followed by reaction of the resulting epoxy groups with monohydric or polyhydric alcohols. The epoxide ring then becomes a hydroxyl group, or in the case of polyfunctional alcohols, a structure with multiple OH groups.Since fats and oils are mostly glycerol esters, the above reaction is also accompanied by a parallel transesterification reaction. The compounds thus obtained preferably have a molecular weight in the range of 500 to 1500 g / mol. Such products are supplied, for example, by BASF (under the trademark Sovermol®) or by Altropol Kunststoff GmbH under the trademark Neukapol®.

[0043] compact In one embodiment of the polyurethane, the polyol composition (ii) comprises any polyetherol, for example, prepared using a catalyst from an epoxide, such as propylene oxide and / or ethylene oxide and / or butylene oxide, and an initiator compound having an active hydrogen atom, such as an aliphatic alcohol, a phenol, an amine, a carboxylic acid, water, or a compound based on a natural substance such as sucrose, sorbitol, or mannitol. Here, basic catalysts or bimetallic cyanide catalysts, such as those described in WO 2006 / 034800 A1, EP 0090444 B1, or WO 05 / 090440 A1, may be mentioned. Preferably, component (ii) comprises a polyetherol obtained by reacting a polyfunctional alcohol with propylene oxide and / or ethylene oxide and / or butylene oxide, and exhibiting less than 10% secondary OH groups.

[0044] In addition, the polyol composition according to (ii) can contain polyol types known to those skilled in the art, such as polybutadienes based on radical or anionic polymerized butadiene, acrylate polyols, polysiloxane polyols, polyols obtainable by Mannich condensation, such as aromatic polyols based on bisphenol A, resorcinol, novolak, or melamine. Further possibilities are polytetrahydrofuran or polycaprolactone, or copolymers from these starting materials. Further possibilities are, for example, polymer polyols based on triols, and particles based on polystyrene, styrene / acrylonitrile, or polyacrylate / polymethacrylate. All of these polyol types are known, for example, from M. Ionescu, Chemistry and Technology of Polyols, Rapra, 2005, pp. 67-75.

[0045] compactIn one embodiment of the polyurethane, the polyol composition (ii) optionally contains a chain extender. Preferably, the chain extender is a substance having a molecular weight of less than 450 g / mol, particularly preferably from 60 to 400 g / mol, where the chain extender has two hydrogen atoms reactive with isocyanate groups, and the crosslinker has three hydrogen atoms reactive with isocyanate groups. These can be used individually or in the form of a mixture. Preferably, diols and / or triols having a molecular weight of less than 400, particularly preferably from 60 to 300, and especially from 60 to 150, are used. Examples of initiator molecules include aliphatic, cycloaliphatic, and / or araliphatic diols having 2 to 14, preferably 2 to 10, carbon atoms, such as monoethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,10-decanediol, 1,2-, 1,3-, or 1,4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,2-butanediol, 1,6-hexahydroxycyclohexane ... Suitable are sandiol, bis(2-hydroxyethyl)hydroquinone (HQEE), bisphenol A, bis(hydroxyethyl ether), triols such as 1,2,4- or 1,3,5-trihydroxycyclohexane, glycerol, and trimethylolpropane, as well as low molecular weight polyalkylene oxides containing hydroxyl groups, the polyalkylene oxides being based on ethylene oxide and / or 1,2-propylene oxide and the diols and / or triols mentioned above.

[0046] Amine chain extenders, such as diethyltoluenediamine (DEDTA), m-phenylenediamine, diethanolamine, or triethanolamine, are more preferred. Monoethylene glycol, butane-1,4-diol, butane-1,2-diol, diethylene glycol, glycerol, or mixtures thereof are particularly preferred as chain extenders. When chain extenders and / or crosslinkers are used, their proportion is typically 1% to 50% by weight, preferably 2% to 20% by weight, based on the total weight of the components of polyol composition (ii). However, the chain extender or crosslinker can also be omitted. However, the addition of a chain extender, crosslinker, or optionally a mixture thereof, may prove advantageous for modifying mechanical properties, such as hardness.

[0047] In one embodiment of the fiber composite material, polyol composition (ii) comprises less than 10% by weight of polyols presenting end groups based on propylene oxide and / or butylene oxide, and polyol composition (ii) preferably does not comprise polyols presenting propylene oxide or butylene oxide end groups. Preferably, polyol composition (ii) comprises less than 10% by weight of polyols presenting propylene oxide and / or butylene oxide groups. Polyol composition (ii) more preferably does not comprise polyols presenting propylene oxide or butylene oxide groups, and / or polyols based on propylene oxide and / or butylene oxide, and / or chain extenders with secondary OH groups.

[0048] In one embodiment of the fiber composite material, polyol composition (ii) comprises at least one reactive diluent, preferably in an amount of 5% to 50% by weight, based on the total weight of polyol composition (ii), and the at least one reactive diluent preferably comprises a substance having at least one olefinic group, preferably a substance having at least two olefinic groups, more preferably a substance having at least one terminal olefinic group, more preferably a substance having at least two terminal olefinic groups. The substance having a terminal olefinic group is preferably selected from the group consisting of allyl ethers, vinyl ethers, acrylates, and methacrylates, more preferably butanediol diacrylate, butanediol dimethacrylate, and mixtures of butanediol diacrylate and butanediol dimethacrylate; ethylene glycol-based acrylates, preferably oligomeric or polymeric ethylene glycol acrylates; propylene glycol-based acrylates, preferably propylene glycol-based oligomeric or polymeric acrylates; bisphenol A-based acrylates, bisphenol A-based acrylates, bisphenol B-based acrylates, bisphenol C ... C-based acrylates, bisphenol B-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol B-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based acrylates, bisphenol C-based The acrylates are selected from the group of F-based acrylates, glycerol-based acrylates, oligomeric glycerol-based acrylates, trimethylolpropane-based acrylates, ditrimethylolpropane-based acrylates, pentaerythritol-based acrylates, isocyanurate-based acrylates, hexahydrotriazine-based acrylates, and methacrylates, and always contain at least one, and preferably two or more, terminal acrylate, methacrylate, allyl ether, or vinyl ether groups, more preferably always contain at least one, and more preferably two or more, terminal acrylate, methacrylate, allyl ether, or vinyl ether groups.

[0049] In one embodiment of the fiber composite material, the polyurethane preferably comprises an epoxy resin in an amount of 1% to 50% by weight, preferably 5% to 25% by weight, always relative to the total weight of the polyol composition (ii).

[0050] Low-viscosity aliphatic, cycloaliphatic, or aromatic epoxides, and mixtures thereof, are particularly well suited as polyepoxides. Polyepoxides can be produced by the reaction of an epoxide, such as epichlorohydrin, with an alcohol. For example, bisphenol A, bisphenol F, bisphenol S, cyclohexanedimethanol, phenol-formaldehyde resin, cresol-formaldehyde novolac, butanediol, hexanediol, trimethylolpropane, or polyether polyols can be used as the alcohol. For example, glycidyl esters of phthalic acid, isophthalic acid, or terephthalic acid, and mixtures thereof, can also be used. Epoxides can also be produced by epoxidation of organic compounds containing double bonds, for example, by epoxidizing fats or oils, such as soybean oil, to give epoxidized soybean oil. Polyepoxides can also include monofunctional epoxides as reactive diluents. These can be produced by the reaction of alcohols with epichlorohydrin, for example, C4-C6. 18 The epoxy equivalent weight is preferably a monoglycidyl ether of alcohol, cresol, or p-(tert-butyl)phenol. Additional epoxides that can be used are described, for example, in "Handbook of Epoxy Resins" by Henry Lee and Kris Neville, McGraw-Hill Book Company, 1967. It is preferable to use a glycidyl ether of bisphenol A having an epoxide equivalent weight in the range of 170 to 250 g / eq, particularly preferably in the range of 176 to 196 g / eq. The epoxy equivalent weight can be determined according to ASTM D-1652. For example, Eurepox 710 or Epilox 828 can be used.

[0051] In one embodiment of the fiber composite, the isocyanate composition (i) and / or the polyol composition (ii), preferably the isocyanate composition (i) and the polyol composition (ii), each exhibit a viscosity of less than 1000 mPa·s, preferably less than 500 mPa·s, at 25°C, the viscosity being determined according to ASTM D445 (25°C).

[0052] In one embodiment of the fiber composite, the polyisocyanate composition (i) and the polyol composition (ii), preferably the polyisocyanate composition (i) and all groups reactive with isocyanates, are used in a ratio that results in an isocyanate index of between 99 and 400, preferably between 100 and 250. The isocyanate index is preferably in the range of 100 to 399, more preferably in the range of 101 to 249. In the context of the present invention, the isocyanate index is understood to mean the stoichiometric ratio of isocyanate groups to groups reactive with isocyanates multiplied by 100. The isocyanate reactive groups in this context are understood to mean all groups present in the reaction mixture that react with isocyanates, including any chemical blowing agents and compounds containing epoxy groups, but excluding the isocyanate groups themselves. The isocyanate index is determined by calculation from the weight percentages or amounts of the components used and their functionality. In the prior art, the prevailing view is that a high isocyanate index generally increases the risk of undesirable reactions between isocyanates and atmospheric moisture during production. Therefore, those skilled in the art have traditionally selected the index to minimize or eliminate excess isocyanate in open-winding processes (isocyanate index of 100-120). For example, WO 03 / 085022(A) discloses isocyanate indexes greater than 120 in open-winding processes, and Examples A9, A10, A11, A12, A13, and A14 all contain only quantitative data, without details regarding processability and foam formation. WO 18 / 036943(A) describes a chemistry similar to that of the present invention (but instead of an EO-based crosslinker, the predominant polyol has a secondary OH group), resulting in an index in the range of up to 200 (preferably up to 110), but is not optimized for fiber winding applications. Surprisingly, it has been found that the polyol compositions according to the invention allow the use of a large excess of isocyanate, between 99 and 400, preferably between 100 and 250.Surprisingly, when using the polyol compositions according to the invention, surprisingly improved properties can also be obtained in terms of high index (especially in terms of heat distortion temperature), and it can be shown that, despite the high index, the processability / tendency to form bubbles is surprisingly good.

[0053] The ratio of isocyanate groups to epoxy groups is between 12:1 and 2:1, preferably between 10:1 and 4:1.

[0054] In one embodiment of the fiber composite material, neither the polyisocyanate composition (i) nor the polyol composition (ii) contains a radical initiator or photoinitiator. In one embodiment of the fiber composite material, a radical inhibitor is present. Substances that terminate or retard radical polymerization of carbon-carbon double bonds can be used as radical inhibitors. Radical inhibitors, also known as radical scavengers, include bis(trifluoromethyl)nitroxide, aminoxyl radical, 2,2-diphenyl-1-picrylhydrazyl, and 2,2,6,6-tetramethylpiperidin-1-yloxy. Preferred radical inhibitors are phenothiazine, nitrobenzene, hydroquinone monomethyl ether, p-benzoquinone, and diphenylpicrylhydrazyl. In a preferred embodiment, the reaction mixture contains 0.0001% to 2.0% by weight, preferably 0.0005% to 1.0% by weight, and particularly 0.001% to 0.5% by weight of the radical inhibitor, based on the total weight of component (ii). The radical inhibitor can in principle be added to component (i) and / or to component (ii).

[0055] Auxiliaries and / or additives (ii.1.4) can also be used optionally. All auxiliaries and additives known for the production of polyurethanes can be used here. For example, mention may be made of surface-active substances, foam stabilizers, cell regulators, deaerators, defoamers, water scavengers, adhesion promoters, wetting agents, flow aids, thixotropic agents, release agents, plasticizers, thinners, fillers, dyes, pigments, flame retardants, additives for suppressing smoke formation, hydrolysis inhibitors, antistatic agents, antioxidants, UV protection agents, and fungistatic and bacteriostatic substances. Such substances are known and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics Handbook, Volume 7, Polyurethanes], Carl Hanser Verlag, 3rd Edition, 1993, Chapters 3.4.4 and 3.4.6 to 3.4.11. Those skilled in the art know that these additives can be used in the range of 0 to 25 weight percent of the polyol composition.

[0056] In one embodiment of the fiber composite, without the addition of a blowing agent, compact A polyurethane is obtained. In the context of the present invention, small amounts of blowing agent, for example water, contained in the polyol as a result of the production process are not to be understood here as constituting an addition of blowing agent. compact The reaction mixture for the production of polyurethanes preferably contains less than 0.2% by weight, particularly preferably less than 0.1% by weight, in particular less than 0.05% by weight, of water, based on the total weight of all components used. Optional auxiliaries and / or additives (ii.1.4) preferably include water scavengers.

[0057] As additives, conventional polyurethane catalysts can be used as catalysts (ii.1.4). These significantly accelerate the reaction of compounds (b) containing hydrogen atoms reactive with isocyanates with di- and polyisocyanates (a). Conventional catalysts that can be used to produce polyurethanes include, for example, amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, or tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dimethylcyclohexylamine, N-methyl-, N-ethyl-, or N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanoic acid, and the like. Mention may be made of diethanolamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane, preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, and dimethylethanolamine. Also suitable are organometallic compounds, preferably organotin compounds, such as tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, and tin(II) laurate, as well as dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate, and also bismuth carboxylates, such as bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, and bismuth octoate, or mixtures thereof. The organometallic compounds can be used alone or, preferably, in combination with a strongly basic amine. When component (ii.1.4) is an ester, exclusively amine catalysts are preferably used.It is also possible to use "latent" catalysts known to those skilled in the art, which do not exhibit or exhibit only little catalytic activity at ambient temperature and become active only, for example, by increasing the temperature. Examples of these catalysts can be found, inter alia, in DE 102008021980 A1 or WO 2009 / 115540 A1.

[0058] The catalyst (ii.1.4) can be used as a catalyst or catalyst combination, for example, in a concentration of 0.001% to 5% by weight, particularly 0.05% to 2% by weight, based on the weight of component (ii). In a further preferred embodiment, the auxiliary and additive (ii.1.4) can include a basic catalyst that is not a conventional polyurethane-forming catalyst. These include, for example, catalysts that catalyze the formation of polyisocyanurates. Polyisocyanurate catalysts include alkali metal carboxylates. These preferably include formates and acetates, particularly acetates, such as sodium acetate, potassium acetate, and cesium acetate.

[0059] In one embodiment of the fiber composite material, the polyisocyanate composition (i) and / or the polyol composition (ii) comprise an alkali metal or alkaline earth metal carboxylate salt. In one embodiment of the fiber composite material, the polyisocyanate composition (i) and / or the polyol composition (ii) comprise an acid-blocked catalyst.

[0060] A further type of additive (ii.1.4) is a degassing agent, which is known to those skilled in the art and is described, for example, in Thomas Brock, Michael Groteklaes, and Peter Mischke: Lehrbuch der Lacktechnologie [Textbook of Paint Technology], edited by Ulrich Zorll, 2nd edition, Vincentz Verlag, Hanover, 2000, ISBN 978-3-87870-569-7, Chapter 2.4.2.1, Defoamers and Deaerators, page 169 ff. In a further embodiment, such components (ii.1.4) that do not contain hydrogen atoms that react with isocyanates can also be added to the polyisocyanate composition (i).

[0061] Some embodiments include a filler as additive (ii.1.4). The group of fillers includes ground minerals such as metal oxides, aluminum hydroxide, bentonite, perlite, fly ash, alkaline earth metal carbonates such as calcium carbonate, talc, mica, kaolin, wollastonite, quartz powder, diatomaceous earth, pyrogenic silica, barium sulfate, calcium sulfate, glass microspheres, hollow glass microspheres, graphite, or soot. Biologically derived fillers are also included, such as wood fibers, wood chips, bamboo fibers, bamboo chips, straw, flax, or cellulose fibers.

[0062] Within the meaning of the present invention, the term "polyurethane" includes all known polyisocyanate addition polymerization products, including addition products of isocyanates with alcohols, and also modified polyurethanes, which may contain isocyanurate, allophanate ester, urea, carbodiimide, uretonimide, or biuret structures, and other isocyanate addition products.

[0063] In one embodiment of the fiber composite material, the material of the fiber (b) is selected from the group consisting of glass fibers, carbon fibers, polyester fibers, polyethylene fibers, natural fibers such as cellulose fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, Zylon fibers (poly(p-phenylene-2,6-benzobisoxazole)), silicon carbide fibers, asbestos fibers, metal fibers, and combinations thereof. More preferably, these are typically glass or carbon fibers. In the context of the present invention, the term "fiber" preferably refers to continuous fibers used as individual fibers or bundled fibers, especially fibers in the form of so-called "rovings," i.e., fibers in the form of bundles, strands, or multifilament yarns made of essentially parallel-oriented filaments (continuous fibers). The cross section of the roving is preferably oval or rectangular, including circular shapes. Rovings having a fineness in the range of 100 to 10,000 tex, preferably in the range of 1,000 to 5,000 tex, more preferably in the range of 1,500 to 3,000 tex, are preferably used. The techniques for wetting the fibers are not limited and are generally known, including, for example, fiber winding, pultrusion, hand lamination, and infusion, preferably as a vacuum infusion method, and also fiber spraying.

[0064] Preferably, the fiber composite is prepared by reacting a reaction mixture in the presence of fibers. Compact It is accordingly obtained or obtainable from a process which omits the use of a blowing agent and which gives a non-cellular polyurethane, and therefore the fiber composite material is preferably produced by a process selected from the group consisting of a fiber winding process, a pultrusion process, an infusion process such as a vacuum infusion process, or an RTM process, a hand-lamination process, a prepreg process, and a mixture of two or more of these processes.

[0065] Less preferred are methods in which the reaction mixture is slightly foamed in the presence of the fibers and then compressed or consolidated, for example, by pressure methods.

[0066] It is possible to supplement this with the use of short or long glass fibres, continuous fibres, non-crimped fabrics, warp knitted fabrics, weft knitted fabrics, knitted fabrics, braids, nonwoven fabrics, mats, e.g. randomly distributed fibre mats, etc. In this context, plies with the same or different fibre orientations are possible, e.g. unidirectional and / or multidirectional.

[0067] Method for the production of fiber composite materials The present invention further provides a method for the production of a fiber composite material, in particular for the production of a fiber composite material as described above, comprising the steps of: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of the fibers (b) to give a polyurethane (a), so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), thereby obtaining a fiber composite material. The present invention relates to a method, including:

[0068] The polyurethanes according to (a) exhibit a density of 850 g / l or more, preferably in the range of 1000 to 1500 g / l (L.J. Gibson and M.F.A. Shby, Cellular Solids, Cambridge Press, 2nd edition, 1997, pp. 54-56), more preferably in the range of 1000 to 1300 g / l. compact Polyurethane, the density is determined using the buoyancy method in accordance with DIN EN ISO 1183-1 (September 2019). compactAll information regarding the density of polyurethanes always refers to the pure polyurethane resin, without taking into account the filler. When fillers are used in accordance with the following explanation for (ii.1.4) below, the specified density of the polyurethanes according to the invention will vary depending on the amount and density of the filler used.

[0069] In one embodiment, a method for the production of a fiber composite material comprises the steps of: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, wherein the at least trifunctional alcohol (ii.1) is an alkoxylated polyether polyol in which at least one terminal alkoxy group is based on ethylene oxide; C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of the fibers (b) to give a polyurethane (a), so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), thereby obtaining a fiber composite material. Includes.

[0070] Alkoxylated polyether polyols in which at least one alkoxy group is based on ethylene oxide are those having the terminal structural unit -[-O-CH2-CH2] p It means a polyether polyol containing the terminal structural unit -[-O-CHR-CH2], where p is an integer ranging from 1 to 6. Preferably, an alkoxylated polyether polyol in which at least one terminal alkoxy group is based on ethylene oxide is a polyether polyol containing the terminal structural unit -[-O-CHR-CH2] p’ [-O-CH2-CH2] p-OH, where p is an integer ranging from 1 to 6, p' is zero or an integer ranging from 1 to 6, and R is independently selected for each p' repeat unit from a methyl group and an ethyl group.

[0071] In one embodiment, a method for the production of a fiber composite material comprises the steps of: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1), C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of the fibers (b) to give a polyurethane (a), so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), thereby obtaining a fiber composite material. Includes.

[0072] Details or specific embodiments regarding the polyisocyanate composition (i), the at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, and also the further components of the polyol composition (ii), and also the fibers (b), have already been described above in connection with the fiber composite material itself and will now be applied accordingly to the production process.

[0073] In one embodiment, a method for the production of a fiber composite material comprises the steps of: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1); C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D.1) reacting a polyurethane reaction mixture (a') in the presence of fibers (b) to give a prepolymerized polyurethane (a), wherein the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a) to obtain a laminate; E) Optionally, a step of shaping the laminate produced in step D.1), for which one or more of the laminates produced in step D.1) can be used to consolidate, F) Completing the curing of the laminate according to D.1) or the formed laminate according to E). Includes.

[0074] In one embodiment, a method for the production of a fiber composite material comprises the steps of: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1); C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D.2) reacting the polyurethane reaction mixture (a') to provide a prepolymerized polyurethane (a); E) reacting the prepolymerized polyurethane (a) in the presence of the fibers (b) so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a) to obtain a laminate; F) optional step of shaping the laminate produced in step E), for which one or more of the laminates produced in step D.1) can be used for consolidation, G) completing the curing of the laminate according to E) or the formed laminate according to F). Includes.

[0075] In one embodiment of the process for the production of a fiber composite material, the ethoxylated polyether polyol (ii.1) is ii.1.1) Polyol initiators with a functionality of 3 to 6, preferably 3 or 4 and, ii.1.2) with ethylene oxide, In the presence of an alkoxylation catalyst (ii.1.3), ii.1.4) optionally in the presence of further auxiliaries and / or additives Obtained or obtainable by reaction.

[0076] In one embodiment of the process for the production of a fiber composite material, the ethoxylated polyether polyol (ii.1) exhibits a hydroxyl number of more than 300 mg KOH / g, preferably more than 450 mg KOH / g, more preferably in the range of 300 to 1400 mg KOH / g, more preferably in the range of 450 to 1300 mg KOH / g, more preferably in the range of 450 to 1260 mg KOH / g.

[0077] In one embodiment of the process for producing a fiber composite material, the ethoxylated polyether polyol (ii.1) exhibits an equivalent molecular weight of less than 200 g / mol, preferably in the range of 50 to 140 g / mol, more preferably in the range of 55 to 135 g / mol, more preferably in the range of 60 to 130 g / mol.

[0078] In one embodiment of the process for producing a fiber composite material, the ethoxylated polyether polyol (ii.1) is used in an amount of 20% to 100% by weight, more preferably 25% to 75% by weight, more preferably 30% to 50% by weight, relative to 100% by weight of the total weight of the polyol composition (ii).

[0079] In one embodiment of the process for the production of fiber composites, the ethoxylated polyether polyol (ii.1) exhibits no propylene oxide-based and / or butylene oxide-based end groups, preferably exclusively ethylene oxide-based end groups. In one embodiment of the process for the production of fiber composites, the ethoxylated polyether polyol (ii.1) exhibits exclusively ethylene oxide-based groups and does not comprise propylene oxide-based and / or butylene oxide-based groups.

[0080] In one embodiment of the process for the production of a fiber composite material, the polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) is a triol having a functionality of 3, preferably of formula (I): [ka] wherein l, m, n, and o are each, independently of one another, an integer ranging from 1 to 6. Preferably, l, m, n, and o of at least one triol (ii.1.1) of formula (I) are each, independently of one another, an integer ranging from 1 to 3, and preferably l, m, n, and o are all 1. Triol (ii.1.1) preferably exhibits a hydroxyl number in the range of 200 to 2000 mg KOH / g, preferably in the range of 250 to 1850 mg KOH / g, more preferably in the range of 300 to 1850 mg KOH / g.

[0081] In one embodiment of the process for the production of fiber composites, the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of any further alkylene oxide.

[0082] In one embodiment of the process for the production of fiber composites, the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of a further initiator, in particular an amine-based initiator.

[0083] In one embodiment of the process for the production of a fiber composite material, the ethoxylated polyether polyol (ii.1) is based on a triol, preferably on the triol (ii.1.1) of formula (I) described above, more preferably on the triol (ii.1.1) of formula (II):

[0084] [ka] [In the formula, l, m, n, and o are each independently an integer ranging from 1 to 6, and more preferably l, m, n, and o are all 1; p, q, and r are each independently zero or an integer ranging from 1 to 6; X 1 , X 2 , and X 3 are each a -CH2-CH2-O- group.

[0085] In one embodiment of the method for producing a fiber composite material, the polyol composition (ii) does not include a polyol based on an amine initiator.

[0086] In one embodiment of the process for the production of a fiber composite material, polyurethane (a) can be obtained or is obtained without the use of polyols based on amine initiators.

[0087] In one embodiment of the process for producing a fiber composite material, the polyol composition (ii) comprises less than 10% by weight of a polyol presenting propylene oxide and / or butylene oxide end groups. In one embodiment of the process for producing a fiber composite material, the polyol composition (ii) comprises one or more further polyols, preferably at least one polyester polyol, more preferably an aromatic polyester polyol or an oleochemical polyol. The at least one polyester polyol, preferably an aromatic polyester polyol or an oleochemical polyol, preferably exhibits a functionality in the range of 2 to 3, more preferably in the range of 2.4 to 3. Details regarding the polyester polyols used, or the preferred aromatic polyester polyols or preferred oleochemical polyols, have already been given at the beginning of the section on fiber composite materials, and the details given there also apply to the present process. In one embodiment of the process for producing a fiber composite material, the polyol composition (ii) does not comprise a polyol presenting propylene oxide or butylene oxide end groups. In one embodiment of the process for producing a fiber composite material, polyol composition (ii) comprises less than 10% by weight of polyols presenting propylene oxide and / or butylene oxide groups. In one embodiment of the process for producing a fiber composite material, polyol composition (ii) does not comprise polyols presenting propylene oxide or butylene oxide groups.

[0088] In one embodiment of the process for the production of a fiber composite material, the polyol composition (ii) comprises at least one reactive diluent, and the at least one reactive diluent preferably comprises a material having at least one olefinic group, preferably a material having at least two olefinic groups, more preferably a material having at least one terminal olefinic group, more preferably a material having at least two terminal olefinic groups.

[0089] In one embodiment of the method for producing a fiber composite material, the polyurethane preferably comprises an epoxy resin in an amount of 1% to 50% by weight, preferably 5% to 25% by weight, always relative to the total weight of the polyol composition (ii).

[0090] In one embodiment of the process for producing a fiber composite material, the isocyanate composition (i) and / or the polyol composition (ii), preferably the isocyanate composition (i) and the polyol composition (ii), each exhibit a viscosity of less than 1000 mPa·s, preferably less than 500 mPa·s, at 25°C, the viscosity being determined according to ASTM D445 (25°C).

[0091] In one embodiment of the process for the production of a fiber composite material, the polyisocyanate composition (i) and the polyol composition (ii), preferably the polyisocyanate composition (i) and all groups reactive with isocyanate, are used in a ratio that results in an isocyanate index between 99 and 400, preferably between 100 and 250. The isocyanate index is preferably in the range of 100-399, more preferably in the range of 101-249.

[0092] In one embodiment of the method for producing a fiber composite material, apart from the polyisocyanate composition (i), the polyol composition (ii), and the fibers (b), no further components are added after mixing (i) and (ii) or after adding (b).

[0093] In one embodiment of the method for producing a fiber composite material, neither the polyisocyanate composition (i) nor the polyol composition (ii) contains urethane, urea, amide, biuret, allophanate, and isocyanurate groups. In one embodiment of the method for producing a fiber composite material, the polyisocyanate composition (i) contains an isocyanate prepolymer.

[0094] In one embodiment of the process for producing fiber composites, further auxiliaries and / or additives (ii.1.4) are added, preferably contained in the polyol composition (ii), more preferably in the at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, more preferably in an ethoxylated polyether polyol (ii.1) comprising further auxiliaries and / or additives, more preferably obtained or obtainable by reaction of a polyol initiator (ii.1.1) having a functionality of 3 to 6, preferably 3 or 4, with ethylene oxide (ii.1.2) in the presence of an alkoxylation catalyst (ii.1.3) and further auxiliaries and / or additives (ii.1.4). In one embodiment of the process for producing fiber composites, further auxiliaries and / or additives are added, preferably contained in the isocyanate composition (i). Further details regarding the further auxiliaries and / or additives (ii.1.4) have already been given in the introduction to the fiber composite material and apply here accordingly to the production method. In one embodiment of the fiber composite material, without the addition of a blowing agent, compact A polyurethane is obtained. In the context of the present invention, small amounts of blowing agent, for example water, contained in the polyol as a result of the production process are not to be construed as constituting the addition of a blowing agent here. compact The reaction mixture for the production of polyurethanes preferably contains less than 0.2% by weight, particularly preferably less than 0.1% by weight, in particular less than 0.05% by weight, of water, based on the total weight of all components used. Optional auxiliaries and / or additives (ii.1.4) preferably include water scavengers.

[0095] For the production of a fiber composite material, the method comprises reacting a reaction mixture in the presence of fibers. CompactA process that omits the use of a blowing agent and that gives a non-porous polyurethane is preferred, so the fiber composite material is preferably produced by a process selected from the group consisting of fiber winding, pultrusion, infusion processes such as vacuum infusion, or RTM, hand lamination, and mixtures of two or more of these processes.

[0096] Less preferred are methods in which the reaction mixture is slightly foamed in the presence of the fibers and then compressed or consolidated, for example, by pressure methods.

[0097] Reacting the reaction mixture in the presence of fibers Compact A method for producing a fiber composite material that omits the use of a blowing agent and that gives a non-cellular polyurethane is preferred, and the fiber composite material is therefore preferably produced by a method selected from the group consisting of fiber winding, pultrusion, infusion methods such as vacuum infusion, or RTM, hand lamination, prepreg, and mixtures of two or more of these methods.

[0098] Less preferred are methods in which the reaction mixture is slightly foamed in the presence of the fibers and then compressed or consolidated, for example, by pressure methods.

[0099] In one embodiment, the process for producing a fiber composite material is carried out using a fiber winding process by mixing the polyisocyanate composition (i) and the polyol composition (ii) and metering them into an impregnation bath where they are contacted with the fiber (b), and subsequently placing the impregnated fiber on a winding spindle, tool, or part.

[0100] The impregnation bath is carried out according to WO 19 / 025439 A1. The bath is directly connected to the mixing head of the dosing system and the temperature can be controlled. The resin capacity of the impregnation bath is dimensioned so that it can function with as little resin as possible and can be changed frequently, several times per minute.

[0101] The resin consumption per minute can be easily calculated from the fiber count, density, and tex count, the desired fiber volume content, the resin density, and the speed at which the fibers are drawn through the bath. The bath geometry is chosen to avoid dead zones where resin can accumulate. Furthermore, the possibility of adding wash liquid or compressed air to the impregnation bath is considered, without the need to disassemble it for this purpose.

[0102] In one embodiment, a method for producing a fiber composite material using a pultrusion molding method is carried out by mixing polyisocyanate composition (i) and polyol composition (ii) and metering the reaction mixture into a closed impregnation device in which the reaction mixture comes into contact with continuously oriented fibers and / or fiber mat (b), which is continuously drawn through a mold and then cured. In one embodiment, a method for producing a fiber composite material is carried out by using a vacuum infusion method, for example an RTM method, to mix polyisocyanate composition (i) and polyol composition (ii) and meter them into an at least partially evacuated mold into which a preform made of fibers (b) has previously been inserted, followed by curing in the mold.

[0103] In one embodiment, the method for the production of a fiber composite material is carried out for the production of fibers or fiber materials pre-impregnated with polyurethane (polyurethane prepreg).

[0104] According to WO 2014 / 170252 A1, for the production of polyurethane prepregs, it is preferred to use polyols with a high proportion of secondary OH end groups (40-100%) using latent catalysts. According to WO 2014 / 170252 A1 and WO 2018 / 219756 A1, for this purpose it is advantageous or necessary to use prepolymers containing isocyanate groups, which are heated to 90°C and then impregnated into the fibers.

[0105] According to the method of the present invention, preferably at least 30% by weight of ethoxylated polyether polyol can be used to produce the prepreg. In this regard, according to one embodiment, the polyisocyanate composition (i) and the polyol composition (ii) can be mixed and contacted with the oriented fibers (b), followed by partial curing. According to one embodiment, the polyisocyanate composition (i) and the polyol composition (ii) are mixed and reacted at a temperature below 80°C. The pre-reacted mixture is then contacted with the oriented fibers (b), followed by partial curing. According to both embodiments, for final curing, the prepreg material (optionally after molding and consolidation with additional prepreg plies, for example under pressure) is heated to 150°C for 3 minutes to 3 hours.

[0106] The method according to the invention is particularly advantageous in this case when, for example, open impregnation baths are used or when production methods for fiber composites are chosen in which long open times (more than 30 minutes) are required in the production of prepregs and the reaction materials are in direct contact with the surrounding atmosphere for a relatively long period of time.

[0107] Alternatively, the method for producing a fiber composite material is carried out by a fiber spray method, in particular a long fiber injection or SMC method. In one embodiment, the method for producing a fiber composite material is carried out using a long fiber injection method by mixing a polyisocyanate composition (i) with a polyol composition (ii), preferably in a mixing head, dripping chopped fibers (b) into the reaction mixture, and then spraying the material onto a mold and / or support, followed by curing there. In one embodiment, the method for producing a fiber composite material for producing an SMC (sheet molding compound) is carried out by mixing a polyisocyanate composition (i) with a polyol composition (ii), applying them to at least one of two carrier films, contacting them with reinforcing fibers, bringing the two carrier films together to form a sandwich, and rolling them, and the SMC is optionally stored in a cut stack or rolled up state, and one or more of the SMC parts are optionally consolidated and cured in a pressure tool after removing the carrier film to form a part.

[0108] The present invention further relates to a fiber composite material obtained or obtainable by the method described above.

[0109] The invention further relates to the use of the above-described fiber composite material or the fiber composite material obtained or obtainable by the above-described method for the production of pipes, in particular conical pipes, pipe connectors, pressure vessels, storage tanks, shielding, masts, strips, rollers, torsion shafts, profiles, pieces of sporting goods, moulded parts, covers, exterior automotive parts, ropes, cables, isogrid structures or semi-finished textile products.

[0110] The present invention is described in more detail by the following embodiments and combinations of embodiments, which can be obtained from the corresponding return references and other references. In particular, it should be noted that wherever a range of embodiments is mentioned, for example, in the context of expressions such as "the method according to any of embodiments 1 to 4," each embodiment within this range is deemed to be clearly disclosed to a person skilled in the art, i.e., a person skilled in the art would understand this phrase as synonymous with "the method according to any of embodiments 1, 2, 3, and 4." Furthermore, it should be noted that the following set of embodiments is not a set of claims that determines the scope of protection, but rather constitutes a suitably constructed part of the description directed to general and preferred aspects of the present invention.

[0111] 1. The following ingredients: a) At least the ingredients: i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups; Polyurethanes obtained or obtainable by the reaction of b) At least partially compact Fibers embedded in polyurethane A fiber composite material comprising:

[0112] 2. The following ingredients: a) At least the ingredients: i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1). Polyurethanes obtained or obtainable by the reaction of b) At least partially compact Fibers embedded in polyurethane 2. The fiber composite of embodiment 1, comprising:

[0113] 3. The ethoxylated polyether polyol (ii.1) is ii.1.1) Polyol initiators with a functionality of 3 to 6, preferably 3 or 4 and, ii.1.2) with ethylene oxide, In the presence of an alkoxylation catalyst (ii.1.3), ii.1.4) optionally in the presence of further auxiliaries and / or additives 3. A fiber composite according to embodiment 2, obtained or obtainable by reaction.

[0114] 4. A fiber composite according to embodiment 2 or 3, in which the ethoxylated polyether polyol (ii.1) exhibits a hydroxyl number of more than 300 mg KOH / g, preferably more than 450 mg KOH / g, more preferably in the range of 300 to 1400 mg KOH / g, more preferably in the range of 450 to 1300 mg KOH / g, more preferably in the range of 450 to 1260 mg KOH / g.

[0115] 5. A fiber composite according to any one of embodiments 2 to 4, in which the ethoxylated polyether polyol (ii.1) exhibits an equivalent molecular weight of less than 200 g / mol, preferably in the range of 50 to 140 g / mol, more preferably in the range of 55 to 135 g / mol, more preferably in the range of 60 to 130 g / mol.

[0116] 6. The fiber composite according to any one of embodiments 2 to 5, wherein the ethoxylated polyether polyol (ii.1) is used in an amount of 15% to 100% by weight, preferably 20% to 100% by weight, more preferably 25% to 75% by weight, more preferably 30% to 50% by weight, relative to 100% by weight of the total weight of the polyol composition (ii).

[0117] 7. A fiber composite according to any of embodiments 2 to 6, in which the ethoxylated polyether polyol (ii.1) does not exhibit end groups based on propylene oxide and / or butylene oxide, preferably exhibits exclusively ethylene oxide based end groups.

[0118] 8. A fiber composite according to any of embodiments 2 to 7, in which the ethoxylated polyether polyol (ii.1) exhibits exclusively ethylene oxide-based groups and does not contain propylene oxide-based and / or butylene oxide-based groups.

[0119] 9. The polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) is a triol having a functionality of 3, preferably a triol of formula (I):

[0120] [ka] 9. A fiber composite according to any one of claims 2 to 8, comprising a triol of the formula: wherein l, m, n, and o are each independently an integer from 1 to 6.

[0121] 10. The fiber composite according to embodiment 9, wherein l, m, n, and o of the at least one triol (ii.1.1) of formula (I) are each, independently of one another, an integer from 1 to 3, preferably l, m, n, and o are all 1.

[0122] 11. The fiber composite according to embodiment 9 or 10, wherein the triol (ii.1.1) exhibits a hydroxyl number in the range of 200 to 2000 mg KOH / g, preferably in the range of 250 to 1850 mg KOH / g, more preferably in the range of 300 to 1850 mg KOH / g.

[0123] 12. A fiber composite according to any one of embodiments 2 to 11, in which the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of additional alkylene oxide.

[0124] 13. A fiber composite according to any one of embodiments 2 to 12, in which the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of any further initiator, in particular an amine-based initiator.

[0125] 14. The ethoxylated polyether polyol (ii.1) is based on a triol, preferably a triol (ii.1.1) of formula (I) according to any of embodiments 8 to 10, more preferably of formula (II):

[0126] [ka] [In the formula, l, m, n, and o are each independently an integer ranging from 1 to 6, and more preferably l, m, n, and o are all 1; p, q, and r are each independently zero or an integer ranging from 1 to 6; X 1 , X 2 , and X 3 are each a -CH2-CH2-O- group] 14. A fiber composite according to any one of claims 2 to 13, exhibiting

[0127] 15. A fiber composite according to any one of the preceding embodiments, wherein the polyol composition (ii) does not comprise a polyol based on an amine initiator.

[0128] 16. A fiber composite according to any of the preceding embodiments, wherein polyurethane (a) is obtainable or is obtainable without the use of polyols based on amine initiators.

[0129] 17. A fiber composite according to any of the preceding embodiments, wherein the polyol composition (ii) comprises less than 10% by weight of polyols exhibiting propylene oxide and / or butylene oxide end groups.

[0130] 18. A fiber composite according to any of the preceding embodiments, wherein the polyol composition (ii) comprises one or more further polyols, preferably at least one polyester polyol, more preferably an aromatic polyester polyol or an oleochemical polyol, and wherein the at least one polyester polyol, preferably an aromatic polyester polyol or an oleochemical polyol, preferably exhibits a functionality in the range of 2 to 3, more preferably in the range of 2.4 to 3.

[0131] 19. A fiber composite according to any of the preceding embodiments, wherein polyol composition (ii) comprises less than 10% by weight of polyols exhibiting end groups based on propylene oxide and / or butylene oxide, and wherein polyol composition (ii) preferably does not comprise polyols exhibiting propylene oxide or butylene oxide end groups.

[0132] 20. A fiber composite according to any of the preceding embodiments, wherein the polyol composition (ii) comprises less than 10% by weight of polyols exhibiting propylene oxide and / or butylene oxide groups.

[0133] 21. A fiber composite according to any of the preceding embodiments, wherein the polyol composition (ii) does not comprise a polyol presenting propylene oxide or butylene oxide groups and / or the polyol composition (ii) does not comprise a polyol based on propylene oxide and / or butylene oxide.

[0134] 22. A fiber composite material according to any one of the preceding embodiments, wherein the polyol composition (ii) comprises at least one reactive diluent, preferably in an amount of 5% to 50% by weight, relative to the total weight of the polyol composition (ii), and wherein the at least one reactive diluent preferably comprises a substance having at least one olefinic group, preferably a substance having at least two olefinic groups, more preferably a substance having at least one terminal olefinic group, more preferably a substance having at least two terminal olefinic groups.

[0135] 23. A fiber composite material according to any one of the preceding embodiments, wherein the polyurethane comprises an epoxy resin.

[0136] 24. A fiber composite according to embodiment 23, wherein the polyurethane comprises an epoxy resin in an amount of 1% to 50% by weight, preferably 5% to 25% by weight, relative to the total weight of the polyol composition (ii).

[0137] 25. A fiber composite according to any one of the preceding embodiments, wherein the isocyanate composition (i) exhibits a viscosity (ASTM D445 (25°C)) of less than 1000 mPa·s at 25°C, preferably less than 500 mPa·s.

[0138] 26. A fiber composite material according to any of the preceding embodiments, wherein the polyisocyanate composition (i) and the polyol composition (ii), preferably the polyisocyanate composition (i) and all groups reactive with isocyanate, are used in a ratio such that the isocyanate index is between 99 and 400, preferably between 100 and 250.

[0139] 27. A fiber composite material according to any of the preceding embodiments, wherein neither the polyisocyanate composition (i) nor the polyol composition (ii) comprises a radical initiator or a photoinitiator.

[0140] 28. A fiber composite material according to any of the preceding embodiments, wherein the polyisocyanate composition (i) and / or the polyol composition (ii) comprise a carboxylate salt of an alkali metal or alkaline earth metal.

[0141] 29. A fiber composite material according to any of the preceding embodiments, wherein the polyisocyanate composition (i) and / or the polyol composition (ii) comprises an acid-blocked catalyst.

[0142] 30. A fiber composite according to any one of the preceding embodiments, wherein the viscosity of the polyol composition (ii) is less than 1000 mPa·s, preferably less than 500 mPa·s (ASTM D445 (25°C)).

[0143] 31. A method for producing a fiber composite material, in particular a method for producing a fiber composite material according to any of the preceding embodiments, comprising: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of the fibers (b) to give a polyurethane (a), so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), thereby obtaining a fiber composite material. A method comprising:

[0144] 32. A method for producing a fiber composite material according to embodiment 31, in particular a fiber composite material according to any of embodiments 1 to 30, comprising: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1), C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of the fibers (b) to give a polyurethane (a), so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), thereby obtaining a fiber composite material. A method comprising:

[0145] 33. A method for producing a fiber composite material according to embodiment 32, comprising: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1), C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D.1) reacting a polyurethane reaction mixture (a') in the presence of fibers (b) to give a prepolymerized polyurethane (a), wherein the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a) to obtain a laminate; E) Optionally, a step of shaping the laminate produced in step D.1), for which one or more of the laminates produced in step D.1) can be used to consolidate, F) Completing the curing of the laminate according to D.1) or the formed laminate according to E). A method comprising:

[0146] 34. A method for producing a fiber composite material according to embodiment 32, comprising: A) preparing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight of an ethoxylated polyether polyol (ii.1), C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D.2) reacting the polyurethane reaction mixture (a') to provide a prepolymerized polyurethane (a); E) reacting the prepolymerized polyurethane (a) in the presence of the fibers (b) so that the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a) to obtain a laminate; F) optional step of shaping the laminate produced in step E), for which one or more of the laminates produced in step D.1) can be used for consolidation, G) completing the curing of the laminate according to E) or the formed laminate according to F). A method comprising:

[0147] 35. The ethoxylated polyether polyol (ii.1) is ii.1.1) Polyol initiators with a functionality of 3 to 6, preferably 3 or 4 and, ii.1.2) with ethylene oxide, In the presence of an alkoxylation catalyst (ii.1.3), ii.1.4) optionally in the presence of further auxiliaries and / or additives 35. A process for the production of a fiber composite material according to any of embodiments 32 to 34, which is obtained or obtainable by reaction.

[0148] 36. A process for producing a fiber composite material according to any of embodiments 32 to 35, wherein the ethoxylated polyether polyol (ii.1) exhibits a hydroxyl number of more than 300 mg KOH / g, preferably more than 450 mg KOH / g, more preferably in the range of 300 to 1400 mg KOH / g, more preferably in the range of 450 to 1300 mg KOH / g, more preferably in the range of 450 to 1260 mg KOH / g.

[0149] 37. A process for producing a fiber composite material according to any of embodiments 32 to 36, wherein the ethoxylated polyether polyol (ii.1) exhibits an equivalent molecular weight of less than 200 g / mol, preferably in the range of 50 to 140 g / mol, more preferably in the range of 55 to 135 g / mol, more preferably in the range of 60 to 130 g / mol.

[0150] 38. A process for producing a fiber composite material according to any of embodiments 32 to 37, wherein the ethoxylated polyether polyol (ii.1) is used in an amount of 15% to 100% by weight, preferably 20% to 100% by weight, more preferably 25% to 75% by weight, more preferably 30% to 50% by weight, relative to 100% by weight of the total weight of the polyol composition (ii).

[0151] 39. A process for producing a fiber composite material according to any of embodiments 32 to 38, in which the ethoxylated polyether polyol (ii.1) does not exhibit end groups based on propylene oxide and / or butylene oxide, preferably exhibits exclusively ethylene oxide based end groups.

[0152] 40. A process for producing a fiber composite material according to any of embodiments 32 to 39, in which the ethoxylated polyether polyol (ii.1) exhibits exclusively ethylene oxide-based groups and does not contain propylene oxide-based groups and / or butylene oxide-based groups.

[0153] 41. The polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) is a triol having a functionality of 3, preferably a triol of formula (I): [ka] 41. A process for producing a fiber composite material according to any of embodiments 32 to 40, comprising a triol of the formula: wherein l, m, n, and o are each independently an integer from 1 to 6.

[0154] 42. A process for producing a fiber composite material according to embodiment 41, in which l, m, n, and o of the at least one triol (ii.1.1) of formula (I) are each, independently of one another, integers from the range of 1 to 3, preferably l, m, n, and o are all 1.

[0155] 43. A process for producing a fiber composite according to embodiment 41 or 42, wherein the triol (ii.1.1) exhibits a hydroxyl number in the range of 200 to 2000 mg KOH / g, preferably in the range of 250 to 1850 mg KOH / g, more preferably in the range of 300 to 1850 mg KOH / g.

[0156] 44. A process for the production of a fiber composite material according to any of embodiments 32 to 43, wherein the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of additional alkylene oxide.

[0157] 45. A process for the production of a fiber composite material according to any of embodiments 32 to 44, in which the ethoxylated polyether polyol (ii.1) is produced exclusively by reaction of a polyol initiator (ii.1.1.), in particular a triol of formula (I), with ethylene oxide (ii.1.2), without the use of any further initiator, in particular an amine-based initiator.

[0158] 46. ​​The ethoxylated polyether polyol (ii.1) is based on a triol, preferably a triol (ii.1.1) of formula (I) according to any of embodiments 8 to 10, more preferably a triol (ii.1.1) of formula (I): [ka] [In the formula, l, m, n, and o are each independently an integer ranging from 1 to 6, and more preferably l, m, n, and o are all 1; p, q, and r are each independently zero or an integer ranging from 1 to 6; X 1 , X 2 , and X 3 are each a -CH2-CH2-O- group] 46. ​​A method for producing a fiber composite material according to any of embodiments 32 to 45, wherein the fiber composite material exhibits

[0159] 47. A method for producing a fiber composite material according to any of embodiments 31 to 46, wherein the polyol composition (ii) does not comprise a polyol based on an amine initiator.

[0160] 48. A process for producing a fiber composite material according to any of embodiments 31 to 47, wherein polyurethane (a) is obtainable or is obtained without the use of a polyol based on an amine initiator.

[0161] 49. A process for producing a fiber composite material according to any of embodiments 31 to 48, wherein the polyol composition (ii) comprises less than 10% by weight of a polyol exhibiting propylene oxide and / or butylene oxide end groups.

[0162] 50. A process for the production of a fiber composite material according to any of embodiments 31 to 49, wherein the polyol composition (ii) comprises one or more further polyols, preferably at least one polyester polyol, more preferably an aromatic polyester polyol or an oleochemical polyol, and wherein the at least one polyester polyol, preferably an aromatic polyester polyol or an oleochemical polyol, preferably exhibits a functionality in the range of 2 to 3, more preferably in the range of 2.4 to 3.

[0163] 51. A process for producing a fiber composite material according to any of embodiments 31 to 48, wherein the polyol composition (ii) does not comprise a polyol exhibiting propylene oxide or butylene oxide end groups.

[0164] 52. A process for producing a fiber composite material according to any of embodiments 31 to 51, wherein the polyol composition (ii) comprises less than 10% by weight of polyols exhibiting propylene oxide and / or butylene oxide groups.

[0165] 53. A process for the production of a fiber composite material according to any of embodiments 31 to 52, wherein the polyol composition (ii) does not comprise a polyol exhibiting propylene oxide or butylene oxide groups.

[0166] 54. A process for producing a fiber composite material according to any of embodiments 31 to 53, wherein the polyol composition (ii) comprises at least one reactive diluent, and the at least one reactive diluent preferably comprises a substance having at least one olefinic group, preferably a substance having at least two olefinic groups, more preferably a substance having at least one terminal olefinic group, more preferably a substance having at least two terminal olefinic groups.

[0167] 55. A method for producing a fiber composite material according to any of embodiments 31 to 54, wherein the polyurethane comprises an epoxy resin.

[0168] 56. A method for producing a fiber composite material according to embodiment 55, wherein the polyurethane comprises an epoxy resin in an amount of 1% to 50% by weight, preferably 5% to 25% by weight, always relative to the total weight of the polyol composition (ii).

[0169] 57. A process for producing a fiber composite material according to any of embodiments 31 to 56, wherein the isocyanate composition (i) and / or the polyol composition (ii), preferably the isocyanate composition (i) and the polyol composition (ii), each exhibit a viscosity (ASTM D445 (25°C)) of less than 1000 mPa·s, preferably less than 500 mPa·s, at 25°C.

[0170] 58. A process for producing a fiber composite material according to any of embodiments 31 to 57, wherein the polyisocyanate composition (i) and the polyol composition (ii), preferably the polyisocyanate composition (i) and all groups reactive with isocyanate, are used in a ratio resulting in an isocyanate index between 99 and 400, preferably between 100 and 250.

[0171] 59. A method for producing a fiber composite material according to any of embodiments 31 to 58, in which, apart from (i), (ii), and fiber (b), no further components are added after mixing (i) and (ii) or after adding (b).

[0172] 60. A method for producing a fiber composite material according to any of embodiments 31 to 59, wherein neither (i) nor (ii) contains urethane, urea, amide, biuret, allophanate, or isocyanurate groups.

[0173] 61. A method for producing a fiber composite material according to any of embodiments 31 to 60, wherein (i) comprises an isocyanate prepolymer.

[0174] 62. Process for the production of fiber composites according to any of embodiments 31 to 61, in which further auxiliaries and / or additives are added, which further auxiliaries and / or additives are preferably contained in the polyol composition (ii), more preferably in the at least trifunctional alcohol (ii.1) exhibiting at least two primary hydroxyl groups, preferably three primary hydroxyl groups, more preferably in the ethoxylated polyether polyol (ii.1) comprising the further auxiliaries and / or additives, more preferably in the ethoxylated polyether polyol (ii.1) which is obtained or obtainable by reaction of a polyol initiator (ii.1.1) having a functionality of 3 to 6, preferably 3 or 4, with ethylene oxide (ii.1.2) in the presence of an alkoxylation catalyst (ii.1.3) and further auxiliaries and / or additives (ii.1.4).

[0175] 63. A process for producing a fiber composite material according to any of embodiments 31 to 62, wherein further auxiliaries and / or additives are added, the further auxiliaries and / or additives being preferably contained in the isocyanate composition (i).

[0176] 64. A method for producing a fiber composite material according to any of embodiments 31 to 63, by using a fiber winding method, mixing the polyisocyanate composition (i) and the polyol composition (ii), metering them into an impregnation bath, contacting them therewith the fibers (b), and subsequently placing the impregnated fibers on a winding spindle, tool, or part.

[0177] 65. A method for producing a fiber composite material according to any of embodiments 31 to 63, by using a long fiber injection method, mixing the polyisocyanate composition (i) with the polyol composition (ii), preferably in a mixing head, dripping chopped fibers (b) into the reaction mixture, and then spraying the material onto a mold and / or support, followed by curing thereon.

[0178] 66. A method for producing a fiber composite material according to any of embodiments 31 to 63, by using a fiber spraying method, mixing the polyisocyanate composition (i) with the polyol composition (ii), contacting the reaction mixture with fibers, and subsequently curing it.

[0179] 67. A method for producing a fiber composite material according to any of embodiments 31 to 63, by using a pultrusion method to mix the polyisocyanate composition (i) and the polyol composition (ii) and metering the reaction mixture into a closed impregnation apparatus in which the reaction mixture comes into contact with continuous oriented fibers and / or fiber mat (b), which are continuously drawn through a mold and then cured.

[0180] 68. A method for producing a fiber composite material according to any of embodiments 31 to 63, by using the RTM method to mix the polyisocyanate composition (i) and the polyol composition (ii) and metering them into an at least partially evacuated mold into which a preform made of fibers (b) has previously been inserted, followed by curing in the mold.

[0181] 69. A method for producing a fiber composite material according to any of embodiments 31 to 63 for producing an SMC (sheet molding compound), by mixing the polyisocyanate composition (i) and the polyol composition (ii), applying them to at least one of two carrier films, contacting them with reinforcing fibers, bringing the two carrier films together to form a sandwich, and rolling them, wherein the SMC is optionally stored in cut stacks or rolled up, and one or more of the SMC parts are optionally consolidated and cured in a pressure tool after removing the carrier film to form a part.

[0182] 70. A method for producing a fiber composite material according to any of embodiments 31 to 63 for producing fibers or fiber materials pre-impregnated with polyurethane (polyurethane prepreg), by mixing a polyisocyanate composition (i) and a polyol composition (ii), contacting them with oriented fibers (b), and subsequently partially curing.

[0183] 71. A method for producing a fiber composite material according to any of embodiments 31 to 63 for producing fibers or fiber materials pre-impregnated with polyurethane (polyurethane prepreg), by mixing a polyisocyanate composition (i) and a polyol composition (ii), polymerizing them at a temperature below 80°C, and subsequently contacting them with oriented fibers (b).

[0184] 72. A fiber composite material obtained or obtainable by the method according to any of embodiments 31 to 71.

[0185] 73. Use of a fiber composite material according to any one of embodiments 1 to 30, or obtained or obtainable by the method according to any one of embodiments 31 to 71, for the production of pipes, in particular conical pipes, pipe connectors, pressure vessels, storage tanks, shielding, masts, strips, rollers, torsion shafts, profiles, pieces of sporting goods, molded parts, covers, exterior automotive parts, ropes, cables, isogrid structures, or semi-finished fiber material products.

[0186] The following examples serve to illustrate the invention but are in no way intended to limit its subject matter.

[0187] Example 1. Chemicals

[0188] [Table 1]

[0189] 2. Test Method Shore D hardness test according to DIN ISO 7619-1 Three-point bending test according to DIN EN ISO 178 Tensile strength according to DIN EN ISO 527 Elongation at break according to DIN EN ISO 527 Charpy impact strength (flatwise) according to DIN EN ISO 179-1 / 1fU Heat deflection temperature: HDT-Bf, flatwise at 0.45 MPa according to DIN EN ISO 75 Hydroxyl number (OH number, OHN): DIN 53240 Epoxy group content: SMS 2026 Viscosity: ASTM D445 (25℃) Shrinkage: Polyol and isocyanate are mixed at ambient temperature and the reaction mixture is poured into a metal mold with dimensions of 1000 mm x 20 mm x 10 mm. Excess material is removed using a doctor blade. The reaction mixture is cured at 80°C for 1 hour and at 120°C for 2 hours. After cooling to ambient temperature, the part is removed from the mold. The length of the test strip is compared to the length of the mold.

[0190] 3. Production of Polyurethane Test Panels for Determination of Mechanical Properties (Examples 1-5 and Comparative Examples 1-3) The compositions of the polyurethanes of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1. All starting materials except the isocyanate (typical batch size: 300 g of polyol composition) were mixed under vacuum at ambient temperature, followed by addition of the isocyanate and mixing for 60 seconds in a Speedmixer (FA Hauschild). The reaction mixture was then poured into a 20 x 30 x 0.4 cm or 20 x 30 x 0.2 cm metal mold. Excess resin was scraped off using a doctor blade, and the mixture was cured at 80°C for 1 hour, then at 120°C for 2 hours, and then at 180°C for 2 hours. Test specimens were then milled from the material after one week of storage at ambient temperature.

[0191] 4. Preparation of fiber composites from polyurethane and glass fibers by the fiber winding method (filament winding method) to determine their tendency to form bubbles at 80% atmospheric humidity (Examples 1-5 and Comparative Examples 1-3) The compositions of the polyurethanes of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1. A conventional fiber winding system (filament winding system) was used, installed in a housing with a take-off system. The desired atmospheric humidity level could be set inside the housing using an air humidifier. A bobbin with continuous glass fiber was used, mounted inside the housing. The glass fiber was guided through an unfilled impregnation bath and then wound onto a mandrel using a winding head. The mandrel was clamped at both ends to a rotating device. The impregnation bath and winding head were mounted on a carriage, which allowed the fiber to be wound over the length of the mandrel. The carriage movement, mandrel rotation, and intended winding angle of the fiber on the mandrel were programmed as a function of time and then controlled by the winding software. The glass fiber used was SE3030 glass fiber (boron-free glass fiber, 17 μm filament diameter, 2400 tex (g / km)) manufactured by 3B. The winding patterns selected were two circumferential plies, one ply ±45°, and two circumferential plies. The tests were carried out at a temperature of 25°C and an atmospheric humidity of 85%. The resin impregnation bath was heated to 20°C. At the start of the test, all starting materials except the isocyanate (usual batch size: 100 g of polyol composition) were mixed at ambient temperature, after which the isocyanate was added and mixed in a Speedmixer (FA Hauschild) for 60 seconds. The material was then introduced into the impregnation bath. The roving was then manually pulled until the resin-impregnated roving could be wound onto the mandrel and secured there. The winding program was then started, and several plies of polyurethane-impregnated glass fiber were wound onto the mandrel. At the end of the winding process, the glass fiber was cut, and the material was left to cure in an enclosure at ambient temperature for 1 hour. Curing was then carried out at 80°C for 1 hour and at 120°C for 2 hours.

[0192] The surface quality of the parts was assessed visually. 1: Smooth surface without microbubbles 2: Comparative example, smooth surface with few microbubbles 3: Many microbubbles 4: Rough, foamy part surface 5: Many air bubbles with a diameter of more than 1 mm, white, foamy part surface

[0193] [Table 2]

[0194] It has been shown that the use of at least 15% by weight of at least trifunctional alcohols, particularly ethoxylated triols, i.e., polyols with reactive primary hydroxyl groups, produces significantly better results in winding tests in terms of preventing unwanted bubble formation. Polyurethanes based on at least 15% by weight of at least trifunctional alcohols, preferably at least 3 primary hydroxyl groups, or at least 15% by weight of ethoxylated polyols, show no or at most very little bubble formation in winding tests, even at high atmospheric humidity of 85%, while the use of propoxylated polyols or less than 15% by weight of the aforementioned polyols results in foaming, i.e., the formation of unwanted bubbles. The examples and comparative examples show that in addition to better processability in the winding process, there are advantages in all of the mechanical properties examined, especially in impact strength.

[0195] Surprisingly, it has also been shown that a high isocyanate index can be used. Traditionally, those skilled in the art have chosen the index so that there is no or only a minimal excess of isocyanate in the open winding process (isocyanate index of 100 to 120). It is generally believed that a high isocyanate index increases the risk of undesirable reactions between the isocyanate and atmospheric moisture during production. Surprisingly, it has been found that the polyol composition according to the invention allows the use of a large excess of isocyanate (index between 99 and 400, preferably between 100 and 250).

[0196] The examples and comparative examples show that when using the polyol compositions according to the invention, surprisingly improved properties are also obtained with respect to high index (especially with respect to heat distortion temperature) and, surprisingly, despite the high index, the processability / tendency to form bubbles is excellent.

[0197] References WO 03 / 085022 A1 WO 2016 / 183073 A1 M. Ionescu, Chemistry and Technology of Polyols, Rapra, 2005, pp 67-75 WO 18 / 036943 A WO 19 / 025439 A1 “Kunststoffhandbuch, Band 7, Polyurethane” [Plastics Handbook, Volume 7, Polyurethane], Carl Hanser Verlag, 3rd Edition, 1993, Chapters 3.4.4 and 3.4.6 to 3.4.11 DE 102008021980 A1 WO 2009 / 115540 A1 Thomas Brock, Michael Groteklaes and Peter Mischke: Lehrbuch der Lacktechnologie [Textbook of Paint Technology], Ed.: Ulrich Zorll, 2nd Edition, Vincentz Verlag, Hanover, 2000, ISBN 978-3-87870-569-7, Chap. 2.4.2.1, Defoamers and Deaerators, pp 169 et seq. “Handbook of Epoxy Resins” by Henry Lee and Kris Neville, McGraw-Hill Book Company, 1967 WO 2014 / 170252 A1 WO 2018 / 219756 A1 L.J. Gibson and M.F. Ashby, Cellular Solids, Cambridge Press, 2nd Edition, 1997, pages 54-56

Claims

1. The following components a) and b): a) A polyurethane obtained or obtainable by reaction of at least the following components i) and ii), wherein said polyurethane (a) is a compact polyurethane exhibiting a density in the range of 850 to 1500 g / l, determined using the buoyancy method in accordance with DIN EN ISO 1183-1 (September 2019): i) a polyisocyanate composition; ii) a polyol composition comprising at least 15% by weight of an at least trifunctional ethoxylated polyether polyol (ii.1) having at least two primary hydroxyl groups and less than 10% by weight of a polyol having end groups based on propylene oxide and / or butylene oxide; b) fibers at least partially embedded in said compact polyurethane; A fiber composite material comprising: A fiber composite material, wherein the polyisocyanate composition (i) and the polyol composition (ii) are used in a ratio such that the isocyanate index is between 99 and 400.

2. The ethoxylated polyether polyol (ii.1) is ii. 1.1) a polyol initiator having a functionality of 3 to 6; and ii. 1.2) Ethylene oxide an alkoxylation catalyst (ii.1.3), optionally further ii. 1.4) A fiber composite material according to claim 1, which is obtained or obtainable by reacting in the presence of auxiliaries and / or additives.

3. 3. The fiber composite material according to claim 1, wherein the ethoxylated polyether polyol (ii.1) has no end groups based on propylene oxide and / or no end groups based on butylene oxide and / or the ethoxylated polyether polyol (ii.1) has only groups based on ethylene oxide and no groups based on propylene oxide and / or no groups based on butylene oxide.

4. A fiber composite material as claimed in claim 1 or 2, in which the ethoxylated polyether polyol (ii.1) has no propylene oxide-based and / or butylene oxide-based end groups but only ethylene oxide-based end groups, and / or the ethoxylated polyether polyol (ii.1) has only ethylene oxide-based groups but does not contain propylene oxide-based and / or butylene oxide-based groups.

5. 5. The fiber composite material according to claim 1, wherein the polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) comprises a triol with a functionality of 3.

6. The polyol initiator (ii.1.1) of the ethoxylated polyether polyol (ii.1) is a polyol initiator of formula (I): 【Chemical 1】 5. The fiber composite material according to claim 1, comprising a triol of the formula: wherein l, m, n, and o are each independently an integer from 1 to 6.

7. 7. The fiber composite material according to claim 1, wherein the ethoxylated polyether polyol (ii.1) is produced solely by reacting the polyol initiator (ii.1.1) with ethylene oxide (ii.1.2) without the use of further alkylene oxides and / or the ethoxylated polyether polyol (ii.1) is produced solely by reacting the polyol initiator (ii.1.1) with ethylene oxide (ii.1.2) without the use of further initiators.

8. 8. The fiber composite material according to claim 1 , wherein the ethoxylated polyether polyol (ii.1) is based on a triol.

9. The ethoxylated polyether polyol (ii.1) of formula (II): 【Chemistry 2】 [In the formula, l, m, n, and o are each independently an integer ranging from 1 to 6; p, q, and r are each independently 0 or an integer ranging from 1 to 6; X 1 , X 2 and X 3 are each a —CH 2 —CH 2 —O— group.

8. The fiber composite material according to claim 1, wherein

10. 10. The fiber composite material according to claim 1, wherein the polyol composition (ii) does not comprise a polyol having propylene oxide or butylene oxide end groups and / or the polyol composition (ii) comprises less than 10% by weight of a polyol having propylene oxide and / or butylene oxide groups.

11. 11. The fiber composite material according to claim 1, wherein the polyol composition (ii) does not comprise a polyol having propylene oxide or butylene oxide groups and / or the polyol composition (ii) does not comprise a polyol based on propylene oxide and / or butylene oxide.

12. 1. A method for producing a fiber composite material, comprising: A) providing a polyisocyanate composition (i); B) providing a polyol composition (ii) comprising at least 15% by weight of an at least trifunctional ethoxylated polyether polyol (ii.1) having at least two primary hydroxyl groups and less than 10% by weight of a polyol having end groups based on propylene oxide and / or butylene oxide; C) mixing the polyisocyanate composition (i) and the polyol composition (ii) to obtain a polyurethane reaction mixture (a'); D) reacting the polyurethane reaction mixture (a') in the presence of fibers (b) to give a polyurethane (a), wherein the fibers (b) are at least partially embedded in the polyurethane reaction mixture (a') or the polyurethane (a), to obtain a fiber composite material; Including, The polyisocyanate composition (i) and the polyol composition (ii) are used in a ratio such that the isocyanate index is between 99 and 400.

13. 13. A method for producing a fiber composite material according to claim 12 for producing fibers or fiber materials pre-impregnated with polyurethane (polyurethane prepreg), comprising mixing a polyisocyanate composition (i) and a polyol composition (ii), contacting them with oriented fibers (b), and subsequently partially curing.

14. 13. A method for producing a fiber composite material according to claim 12, which is intended to produce fibers or fiber materials pre-impregnated with polyurethane, by mixing a polyisocyanate composition (i) and a polyol composition (ii), polymerizing them at a temperature below 80°C, and subsequently contacting them with oriented fibers (b).

15. 15. Use of a fibre composite material according to any one of claims 1 to 11 or obtained or obtainable by the method according to any one of claims 12 to 14 for the production of a pipe, a pipe connector, a pressure vessel, a storage tank, shielding, a mast, a strip, a roller, a torsion shaft, a profile, a piece of sporting goods, a moulded part, a cover, an exterior automotive part, a rope, a cable, an isogrid structure or a semi-finished fibre product.

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