ITUB20159132A1 - POLYURETHANE-BASED RESINS FOR COILING - Google Patents

Description

"POLYURETHANE-BASED RESINS FOR WINDING"

Field

[0001] Embodiments relate to polyurethane-based resins for winding, to a process for the production of polyurethane-based resins, to winding equipment which includes the use of polyurethane-based resins, to processes of winding which includes the use of polyurethane-based resins, and a resin bath for winding processes which includes polyurethane-based resins.

Introduction

[0002] An exemplary method for forming composite articles is winding, which can be used for the production of articles of various sizes. A winding method may include winding filaments under tension on a rotating substrate to form the composite article. The filaments may be fibers which include glass, aramid, carbon, boron, and / or other materials which a person of ordinary skill in the art would consider usable in a winding process. The fibers may be continuously passed through a resin bath, for example, which includes polyester, vinyl ester, phenolic, polyimide, epoxy, and / or polyurethane polymers, before being wound onto the rotating substrate. Thereafter, the resin coated fibers can be cured, for example thermally cured, to form the composite article. The winding process can be open to the environment and resins are sought that allow long operating times in such conditions (for example, which have a sufficiently low viscosity over an extended period of time in environmental conditions such as to allow the coating of the fibers and / or which have a sufficiently long gelation time in ambient conditions).

Summary

Embodiments can be accomplished by providing a polyurethane-based coil resin reaction mixture comprising an isocyanate component including one or more isocyanates and an isocyanate reactive component including 5% to 95% by weight % by weight of one of several polyols having an average molecular weight in number from 50 g / mol to 8,000 g / mol, from 2% by weight to 30% by weight of one or more propane-based triols, and from 1 % by weight to 15% by weight of one or more triester-phosphates, based on the total weight of the isocyanate reactive component. A ratio of a total weight of the one or more propane-based triols to a total weight of the one or more triester-fostates is comprised between 1.1 and 5.0.

Brief description of the drawings

FIGURE 1 illustrates an exemplary winding method.

Detailed description

[0005] Polyurethanes are highly versatile materials with a wide range of applications and uses. Polyurethanes can be prepared in the form of a one-component system or as a two-component system. That said, the one-component system may be a pre-formed (pre-reacted) curable composition based on polyurethane which is included in the resin bath of a winding process. The two component system can be a composition in which separate components are combined immediately prior to forming the resin bath or are fed separately to form the resin bath, of a winding process,

One-component polyurethane materials and two-component polyurethane materials can be prepared by reacting an isocyanate material with an isocyanate reactive material. For example, polyurethane materials can be prepared by reacting an isocyanate component that includes one or more isocyanates, for which each isocyanate can be a polyisocyanate or an isocyanate-terminated prepolymer, with an isocyanate-reactive component that includes at least one material with a active hydrogen, such as a polyol. In exemplary embodiments, for a winding process, the isocyanate component and the isocyanate reactive component may be separate components which are combined immediately prior to entering the resin bath to form a reaction mixture or are fed separately to the resin bath. to form a reaction mixture.

For a winding process, polyurethane-based resins are sought which allow long operating times, for example, a viscosity of the reaction mixture at 25 ° C of less than 5,000 cps after 20 minutes and / or high operating times gelation of the reaction mixture for at least 25 minutes at room temperature. For example, for the winding process of fully impregnated (wet-out) fibers with a high content of glass fibers, lower viscosities are sought for polyurethane-based resins in order to improve workability during the portion of wrapping the process. Furthermore, for some high end applications, the strength requirement is important and the tensile strength of the resin as it should be high (such as at least 55 MPa) and the flexural strength of the resin as it should be high. (such as at least 70 MPa). However, with polyurethane materials there may be some conflict between low viscosity and high mechanical properties. For example, the use of low-functional, long-chain polyols may result in a reduction in viscosity reduction, but mechanical properties may be relatively poor. Furthermore, the use of high functionality and short chain polyols can provide improved mechanical properties, but the rapid reactivity of the polymer can lead to a rapid increase in viscosity, which can cause problems during a winding process. Accordingly, embodiments relate to a polyurethane-based coil resin reaction mixture (for use in a resin bath) that provides good mechanical properties (e.g., a tensile strength of at least 55 MPa and a flexural strength of at least 70 MPa) of the polyurethane resin as it is, while continuing to ensure a viscosity of the reaction mixture at 25 ° C lower than 5,000 cps, twenty minutes after mixing the isocyanate component and the reactive component with isocyanate.

The polyurethane-based coil resin reaction mixture is formed by using an isocyanate component and an isocyanate reactive component. The isocyanate component includes one or more isocyanates. The isocyanate reactive component includes from 5% by weight to 95% by weight of one of more polyols having a number average molecular weight of 50 g / mol to 8,000 g / mol. The one or more polyols may include one or more low molecular weight polyols and / or one or more polyols derived from natural oil. The isocyanate reactive component includes from 2% by weight to 30% by weight of one or more propane-based triols and from 1% by weight to 15% by weight of one or more triester-phosphates, based on total weight of the reactive component with isocyanate. A ratio of a total weight of the one or more propane-based triols to a total weight of the one or more triester-phosphates is between 1.1 and 5.0. The isocyanate component and / or the isocyanate reactive component may further include additives. Of the additives, the polyurethane-based coiling resin reaction mixture can exclude low viscosity solvents acting as viscosity reducing compounds that are known in the art, such as propylene carbonate. The resin bath for the winding process can include from 50% by weight to 100% by weight (for example, from 60% by weight to 100% by weight, from 70% by weight to 100% by weight, from 80% to 100% by weight % by weight to 100% by weight, 90% by weight to 100% by weight, 95% by weight to 100% by weight, etc.) of the polyurethane-based coiling resin reaction mixture.

Isocyanate component

The isocyanate component includes at least one isocyanate, such as at least one polyisocyanate and / or at least one isocyanate-terminated prepolymer derived from at least one polyisocyanate. In exemplary embodiments, the isocyanate component may include additional additives.

Exemplary polyisocyanates include aromatic, cycloaliphatic, and alitatic polyisocyanates. For example, polyisocyanates known in the art can be used. Examples of polyisocyanates include the 4,4 ', 2,4' and 2,2 'isomers of methane diphenyl diisocyanate (MDI), their modifications, and their mixtures (e.g., mixtures of polymeric or monomeric MDI), 2,4 isomers and 2,6 of toluene-diisocyanate (TDI) (for example, their modifications, and their mixtures), m- and ρ-phenylenedisocyanate, chlorophenylene-2, 4-diisocyanate, diphenylene-4,4 '-diisocyanate, 4,4 '-diisocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenyl-met an-4,4'-diisocyanate, diphenyletherdiisocyanate, 2,4,6-triisocyanatotoluene, 2,4,4'-triisocyanate-phenyl-ether, ethylene diisocyanate , and 1,6-hexamethylene diisocyanate. Derivatives of any of the above polyisocyanate groups which contain, for example, biuret, urea, carbodiimide, allophonate, and / or isocyanurate groups can also be used. In exemplary embodiments, the isocyanate component includes from 20% by weight to 100% by weight (for example, from 30% by weight to 100% by weight, from 50% by weight to 100% by weight, from 70% by weight weight to 100% by weight, from 80% by weight to 100% by weight, from 90% by weight to 100% by weight, from 95% by weight to 100% by weight, and so on) of polymeric MDI.

If included, the isocyanate-terminated prepolymer may have a free isocyanate group (NCO) content of 1% by weight to 35% by weight (e.g., 5% by weight to 30% by weight, 10 % by weight to 30% by weight, from 15% by weight to 25% by weight, from 15% by weight to 20% by weight, and so on), based on the total weight of the prepolymer. If present, one or more isocyanate-terminated prepolymers may account for from 20% by weight to 100% by weight of the isocyanate component, and a remainder (if present) of the isocyanate component may be one or more polyisocyanates and / or one or more additives. The isocyanate-terminated prepolymer can be formed by the reaction of another isocyanate component with another isocyanate-reactive component (both different and separated from the isocyanate component and the isocyanate-reactive component for the formation of the reaction mixture), in which the isocyanate component is present in stoichiometric excess.

An isocyanate index for the formation of the cured composition is 85 to 150 (for example, 90 to 130, 90 to 120, 90 to 110). By isocyanate index, we mean a ratio of equivalents of isocyanate groups in the reaction mixture for the formation of the hardened composition on the active hydrogen atoms in the reaction mixture for the formation of the hardened composition, for the formation of the polyurethane polymers, multiplied by 100 Stated another way, the isocyanate index is the molar equivalent of isocyanate groups (NCO) divided by the total molar equivalent of isocyanate-reactive hydrogen atoms present in a formulation, multiplied by 100. understood by a person of ordinary skill in the art, the isocyanate groups in the reaction mixture for forming the cured composition can be provided through the isocyanate component, and the active hydrogen atoms can be provided through the isocyanate reactive component.

Polyols

The isocyanate reactive component includes from 5% by weight to 95% by weight of one or more polyols, based on the total weight of the isocyanate reactive component. Each polyol has an average molecular weight in number from 50 g / mol to 8,000 g / mol. Polyols contain active hydroxyl groups, the reaction of which active hydroxyl groups with isocyanate groupings results in the formation of a urethane bond. The one or more polyols may include one or more polyether polyols, one or more polyester polyols, and / or one or more polyols derived from natural oil. Each polyether polyol can be derived from propylene oxide, ethylene oxide, and / or butylene oxide.

According to exemplary embodiments, the one or more polyols may include one or more low molecular weight polyether polyols. For example, a number average molecular weight of each of the one or more low molecular weight polyether polyols may be 50 g / mol to 1000 g / mol (e.g., 50 g / mol to 700 g / mol, 50 g / mol g / mol to 500 g / mol, 50 g / mol to 400 g / mol, 50 g / mol to 300 g / mol, and so on). Each low molecular weight polyether polyol can have a nominal hydroxyl functionality of 2 to 4 (for example, it can be a diol or a triol). Each low molecular weight polyether polyol can be derived from propylene oxide, ethylene oxide, and / or butylene oxide. For example, the low molecular weight polyether polyol may be a triol derived from propylene oxide. The one or more low molecular weight polyols can account for from 5% by weight to 60% by weight (for example, from 10% by weight to 50% by weight, from 15% by weight to 45% by weight, from 15% by weight to 40% by weight, from 15% by weight to 35% by weight, from 20% by weight to 35% by weight, from 20% by weight to 30% by weight, and so on) of the total weight of the reactive component with isocyanate.

The one or more polyols may include one or more simple polyols, such as glycols. Exemplary simple polyols include glycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, sorbitol, and sucrose. The one or more simple polyols may be different from (supplied separate from) the propane-based triol. Exemplary simple polyols include polyether polyol type initiators known to a person of ordinary skill in the art, crosslinkers having a polyol structure known to a person of ordinary skill in the art, and / or chain elongation compounds having a polyol structure known to a person with normal experience in the trade. The one or more simple polyols can account for from 1% by weight to 20% by weight (for example, from 1% by weight to 15% by weight, from 1% by weight to 10% by weight, from 1% by weight to 8% by weight, 2% by weight to 7% by weight, and so on) of the total weight of the isocyanate reactive component.

The one or more polyols may include one or more polyols derived from natural oil. Exemplary polyols derived from natural oil include castor oil (and polyols derived therefrom), cardanol (and polyols derived therefrom), and / or plant derived polyols (such as soy-derived polyols).

For example, the polyol derived from natural oil may be di- and / or tri-glycerides of aliphatic carboxylic acids of 10 carbon atoms or more, for example, triglycerides of aliphatic carboxylic acids substituted by hydroxyl. One example is castor oil, which is a vegetable oil obtained from the seeds / castor plant. A majority of the fatty acids in castor oil can be ricinoleate / ricinoleic acid (i.e., 12-hydroxy-9-cisoctadecenoic acid), which can be referred to as 18-carbon monounsaturated fatty acid having a hydroxyl functional group at the twelfth carbon. This functional group causes ricinoleic acid (and castor oil) to be polar, i.e. it has a polar dielectric with a relatively high dielectric constant (4.7) for highly refined and dried castor oil. An exemplary castor oil may include at least 85% by weight of ricinoleic acid (12-hydroxyoleic acid) and minor amounts of linoleic acid, oleic acid, stearic acid, paimitic acid, dihydroxystearic acid, linolenic acid, eicosanoic acid, and / or water. Castor oil may have a true hydroxyl functionality of approximately 2.64 and an equivalent weight of approximately 342. Castor oil may be modified or unmodified, for example, modified castor oil may contain an additive such as a formaldehyde or polyester polyol. The hydrophobic natural oil polyol (such as castor oil) can account for 10% by weight to 80% by weight (for example, 10% by weight to 70% by weight, 20% by weight to 60% by weight, from 30% by weight to 55% by weight, from 35% by weight to 55% by weight, from 40% by weight to 55% by weight, from 45% by weight to 55% by weight, and so on ) of the total weight of the isocyanate reactive component.

For example, cardanol may be included within the liquid of the cashew nut shell, which may be a byproduct of cashew nut processing (for example, it can be extracted from a layer placed between a kernel and a shell of a cashew nut). The cashew nut shell liquid may include a cardanol content of at least 50% by weight, based on a total weight of the cashew nut shell liquid. The cashew nut shell liquid may include cardanol as a primary component and may additionally include cardol, methylcardol, and / or anacardic acid as secondary components.

The one or more polyols may include other polyols, such as a hydroxyl-terminated polybutadiene and / or a polytethamethylene ether glycol (PTMEG).

In exemplary embodiments, the one or more polyols include a mixture of (i) one or more polyether polyols having an average molecular weight in number greater than 175 g / mol and less than 1000 g / mol, and a functionality 2 to 3 nominal hydroxyl, and (ii) one or more natural oil polyols. For example, the one or more polyols may include a mixture of (i) 1% by weight to 15% by weight of a simple polyol having a number average molecular weight of 50 g / mol to 175 g / mol and a 2 to 3 nominal hydroxyl functionality, (ii) 10% by weight to 40% by weight of a polyether polyol having an average molecular weight in number greater than 175 g / mol and less than 1000 g / mol, and a hydroxyl functionality nominal 2 to 3, and (iii) 20% by weight to 60% by weight of a natural oil polyol including castor oil.

Triol based on propane

The isocyanate reactive component includes 2% by weight to 30% by weight (for example, 2% by weight to 25% by weight, 5% by weight to 20% by weight, 5% by weight 15% by weight, and so on) of one or more propane-based triols. By propane-based triol is meant a compound that is a triol and that can be identified by a conventional naming protocol as a base structure of substituted propane, in such a way as to enable triol functionality. Exemplary propane-based triols include trimethylolpropane. In exemplary embodiments, it can be included from 2% by weight to 30% by weight (for example, from 2% by weight to 25% by weight, from 5% by weight to 20% by weight, from 5% by weight 15% by weight, etc.) of trimethylolpropane, based on the total weight of the isocyanate reactive component (for example, the one or more propane-based triols may include trimethylolpropane only).

Triester- phosphates

The isocyanate reactive component includes 1% by weight to 15% by weight (for example, 1% by weight to 10% by weight, 2% by weight to 9% by weight, 2% by weight by weight to 7% by weight, from 3.0% by weight to 7% by weight, and so on) of one or more triester-phosphates. Exemplary triester phosphates include triethylphosphate, trimethylphosphate, and tripropylphosphate. In exemplary embodiments, it can be included from 1% by weight to 15% by weight (for example, from 1% by weight to 10% by weight, from 2% by weight to 9% by weight, from 2% by weight by weight to 7% by weight, from 3.0% by weight to 7% by weight, etc.) of triethylphosphate, based on the total weight of the isocyanate reactive component (for example, the one or more triester-phosphates may include triethylphosphate only).

A ratio of a total weight of the one or more propane-based triols to a total weight of the one or more triester-phosphates in the isocyanate-reactive component is between 1.1 and 5.0 (for example, 1 , 2 to 4.9, 1.5 to 4.5, 2.0 to 4.5, 2.0 to 4.0, 2.4 to 3.5, 2.4 to 3, 1, 2.5 to 3.0, and so on). For example, a ratio of t-rimethylolpropane to triethylphosphate is 1.1 to 5.0 (for example, 1.2 to 4.9, 1.5 to 4.5, 2.0 to 4.5 , 2.0 to 4.0, 2.4 to 3.5, 2.4 to 3.1, 2.5 to 3.0, and so on). Additives

Various additives can be added to the polyurethane-based coil resin reaction mixture to adjust the characteristics of the resulting resin, for example, additives known to those of ordinary skill in the art can be used. The additives can be added as part of the isocyanate component and / or the isocyanate reactive component. Examples of additives include a moisture sequestering agent, an antifoam agent, a catalyst, a chain elongation compound (other than polyols), an adhesion promoter, phosphoric acid, a hardener, a pH neutralizer, a plasticizer, a compatibilizer. , a filler (such as functional fillers, silica based fillers and mineral based fillers), pigments / dyes, and / or a crosslinker (other than polyols). Exemplary additives that may be excluded include known low viscosity solvents which act as viscosity cutting compounds, such as propylene carbonate and / or trichloropropyl phosphate, Alternatively, known low viscosity solvents which act as viscosity cutting compounds, such as propylene carbonate and / or trichloropropyl phosphate, may be included in a small amount (for example, in an amount less than 20% by weight, less than 10% by weight, less than 5% by weight, and / or less than 1% by weight, on the basis of the total weight of the reactive component with isocyanate).

A moisture sequestering component may be added which includes one or more moisture sequestrants, for example, it may be added to the isocyanate reactive component. If included, the moisture sequestering component can account for 1% by weight to 20% by weight (e.g., 2% by weight to 15% by weight, 2% by weight to 10% by weight , from 3% by weight to 9% by weight, from 4% by weight to 8% by weight, and so on) of the total weight of the reactive component with isocyanate. Examples of moisture sequestrants include zeolites or molecular sieves, reactive silanes (such as vinyltrialkoxysilanes), and minerals (such as calcium oxide).

An antifoam agent component that includes one or more antifoam agents may be added, for example, it can be added to the isocyanate reactive component. If included, the defoamer component may account for less than 5 wt% (e.g., less than 1 wt%, and so on) of the total weight of the isocyanate reactive component. As discussed in international publication No. WO 2008/065090, the defoamer can also act as a compound that cuts viscosity.

Phosphoric acid can be added, for example, it can be added to the isocyanate reactive component. If included, phosphoric acid can account for less than 1% by weight of the total weight of the isocyanate reactive component. For a coil resin reaction mix, phosphoric acid can help reduce the pH value of the isocyanate reactive component and / or the reaction mix, which can delay reactivity. Accordingly, the operating time for the winding process can be increased.

A catalyst component which includes one or more catalysts may be added, for example, it may be added to the isocyanate reactive component. For example, the catalyst component may have tin and / or amine based catalysts, for example, accounting for 5 wt% of a total weight of the isocyanate reactive component. Examples of catalysts include tertiary amines, tin carboxylates, organotin compounds, tertiary phosphines, various metal chelates, and / or metal salts of strong acids (such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate, and bismuth chloride).

A chain elongating component may be added which includes one or more chain elongating compounds (which are not polyols), for example, it may be added to the isocyanate reactive component. If included, the chain elongation component may account for less than 25% by weight of the total weight of the isocyanate reactive component.

An adhesion promoter component may be added which includes one or more adhesion promoters, for example, it can be added to the isocyanate reactive component. For example, the adhesion promoter component may include at least one silane-based adhesion promoter. If included, the optional adhesion promoter can account for less than 5% by weight of a total weight of the isocyanate reactive component.

Fillers may be present to provide the desired rheological properties, mechanical reinforcement, chemical resistance and / or to reduce cost. Fillers can be added to the isocyanate reactive component and / or the isocyanate component. Examples of fillers include inorganic particulate materials such as talc, titanium dioxide, calcium carbonate, calcium oxide, silica, mica, wollastonite, fly ash, metal particles, carbon black, graphite, high melting point organic polymers, and / or reinforcing materials. The fillers also include reinforcement type fillers, for example flake or ground glass and / or pyrogenic silica, which can be used for the purpose of imparting certain properties. The fillers can constitute up to 90% by weight of the hardenable composition.

A plasticizer may be present. The plasticizer can allow for higher loading with fillers, reduce costs and / or reduce module. Examples of plasticizers include liquid esters (at 25 ° C) of monocarboxylic acids and diesters of dicarboxylic acids having molecular weights up to 300 g / mol.

Pigments and / or dyes can be present, for example, titanium dioxide and / or carbon black, can be used for the purpose of imparting color properties. Other additives include for example UV stabilizers, antioxidants, and air release agents, which can be used independently depending on the desired characteristics.

Resin bath for winding

The individual components of the polyurethane-based coil resin reaction mixture, such as the isocyanate reactive component, can be mixed before being added to the resin bath. Further, the polyurethane-based coiling resin reaction mix can be mixed within the resin bath and / or prior to being added to the resin bath. The mixing can be carried out in any convenient manner, depending on the particular application and available equipment. The mixing of the components can be carried out in batches (by batches), by hand mixing, or by using various types of batch mixing devices.

In case the ingredients are formulated in two components (for example, isocyanate component and isocyanate reactive component separate), the components can be combined at room temperature or any desirable high temperature within the resin bath, applied as a coating on filaments and / or left to react and then harden. The two components can be packaged in separate cartridges and dispensed simultaneously through a mixing device to mix and deposit in the resin bath.

Winding

Winding is used for the production of composites, for example, on the basis of a cross-linking matrix of polyurethane-based filaments and resins. In a winding operation using the polyurethane resin according to embodiments, a filament can be passed through the resin bath and / or the resin bath can be passed through an injection die to be applied to the filament to form coated filaments. Then, the coated filaments can be wrapped around a substrate. The polyurethane resin can be a one-component system (for example, the isocyanate component and the isocyanate-reactive component are mixed to form the resin bath and then applied to the filament) or a two-component system (for example, the isocyanate component). isocyanate component and the isocyanate reactive component are applied separately to the filament). The resulting product can be cured (for example, by the application of heat and / or radiation) to form a final composite article.

Referring to FIGURE 1, an exemplary winding method includes tows of fibers that contain filaments / fibers used in the winding method. Exemplary filaments include glass fibers (e.g., E-glass, S-glass, and the like), carbon fibers (e.g., polyacrylonitrile-based and pitch-based), aramid fibers, ceramic fibers (e.g., silicon carbide, aluminum oxide and the like) or mixtures thereof. The filaments / fibers are fed from the fiber tows to the fiber guides which are used to sort the filaments / fibers. From the fiber guides, the filaments / fibers are macerated in the resin bath. According to exemplary embodiments, the resin bath includes a polyurethane-based coil resin reaction mixture, as described in the present patent. From the resin bath, coated filaments / fibers are passed through additional fiber guides. The combination of the fiber guides and the resin bath forms the movable carriage of the exemplary winding process. After exiting the moving carriage, the coated filaments / fibers are applied as a coating around a moving mandrel (substrate).

[0037] For example, the filaments / fibers are wetted by the resin bath (through soaking or the use of the injection die) and are wrapped around a substrate (such as the mandrel shown in FIGURE 1) which defines the shape of the final composite article. The wetting of the filament can be carried out either before or simultaneously with the winding operation. For example, the filament may be wetted on an ongoing basis with a one-component polyurethane resin just before it is wrapped around the substrate. The winding operation can be accomplished by rotating the substrate while the coated filament is under a controlled level of tension, and moving the filament up and down the length of the mandrel in any desired pattern. During the winding operation, it is important to minimize the formation of voids in the filament-wrapped article and to control the degree of wetting of the filament (better wetting is preferred in most applications). For example, the resin coating on the filament and the winding operation should both take place while the resin is still fluid (for example it should be homogeneous and the separation of solids or gel particles between the liquid mass of the resin is minimum).

In relation to the gelling time of the resin, a balance can be achieved between the need for a fast curing time to form the article of the final composition, the need for adequate flowability of the resin during the material formation process composite, and the need to avoid excessive flow, with unnecessary waste, of the polyurethane resin during the winding operation. Equilibrium can be achieved by having a gelation time which is from 25 minutes to 150 minutes.

[0039] All percentages are by weight, unless otherwise indicated. All values for molecular weight are based on the number average molecular weight unless otherwise indicated.

Examples

Approximate properties, characters, parameters, and so on are given below in connection with various working examples, comparative examples, and materials used in the working examples and comparative examples.

The following materials are those mainly used for the isocyanate reactive components and the isocyanate components shown below in Table 1:

TPP Trimethylolpropane, which is propane-based trio (available from Hengfeng).

TEP Triethylphosphate, which is the triester of ethanol and phosphoric acid (available from Jiangsu Yoke).

Castor Oil A polyol derived from natural oil (available from Sinopharm). Polyether Polyol A propoxylated glycerin triol, having a number average molecular weight of 255 (available from The Dow Chemical Company as

VORANOL ™ CP 260).

DPG Dipropylene glycol, which can act as a crosslinker (available from Sinopharm).

Zeolite A molecular sieve powder (available from W.R. Grace & Company as SYLOSIV® Molecular Sieve Powders).

Additive A silicone and polymer foam abateer (available from Byk as BYK® A-53Q).

Propylene Carbonate A viscosity cutting compound which is a carbon ester derived from propylene glycol (available from Sinopharm).

Polymeric isocyanate Methylene diphenyl diisocyanate, also referred to as PMDI (available from The Dow Chemical Company as SpecFlex ™ NS 540).

Working Examples 1 to 3 and Comparative Examples A to D are prepared according to the formulations presented below in Table 1.

[0043] Table 1

Εε. 1 Ex. 2 Ex. 3 Example Example Example Example Work Work Work comparison A comparison B comparison C comparison D Reactive component with isocyanate (% by weight)

TPP 9.0 11.0 15.0 6.0 10.0 11.0 11.0

IEP 3.0 4.0 6.0 - 2.0 10.0

Castor oil 48.8 48.8 48.8 48.8 48.8 48.8 48.8 Polyether polyol 27.0 25.0 23.0 30.0 27.0 23.0 25.0

DPG 5.0 4.0 5.0 5.0 4.0

Zeolite 3.0 3.0 3.0 10.0 3.0 3.0 3.0 Additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Phosphoric acid <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Propylene carbonate - - - - - 4.0

Isocyanate component (Isocyanate index}

Isocyanate 101 101 101 101 101 101 101

Property

TPP ratio: TOE 3.0 2.8 2.5 - 5.0 1.1 - Viscosity of the mixture

at 25 ° C, 20 minutes after 1600 1400 1900> 5000 1900 1200 1800 mixing (cps)

Gel time

at room temperature 24 28 27 23 23 29 26 (min)

Resistance to

63 63 65 60 67 47 56 traction (MPa}

Resistance to

93 93 92 78 78 53 68 flexion (MPa)

Referring to Table 1, each of the Working Examples 1 to 3 provides desirable values of viscosity, gel time, tensile strength, and flexural strength, for example in such a way as to be usable as a resin bath in a winding process. Referring to Comparative Example A, it can be seen that if there are no both TPP and TEP, the resulting viscosity of the reaction mixture after twenty minutes is too high (i.e., greater than 5000 cps) so that the formulation may be which is not preferred for use as a resin bath in a winding process. Referring to Comparative Example B, at a higher ratio of TPP to TEP, a reduction in flexural strength can be realized so that certain properties of the resulting filament-wrapped article can be disadvantaged. Referring to Comparative Example C, at a lower ratio of TPP to TEP, lower than desirable tensile strength and flexural strength can be achieved, so that certain properties of the resulting filament-wrapped article they can be adversely affected. Accordingly, referring to Comparative Examples B and C, a ratio of TPP to TEP can be between 1.1 and 5.0. Further, referring to Comparative Example D, when TEP is replaced with propylene carbonate (as a known viscosity-cutting compound), lower than desirable tensile strength and flexural strength can be achieved, by so that certain properties of the resulting filament-wrapped article can be adversely affected,

The ratio of TPP to TEP is a calculated ratio of the weight percentage of TPP in the isocyanate reactive component to the weight percentage of TEP in the isocyanate reactive component. Viscosity is a measure of the resistance of the formulation to gradual deformation due to shear or tensile stress. Here, the materials in the isocyanate reactive component are first mixed in a Flacktek fast mixing cup for 3 minutes at 2000 rpm. Second, the isocyanate reactive component and the premixed isocyanate component are mixed for three minutes in the Flacktek fast mixing cup at 500 rpm to form a reaction mixture. After twenty (20) minutes, 3 grams of the reaction mixture is used to measure viscosity using an ARES-G2 Rheology meter available from TA Instruments. A high viscosity, such as greater than 5,000 cps, is an indication of poor storage stability and / or ineffectiveness of using the formulation as a resin bath in a winding process.

The gelation time is measured as the time after which the reaction mixture is substantially unable to flow, and in molecular terms the gelation time refers to the point at which an infinite lattice is formed. The gel time is determined as the interval between when the reactive components are first mixed to form a reactive liquid mixture, until the reactive liquid mixture becomes unable to flow, for example the material has developed a molecular weight sufficient to undergo a transition from a liquid to a solid. Gel time is measured at room temperature (approximately 23 ° C) using a Gardner Standard Model Gel Timer.A high gel time, for example at least 25 minutes, is sought for reaction mixes that can be used as resin bath in a winding process.

Mechanical properties, such as tensile strength and flexural strength, are measured by pouring the reaction mixture into a mold and allowing it to cure for two hours at 120 ° C (so that mechanical properties are measured on the resin such and which). Then, the resulting samples are cooled, taken out of the mold and cut into dumbbell shapes to perform the controls according to ASTM and / or ISO methods. Tensile strength, which is the breaking strength (stress / deformation of the product at break) per unit area of the material, is measured according to ISO 527. Flexural strength, which is the measure of a material's ability to resist failure as a result of bending, is measured according to the ASTM D-790 method.

Claims (10)

CLAIMS 1. A polyurethane-based coiling resin reaction mixture, the reaction mixture comprising; an isocyanate component inclading one or more isocyanates; And an isocyanate reactive component including from 5% by weight to 95% by weight of one of several polyols having a number average molecular weight of from 50 g / mol to 8,000 g / mol, from 2% by weight to 30% by weight of one or more propane-based triols, and from 1% by weight to 15% by weight of one or more triester-phosphates, based on the total weight of the isocyanate reactive component, a ratio of a total weight of the one or more triols based on propane on a total weight of the one or more triester-phosphates ranging from 1.1 to 5.0. The polyurethane-based coiling resin reaction mixture as claimed in claim 1, wherein the mixture exhibits a viscosity at 25 ° C of less than 5,000 cps, twenty minutes after mixing the isocyanate component and the reactive component with isocyanate . The polyurethane-based coiling resin reaction mixture as claimed in claim 1 or claim 2, wherein the one or more triester phosphates include triethylphosphate. The polyurethane-based coiling resin reaction mixture as claimed in any one of claims 1 to 3, wherein the one or more propane-based triols include trimethylolpropane. The polyurethane-based coiling resin reaction mixture as claimed in any one of claims 1 to 4, wherein the one or more polyols include (i) a polyether polyol having an average molecular weight in number greater than 175 g / mol and less than 1000 g / mol, and a nominal hydroxyl functionality of 2 to 3, and (ii) a natural oil polyol. The polyurethane-based coiling resin reaction mixture as claimed in any one of claims 1 to 4, wherein the one or more polyols include (i) 1% by weight to 15% by weight of a simple polyol having a number average molecular weight from 50 g / mol to 175 g / mol and a nominal hydroxyl functionality of 2 to 3, (ii) 10% by weight to 40% by weight of a polyether polyol having a molecular weight average in number greater than 175 g / mol and less than 1000 g / mol, and a nominal hydroxyl functionality of 2 to 3, and (ii) 20% by weight to 60% by weight of a natural oil polyol including oil of castor. The polyurethane-based coiling resin reaction mixture as claimed in any one of claims 1 to 6, wherein an isocyanate index is 85 to 150. The polyurethane-based spool resin reaction mixture as claimed in any one of claims 1 to 7, wherein the isocyanate reactive component further includes phosphoric acid. A resin bath for a winding process, the resin bath including the polyurethane-based winding resin reaction mixture as claimed in any one of claims 1 to 8. 10. A winding apparatus, where the apparatus includes: fiberglass filaments; a resin bath including the polyurethane-based spool resin reaction mixture as claimed in any one of claims 1 to 8, the resin bath being applied to the glass fiber filaments to form coated glass fiber filaments; And a substrate for forming a composite article using the coated glass fiber filaments.