Fiber reinforced composites and materials for forming fiber reinforced composites

Abstract

A mixture comprising i) a first polyol, ii) a second polyol, iii) an optional third polyol, and a non- halogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof, wherein the mixture is capable of being reacted with an isocyanate-containing component to produce a reactive mixture having a viscosity at 25 °C is less than about 4000 cps [mPa·s] as measured by a Brookfield viscometer.

Description

FIBER REINFORCED COMPOSITES AND MATERIALS FOR FORMING FIBER REINFORCED COMPOSITESCLAIM OF PRIORITY

[0001] This application claims the benefit of the filing date of United States Provisional Application No. 63 / 669,364, filed on July 10, 2024. The entirety of the contents of that application are incorporated by reference herein in their entirety and for all purposes.FIELD

[0002] The present teachings generally relate to formulations for improved pultrusion processes and resulting pultruded products, particularly for the objective of improving pultrusion flammability resistance.BACKGROUND

[0003] Pultrusion technology is utilized in a wide range of industries. Some of the shortcomings of current pultrusion technologies include speed of the process, complexity of the matrix materials utilized, and challenges relating to imparting certain physical characteristics to the resulting pul- trudate.

[0004] United States Patent Nos. 8,097,334, 7,901 ,762, and 7,875,675 disclose materials for pultrusion that provide for improved strength of the resulting pultrudate while avoiding the use of transverse fibers. Line speed is addressed by removing transverse fibers from the system. The resulting line speed is still relatively slow.

[0005] United States Patent Nos. 7,056,976, and 7,507,361 disclose formulations for use in pultrusion processes that have increased pot life and fast cure time. The process utilizes injection die pultrusion and a curing die.

[0006] There are certain challenges to formulating polyurethane materials for pultrusion that are flame retardant. The process of pultrusion greatly limits the use of traditional flame retardant additives due to the particulate nature of these traditional additives and their effect on rheology, viscosity, and fiber packing within the pultrusion.

[0007] There remains a desire to improve the processing speed of pultrusion, reduce the complexity of the formulated materials used, and improve certain properties of pultrudates including, but not limited to, strength and flame retardancy.SUMMARY

[0008] The present disclosure relates to a mixture comprising:- a first polyol, a second polyol, and optional third polyol, and- a non-halogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof, wherein the mixture is capable of being reacted with an isocyanate-containing component to produce a reactive mixture having a viscosity at 25 °C is less than about 4000 cps [mPa s] as measured by a Brookfield viscometer.

[0009] The present disclosure further relates to a reactive mixture comprising i) a polyol component comprising- a first polyol and a second polyol, and- a non-halogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof, and ii) an isocyanate-containing component, wherein the viscosity of the reactive mixture at 25°C is less than about 4000 cps [mPa s] as measured by a Brookfield viscometer.

[0010] The mixture is reactive because the polyols in the polyol component are capable of reacting with isocyanate in the isocyanate-containing component under suitable reaction conditions, which may include ambient conditions.

[0011] The reactive mixture may be impregnated in a continuous fiber component.

[0012] The phosphorous-containing material may be a phosphorous-containing polyol.

[0013] The mixture or the reactive mixture may comprise a third polyol, which is then part of the polyol component.

[0014] The flame retardant package may include both a phosphorus-containing material and expandable graphite.

[0015] The first polyol may have a nominal molecular weight that is greater than 300 g / mol.

[0016] The second polyol may have a nominal molecular weight that is greater than 300 g / mol.

[0017] The first polyol and second polyol may have substantially equal molecular weights.

[0018] The polyol component may include a third polyol having a molecular weight of less than 300 g / mol.

[0019] The polyol component may include a mold release component.

[0020] The non-halogenated flame retardant package may comprise both a phosphorous-containing material and an expandable graphite, wherein preferably the phosphorus-containing material is present in an amount that is at least double the amount of the expandable graphite byweight percent In other words, the weight ratio of the amount of the phosphorus-containing material to the amount of the expandable graphite is preferably at least 2:1 .

[0021] The reactive mixture may be impregnated in fiberglass.

[0022] At least one polyol may have a functionality, i.e. free hydroxyl functionality, of at least 4.

[0023] The polyol component may include a third polyol, wherein preferably at least the second and third polyols have an initial viscosity of at least about 1200 cps [mPa s] at 25°C as measured by a Brookfield viscometer.

[0024] The polyol component may include an adhesion promoter.

[0025] The first polyol and the second polyol may be present in a ratio of from about 6:1 to about 9:1 by weight percent first polyol to second polyol. In other words, the weight ratio of the amount of the first polyol to the amount of the second polyol is preferably within the range of from about 6:1 to about 9:1.

[0026] The viscosity of the isocyanate-containing component may be less than 100 cps [mPa s] at 25°C as measured by a Brookfield viscometer.

[0027] The viscosity of the reactive mixture at 25°C may be less than about 3000 cps [mPa s] as measured by a Brookfield viscometer.

[0028] The viscosity of the reactive mixture at 25°C may be less than about 2000 cps [mPa s] as measured by a Brookfield viscometer.

[0029] The fiberglass may be an e-glass having a TEX (weight in grams per kilometer) range of 1100-4400.

[0030] The gel-time of the reactive mixture at 25°C may be at least about 10 minutes.

[0031] The gel-time of the reactive mixture at 175°C may be less than about 1 minute.

[0032] The mixture or the reactive mixture may include a third polyol.

[0033] The first polyol, second polyol and optionally present third polyol may be independently from one another selected from- propoxylated orthophosphoric acid;- trispoly(propylene oxide) phosphate;- polyoxypropylene glyceryl ether such as polyoxypropylene (10) glyceryl ether;- propoxylated glycerol;- propoxylated pentaerythritol; or combinations thereof.

[0034] The reactive mixture may be pultruded with a fiber component to form a pultruded and cured product having a post-processing flexural strength of at least about 1200 MPa and a flexural modulus of at least about 49 GPa measured in the 0° direction as measured by ASTM D7264.

[0035] The reactive mixture may be impregnated in a continuous fiber component to form an impregnated fiber component comprising at least 80% by weight e-glass.

[0036] The reactive mixture may be adapted for a pultrusion process with a line speed of at least 8 feet per minute (fpm) in a plaque die (3mm by 150mm (thickness X width)).

[0037] The reactive mixture may be adapted for downstream processing steps including injection molding, filament winding, compression molding, resin transfer molding, or combinations thereof.

[0038] The reactive mixture may be pultruded with or without fibers and a resulting pultrudate may have a UL-94 flammability rating of V-0.

[0039] The reactive mixture may be pultruded with a plurality of fibers that may include from glass, carbon, aramid, basalt, flax, hemp, jute, sisal, wool, silk, bamboo, cotton, or combinations thereof.

[0040] The teachings herein are further directed to a two-part material comprising- a part A (polyol component) including- a first polyol and a second polyol, and- a non-halogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof and- a part B including an isocyanate-containing component having a viscosity of less than 100 cps [mPa s] at 25°C as measured by a Brookfield viscometer, wherein part A and part B are combined to form a reactive mixture.

[0041] The first polyol and second polyol may independently of one another have molecular weights that are greater than 300 g / mol.

[0042] The first and second polyols may have molecular weights that are substantially similar to one another.

[0043] At least one or the first polyol, second polyol, and optionally present third polyol may have a functionality of at least 4.

[0044] The reactive mixture may be contacted with a plurality of fibers.

[0045] The fibers may be from glass, carbon, aramid, basalt, flax, hemp, jute, sisal, wool, silk, bamboo, cotton, or combinations thereof.

[0046] At least the second polyol and the third polyol may independently of one another have an initial viscosity of at least about 1200 cps [mPa s] at 25°C as measured by a Brookfield viscometer.

[0047] The first polyol and the second polyol may be present in a ratio of from about 6:1 to about 9:1 by weight percent first polyol to second polyol.

[0048] The viscosity of the reactive mixture at 25°C may be less than about 3000 cps [mPa s] as measured by a Brookfield viscometer.

[0049] The viscosity of the reactive mixture at 25°C may be less than about 2000 cps [mPa s] as measured by a Brookfield viscometer.

[0050] The gel-time of the reactive mixture at 25°C may be at least about 10 minutes.

[0051] The gel-time of the reactive mixture at 175°C may be less than 1 minute.

[0052] The first polyol, second polyol, and optionally present third polyol may be independently of one another selected from- propoxylated orthophosphoric acid;- trispoly(propylene oxide) phosphate;- polyoxypropylene glyceryl ether such as polyoxypropylene (10) glyceryl ether;- propoxylated glycerol;- propoxylated pentaerythritolor; or combinations thereof.

[0053] The reactive mixture may be pultruded with a fiber component to form a pultruded and cured product having a post-processing flexural strength of at least about 1200 MPa and a flexural modulus of at least about 49 GPa measured in the 0° direction as measured by ASTM D7264.

[0054] The teachings herein are further directed to use of the mixture or reactive mixture described herein for pultruding a flame resistant product having a UL94 flame retardancy rating of V0.

[0055] The teachings herein are further directed to use of the mixture or reactive mixture described herein for pultruding a product at a pull speed of at least 5 feet per minute (152 cm / mi- nute).

[0056] The teachings herein are also directed to a method comprising reacting the mixture described herein with an isocyanate component to form a reactive mixture; and impregnating the reactive mixture into a continuous fiber component.DETAILED DESCRIPTION

[0057] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the teachings, its principles, and its practical application. Those skilled in the art may adapt and apply the teachings in its numerous forms, as may be best suited to the requirements of a particular use. Accordingly, the specific embodiments of the present teachings as set forth are not intended as being exhaustive or limiting of the teachings. The scope of the teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents towhich such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[0058] The materials, formulations, mixtures, components, and products described herein are provided for use in pultrusion systems. Specifically, the teachings herein are directed to polyol and isocyanate-based resin systems for use with a plurality of fibers. The polyol component may include multiple polyols. The isocyanate component may include one or more isocyanates.

[0059] Unless expressly stated otherwise, all properties of the "reactive mixture" refers to the polyol component reacted with the isocyanate-containing component, whereas "mixture" refers to the polyol component only. “Total reacted mixture” refers to the reactive mixture once combined with a fiber component.

[0060] Unless expressly stated otherwise, all "post-processing" properties refer to the fully reacted state, preferably pultruded and cured.

[0061] Unless expressly stated otherwise, all percentages related to the polyol component are based on the total weight of the polyol component including the first polyol, the second polyol, the optionally present third polyol, as well as the non-halogenated flame retardant package.

[0062] For the purpose of the specification, the terms "polyol component" and "polyol-containing component" are used interchangeably.

[0063] For the purpose of the specification, the terms "isocyanate component" and "isocyanate- containing component" are used interchangeably.

[0064] For the purpose of the specification, the terms "non-halogenated flame retardant package", "non-halogenated flame retardant component" and " non-halogenated flame retardant-containing component" are used interchangeably.

[0065] For the purpose of the specification, the terms "nominal molecular weight" and "molecular weight" are used interchangeably.

[0066] For the purpose of the specification, the terms "nominal functionality" and "functionality" are used interchangeably.

[0067] For the purpose of the specification, functionality of a polyol refers to the free hydroxyl functional groups of the polyol. This also applies to the functionality of a phosphorous-containing polyol.

[0068] For the purpose of the specification, viscosity measured by a Brookfield viscometer is preferably measured in accordance with ASTM D2983.

[0069] For the purpose of the specification, TEX of fiberglass, e.g. e-glass, as weight in grams per kilometer is preferably determined in accordance with ASTM D4031 .

[0070] For the purpose of the specification, "gel-time" is preferably determined in accordance with D2471.

[0071] For the purpose of the specification, "initial viscosity" refers to the viscosity of a substance in its neat state.

[0072] The example formulations described herein are shown without reference to the fibers added during a pultrusion (or other processing) process. It should be understood that the formulations described herein can be mixed with one or more fiber components such that the one or more fiber components comprise at least 60%, at least 70%, or even at least 80% by weight of the total reacted mixture (polyol component plus isocyanate-containing component plus fiber component).

[0073] The polyol component may include a first polyol.

[0074] The first polyol may be present in an amount of at least 20%, at least 40%, or even at least 60% of by weight of the polyol component. The first polyol may be present in an amount of less than 90%, less than 80%, or even less than 70% of by weight of the polyol component.

[0075] The first polyol may include a glycerin initiated polyether polyol having a hydroxyl number of from 350 to 450 mg KOH / gm and a nominal functionality of from 2.5 to 3.5.

[0076] One suitable first polyol is commercially available as Pluracol® GP430 from BASF Corporation, Wyandotte, Michigan. The structure of Pluracol® GP430 is shown below:

[0077] The polyol component may include a second polyol.

[0078] The second polyol may be present in an amount of at least 5%, at least 10%, or even at least 15% of by weight of the polyol component. The second polyol may be present in an amount of less than 40%, less than 30%, or even less than 20% of by weight of the polyol component.

[0079] The second polyol may have a functionality of three, preferably with all of the hydroxyl groups being secondary hydroxyls.

[0080] The second polyol may be a polyester or polyether polyol, preferably a polyether polyol. The second polyol may have an OH value between approximately 800 and 1200 mg KOH / g, preferably between approximately 900 and 1100 mg KOH / g, and most preferably between approximately 935 and 1050 mg KOH / g.

[0081] The second polyol may have a nominal molecular weight between approximately 100 and 300 g / mol, preferably between approximately 125 and 200 g / mol, and most preferably between approximately 150 and 190 g / mol.

[0082] The second polyol may have a viscosity below approximately 2,000 cps [mPa-s], preferably below approximately 1 ,500 cps [mPa s], as measured by a Brookfield viscosimeter.

[0083] Suitable polyols for use as the second polyol include Pluracol® 858, commercially available from BASF Corporation, Wyandotte, Michigan.

[0084] The polyol component may include a third polyol.

[0085] The third polyol may be present in an amount of at least 1%, at least 3%, or even at least 5% of by weight of the polyol component. The third polyol may be present in an amount of less than 15%, less than 12%, or even less than 8% of by weight of the polyol component.

[0086] The third polyol may have a hydroxyl functionality of 4 to 6. In some embodiments, the third polyol may have a hydroxyl functionality of 4.

[0087] The third polyol may be a liquid and freely pourable at 20°C, i.e. the polyol is a liquid having a viscosity of 1 to 10,000 centipoise at 20° C.

[0088] Examples of polyols having a hydroxyl functionality of 4 that are liquid at 20° C include 1 ,1 ,2,2-ethanetetrol and polyether polyols that are the reaction product of an initiator tetrol with ethylene oxide, propylene glycol, or a combination thereof. The initiator can be, for example erythritol, pentaerythritol, 1 , 1 ,2,2-tetrol, or a combination thereof.

[0089] Specific examples of polyether polyols having a functionality of 4 include Pluracol® PEP 450, PEP 550, and 355, available from BASF Corporation, Wyandotte, Michigan.

[0090] The first polyol and the second polyol may be present in a ratio of from about 6:1 to about 9:1 by weight percent first polyol to second polyol. The second polyol and the third polyol may be present in a ratio of from about 2:1 to about 4:1 by weight percent second polyol to third polyol. The first polyol and the third polyol are present in a ratio of from about 10:1 to about 15:1 by weight percent first polyol to second polyol.

[0091] In the event that a flame retardant end-product is desired, the polyol component may include one or more non-halogenated flame retardant components. Such components may include an additional phosphorous-based polyol (e.g., a fourth polyol). The phosphorous-based polyolmay comprise orthophosphoric acid, propoxylated. A specific commercial example is available under the tradename PhosGard® 675 from St. Louis Group.

[0092] A non-limiting selection of potential polyols are provided at Table A.

[0093] Table A

[0094] Typically, the polyol component is mixed and later impregnated into a plurality of fibers. The fibers may be selected from glass, carbon, aramid, basalt, flax, hemp, jute, sisal, wool, silk, bamboo, cotton, or any fiber capable of receiving the polyol component and providing a stretching characteristic to the resulting pultrudate. The plurality of fibers may comprise fiberglass, which may be an e-glass. The fibers may have a TEX (weight in grams per kilometer) range of 1100- 4400. One non-limiting example of suitable fibers are sold under the tradename ADVANTEX® 366 TYPE 30® ROVINGS available from Owens Corning.

[0095] It is possible that a flame retardant property of the resulting pultrudate may be desired. The choice of the flame retardant will depend upon the use envisaged for the formulation and the fire-related specifications and requirements associated with that use. Where the resulting pultrudate material is required to satisfy fire, smoke and toxicity tests a range of fire retardants may be used and useful fire retardants include, halogenated or non-halogenated materials, materials (e.g. polymers) including phosphorous, bromine, chlorine, oxide and combinations thereof. Exemplary flame retardants include, without limitation, flame retardant polyols as discussed above (e.g., or- thophsphoric acid-based materials), chloroalkyl phosphate, dimethyl methylphosphonate, bro- mine-phosphorus compounds, ammonium polyphosphate, neopentylbromide polyether, bromin- ated polyether, antimony oxide, calcium metaborate, chlorinated paraffin, brominated toluene, hexabromobenzene, antimony trioxide, graphite (e.g. expandable graphite), combinations thereof or the like. Other flame retardants that may be used include tricresyl phosphate and aluminum trihydrate.

[0096] It may be preferred that the flame retardant be halogen free. In order to obtain the desired flame retardant properties it may be necessary to include up to 70 wt % based on the weight of the formulation of the polyol component. Preferred formulations contain from 20 wt % to 50 wt % flame retardant of the total polyol component. The flame retardant system that is particularly useful for combining with the polyol component described herein includes a phosphorus containing fire retardant and an expandable graphite. The polyol component may comprise from 15% to 40% by weight of a phosphorus-containing fire retardant, from 5% to 25% by weight of expandable graphite, or a combination thereof.

[0097] The carbon content of heat expandable graphite that exhibits (under heating conditions experienced during downstream processing) a volume expandability of 50 times or higher, should be 65% to 87% (preferably 67.5% to 85%) by weight for serving as a good carbonaceous barrier and for providing a high level of fire retardancy in combination with N-containing flame-retardants.

[0098] In the addition of flame retardant materials to a formulation intended for pultrusion, there are a number of challenges to overcome. There is a desirable balance of mechanical properties (e.g., strength), processing suitability (cure time, fiber wetting, line speed, pull force, viscosity), and the ability to meet flame retardancy standards. With many existing commercial flame retardancy products, the resulting pultrudate has decreased mechanical characteristics or processing challenges that can include one or more of those issues identified above. Tables D, E, and F address example formulations where various flame retardant material were utilized. The results are discussed below.

[0099] The isocyanate-containing component is not particularly limited.

[0100] Suitable polyisocyanates are known to those skilled in the art and include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers. Such organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates.

[0101] Examples of suitable isocyanates include: ethylene diisocyanate; 1 ,4-tetramethylene diisocyanate; 1 ,6-hexamethylene diisocyanate; 1 ,12-dodecane diisocyanate; cyclobutane-1 ,3- diisocyanate; cyclohexane-1 ,3- and -1,4-diisocyanate, and mixtures of these isomers; 1-isocya- nato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate); 2,4- and 2,6- hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4'-diisocy- anate (hydrogenated MDI, or HMDI); 1 ,3- and 1 ,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4'- and / or -4,4'-diisocya- nate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl- polymethylene-polyisocyanates of the type which may be obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI); norbornane diisocyanates; m- and p-isocyanatophenyl sulfonylisocyanates; perchlorinated aryl polyisocyanates; modified polyisocyanates containing carbodiimide groups; modified polyisocyanates containing urethane groups; modified polyisocyanates containing allophanate groups; modified polyisocyanates containing isocyanurate groups; modified polyisocyanates containing urea groups; polyisocyanates containing biuret groups; polyisocyanates obtained by telomerization reactions; polyisocyanates containing ester groups; reaction products of the above-mentioned isocyanates with acetals; and polyisocyanates containing polymeric fatty acid groups.

[0102] Preferably, the viscosity of the isocyanate-containing component may be less than 100 cps [mPa-s] at 25°C as measured by a Brookfield viscometer.

[0103] The isocyanate-containing component comprises a first isocyanate and optionally a second isocyanate.

[0104] In preferred embodiments, the isocyanate-containing component comprises polymeric diphenylmethane diisocyanate.

[0105] In preferred embodiments, the isocyanate-containing component comprises one or more of 2,2'-diphenylmethandiisocyanate, 2,4'-diphenylmethandiisocyanate and / or 4,4'-diphenylme- thandiisocyanate.

[0106] In preferred embodiments, the isocyanate-containing component comprises a blend of pMDI and 2,4’-MDI.

[0107] Generally, pultrusion of polyol and isocyanate systems with fibers to form reinforced composites is performed by supplying the isocyanate and polyol components to a mixing device, which could be a static mixer, to produce a reactive mixture. The reactive mixture is then supplied to an injection die where it impregnates fibers being pulled concurrently into the injection box. The resulting uncured pultrudate is pulled through a heating die where it is shaped and cured. To pull the pultrudate through the die, a pulling machine adapted to grip and pull the pultrudate with sufficient force. It may be desirable for this entire process to occur as quickly as possible to maximize production opportunity.

[0108] A list of materials that may be included in the polyol component and isocyanate component are listed below in Table B.

[0109] Table B

[0110] Example formulations are prepared that include formulations aligned with the current teachings and also comparative formulations. Flexural strength and flexural modulus are both measured in accordance with ASTM D7264. The example formulations, when pultruded, are loaded with a fiber component in an amount such that approximately 80% (e.g., 60%-90%) by weight of the pultrudate is the fiber component with the formulations described making up the approximately 20% remaining weight.

[0111] Tables C, D, and E below include varying amounts and types of flame retardant material. Table C discloses a formulation using a combination of an organo-phosphorous liquid (phospho- rous / nitrogen-based flame retardant) (one example is Flamecheck® available from Technick Products), organic phosphinate (phosphorous-based flame retardant) (one example is Exolit® available from Clariant) and magnesium hydroxide (magnesium-based flame retardant) (one example is MDH available from Huber Engineered Materials). In the resulting pultrudate, the organo-phosphorous causes a slowing reaction in the heated die causing only partial cure. In addition, the viscosity is undesirably high due to the relatively high amount of powder additives (magnesium hydroxide and organic phosphinate). The high percentage of powder additives also displaces some fibers, resulting in reduced overall strength. Lastly, the UL94 flame retardancy rating is only V1 as opposed to the desired VO.

[0112] Table C

[0113] Table D discloses a formulation using a combination of a phosphorous-based polyol liquid (one example is Phosgard® 675 available from St. Louis Group), and expandable graphite (one example is Graphguard® available from NeoGraph® Solutions and another is Nyagraph® available from Nyacol®). The phosphorous based polyol is used as a replacement for the polyether polyol (one example is Pluracol® 430, available from BASF) which has the undesired effect of reducing the glass transition temperature (Tg) and strength of the resulting pultrudate. However, the processability (viscosity, line speed and pull force) is improved as compared to the formulation of Table D. Lastly, the UL94 flame retardancy rating is VO as desired.

[0114] Table D

[0115] T able E below discloses a formulation using a combination of a phosphorous-based polyol liquid (one example is Phosgard® 675 available from St. Louis Group), and expandable graphite (expandable graphite 2) (one example is Graphguard® available from NeoGraph® Solutions). As compared to the formulation from Table D, the phosphorous based polyol is used in addition to the polyether polyol (polyol 1) (one example is Pluracol® 430, available from BASF). This inclusion of the polyether polyol helped to maintain Tg and strength properties while still enjoying improved processability and the desired UL94 flame retardancy rating of VO.

[0116] Table E

[0117] Table F below shows various characteristics of the formulation disclosed at Table E, Example 1 (e.g., formulation with fire retardancy characteristics). The glass transition temperature (Tg), flexural modulus in the 0° direction, and flexural modulus in the 90° direction are all provided at various pull speeds.

[0118] Table F

[0119] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints.

[0120] The terms “generally” or “substantially” to describe angular measurements may mean about + / - 10° or less, about + / - 5° or less, or even about + / - 1° or less. The terms “generally” or “substantially” to describe angular measurements may mean about + / - 0.01° or greater, about + / - 0.1° or greater, or even about + / - 0.5° or greater. The terms “generally” or “substantially” to describe linear measurements, percentages, or ratios may mean about + / - 10% or less, about + / - 5% or less, or even about + / - 1% or less. The terms “generally” or “substantially” to describe linear measurements, percentages, or ratios may mean about + / - 0.01% or greater, about + / - 0.1 % or greater, or even about + / - 0.5% or greater.

[0121] Unless otherwise stated, any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, a property, or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, from 20 to 80, or from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc.) are within the teachings of this specification. Likewise, individual intermediate values are also within the present teachings. For values which are less than one, one unit is considered to be 0.0001 , 0.001 , 0.01 , or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints.

[0122] As can be seen, the teaching of amounts expressed as “parts by weight” herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the of a range in terms of “at least ‘x’ parts by weight of the resulting composition” also contemplates a teaching of ranges of same recited amount of “x” in percent by weight of the resulting composition.

[0123] The term “consisting essentially of” to describe a combination shall include the elements, ingredients, components, or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components, or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components, or steps.

[0124] The term "substantially equal" in connection with a property of a first element and a second element shall mean that said property of the second element preferably deviates from said property of the first element by not more than 10%, more preferably not more than 5%, still more preferably not more than 2%, yet more preferably not more than 1%.

[0125] The term "substantially similar to one another" in connection with a property of a first element and a second element shall mean that said property of the second element preferably deviates from said property of the first element by not more than 25%, more preferably not more than 20%, still more preferably not more than 15%, yet more preferably not more than 10%.

[0126] Plural elements, ingredients, components, or steps can be provided by a single integrated element, ingredient, component, or step. Alternatively, a single integrated element, ingredient, component, or step might be divided into separate plural elements, ingredients, components, or steps. The disclosure of “a” or “one” to describe an element, ingredient, component, or step is not intended to foreclose additional elements, ingredients, components, or steps.

[0127] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as channel as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not consider such subject matter to be part of the disclosed inventive subject matter.

Claims

CLAIMSWhat is claimed is:

1. A mixture comprising: i) a first polyol; ii) a second polyol; iii) an optional third polyol; and iv) a non-halogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof; wherein the mixture is capable of being reacted with an isocyanate-containing component to produce a reactive mixture having a viscosity at 25 °C is less than about 4000 cps [mPa s] as measured by a Brookfield viscometer.

2. The mixture of claim 1 , wherein the mixture is reacted with a isocyanate-containing component to form the reactive mixture.

3. A reactive mixture comprising: i) a polyol component comprising a first polyol and a second polyol and a non-halogen- ated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof; ii) an isocyanate-containing component; wherein the viscosity of the reactive mixture at 25 °C is less than about 4000 cps [mPa-s] as measured by a Brookfield viscometer.

4. The reactive mixture of any of the preceding claims, wherein the reactive mixture is impregnated in a continuous fiber component.

5. The reactive mixture of any of the preceding claims, wherein the phosphorous-containing material is a phosphorous-containing polyol.

6. The mixture or the reactive mixture of any of the preceding claims, comprising a third polyol.

7. The reactive mixture of any of the preceding claims, wherein the flame retardant package includes both a phosphorus-containing material and expandable graphite.

8. The reactive mixture of any of the preceding claims, wherein the first polyol has a nominal molecular weight that is greater than 300 g / mol.

9. The reactive mixture of any of the preceding claims, wherein the second polyol has a nominal molecular weight that is greater than 300 g / mol.

10. The reactive mixture of any of the preceding claims, wherein the first polyol and second polyol have substantially equal molecular weights.

11. The reactive mixture of any of the preceding claims, wherein the polyol component includes a third polyol having a molecular weight of less than 300 g / mol.

12. The reactive mixture of any of the preceding claims, wherein the polyol component includes a mold release component.

13. The reactive mixture of any of the preceding claims, wherein the non-halogenated flame retardant package comprises both a phosphorous-containing material and an expandable graphite and the phosphorus-containing material is present in an amount that is at least double the amount of the expandable graphite by weight percent.

14. The reactive mixture of any of the preceding claims, wherein the reactive mixture is impregnated in fiberglass.

15. The reactive mixture of claim 12, wherein the fiberglass is an e-glass having a TEX (weight in grams per kilometer) range of 1100-4400.

16. The reactive mixture of any of the preceding claims, wherein at least one polyol has a functionality of at least 4.

17. The reactive mixture of any of the preceding claims, wherein the polyol component includes a third polyol and wherein at least the second and third polyols have an initial viscosity of at least about 1200 cps [mPa s] at 25°C as measured by a Brookfield viscometer.

18. The reactive mixture of any of the preceding claims, wherein the polyol component includes an adhesion promoter.

19. The reactive mixture of any of the preceding claims, wherein the first polyol and the second polyol are present in a ratio of from about 6:1 to about 9:1 by weight percent first polyol to second polyol.

20. The reactive mixture of any of the preceding claims, wherein the viscosity of the reactive mixture at 25°C is less than about 3000 cps [mPa s] as measured by a Brookfield viscometer.

21. The reactive mixture of any of the preceding claims, wherein the viscosity of the reactive mixture at 25°C is less than about 2000 cps [mPa s] as measured by a Brookfield viscometer.

22. The reactive mixture of any of the preceding claims, wherein the gel-time of the reactive mixture at 25°C is at least about 10 minutes.

23. The reactive mixture of any of the preceding claims, wherein the gel-time of the reactive mixture at 175°C is less than 1 minute.

24. The reactive mixture of any of the preceding claims, wherein the first polyol, the second polyol and the optionally present third polyol are independently of one another selected from propoxylated orthophosphoric acid; trispoly(propylene oxide) phosphate; polyoxypropylene glyceryl ether such as polyoxypropylene (10) glyceryl ether; propoxylated glycerol; propoxylated pentaerythritol; or combinations thereof.

25. The reactive mixture of any of the preceding claims, wherein the reactive mixture is pul- truded with a fiber component to form a pultruded and cured product having a post-processing flexural strength of at least about 1200 MPa and a flexural modulus of at least about 49 GPa measured in the 0° direction as measured by ASTM D7264.

26. The reactive mixture of claim 23, wherein the reactive mixture is impregnated in a continuous fiber component to form an impregnated fiber component comprising at least 80% by weight e-glass.

27. The reactive mixture of any of the preceding claims, wherein the reactive mixture is adapted for a pultrusion process with a line speed of at least 8 feet per minute (fpm) in a plaque die (3mm by 150mm (thickness X width)).

28. The reactive mixture of any of the preceding claims, wherein the reactive mixture is adapted for downstream processing steps including injection molding, filament winding, compression molding, resin transfer molding, or combinations thereof.

29. The reactive mixture of any of the preceding claims, wherein the reactive mixture is pul- truded with or without fibers and a resulting pultrudate will have a UL-94 flammability rating of V-0.

30. The reactive mixture of any of the preceding claims, wherein the reactive mixture is pul- truded with a plurality of fibers selected from glass, carbon, aramid, basalt, flax, hemp, jute, sisal, wool, silk, bamboo, cotton, or combinations thereof.

31. A two-part material comprising: i) a part A (polyol component) including a first polyol and a second polyol, and a nonhalogenated flame retardant package comprising a phosphorus-containing material, expandable graphite, or some combination thereof; ii) a part B including an isocyanate-containing component having a viscosity of less than 100 cps [mPa s] at 25°C as measured by a Brookfield viscometer wherein part A and part B are combined to form a reactive mixture.

32. The two-part material of claim 29, wherein the first and second polyols have molecular weights that are greater than 300 and substantially similar to one another and wherein at least one or the first, second, and third polyols has a functionality of at least 4.

33. The two-part material of claim 29 or 30, wherein the reactive mixture is contacted with a plurality of fibers.

34. The two-part material of claim 31 , wherein the fibers are selected from glass, carbon, aramid, basalt, flax, hemp, jute, sisal, wool, silk, bamboo, cotton, or combinations thereof.

35. The two-part material of any of claims 29 through 32, wherein the first polyol and the second polyol are present in a ratio of from about 6:1 to about 9:1 by weight percent first polyol to second polyol.

36. The two-part material of any of claims 29 through 33, wherein the viscosity of the reactive mixture at 25°C is less than about 3000 cps [mPa s] as measured by a Brookfield viscometer.

37. The two-part material of any of claims 29 through 34, wherein the viscosity of the reactive mixture at 25°C is less than about 2000 cps [mPa s] as measured by a Brookfield viscometer.

38. The two-part material of any of claims 29 through 35, wherein the gel-time of the reactive mixture at 25°C is at least about 10 minutes.

39. The two-part material of any of claims 29 through 36, wherein the gel-time of the reactive mixture at 175°C is less than 1 minute.

40. The two-part material of any of claims 29 through 37, wherein the first polyol and the second polyol are independently of one another selected from propoxylated orthophosphoric acid; trispoly(propylene oxide) phosphate; polyoxypropylene (10) glyceryl ether such as polyoxypropylene glyceryl ether; propoxylated glycerol; propoxylated pentaerythritol; or combinations thereof.

41. The two-part material of any of claims 29 through 38, wherein the reactive mixture is pul- truded with a fiber component to form a pultruded and cured product having a post-processing flexural strength of at least about 1200 MPa and a flexural modulus of at least about 49 GPa measured in the 0° direction as measured by ASTM D7264.

42. The two-part material of claim 39, wherein the reactive mixture is impregnated in a continuous fiber component to form an impregnated fiber component comprising at least 80% by weight e-glass.

43. The two-part material of any of claims 29 through 40, wherein the reactive mixture is adapted for a pultrusion process with a line speed of at least 8 feet per minute (fpm) in a plaque die (3mm by 150mm (thickness X width)).

44. The two-part material of any of claims 29 through 41 , wherein the reactive mixture is adapted for downstream processing steps including injection molding, filament winding, compression molding, resin transfer molding, or combinations thereof.

45. Use of the mixture or reactive mixture of any of claims 1 through 30, for pultruding a flame resistant product having a UL94 flame retardancy rating of V0.

46. Use of the two-part material of any of claims 31 through 44, for pultruding a flame resistant product having a UL94 flame retardancy rating of V0.

47. Use of the mixture or reactive mixture of any of claims 1 through 30, for pultruding a product at a pull speed of at least 5 feet per minute (152 cm / minute).

48. Use of the two-part material of any of claims 31 through 44, for pultruding a product at a pull speed of at least 5 feet per minute (152 cm / minute).

49. A method comprising: i) reacting the mixture of claim 1 with an isocyanate component to form a reactive mixture; ii) impregnating the reactive mixture into a continuous fiber component.

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