Polyurethane foam articles and methods of forming polyurethane foam articles

Abstract

A polyurethane foam article and method for forming the same are provided. [Solution] The polyurethane foam article comprises the reaction product of an isocyanate component and an isocyanate-reactive composition in the presence of a blowing agent. The isocyanate component comprises an isocyanate prepolymer comprising the reaction product of a first polyether polyol and methylene diphenyl diisocyanate. The isocyanate-reactive composition comprises a second polyether polyol having secondary terminal hydroxyl groups and an amine-initiated catalyzed polyether polyol having primary hydroxyl groups. A method of making the polyurethane foam article comprises reacting the first polyether polyol with methylene diphenyl diisocyanate to form an isocyanate prepolymer, and reacting the isocyanate prepolymer and the isocyanate-reactive composition in the presence of a blowing agent to form the polyurethane foam article.

Description

[Technical field]

[0001] The present invention relates generally to polyurethane foam articles and methods of forming the polyurethane foam articles. More specifically, the present invention relates to methods of forming polyurethane foam articles comprising the reaction product of an isocyanate-reactive composition and an isocyanate component in the presence of a blowing agent. [Background technology]

[0002] The use of polyurethane foam articles throughout the transportation, construction, sports, and other industries is known in the art. In the sports industry, polyurethane foam articles are used to make surfboards. As surfboards, polyurethane foam articles provide excellent buoyancy along with excellent strength and durability.

[0003] As is known in the art, polyurethane foam articles are formed via the exothermic reaction of an isocyanate-reactive resin composition with an isocyanate in the presence of a blowing agent. The isocyanate-reactive resin composition, the isocyanate, and the blowing agent are collectively known as a polyurethane system and are selected to optimize the manufacturing efficiency and performance characteristics of the polyurethane foam article for a particular use. For example, when the polyurethane foam is used in a surfboard, the components of the polyurethane system are selected for molding efficiency and to produce a polyurethane foam article (e.g., a surfboard blank) with exceptional buoyancy, strength, durability, color, color stability, and other performance characteristics. Summary of the Invention [Problem to be solved by the invention]

[0004] In surfboard applications, the isocyanate-reactive resin composition and the isocyanate are mixed, typically in the presence of a blowing agent, to form a reaction mixture that is poured into a mold and allowed to react to form the surfboard blank. In past surfboard applications, toluene diisocyanate was used to form buoyant surfboard blanks with good strength and color (i.e., white). However, due to safety and environmental concerns, surfboard manufacturers have begun to eliminate the use of toluene diisocyanate.

[0005] Recently, surfboard manufacturers have attempted to use monomeric and polymeric diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and other isocyanates in the manufacture of surfboard blanks. Many of these attempts have failed. For example, the use of monomeric and polymeric diphenylmethane diisocyanate often results in the surfboard blank discoloring, cracking, scorching, burning, sticking to the mold, and other problems associated with uncontrolled heat generation that occurs during the formation of the surfboard blank. Additionally, surfboard blanks formed with monomeric and polymeric diphenylmethane diisocyanate may have poor strength and color stability once formed.

[0006] To this end, various polyurethane systems that do not utilize toluene diisocyanate have been developed in an attempt to produce surfboard blanks. Despite such developments, there remains a need for further improvements in polyurethane systems and surfboard blanks formed therefrom. [Means for solving the problem]

[0007] Summary of the Invention and Advantages The present invention provides a polyurethane foam article comprising the reaction product of an isocyanate component and an isocyanate-reactive composition in the presence of a blowing agent, the isocyanate component comprising an isocyanate prepolymer comprising the reaction product of a first polyether polyol and methylene diphenyl diisocyanate, the isocyanate-reactive composition comprising a second polyether polyol having secondary terminal hydroxyl groups and an amine-initiated catalyzed polyether polyol having primary hydroxyl groups.

[0008] The invention also provides a method of making a polyurethane foam article, comprising the steps of reacting a first polyether polyol with methylene diphenyl diisocyanate to form an isocyanate prepolymer, and reacting the isocyanate prepolymer with an isocyanate-reactive composition in the presence of a blowing agent to form the polyurethane foam article.

[0009] Advantageously, polyurethane foam articles can be safely and efficiently made to produce polyurethane foam articles (e.g., surfboard blanks) that have exceptional buoyancy, strength, durability, color, color stability, and other performance characteristics. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] A polyurethane foam article is disclosed. The polyurethane foam article is obtained from an exothermic reaction of a polyurethane system comprising an isocyanate-reactive resin composition and an isocyanate component in the presence of a blowing agent. The polyurethane foam article of the present invention is typically used as a surfboard blank. However, it should be understood that the rigid polyurethane foam of the present disclosure can be used in many other applications.

[0011] The present invention provides a polyurethane foam article comprising the reaction product of an isocyanate component and an isocyanate-reactive composition in the presence of a blowing agent. The isocyanate component comprises an isocyanate prepolymer comprising the reaction product of a first polyether polyol and methylene diphenyl diisocyanate. The isocyanate-reactive composition comprises a second polyether polyol having secondary terminal hydroxyl groups and an amine-initiated catalyzed polyether polyol having primary hydroxyl groups. The unreacted isocyanate-reactive resin composition, the isocyanate component, and the blowing agent are collectively referred to as a polyurethane system.

[0012] The polyurethane foam article comprises the reaction product of an isocyanate component and an isocyanate-reactive composition in the presence of a blowing agent. That is, an isocyanate prepolymer and a polyol of an isocyanate-reactive component are chemically reacted in the presence of a blowing agent. The present disclosure also describes polyurethane systems that include an isocyanate component and an isocyanate-reactive component. The systems are typically provided in two or more separate components, such as an isocyanate component and an isocyanate-reactive (or resin) composition, i.e., as a two-component (or 2K) system, as described further below. It should be understood that the references to an isocyanate component and an isocyanate-reactive composition used herein are merely intended to establish a reference point for placing the individual components of the system and to establish a parts by weight basis. Thus, the present disclosure should not be construed as being limited to only 2K systems. For example, the individual components of the system can all be kept separate from one another and mixed individually before application. As another example, the components typically included in an isocyanate-reactive composition (and described as such herein) may be used in admixture with the isocyanate component.

[0013] The polyurethane foam articles of the present disclosure typically have a closed cell content of greater than about 85%, or from about 85 to about 95%, when tested according to ASTM D2856-94.

[0014] The polyurethane foam articles of the present disclosure typically have a compressibility of from about 16 to about 240 kg / m when tested according to ASTM D1622-14. 3 , about 24~80kg / m 3 , about 28~60kg / m 3 , about 40~60kg / m 3 , about 47~52kg / m 3 has a density of

[0015] The polyurethane foam articles of the present invention can be described as "rigid polyurethane foams." The term "rigid polyurethane foams" is a description of a particular class of polyurethane foams and is in contrast to flexible polyurethane foams. Rigid polyurethane foams are generally non-porous, have closed cells and minimal elastic properties, whereas flexible polyurethane foams are generally porous and have open cells.

[0016] Isocyanate component The polyurethane system of the present disclosure includes an isocyanate component. The isocyanate component includes an isocyanate prepolymer. The isocyanate prepolymer includes a reaction product of a first polyether polyol and methylene diphenyl diisocyanate. In some embodiments, the isocyanate prepolymer consists essentially of a reaction product of a first polyether polyol and methylene diphenyl diisocyanate in the presence of various additives. In some embodiments, the isocyanate prepolymer consists of a reaction product of a first polyether polyol and methylene diphenyl diisocyanate.

[0017] Polyether polyols described herein and suitable for the purposes of the present invention include, but are not limited to, products obtained by polymerization of cyclic oxides (i.e., alkylene oxides), such as ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), or tetrahydrofuran, in the presence of a polyfunctional initiator. Suitable initiator compounds contain multiple active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol (PG), diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluenediamine, diethyltoluenediamine, phenyldiamine, diphenylmethanediamine, ethylenediamine, cyclohexanediamine, cyclohexanedimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and combinations thereof.

[0018] For this purpose, the polyether polyols described herein contain a plurality of alkyleneoxy groups. The term alkyleneoxy group describes a monomer or unit. An alkyleneoxy group is a unit resulting from the polymerization of an alkylene oxide, such as an EO group, a PO group, and a BO group. When referred to, the amount of alkyleneoxy groups in a polyether polyol is referred to in parts by weight, based on the total weight of alkyleneoxy groups used to form the polyether polyol. A plurality of alkyleneoxy groups can be arranged to form a polyether polyol, which can be described as a polyol having random alkyleneoxy groups (constituting heterosegments), a polymer having repeating alkyleneoxy groups, and a polymer having block alkyleneoxy groups. A plurality of polymer side chains have alkoxyl end caps selected from the group of ethyleneoxy end caps, propyleneoxy end caps, butyleneoxy end caps, and combinations thereof. The amount of alkyleneoxy endcaps in a polyether polyol is referred to as a percentage (%) relative to the total number of endcaps in a particular sample of polyether polyol.

[0019] wherein, with respect to the first polyether polyol, the first polyether polyol typically has a functionality of greater than about 2, alternatively greater than about 3, alternatively from about 2 to about 5, alternatively from about 3 to about 5, alternatively from about 4; a weight average molecular weight of from about 200 to about 900 g / mol, alternatively from about 300 to about 700 g / mol, alternatively from about 300 to about 500 g / mol, alternatively from about 350 to about 450 g / mol; a hydroxyl number of from about 30 to about 1,100 mg KOH / g, alternatively from about 400 to about 900 mg KOH / g, alternatively from about 435 to about 570 mg KOH / g, alternatively from about 435 to about 465 mg KOH / g, alternatively from about 540 to about 570 mg KOH / g; and a viscosity of from about 1,000 to about 8,000 cps at 20° C. when tested according to ASTM D2196-15. (mPa·s) , or about 4,000 to 6,000 cps (mPa·s) , or about 4,800 to about 5,600 cps (mPa·s) In various non-limiting embodiments, all values ​​and ranges of values ​​between the preceding values ​​are expressly contemplated herein.

[0020] In some embodiments, the first polyether polyol is initiated with pentaerythritol. The initiator, also referred to as a starter, serves as a reactive base for compounds such as alkylene oxides that polymerize to form the polyol, and also serves to anchor the polyol during formation. The first polyether polyol of these embodiments can include EO, PO, and / or BO groups and has various percentages of PO capping. The first polyether polyol has a PO capping of greater than about 90%, alternatively greater than about 95%, alternatively greater than about 99%, or even about 100%. More specifically, "about" 100% PO capping means that all intended capping of the first polyether polyol is PO capping, without any EO capping due to trace amounts of other alkylene oxides or other impurities. Thus, capping is typically about 100% PO capping, but may be slightly lower, such as at least about 99% PO capping, depending on process variables and the presence of impurities during the production of the first polyether polyol.

[0021] In one embodiment, the first polyether polyol is a pentaerythritol-initiated polyether polyol with PO capping and has a functionality of about 4, a weight average molecular weight of about 400 g / mol, and a hydroxyl number of about 555 mg KOH / g.

[0022] Here, with respect to methylene diphenyl diisocyanate, methylene diphenyl diisocyanate is a liquid having an NCO content (wt%) of about 33.5. Determination of the NCO content (%NCO) is accomplished by standard chemical titration analysis known to those skilled in the art. Methylene diphenyl diisocyanate includes isomers selected from the group of 2,2'-isomer, 2,4'-isomer, and 4,4'-isomer.

[0023] In some embodiments, the methylene diphenyl diisocyanate comprises: less than 12% by weight, alternatively less than 10% by weight, alternatively less than 5% by weight, alternatively less than 1% by weight, alternatively about 0% by weight, alternatively about 2% to about 12% by weight of the 2,2'-isomer, greater than 40% by weight, alternatively about 0% to about 90% by weight, alternatively about 20% to about 60% by weight, alternatively about 40% to about 55% by weight, alternatively about 50% by weight of the 2,4'-isomer, and greater than 40% by weight, alternatively about 0% to about 90% by weight, alternatively about 20% to about 60% by weight, alternatively about 40% to about 55% by weight, alternatively about 50% by weight of the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0024] In one embodiment, the methylene diphenyl diisocyanate contains: less than 10% by weight of the 2,2'-isomer, about 40 to about 60% by weight of the 2,4'-isomer, and about 40 to about 60% by weight of the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0025] In another embodiment, the methylene diphenyl diisocyanate contains: a trace amount (e.g., less than 1%, less than 0.5%) of the 2,2'-isomer; about 50% (e.g., 50±0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10%) of the 2,4'-isomer; and about 50% (e.g., 50±0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10%) of the 4,4'-isomer.

[0026] In yet another embodiment, the methylene diphenyl diisocyanate contains about 50% by weight of the 2,4'-isomer and about another 50% by weight of any combination of the 2,2'-isomer and the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate.

[0027] As described above, the isocyanate prepolymer comprises a reaction product of a first polyether polyol and methylene diphenyl diisocyanate. In various embodiments, the first polyether polyol is present in the isocyanate prepolymer in an amount of about 2 to about 20 weight percent, alternatively about 5 to about 15 weight percent, alternatively about 7 to about 10 weight percent, based on the total weight of the isocyanate prepolymer, and the methylene diphenyl diisocyanate is present in the isocyanate prepolymer in an amount of about 80 to about 98 weight percent, alternatively about 85 to about 95 weight percent, alternatively about 90 to about 93 weight percent, based on the total weight of the isocyanate prepolymer. Of course, the isocyanate prepolymer comprises a reaction product of a first polyether polyol and methylene diphenyl diisocyanate, and the above ranges can be considered essentially or alternatively the amounts of the first polyether polyol and methylene diphenyl diisocyanate that react to form the isocyanate prepolymer. In various non-limiting embodiments, all values ​​and ranges of values ​​between the recited values ​​are expressly contemplated herein.

[0028] Additionally, embodiments are contemplated herein in which the isocyanate prepolymer comprises the reaction product of more than one isocyanate (e.g., a different isocyanate in addition to methylene diphenyl diisocyanate) and / or more than one polyol (e.g., a different polyol in addition to the first polyether polyol). In such embodiments, the total amount of all polyols included is within the ranges described above.

[0029] The chemical reaction of the first polyether polyol with methylene diphenyl diisocyanate to form the isocyanate prepolymer can be carried out in the presence of one or more additives. Additives suitable for the purposes of the present invention include, but are not limited to, catalysts, chain extenders, crosslinkers, chain terminators, reaction inhibitors, processing additives, plasticizers, adhesion promoters, antioxidants, defoamers, anti-foaming agents, water scavengers, molecular sieves, fumed silica, UV stabilizers, fillers, thixotropic agents, silicones, colorants, inert diluents, and combinations thereof. In some embodiments, the reaction occurs in the presence of a reaction inhibitor, such as benzoyl chloride, and / or a plasticizer, such as tributyl phosphite. When included, additives can be included in the isocyanate-reactive resin composition in various amounts. For example, an amount of 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, less than 0.5%, or 0.005 to 0.03% by weight based on the total weight of reactants used to form the prepolymer or based on the total weight of the prepolymer.

[0030] In many embodiments, the isocyanate prepolymer has a viscosity of about 1.05 to 1.10 g / cm 3 and is a liquid at 25° C. Further, in many such embodiments, the isocyanate prepolymer has a specific gravity of about 900 to about 1300 cps at 25° C. (mPa·s) , or about 900 to about 1300 cps (mPa·s) Further, in many such embodiments, the isocyanate prepolymer has an NCO content of from about 15 to about 40 weight percent, alternatively from about 20 to about 30 weight percent, alternatively from about 26 to about 28 weight percent. Determination of NCO content (% NCO) is accomplished by standard chemical titration analysis known to those of skill in the art. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0031] In some embodiments, the isocyanate component includes one or more auxiliary isocyanates. The auxiliary isocyanates can be polyisocyanates having a functionality of 2 or more, such as an NCO functionality of 2 or more. Suitable auxiliary isocyanates for the purposes of the present disclosure include, but are not limited to, aliphatic and aromatic isocyanates. In various embodiments, the auxiliary isocyanate is selected from the group of diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and combinations thereof.

[0032] The auxiliary isocyanate may be an auxiliary isocyanate prepolymer different from the isocyanate prepolymers mentioned above. The auxiliary isocyanate prepolymer is typically a reaction product of an isocyanate with a polyol and / or a polyamine. The isocyanate used in the auxiliary isocyanate prepolymer can be any of the isocyanates mentioned above. The polyol used to form the auxiliary isocyanate prepolymer is typically selected from the group of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, biopolyol, and combinations thereof. The polyamine used to form the prepolymer is typically selected from the group of ethylenediamine, toluenediamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines, aminoalcohols, and combinations thereof. Examples of suitable aminoalcohols include ethanolamine, diethanolamine, triethanolamine, and combinations thereof.

[0033] Specific auxiliary isocyanates that may be used for purposes of this disclosure include toluylene diisocyanate; 4,4'-diphenylmethane diisocyanate; m-phenylene diisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1,3-phenylene diisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate; 1,4-dicyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate, 2,4,6-toluylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate; 1-methyl-3,5-diethylphenylene-2,4-diisocyanate; 1,3,5-triethylphenylene-2,4-diisocyanate. cyanate; 1,3,5-triisopropyl-phenylene-2,4-diisocyanate; 3,3'-diethyl-bisphenyl-4,4'-diisocyanate; 3,5,3',5'-tetraethyl-diphenylmethane-4,4'-diisocyanate; 3,5,3',5'-tetraisopropyldiphenylmethane-4,4'-diisocyanate; 1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate; 1,3,5-triethylbenzene-2,4,6-triisocyanate; 1-ethyl-3,5-diisopropylbenzene-2,4,6-triisocyanate and 1,3,5-triisopropylbenzene-2,4,6-triisocyanate.

[0034] The isocyanate component can include one or more additives. The additives can be included in the isocyanate component as part of the isocyanate prepolymer, or can be added to the isocyanate prepolymer for a specific purpose. Additives suitable for purposes of the present invention include any of the additives described herein, as well as other additives known in the art.

[0035] Isocyanate-reactive composition The polyurethane system of the present invention comprises an isocyanate-reactive resin composition comprising a second polyether polyol having secondary terminal hydroxyl groups, an optional third polyether polyol, and an amine-initiated catalyzed polyether polyol having primary hydroxyl groups.

[0036] wherein, with respect to the second polyether polyol, the second polyether polyol typically has a functionality of greater than about 4, alternatively greater than about 5, alternatively from about 4 to about 8, alternatively from about 5 to about 7, alternatively from about 6; a weight average molecular weight of from about 400 to about 2,000 g / mol, alternatively from about 500 to about 900 g / mol, alternatively from about 600 to about 800 g / mol, alternatively from about 650 to about 725 g / mol; a hydroxyl number of from about 30 to about 1,100 mg KOH / g, alternatively from about 300 to about 900 mg KOH / g, alternatively from about 400 to about 600 mg KOH / g, alternatively from about 450 to about 550 mg KOH / g; and a viscosity of from about 15,000 to about 30,000 cps at 25° C. when tested according to ASTM D2196-15. (mPa·s) , or about 20,000 to about 24,000 cps (mPa·s) , or about 21,000 to about 23,000 cps (mPa·s) In various non-limiting embodiments, all values ​​and ranges of values ​​between the preceding values ​​are expressly contemplated herein.

[0037] In some embodiments, the second polyether polyol is initiated with sorbitol. The initiator, also called starter, functions as a reactive base for compounds such as alkylene oxides that polymerize to form the polyol, and also serves to anchor the polyol during formation. The second polyether polyol of these embodiments can include EO, PO, and / or BO groups and has various percentages of PO capping. The second polyether polyol has a PO capping of greater than about 90%, alternatively greater than about 95%, alternatively greater than about 99%, or about 100%. More specifically, "about" 100% PO capping means that all the intended capping of the second polyether polyol is PO capping, without any PO capping due to trace amounts of other alkylene oxides or other impurities. Thus, capping is typically about 100% PO capping, but may be slightly lower, such as at least about 99% PO capping, depending on process variables and the presence of impurities during the second polyether polyol production.

[0038] About 100% PO capping provides substantially (about 100%) all secondary hydroxyl groups, which typically react slower than primary hydroxyl groups and produce a more controlled exotherm. In other words, a second polyether polyol having about 100% PO endcapping is also typically slower reacting than a polyol having EO endcapping, because the PO-capped polyol is sterically hindered and the EO-capped polyol is not sterically hindered.

[0039] In one embodiment, the second polyether polyol is a sorbitol-initiated polyether polyol with PO capping: has a functionality of about 6; a weight average molecular weight of about 687 g / mol; and a hydroxyl number of about 490 mg KOH / g.

[0040] In various embodiments, the second polyether polyol is present in the isocyanate-reactive composition in an amount from about 20 to about 90 weight percent, alternatively from about 20 to about 70 weight percent, alternatively from about 20 to about 60 weight percent, alternatively from about 30 to about 50 weight percent, or alternatively from about 35 to about 45 weight percent, based on the total weight of the isocyanate-reactive composition. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0041] With respect to the third polyether polyol (if included), the third polyether polyol is different from the second polyether polyol. The third polyether polyol typically has a functionality of greater than about 2, alternatively from about 2 to about 4, alternatively from about 3; a weight average molecular weight of about 300 to about 1,500 g / mol, alternatively from about 400 to about 1,300 g / mol, alternatively from about 500 to about 1,100 g / mol, alternatively from about 600 to about 800 g / mol, alternatively from about 650 to about 750 g / mol; a hydroxyl number of about 100 to about 400 mg KOH / g, alternatively from about 150 to about 300 mg KOH / g, alternatively from about 200 to about 260 mg KOH / g; and a viscosity of about 200 to about 1,000 cps at 25° C. when tested according to ASTM D2196-15. (mPa·s) , or about 200 to about 500 cps (mPa·s) , or about 250 to about 300 cps (mPa·s) In various non-limiting embodiments, all values ​​and ranges of values ​​between the preceding values ​​are expressly contemplated herein.

[0042] In some embodiments, the third polyether polyol is initiated with glycerin. The initiator, also called starter, acts as a reactive base for compounds such as alkylene oxides that polymerize to form the polyol, and also serves to anchor the polyol during formation. The third polyether polyol of these embodiments can include EO, PO, and / or BO groups and has various percentages of PO capping. The third polyether polyol has a PO capping of greater than about 90%, alternatively greater than about 95%, alternatively greater than about 99%, or about 100%. More specifically, "about" 100% PO capping means that all the intended capping of the third polyether polyol is PO capping, without any PO capping due to trace amounts of other alkylene oxides or other impurities. Thus, capping is typically about 100% PO capping, but may be slightly lower, such as at least about 99% PO capping, depending on process variables and the presence of impurities during the third polyether polyol production.

[0043] About 100% PO capping provides substantially (about 100%) all secondary hydroxyl groups, which typically react slower than primary hydroxyl groups and produce a more controlled exotherm. In other words, a third polyether polyol having about 100% PO endcapping is also typically slower reacting than a polyol having EO endcapping, because the PO polyol is sterically hindered and the EO-capped polyol is not sterically hindered.

[0044] In one embodiment, the third polyether polyol is a glycerin-initiated polyether polyol with PO capping: a functionality of about 3; a weight average molecular weight of about 700 g / mol; and a hydroxyl number of about 222 to about 237 mg KOH / g.

[0045] In various embodiments, the third polyether polyol is present in the isocyanate-reactive composition in an amount from about 20 to about 70 weight percent, alternatively from about 20 to about 60 weight percent, alternatively from about 30 to about 50 weight percent, alternatively from about 35 to about 45 weight percent, based on the total weight of the isocyanate-reactive composition. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0046] With respect to the amine-initiated catalyzed polyether polyols herein, the amine-initiated catalyzed polyether polyols typically have a functionality of greater than about 3, alternatively from about 2 to about 6, alternatively from about 3 to about 5, alternatively from about 4; a weight average molecular weight of from about 200 to about 1,500 g / mol, alternatively from about 200 to about 1,000 g / mol, alternatively from about 200 to about 500 g / mol, alternatively from about 250 to about 450 g / mol, alternatively from about 300 to about 400 g / mol; a hydroxyl number of from about 100 to about 1,000 mg KOH / g, alternatively from about 300 to about 700 mg KOH / g, alternatively from about 400 to about 500 mg KOH / g, alternatively from about 450 to about 550 mg KOH / g; and a viscosity of from about 200 to about 1,000 cps at 25° C. when tested according to ASTM D2196-15. (mPa·s) , or about 200 to about 500 cps (mPa·s) , or about 250 to about 350 cps (mPa·s) In various non-limiting embodiments, all values ​​and ranges of values ​​between the preceding values ​​are expressly contemplated herein.

[0047] In some embodiments, the amine-initiated catalytic polyether polyol is initiated with monoethanolamine. The initiator, also called starter, functions as a reactive base for compounds such as alkylene oxides that polymerize to form the polyol, and also serves to anchor the polyol during formation. As described above, the catalytic polyol is derived from an amine-based initiator. The catalytic polyol is referred to as a "catalytic" polyol because the catalytic polyol can be used in place of a catalyst to facilitate the chemical reaction between the isocyanate and the polyol component. In other words, a polyol component that includes a catalytic polyol will typically react chemically with the isocyanate at a lower temperature in the presence of less catalyst (even no catalyst) than a polyol component that does not include a catalytic polyol. Without being bound or limited to any particular theory, it is believed that the amine content of the catalytic polyol facilitates the reaction between the isocyanate and the polyol component.

[0048] The amine-initiated catalyzed polyether polyols of these embodiments can include EO, PO, and / or BO groups and have various percentages of EO capping. The amine-initiated catalyzed polyether polyols have EO capping of more than about 90%, alternatively more than about 95%, alternatively more than about 99%, or even about 100%. More specifically, "about" 100% EO capping means that all intended capping of the amine-initiated catalyzed polyether polyol is EO capping, without any EO capping due to trace amounts of other alkylene oxides or other impurities. Thus, capping is typically about 100% EO capping, but may be slightly lower, such as at least about 99% EO capping, depending on process variables and the presence of impurities during the amine-initiated catalyzed polyether polyol production.

[0049] About 100% EO capping provides substantially (about 100%) all primary hydroxyl groups, which typically react faster than secondary hydroxyl groups, increasing the catalytic efficiency. In other words, an amine-initiated catalyzed polyether polyol having about 100% EO endcapping typically reacts faster than second and third polyether polyols having PO endcapping, because the PO-capped polyols are subject to steric hindrance.

[0050] In one embodiment, the amine-initiated catalyzed polyether polyol is an EO-capped polyether polyol having: a functionality of about 4; a weight average molecular weight of about 334 g / mol; and a hydroxyl number of about 500 mg KOH / g.

[0051] In various embodiments, the amine-initiated catalyzed polyether polyol is present in the isocyanate-reactive composition in an amount less than about 10 weight percent, less than about 8 weight percent, from about 1 to about 10 weight percent, alternatively from about 2 to about 8 weight percent, alternatively from about 3 to about 7 weight percent, alternatively from about 4 to about 6 weight percent, based on the total weight of the isocyanate-reactive composition. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0052] The isocyanate-reactive resin composition may optionally include one or more auxiliary polyols different from the second polyether polyol, the third polyether polyol, and the amine-initiated catalyst polyol. The auxiliary polyol includes one or more OH functional groups, typically at least two OH functional groups. Typically, the auxiliary polyol is selected from the group of polyether polyols, polyester polyols, polyether / ester polyols, and combinations thereof. However, other polyols may also be used. The auxiliary polyol may be included in the isocyanate-reactive resin composition in various amounts.

[0053] The isocyanate-reactive resin composition typically includes a catalyst. The isocyanate-reactive resin composition may include one or more suitable catalysts selected from those known in the art. The catalyst is typically present in the isocyanate-reactive resin composition to catalyze the exothermic reaction between the isocyanate-reactive resin composition and the isocyanate. It should be understood that the catalyst is typically not consumed in the exothermic reaction between the isocyanate-reactive resin composition and the isocyanate. That is, the catalyst typically participates in the exothermic reaction but is not consumed. Examples of suitable catalysts include, but are not limited to, gelling catalysts, such as amine catalysts in dipropylene glycol; blowing catalysts, such as bis(dimethylaminoethyl)ether in dipropylene glycol; and metal catalysts, such as tin, bismuth, lead, and the like. In some embodiments, the isocyanate-reactive resin composition includes one or more amine catalysts, such as N,N-dimethylcyclohexylamine (DMCHA). When included, the catalyst can be included in various amounts.

[0054] The isocyanate-reactive resin composition typically includes a foam stabilizer. The isocyanate-reactive resin composition may include one or more suitable foam stabilizers selected from those known in the art. Non-limiting examples of suitable foam stabilizers include siloxane oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, castor oil esters, ricinoleic acid esters, turkey red oil, and peanut oil. In one embodiment, the foam stabilizer is a hydrolysis-resistant polyether siloxane copolymer. When included, the foam stabilizer may be included in the isocyanate-reactive resin composition in various amounts.

[0055] The isocyanate-reactive resin composition may optionally include a surfactant. The isocyanate-reactive resin composition may include one or more suitable surfactants selected from those known in the art. The surfactant typically supports homogenization of the blowing agent and polyol and adjusts the cell structure of the polyurethane foam. Non-limiting examples of suitable surfactants include various silicone surfactants, salts of sulfonic acids such as alkali metal and / or ammonium salts of oleic acid, stearic acid, dodecylbenzene- or dinaphthylmethane-disulfonic acid, and ricinoleic acid, foam stabilizers such as siloxaneoxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, castor oil, castor oil esters, and ricinoleic acid esters, and cell regulators such as paraffins, fatty alcohols, and dimethylpolysiloxanes. If included, the surfactant may be included in the isocyanate-reactive resin composition in various amounts.

[0056] The isocyanate-reactive resin composition may optionally include a UV package (e.g., a UV component including one or more UV components such as a UV component selected from ultraviolet absorbers; sterically hindered amine light stabilizers, optical brighteners, and combinations thereof).

[0057] In many embodiments, the UV package includes one or more amines, i.e., a single type of amine or more than one type of amine. The amines can include one or more amine groups. That is, the amines can be mono-, di-, tri-, etc. amines. The amines can include tertiary amine groups, secondary amine groups, primary amine groups, or combinations thereof. The amines can include any combination of tertiary, primary, and secondary amines. For example, the amines can include two tertiary amine groups. In many embodiments, the amines can include one or more -COOC- groups, one or more piperidinyl groups, and / or one or more sebacate groups. In various embodiments, the amines are hydroxy-functional, i.e., include one or more hydroxyl groups. The one or more amines of the UV package are different from the amine-initiated polyols and additives described above.

[0058] In various embodiments, the amine has a weight average molecular weight (M) of about 100 to about 2,000 g / mol, alternatively about 100 to about 1,500 g / mol, alternatively about 100 to about 1,000 g / mol, alternatively about 100 to about 900 g / mol, alternatively about 100 to about 700 g / mol, alternatively about 100 to about 600 g / mol, alternatively about 100 to about 500 g / mol, alternatively about 100 to about 400 g / mol, alternatively about 200 to about 300 g / mol. w ).

[0059] In one particular embodiment, the UV package includes (1) at least one piperidinyl-functional multiple diamine and at least one first amine.

[0060] For example, in one such embodiment, the UV package comprises: (1) a first liquid sterically hindered amine light stabilizer component typically comprising a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate dispersed in water; (2) a second liquid hindered amine light stabilizer (hydroxyphenyl-triazine (HPT) UV absorber) comprising a mixture of 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine dispersed in 1-methoxy-2-propanol; and (3) A mixture of N-(4-ethoxycarbonylphenyl)-N-phenylformamidine having an OH content of about 13 to about 15 mg / KOH / g and a viscosity of about 700 to about 1,500 cps at 25° C. when tested in accordance with ASTM D2196-15. (mPa·s) a fluorescent whitening agent having a viscosity of Includes.

[0061] In various embodiments, the one or more amines of the UV package are present in the isocyanate-reactive composition in an amount less than about 10% by weight, less than about 8% by weight, from about 0.1 to about 6% by weight, alternatively from about 0.2 to about 8% by weight, alternatively from about 0.3 to about 7% by weight, alternatively from about 0.4 to about 6% by weight, based on the total weight of the isocyanate-reactive composition. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein. For example, the one or more amines may be present in the isocyanate-reactive composition in an amount ranging from the lower end of the following numerical ranges, based on the total weight of the isocyanate-reactive composition: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5, to the higher end of the following numerical ranges, based on the total weight of the isocyanate-reactive composition: 1, 1.2, 1. 3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.1, Of course, it should be understood that more than one amine can be included in the lubricant composition, in which case the total amount of all amines included will be within the above ranges.

[0062] The isocyanate-reactive resin composition may optionally include one or more additives. The additives may include any suitable additive or mixture of additives known in the art. Additives suitable for the purposes of the present invention include, but are not limited to, chain extenders, crosslinkers, chain terminators, processing additives, adhesion promoters, antioxidants, defoamers, anti-foaming agents, water scavengers, molecular sieves, flame retardants, fumed silica, fillers, thixotropic agents, silicones, colorants, inert diluents, and combinations thereof. When included, additives can be included in the isocyanate-reactive resin composition in various amounts.

[0063] The isocyanate component and the isocyanate-reactive composition are reacted in the presence of a blowing agent to form a polyurethane foam article. As is known in the art, during the exothermic reaction of the isocyanate-reactive resin composition with the isocyanate, the blowing agent facilitates the release of blowing gases that form voids or bubbles in the polyurethane foam article. The blowing agent can be a physical blowing agent, a chemical blowing agent, or a combination of a physical blowing agent and a chemical blowing agent. The blowing agent can be included in the isocyanate-reactive composition.

[0064] The term physical blowing agent describes a blowing agent that does not chemically react with isocyanates and / or isocyanate-reactive components. Physical blowing agents can be gases or liquids. Liquid physical blowing agents typically vaporize to a gas when heated and typically revert to a liquid when cooled. Non-limiting examples of physical blowing agents include hydrofluorocarbons (HFCs), hydrocarbons, and combinations thereof.

[0065] The term chemical blowing agent describes a blowing agent that chemically reacts with an isocyanate or other component to release a foaming gas. Two non-limiting examples of chemical blowing agents are water and formic acid. In various embodiments, the blowing agent includes formic acid, water, and combinations thereof.

[0066] As noted above, the polyurethane foam article comprises the reaction product of an isocyanate component and an isocyanate-reactive composition. Typically, the isocyanate-reactive resin composition and the isocyanate are combined at an Isocyanate Index of from about 75 to about 140, alternatively from about 90 to about 140, alternatively from about 90 to about 130, alternatively from about 90 to about 130, alternatively from about 100 to about 130, alternatively from about 110 to about 130, alternatively from about 115 to about 125.

[0067] In many embodiments, the polyurethane foam article is a surfboard blank, i.e., used to form a surfboard. The polyurethane system herein produces polyurethane foam articles with excellent strength, color, and color stability. Without being bound by theory, it is believed that the formation of certain polyols and prepolymers that react to create isocyanate prepolymers reduces the exotherm that occurs when the isocyanate component reacts with the isocyanate-reactive component to form the surfboard blank. Furthermore, the specific combination of slow and "slow" secondary terminated polyols and "catalyst" polyols contained in the isocyanate-reactive composition react to produce surfboard blanks with excellent strength, uniform cell structure, and a white appearance with excellent UV stability. That is, exotherm is controlled by first producing the isocyanate prepolymer, and then further controlled by reacting the isocyanate with a specific combination of "slow" and "catalyst" polyols, resulting in unexpectedly superior results.

[0068] Additionally, the polyurethane system produces a surfboard blank that molds and sands well, and surfboards formed from the surfboard blanks of the present invention perform better than surfboards formed from conventional foam blanks including toluene diisocyanate-based foams or styrene-based foams.

[0069] Also disclosed herein, in one embodiment, is a composite article comprising a polyurethane foam article as a core / surfboard blank, and a laminate composition comprising epoxy resin and fiberglass disposed on the polyurethane foam article. In another embodiment, the surfboard blank is coated with a laminate composition comprising polyester resin (as opposed to a laminate composition comprising epoxy resin and fiberglass) to form a laminate. In various embodiments, the polyurethane foam article / surfboard blank has a uniform cell structure and excellent strength, so that only a single coat or layer of the laminate composition is required.

[0070] Method for Making Polyurethane Foam Articles The present invention also provides a method of making a polyurethane foam article comprising the steps of reacting a first polyether polyol with methylene diphenyl diisocyanate to form an isocyanate prepolymer, and reacting the isocyanate prepolymer with an isocyanate-reactive composition in the presence of a blowing agent to form the polyurethane foam article, wherein the isocyanate component, the isocyanate prepolymer, and the isocyanate-reactive composition are exactly as described above.

[0071] The unreacted isocyanate-reactive resin composition, the isocyanate component, and the blowing agent are collectively referred to as a polyurethane system. The method includes the step of providing an isocyanate-reactive resin composition, an isocyanate component, and a blowing agent. In other words, the isocyanate-reactive resin composition, the isocyanate component, and the blowing agent can be provided for use in the method. The blowing agent can be provided together with the isocyanate-reactive resin composition or separately. Typically, the isocyanate-reactive resin composition and the isocyanate component are compounded off-site and shipped to the location of use. Typically, the polyurethane system including the isocyanate-reactive resin composition and the isocyanate is provided together.

[0072] The isocyanate-reactive resin composition and the isocyanate may be combined (reacted) by any mechanism known in the art to form a reaction mixture. Typically, the combining step is carried out in a mixing device such as a static mixer, an impingement mixing chamber, or a mixing pump. The isocyanate-reactive resin composition and the isocyanate may also be mixed in a spray nozzle.

[0073] In an exemplary embodiment, the step of reacting the isocyanate prepolymer with the isocyanate-reactive composition is further defined as molding the reaction mixture comprising the isocyanate prepolymer and the isocyanate-reactive composition. For example, the reaction mixture may be molded into a surfboard shape, i.e., a surfboard blank. In such an embodiment, the molding step may be performed in a period of about 100 minutes. (100×6894.76Pa) ~ approx. 2,000 psi (2000×6894.76Pa) , or about 200 (200×6894.76Pa) ~About 2,000 (2000×6894.76Pa) , or about 1,000 (1000×6894.76Pa) ~ approx. 2,000 psi (2000×6894.76Pa) , or about 1,250 (1250×6894.76Pa) ~1,750psi (1750×6894.76Pa) , and / or at a temperature of about 25 to about 95° C. In various non-limiting embodiments, all values ​​and ranges of values ​​between the aforementioned values ​​are expressly contemplated herein. For example, the molding step can be performed at the lower end of the following ranges: 50 (50×6894.76Pa) , 100 (100×6894.76Pa) , 150 (150×6894.76Pa) , 200 (200×6894.76Pa) , 300 (300×6894.76Pa) , 400 (400×6894.76Pa) , 500 (500×6894.76Pa) , 600 (600×6894.76Pa) , 700 (700×6894.76Pa) , 800 (800×6894.76Pa) , 900 (900×6894.76Pa) , 1,000 (1000×6894.76Pa) , 1,100 (1100×6894.76Pa) , 1,200 (1200×6894.76Pa) , 1,300 (1300×6894.76Pa) , 1,400 (1400×6894.76Pa) or 1,500 (1500×6894.76Pa) From the higher of the following range: 200 (200×6894.76Pa) , 300 (300×6894.76Pa) , 400 (400×6894.76Pa) , 500 (500×6894.76Pa) , 600 (600×6894.76Pa) , 700 (700×6894.76Pa) , 800 (800×6894.76Pa) , 900 (900×6894.76Pa) , 1,000 (1000×6894.76Pa) , 1,100 (1100×6894.76Pa) , 1,200 (1200×6894.76Pa) , 1,300 (1300×6894.76Pa) , 1,400 (1400×6894.76Pa) , 1,500 (1500×6894.76Pa) , 1,600 (1600×6894.76Pa) , 1,700 (1700×6894.76Pa) , 1,800 (1800×6894.76Pa) , 1,900 (1900×6894.76Pa) or 2,000 psi (2000×6894.76Pa) For example, the molding step can be carried out at a temperature ranging from the lower end of the following ranges: 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90°C to the higher end of the following ranges: 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95°C.

[0074] In some embodiments of the method, the polyurethane foam article is cured (in or out of the mold) at a temperature ranging from the lower end of the following ranges: 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 90° C. to the higher end of the following ranges: 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 90, 95° C.; and for a time ranging from the lower end of the following ranges: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 minutes to the higher end of the following ranges: 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 minutes.

[0075] In various non-limiting embodiments, all values ​​and ranges of values ​​between the recited values ​​are expressly contemplated herein.

[0076] In some embodiments of the method, the isocyanate-reactive resin composition and the isocyanate are heated to a temperature of from about 30° C. to about 55° C. prior to the reacting / molding step. In the method, the isocyanate-reactive resin composition and the isocyanate component or isocyanate prepolymer are reacted at an isocyanate index as described above, for example, an isocyanate index of from about 90 to about 120.

[0077] The method may include applying a laminate composition onto an exterior surface polyurethane foam article (e.g., a surfboard blank) to form a laminate. In some embodiments, the laminate composition of the method includes a polyester resin. In other embodiments, the laminate composition of the method includes an epoxy resin and fiberglass. Additionally, the method may include heating the polyurethane foam article having the laminate composition thereon to cure the laminate composition to form a laminate. For example, the polyurethane foam article having the laminate composition disposed thereon is heated to a temperature of 35-85° C. for up to 8 hours. In various non-limiting embodiments, all values ​​and ranges of values ​​between the foregoing values ​​are expressly contemplated herein.

[0078] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way. EXAMPLES

[0079] Example 1 is described herein. The isocyanate component of Example 1 consists essentially of an isocyanate prepolymer. The isocyanate prepolymer is described in Table 1. The amounts are expressed as weight percent of the total weight of the components used to form the isocyanate prepolymer, or the total weight of the isocyanate prepolymer. The components in Table 1 are combined or reacted to form the isocyanate prepolymer.

[0080] [Table 1]

[0081] The isocyanate is methylene diphenyl diisocyanate containing trace amounts (eg, less than 0.5% by weight) of the 2,2'-isomer, about 50% by weight of the 2,4'-isomer, and about 50% by weight of the 4,4'-isomer.

[0082] The first polyether polyol is a pentaerythritol-initiated polyether polyol with PO capping: having a functionality of about 4; a weight average molecular weight of about 400 g / mol; and a hydroxyl number of about 555 mg KOH / g.

[0083] The isocyanate system of Example 1 is described in Table 2. The amounts are expressed as weight percent based on the total weight of the isocyanate-reactive composition. The ingredients in Table 2 are reacted in a mold under pressure to form a polyurethane foam article having the shape of a surfboard blank.

[0084] [Table 2]

[0085] The second polyether polyol is a sorbitol-initiated polyether polyol with PO capping: having a functionality of about 6; a weight average molecular weight of about 687 g / mol; and a hydroxyl number of about 490 mg KOH / g.

[0086] The third polyether polyol is a glycerin-initiated polyether polyol with PO capping: having a functionality of about 3; a weight average molecular weight of about 700 g / mol; and a hydroxyl number of about 222 to about 237 mg KOH / g.

[0087] The amine-initiated catalyzed polyol is a polyether polyol with EO capping: a functionality of about 4; a weight average molecular weight of about 334 g / mol; and a hydroxyl number from about 500 mg KOH / g.

[0088] The foam stabilizer is a hydrolysis resistant polyether siloxane copolymer.

[0089] Catalysts A and B are amine catalysts.

[0090] The UV package includes bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and N-(4-ethoxycarbonylphenyl)-N-phenylformamidine.

[0091] Blowing agent A is water.

[0092] Blowing agent B is formic acid.

[0093] Advantageously, the polyurethane foam article of the present invention improves upon the prior art. That is, the polyurethane system of Example 1 produces a polyurethane foam article with excellent strength, color, and color stability when used as / in a surfboard blank. The specific combination of slow and "slow" secondary terminated polyols and "catalyst" polyols contained in the isocyanate-reactive composition react to produce a surfboard blank with excellent strength, uniform cell structure, and a white appearance with excellent UV stability. That is, the exotherm of the polyurethane is controlled by first producing an isocyanate prepolymer, and then the exotherm of the polyurethane is further controlled by reacting the isocyanate with a specific combination of "slow" and "catalyst" polyols, resulting in unexpected and superior results.

[0094] Additionally, the polyurethane system of Example 1 produces surfboard blanks that mold and sand well. Additionally, surfboards formed from the surfboard blanks of the present invention perform better than surfboards formed from conventional foam blanks including toluene diisocyanate-based foams or styrene-based foams.

[0095] Any ranges and subranges relied upon to describe various embodiments of the present invention should be understood to fall within the scope of the appended claims, both individually and collectively, and all ranges including whole and / or partial values ​​herein are understood to be described even if such values ​​are not expressly recited herein. Those skilled in the art will readily recognize that the recited ranges and subranges are sufficient to describe and enable various embodiments of the present invention, and that such ranges and subranges may be further divided into relevant halves, thirds, quarters, fifths, etc. As an example, the range "from 0.1 to 0.9" may be further divided into a lower third, i.e., 0.1 to 0.3, a middle third, i.e., 0.4 to 0.6, and an upper third, i.e., 0.7 to 0.9, which are individually and collectively within the scope of the appended claims and may be relied upon individually and / or collectively to provide appropriate support for particular embodiments within the scope of the appended claims. Furthermore, with respect to language defining or modifying a range, such as "at least," "greater than," "less than," "not more than," such language should be understood to include subranges and / or upper or lower limits. As another example, the range "at least 10" inherently includes subranges of at least 10 to 35, at least 10 to 25, 25 to 35, etc., each of which may be relied upon individually and / or collectively to provide appropriate support for particular embodiments within the scope of the appended claims. Finally, individual numbers within the disclosed ranges may be relied upon to provide appropriate support for particular embodiments within the scope of the appended claims. For example, the range "from 1 to 9" includes various individual integers, such as 3, and individual numbers including decimal points (or fractions), such as 4.1, which may be relied upon to provide appropriate support for particular embodiments within the scope of the appended claims.

[0096] While the present invention has been described in an illustrative manner, it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Claims

1. In the presence of a blowing agent, (A) (i) a first polyether polyol, a pentaerythritol-initiated polyether polyol; (ii) methylene diphenyl diisocyanate, 40% to 60% by weight of the 2,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; 40% to 60% by weight of the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; and Less than 10% by weight of the 2,2'-isomer, based on the total weight of said methylene diphenyl diisocyanate methylene diphenyl diisocyanate an isocyanate component comprising an isocyanate prepolymer comprising the reaction product of (B) (i) a second polyether polyol having secondary terminal hydroxyl groups; and (ii) Amine-initiated polyether polyols having primary terminal hydroxyl groups. an isocyanate-reactive composition comprising comprising the reaction product of the second polyether polyol has a hydroxyl functionality of 5 to 7; the amine-initiated catalyzed polyether polyol is present in the isocyanate-reactive composition in an amount of less than 10 weight percent, based on the total weight of the isocyanate-reactive composition; Polyurethane foam articles.

2. The polyurethane foam article of claim 1 , wherein the first polyether polyol has a weight average molecular weight of 200 to 900 g / mol.

3. The polyurethane foam article according to claim 1 or 2, wherein the first polyether polyol has a hydroxyl functionality of 2-5.

4. 4. The polyurethane foam article of claim 1, wherein the first polyether polyol contains greater than 99% propyleneoxy endcaps, based on the total number of endcaps present in the first polyether polyol.

5. 5. The polyurethane foam article of any one of claims 1 to 4, wherein the first polyether polyol is present in the isocyanate prepolymer in an amount from 2 to 20 weight percent, based on the total weight of the isocyanate prepolymer, and the methylene diphenyl diisocyanate is present in the isocyanate prepolymer in an amount from 80 to 98 weight percent, based on the total weight of the isocyanate prepolymer.

6. The polyurethane foam article according to any one of claims 1 to 5, wherein the isocyanate prepolymer has an NCO content of 15 to 40 weight percent, based on the total weight of the isocyanate prepolymer.

7. The polyurethane foam article of any one of claims 1 to 6, wherein the second polyether polyol has a weight average molecular weight of 400 to 2,000 g / mol.

8. 8. The polyurethane foam article according to any one of claims 1 to 7, wherein the second polyether polyol is present in the isocyanate-reactive composition in an amount of 20 to 90 weight percent, based on the total weight of the isocyanate-reactive composition.

9. 9. The polyurethane foam article according to any one of claims 1 to 8, wherein the isocyanate-reactive composition further comprises a third polyether polyol having different secondary terminal hydroxyl groups than the second polyether polyol.

10. 10. The polyurethane foam article of claim 9, wherein the third polyether polyol has a weight average molecular weight of 300 to 1,500 g / mol and / or a hydroxyl functionality of 2 to 4.

11. The polyurethane foam article according to claim 9 or 10, wherein the third polyether polyol is present in the isocyanate-reactive composition in an amount of 20 to 60 weight percent, based on the total weight of the isocyanate-reactive composition.

12. The polyurethane foam article of any one of claims 1 to 11, wherein the amine-initiated catalyzed polyether polyol has a weight average molecular weight of 200 to 1,500 g / mol and / or a hydroxyl functionality of 2 to 6.

13. 13. The polyurethane foam article according to any one of the preceding claims, wherein the amine-initiated catalyzed polyether polyol is present in the isocyanate-reactive composition in an amount less than 8 weight percent, based on the total weight of the isocyanate-reactive composition.

14. 14. The polyurethane foam article of any one of claims 1 to 13, wherein the isocyanate-reactive composition further comprises an optical brightener comprising a first amine that is hydroxy-functional.

15. The polyurethane foam article of claim 14, wherein the first amine is a diamine.

16. 16. The polyurethane foam article according to any one of the preceding claims, wherein the isocyanate-reactive composition further comprises a UV stabilizer comprising a second amine comprising a piperidine.

17. 40-60kg / m ３ 17. The polyurethane foam article of claim 1 having a density of

18. A core comprising the polyurethane foam article of any one of claims 1 to 17, and A composite article comprising a laminate comprising fiberglass and epoxy disposed on said polyurethane foam article.

19. 20. A surfboard comprising the composite article of claim 18.

20. The following steps: (A) a pentaerythritol-initiated polyether polyol that is a first polyether polyol, and methylene diphenyl diisocyanate; 40% to 60% by weight of the 2,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; 40% to 60% by weight of the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; and Less than 10% by weight of the 2,2'-isomer, based on the total weight of said methylene diphenyl diisocyanate methylene diphenyl diisocyanate to form an isocyanate prepolymer; and (B) reacting the isocyanate prepolymer with an isocyanate-reactive composition in the presence of a blowing agent to form a polyurethane foam article; The isocyanate-reactive composition comprises: (i) a second polyether polyol having secondary terminal hydroxyl groups, and (ii) Amine-initiated polyether polyols having primary terminal hydroxyl groups. Including, the second polyether polyol has a hydroxyl functionality of 5 to 7; the amine-initiated catalyzed polyether polyol is present in the isocyanate-reactive composition in an amount of less than 10 weight percent, based on the total weight of the isocyanate-reactive composition; A method for making a polyurethane foam article.

21. 21. The method of claim 20, wherein the step of reacting the isocyanate prepolymer and the isocyanate-reactive composition is further defined as molding a reaction mixture comprising the isocyanate prepolymer and the isocyanate-reactive composition.

22. 22. The method of claim 21, wherein the molding step is carried out at a pressure of from 1,000 psi (1000 x 6894.76 Pa) to 2,000 psi (2000 x 6894.76 Pa) and / or a temperature of from 25 to 95°C.

23. 23. The method of any one of claims 20 to 22, wherein the isocyanate-reactive composition and the isocyanate prepolymer are reacted at an Isocyanate Index of 90 to 140.

24. 24. The method of any one of claims 20 to 23, further comprising applying a laminate composition comprising fiberglass and epoxy over the polyurethane foam article.

25. 25. The method of claim 24, further comprising heating the polyurethane foam article having the laminate composition disposed thereon at a temperature of from 35 to 85°C for up to 8 hours.

26. 1. A polyurethane system for use in forming a polyurethane foam article for a surfboard, comprising: (A) an isocyanate component, (i) a first polyether polyol, a pentaerythritol-initiated polyether polyol; (ii) methylene diphenyl diisocyanate, 40% to 60% by weight of the 2,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; 40% to 60% by weight of the 4,4'-isomer, based on the total weight of the methylene diphenyl diisocyanate; and Less than 10% by weight of the 2,2'-isomer, based on the total weight of said methylene diphenyl diisocyanate methylene diphenyl diisocyanate an isocyanate component comprising an isocyanate prepolymer comprising the reaction product of (B) an isocyanate-reactive composition comprising: (i) a second polyether polyol having secondary terminal hydroxyl groups and a hydroxyl functionality of 5 to 7; (ii) a third polyether polyol having secondary terminal hydroxyl groups and a hydroxyl functionality of 2 to 4; (iii) a polyurethane system comprising an isocyanate-reactive composition comprising an amine-initiated catalyzed polyether polyol having primary terminal hydroxyl groups, present in the isocyanate-reactive composition in an amount less than 10 weight percent, based on the total weight of the isocyanate-reactive composition.

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