Title of Invention	METHOD OF MAKING FLEXIBLE POLYURETHANE
Abstract	A method of making a polyurethane product, a hydroxyl terminated precursor for polyurethane, and a compound are disclosed. The method comprises heating a vegetable oil-polyol mixture of modified vegetable oil containing about two or more hydroxyl groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. The mixture has a hydroxyl equivalent ratio of about 1 :1 vegetable oil to polyol. The method further comprises mixing for at least about 10 minutes an isocyanate containing about two or more isocyanato groups per molecule at least about 25 degrees Celsius to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate to react the isocyanate with the mixture to form the hydroxyl terminated precursor.

Title of Invention

METHOD OF MAKING FLEXIBLE POLYURETHANE

Abstract

A method of making a polyurethane product, a hydroxyl terminated precursor for polyurethane, and a compound are disclosed. The method comprises heating a vegetable oil-polyol mixture of modified vegetable oil containing about two or more hydroxyl groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. The mixture has a hydroxyl equivalent ratio of about 1 :1 vegetable oil to polyol. The method further comprises mixing for at least about 10 minutes an isocyanate containing about two or more isocyanato groups per molecule at least about 25 degrees Celsius to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate to react the isocyanate with the mixture to form the hydroxyl terminated precursor.

Full Text	FIELD OF THE INVENTION [0001] The present invention relates to hydroxyl terminated precursors and methods of making hydroxyl terminated precursors. BACKGROUND OF THE INVENTION [0002] Due to their widely ranging mechanical properties and their ability to be relatively easily machined and formed, plastic foams and elastomers have found wide use in a multitude of industrial and consumer applications. In particular, urethane foams and elastomers have been found to be well suited for many applications. Automobiles, for instance, contain a number of components, such as cabin interior parts, that are comprised of urethane foams and elastomers. Such urethane foams are typically categorized as flexible, semi-rigid, or rigid foams with flexible foams generally being softer, less dense, more pliable, and more subject to structural rebound subsequent to loading than rigid foams. [0003] Urethanes (or more accurately for polymers, polyurethanes.) are formed when isocyanate (NCO) groups (or A-side reactants) react with hydroxyl (OH) and other active hydrogen groups (or B-side reactants). Specifically, a carbamate linkage (or urethane bond) is formed upon the reaction between an isocyanate group and a hydroxyl group. The polyurethane polymer-forming reaction occurs between substances with more than one isocyanate group per molecule (or A-side reactants) and substances with more than one hydroxyl or other active hydrogen group per molecule (B-side reactants). The most common method of polyurethane production is via the reaction of a polyol (a B-side reactant) and an isocyanate (an A-side reactant) which forms the backbone urethane group. A cross- linking agent may also be added. Depending on the desired qualities of the final polyurethane product, the precise formulation may be varied. VariaWes in the formulation include the type and amounts of each of the reactants. [0004] Although vegetable-based polyurethane foams have been used in various polyurethane foam markets, the use of vegetable-based polyurethane foam has not gain acceptance in industries, such as the automotive industry. For example, vegetable-based polyurethanes have not been able to meet specification requirements for use in automotive interior components. [0005] Thus, there is a need to provide a high quality polyurethane product made from a relatively high level of bio-based raw materials. BRIEF SUMMARY OF THE INVENTION [0006] The present Invention generally provides a hydroxyl terminated precursor to be used In making a relatively high quality polyurethane product. The hydroxyl terminated precursor is made from a relatively high level of bio-based raw materials. The hydroxy! terminated precursor may be then used as the B-side reactant and reacted with an A-side reactant from standard petrochemical isocyanates to produce a relatively high quality polyurethane product or foam. Depending on the choice of isocyanate and polyols, the polyurethane is suitable for a number of applications ranging from automotive seating to rigid strtrctural urethane parts, it is to be understood that the terms "isocyanate group" and "isocyanate group" are used interchangeably in this application. [0007] In one aspect, the present invention provides a method of making a hydroxyl terminated precursor for polyurethane. The method comprises heating a vegetable oil-polyol mixture of modified vegetable oil cwntaining about two or more hydroxy! groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. The mixture has a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol. The method further comprises mixing for at least about 10 minutes an isocyanate containing about two or more isocyanato groups per molecule at least about 25 degrees Celsius to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate. This reacts the isocyanate with the mixture to form the hydroxyl terminated precursor. [0008] In another aspect, the isocyanate is at least one of 1,1'-methylenebis[isocyanatobenzene], polymethylenepolyphenylene isocyanate, and any isomer or isomer ratio of tolylene diisocyanate. [0009] In another aspect, the method comprises the step of adding and mixing additional polyol to the isocyanate and the vegetable oil-polyol mixture. [0010] In another aspect, the vegetable oil-polyol mixture has a temperature of between about 35 and 50 degrees Celsius. [0011] In another aspect, the method comprises cooling the hydroxyl terminated precursor to room temperature. [0012] In another aspect, mixing reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows: wherein (HO)n—R—OH represents polyether polyo!, HO—R'—(OH)m represents oxidized polymerized soybean oil, and OCN—Ar—NCO represents 1,1'- methylenebis[isocyanatobenzene]. [0013] In another aspect, the method comprises adding about 0.3 weight percent based on vegetable oil content of antioxidant at room temperature to the mixture. [0014] In another aspect, the method comprises adding a catalyst in an amount of about 0.05 weight percent based on vegetable oil content, the catalyst comprising about 33% weight triethylene diamine of the catalyst and about 67% weight dipropyleneglycol of the catalyst at room temperature. [0015] In another aspect, the method comprises adding a polyoxyethylene- oxypropylene copolymer polyol in an amount of up to about 500 weight percent based on vegetable oil content, after mixing the isocyanate with the vegetable oil- polyol mixture. [0016] In another aspect, the method comprises cooling the hydroxy! terminated precursor to room temperature. [0017] In another aspect, mixing the isocyanate and the vegetable oil-polyol mixture reacts the vegetable oil-polyol mixture with the isocyanate, defining the hydroxyl terminated precursor as follows: wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group. [0018] In another aspect, the method comprises making a polyurethane product from the hydroxyl terminated precursor by mixing a base isocyanate as an A-side reactant with B-side reactants comprising the hydroxyl temninated precursor and optional catalyst and optional additive in a weight ratio so that the isocyanato content of the isocyanate in equivalent units is between about 60:100 and 100:80 to the active hydrogen content in equivalent units of the B-side reactants, the mixing of the A-side and the B-side reactants occurring at a predetermined pressure and a temperature of between about 20 and 50 degrees Celsius, and defining a liquid polyurethane mixture; and reacting the polyurethane mixture in situ to form the polyurethane product, [00191 In another aspect, adding an isocyanate to the vegetable oil-polyol mixture comprises adding up to about 5 weight percent antioxidant at room temperature; adding up to about 40 weight percent polypropylene glycol at room temperature defining the polyol; adding up to about 40 weight percent vegetable oil at room temperature; mixing the antioxidant, polyol, and the vegetable oil to define the vegetable oil-polyol mixture; and adding up to about 40 weight percent of the isocyanate, the isocyanate being 1,1'-mefriylenebis[isocyanatobenzene] at room temperature to the vegetable oil-polyol mixture. [0020] In another aspect, the predetemnined pressure is up to about 203 kPa (2 atm). [0021] In another aspect, the predetermined pressure is t>etween about 10.3 MPa (1500 psi) and 20.7 MPa (3000 psi). [0026] Further aspects, features, and advantages of the invention will become apparent from consideration of the following description and the appended claims when taken in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS lOO^^j Figure ia is a micrograph of a prior crt pclyurethane foam; and [0028] Figure 1 b is a micrograph of a polyurethane foam made by reacting B-side reactants in a mixture containing a hydroxyl terminated precursor in accordance with one example of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0029] Examples of the present invention provide a tiydroxyl terminated precureor, methods of making a hydroxyl terminated precursor for polyurethane, and methods of making a polyurethane foam from a hydroxyl terminated precursor. In one example, hydroxyl groups (-0H) on two precureor substances react with isocyanato groups (-NCO) on a third precursor substance to fomn carbamate linkages (-NHCOO-). The hydroxyl-containing precursor substances are used in excess so that molecules of the hydroxyl terminated precursor (a new chemical substance) contain, on average, two carbamate groups and at least two hydroxyl groups. [0030] In accordance with one example, the present invention provides a method of making a hydroxyl terminated precursor for polyurethane. The method comprises providing a modified vegetable oil comprising hydroxyl groups. For example, the modified vegetable oil may be any suitable oil having hydroxyl groups, or modified to contain hydroxyl group, such as a modified soybean oil (polymerized, oxidized), palm oil, canola oil, rapeseed oil, castor oil, or olive oil. Any other modified non-petroleum based oil may be used without falling beyond the scope or spirit of the present invention. [00311 In this example, the modified vegetable oil is a modified soybean oil (polymerized, oxidized). Soybean oil, and other plant based oils, is a mixture of triglycerides, i.e., triesters of glycerol and fatty acids. A triglyceride may have the general structure as follows: where R\ R^, and R' can have any of a number of structures. A naturally occumng triglyceride typically exists as a mixture of different structures in which R\ R^, and R^ vary from structure to structure. [0032] A fatty acid is a carboxylic acid and may have a general formula of HO2CR, where R is usually an unbranched aliphatic chain attached to a carboxyl group. The chain may contain double or triple bonds. Other functional groups may also be present, such as hydroxyl groups, as in ricinoleic acid. [0033] The most common R groups in vegetable oils are listed in Table 1 below [0034] It is to be noted that Table 1 Is not exhaustive and that a number of other fatty acids may be present in triglycerides without falling beyond the scope or spirit of the present invention. [0035] When a plant based oil is exposed to oxidizing agents, especially with added heat or ultraviolet light, the R groups can react to form a number of other staictures. The positions of double bonds may change, and polymerization may occur via free radical, ionic, or electrocyclic reactions. Hydroxyl groups may also be introduced into the molecule. [0036] The chemical structure of oxidized, polymerized soybean oil may be generally described as follows: where R\ R^, and R^ are groups derived from the original R groups of the starting triglyceride; A\ A^, and A^ are chemically bonded to R\ R^, and R^ and may be hydroxyl or other triglyceride moieties whose R groups themselves may have undergone similar reactions to those undergone by R\ R^, and R^; and x, y, and z may be any whole number 0 or above, but will usually be 0,1, or 2. Ntoreover, if x is 2 or greatfir A^ may represent two or more different groups, for example, a hydroxyl group and a triglyceride moiety, or a triglyceride moiety that contains hydroxyl groups. Furthermore, the same is for y and z. [00371 Examples of structures generally having the above description include as follows, but are not limited to: [0038] More specifically, the modified soybean oil (polymerized, oxidized) may be Soyol™ R2-052, a di-functional, 52 hydroxy! number biobased polyol suitable for urethane applications and manufactured by Urethane Soy Systems Company of Volga, SD. [0039] The method further comprises providing a poiyol, preferably a polyether polyol. For example, a general description of a polyether poiyol that may be used in accordance with an example of the present invention includes polymers formed by the addition of alkylene oxide monomers to an initiator compound containing two or more active hydrogen atoms. That is, the active hydrogen compound in the presence of a catalyst initiates a ring opening and an oxide addition, which continue until the desired molecular weight is obtained. In one example, the preferred alkylene oxides are propylene oxide and ethylene oxide. Polymers may be formed from one or more of the following or similar initiators: water, ethylene glycol, propylene glycol, dipropylene glycol, glycerine, trimethylolpropane, ethylene diamine, pentaerythritol, diethylene triamine, sorbitol, and sucrose. Example of some trade names for the polyols described above and useful in this invention are: Dow Chemical's Voranol™ 5815, Voractiv™ DW6340, Voranol™ 4240; Bayer MaterialScience's Multranol™ 3901 and BASF's Pluracol™ 1596. Furthermore, graft (or "filled") copolymer polyol produced by free radical polymerization of styrene and acrylonitrile ("SAN") in situ with a polyether polyol have proven to be useful in this invention; Dow Chemical's Specflex™ NC701 and BASF Pluracol™ 1528 are examples of these type of polyols. Another class of copolymer polyol suitable in this tolylene diisbcyanate or alkanolamine with an isocyanate in the presence of a polyether polyol; an example of the former is Bayer MaterialScience's Multranol™ 9151. [0040] The polyol used herein may be an ethylene oxide-propylene oxide copolymer polyether polyol with average functionality (number of hydroxyl groups per molecule) greater than 1 and less than about 5. The molecular weight may be between about 200 and about 6500. Preferably, the polyol is a polypropylene glycol (diol or triol) with a molecular weight between about 400 and 3000. For example, polyols with a tradename of Pluracol™ P410R by BASF, Pluracol™ PI 010 by BASF, Voranol™ 220-110 by Dow, and Voranol™ 230-238 by Dow may be used. [0041] The modified vegetable oil containing about two or more hydroxyl groups per molecule is then mixed with the polyol having about two or more hydroxyl groups per molecule to define a vegetable oil-polyol mixture. In this example, the mixture has a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol. Preferably, the vegetable oil-polyol mixture is heated to a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. More preferably, the vegetable oil-polyol mixture is heated to a temperature of between about 35 and 50 degrees Celsius. [0042] The method further comprises providing an isocyanate containing about two or more isocyanato groups per molecule. In one embodiment, the isocyanate may be any suitable isocyanate such as one of 1,1'-methylenebis[isocyanatobenzene] (MDI), polymethylenepolyphenylene isocyanate (polymeric MDI), and all isomers and isomer ratios of toluene diisocyanate (TDI). present invention. The isocyanate is heated to a temperature of at least about 25 degrees Celsius, preferably between about 25 and 60 degrees Celsius, and more preferably between about 35 and 50 degrees Celsius at a pressure of preferably about 1 atmosphere. [0043] The isocyanate is added to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate. The isocyanate is then mixed with the vegetable oil-polyol mixture for at least about 10 minutes to react the isocyanate with the mixture, thereby forming the hydroxyl terminated precursor. The mixing of the isocyanate and the vegetable oil-polyol mixture reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows: wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group. [0044] Additional polyol may then be added and mixed with the vegetable oil-polyol mixture and isocyanate. In this example, up to about 500 weight percent based on vegetable oil content of a polyoxyethylene-oxypropylene copolymer polyol may be added after mixing the isocyanate with the mixture. However, other polyols may be used as provided above without falling beyond the scope or spirit of the present invention. [0045] Catalyst(s) may then be added in accordance with one example of the present invention. The catalysts added may include tertiary amines such as triethyiamine, tributylamine, N-methylmorpho!ine, N-ethylmorpholine, N- cocomorpholine, N.N.N'.N'-tetramethyl-ethylenediamine, 1,4-clia2abicyclo-(2,2,2)- octane (DABCO), N-methyl-N'-dimethylaminoethylpiperazine, N.N-dimethyl- benzylamine, bis-(N,N-cliethylaminoethyl)aclipate, N.N-diethylbenzylamine, pentamethyl diethylenetriamine, N.N-dimethylcyclohexylamine, N.N.N'.N'- tetramethyl-1,3-butanecliamine, N.N-dimethyl-p-phenylethylamine, 1,2- dimethylimidazole, 2-methylimidazole, 3-(2-(dimethylamino)ethoxy]-N,N- dimethylpropylamine, N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine), 2,4,6- tris(dimethylaminomethyl)phenol, 1,3-bis(dimethylamino)-2-propanol, diazabicyclo[5.4.0]undec-7-ene (DBU) and the like. [0046] Also useful are commercially available delayed action catalysts such as 1-(2-hydroxypropyl)imidazole fomnic acid salt; 2-[[2- (dimethylamino)ethyl]methylamino]ethanol fomnic acid salt; bis(2-dimethylaminoethyl) ether diformate; N,N,N',N'-tetramethyl-1,2-ethanediamine formic acid salt; 1,8-diazabicyclo[6.4.0]undec-7-ene 2-ethylhexanoic acid salt; 1,8-diazabicyclo[5.4.0]undec-7-ene phenol salt; and the like. Mannich bases known per se obtained from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols such as phenol nnnyiphfinol or bisphenol may also be used as catialysts. Examples of catalysts which include tertiary amines having hydrogen atoms reactive with isocyanate groups include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine and their reaction products with alkylene oxides such as propylene oxide and/or ethylene oxide. [0047] Basic nitrogen compounds such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium phenolate and alkali metal alcoholates such as sodium methylate may also be used as catalysts. Hexahydrotriazines are also suitable catalysts. [0048] Organic metal compounds may also be used as catalysts according to the invention, in particular organic tin compounds. The organic tin compounds used are preferably tin(ll) salts such as tin(ll) acetate, tin(ll) octoate, tin(ll) ethyl hexoate and tin(ll) laurate; and tin(IV) compounds such as dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurylmercaptide, dibutyl tin maleate dioctyl tin diacetate, dimethyl tin dichloride, dimethyl tin dilaurate, or dimethyl tin dilauryl mercaptide. All the above-mentioned catalysts may, of course, be used as mixtures. [0049] Salts of other metals may also be used as catalysts, in particular, organobismuth compounds such as bismuth 2-ethylhexanoate. bismuth neodecanoate and the like, organozirconium compounds such as tetrakis(2,4-pentanedionato)zirconium and the like, or organomercury compounds such as phenyl mercuric neodecanoate and the like. [0050] Further examples of catalysts that may be used in accordance with one exdiiiplc of the present invention are described 'n KunRtstoff-Handbuch, Volume VII. published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 96 to 102, each of which are incorporated herein by reference in its entirety. [0051] The catalysts, when used, are generally used in a quantity of between about 0.001 and 10%, by weight, based on the quantity of reactants. Any other suitable catalyst may be used. For example, catalysts are listed in U.S. patent numbers 5,229,427 and 7,211,616, each of which is incorporated herein by reference in its entirety. [0052] In another example, about 0.05 weight percent based on vegetable oil content of catalyst may be added. In this example, the catalyst comprises about 33% weight triethylene diamine of the catalyst and about 67% weight dipropyleneglycol of the catalyst at room temperature. Optionally, the method may further comprise adding about 0.2 weight percent based on vegetable oil content of antioxidant at room temperature to the mixture. [0053] As discussed in greater detail below, the hydroxyl terminated precursor may be then used as the B-side reactant alone or blended with additional polyol(s), catalyst(s) and additives as B-side reactants and then mixed with an A-side reactant using standard petrochemical isocyanates. It has been found that this produces a relatively high quality polyurethane foam. Depending on the choice of isocyanate, and other B-side reactants, the foam is suitable for a number of applications ranging from automotive seating to rigid structural urethane parts. [0054] A compound in accordance with one example of the present invention include formula A as follows: [0058] In another example, the present invention provides a method of making a polyurethane product from a hydroxyl terminated precursor. As mentioned above, polyurethane foam may be prepared by reacting what is known as an A-side reactant (or A-side reactants) with what is known as a B-side reactant (or B-side reactants). The A-side reactant is generally considered to include at least one isocyanate. The B-side reactant may comprise the hydroxyl terminated precursor alone but generally Is a solution or mixture of an isocyanate-reactive component, such as a polyol and optionally catalyst(s) and/or additive(s). [0059] The method comprises forming the hydroxyl terminated precursor as described herein. The hydroxyl terminated precursor may be used as the B-side reactant. The method further comprises mixing a base isocyanate with a catalyst (mentioned above) and optionally any additive to define an isocyanate mixture. In this example, catalysts may or may not be added to the isocyanate except for isocyanato terminated prepolymers where catalysts are frequently used in their preparation. The catalysts to accelerate the polyurethane reaction may be added to the B-side reactants which will include hydroxyl terminated precursor for one example of the present invention and optionally additional polyol(s), optionally additive(s) (such as crosslinkers or chain extenders, surfactants, water, blowing agents, pigments, etc.) and optionally catalyst(s). The isocyanate mixture may be used as the A-side reactant. It is to be noted that isocyanate mixtures are mixtures or solutions of different types of isocyanates or isomers. Optionally, some A-side reactants may contain surfactants, flame-retardants, special additives or dilulents or in some cases additional catalyst may be added. The isocyanate mixture (A-side reactants) may have a weight ratio with the hydroxyl terminated precursor and optionally other B-side reactants so that the isocyanato content of the isocyanate mixture in equivalent units is between about 100:80 and 60:100 to the active hydrogen content in equivalent units in the hydroxyl temninated prwursor and optionally other B-side reactants. [0060] In this example, the isocyanate, A-side reactant, (or reactants) is (are) then mixed with the B-side reactants containing the hydroxyl terminated precursor plus optionally additional polyol(s), catalyst(s) and additive(s) at a predetennined pressure and a temperature of between about 20 and 50 degrees Celsius, defining a liquid polyurethane mixture. In one example, the predetermined pressure may be up ly about 2 atmospheres, depending on the gpnaratus. However, in another example, the predetermined pressure may be between about 1500 and 3000 pounds per square inch gauge. [0061] The liquid polyurethane mixture may then be injected or poured in a cavity of a mold. The polyurethane mixture reacts in situ to form the polyurethane product. That is, in the cavity, the liquid polyurethane mixture reacts and for foam formulations rises to fill the cavity and form the polyurethane product in situ. For non-foam formulations, the liquid polyurethane mixture fills the cavity to the volume injected or poured and then cures to a solid to form the polyurethane product in situ. In this example, the mold may be made of aluminum, polymeric material, or steel, or any other suitable material. After a defined period of time, the polyurethane product is removed from the mold, thereby retaining the predetermined shape. [0062] Figures 1a and 1b illustrate a comparison betv^een a prior art polyurethane foam and a polyurethane foam made in accordance with an example of the present invention. Figure la depicts a prior art polyurethane foam made from made from a TDI based isocyanate. More specifically, the prior art polyurethane foam of Figure la was made by reacting B-side reactants containing about 7% polymerized, oxidized soybean oil based on the total B-side reactants in a mixture of standard petrochemical based molding polyether polyols, catalysts and additives with A-side reactants of 80/20% 2,4-, 2,6-tolylenedilsocyanate. As shown, the cell stmcture of the prior art polyurethane foam is relatively coarse and highly in^egular. Moreover, the foam tends to have a "tight" and "dead" feel. [0063] Figure lb shows a polyurethane foam made from the hydnoxyl terminated precursor in accordance with one example of the present invention, morc spccificnlly, the polyurethgne foam of Finurft lb was made by reactinq B-side reactants in a mixture containing a hydroxyl terminated precursor in accordance with one example of the present invention, petrochemical based molding polyether polyols, catalysts and additives with A-side reactants of 80/20% 2,4-, 2,6-tolylenediisocyanate. The hydroxyl terminated precursor in the foam depicted by Figure lb contains about 7% polymerized, oxidized soybean oil based on the total B- side reactants. As depicted, the cell structure of the polyurethane foam is relatively fine and significantly more consistent. Additionally, the foam tends to have an open and resilient "flexible" feel. [0064] Furthermore, it is understood that the hydroxyl terminated precursor may be used alone as the B-side reactant. EXAMPLE [0065] This example provides a method of making a hydroxyl terminated precursor to be used in making a polyurethane product. About 1 weight percent of polypropylene glycol (Pluracol™ P-1010 by BASF) mixture with about 0.04 weight percent antioxidant (Irganox™ 245 by Ciba Specialty Chemicals) was predispersed in a separate mixing container to define a polypropylene glycol-antioxidant blend. The polypropylene glycol-antioxidant blend was heated to about 65 degrees Celsius. [0066] About 16 weight percent of a modified soybean oil (polymerized, oxidized), Soyol™ R2-052, from Urethane Soy Systems Company of Volga, SD was weighed and loaded into a lined, open reactor vessel equipped with a band style heater and a Patterson™ mixer. The mixer was turned on low and the batch heated to about 25 degrees Celsius. About 7 weight percent of polypropylene glycol (Pluracol™ P-1010 by BASF) at room temperature was added to the batch. [0067] The noiynronyienfi glycol-antioxidant blend was then added to the batch, and the batch was mixed and heated to between about 39 and 44 degrees Celsius. The batch was maintained at a temperature no higher than about 45 degrees Celsius. As mixing continued, about 1.452 weight percent of 1,1'-methylenebis[isocyanatobenzene] (MDI) labeled MONDUR IVIL™ by Bayer MaterialScience was charged to the batch. About 5 minutes after the MDI was added, about 0.008 weight percent triethylene diamine catalyst dispersed in dipropyleneglycol (Dabco™ 33LV by Air Products) was added to the batch. For about 20 to 30 minutes, the batch was continuously mixed and held at a batch temperature of between about 45 and 51 degrees Celsius. The batch temperature did not exceed 55 degrees Celsius and the reaction time did not exceed about 40 minutes. [0068] Then, about 74.5 weight percent polyoxyethylene-polyoxypropylene copolymer polyol, Dow DVV6340™ by Dow Chemical, was added to the batch. Heating was stopped and mixing was continued for about 60 minutes. [0069] The reaction batch containing the hydroxy! terminated precursor was cooled to room temperature and was then was sealed in a storage container. The hydroxy! terminated precursor was ready to be used in malting a polyurethane product. [0070] While the present invention has been described in terms of preferred embodiments, it will be understood, of course, that the invention is not limited thereto since modifications may be made to those s! foregoing teachings. CLAIMS 1. A method of making a hydroxyl terminated precursor for polyurethane, the method comprising: heating a vegetable oil-polyol mixture of modified vegetable oil containing about two or more hydroxyl groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere, the mixture having a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol; and adding an isocyanate at a temperature of at least 25 degrees Celsius and containing about two or more isocyanato groups per molecule to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate, and mixing to react the isocyanate with the vegetable oil-polyol mixture for at least about 10 minutes to form the hydroxyl terminated precursor. 2. The method of claim 1 wherein the isocyanate is at least one of 1,1'-methylenebis[isocyanatobenzene], polymethylenepolyphenylene isocyanate, and any isomer or isomer ratio of tolylene diisocyanate. 3. The method of any preceding claim further comprising the step of adding and mixing additional polyol to the isocyanate ddci liie vegetabie oii-pciyo! mixture. 4. The method of any preceding claim wherein the vegetable oil-polyol mixture has a temperature of between about 35 and 50 degrees Celsius. 5. The method of any preceding claim 1 further comprising cooling the hydroxyl terminated precursor to room temperature. 6. The method of any preceding claim wherein mixing reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows: wherein (HO)n—R—OH represents polyether polyol, HO—R'—(OH)m represents oxidized polymerized soybean oil, and OCN—^Ar—NCO represents 1,1'-methylenebis[isocyanatobenzene]. 7. The method of any preceding claim further comprising adding about 0.3 weight percent based on vegetable oil content of antioxidant at room temperature to the mixture. 8. The method of any preceding claim further comprising adding a catalyst in an amount of about 0.05 weight percent based on vegetable oil content, the catalyst comprising about 33% weight triethylene diamine of the catalyst and about 67% weight dipropyleneglycol of the catalyst at room temperature. 3. The method of any preceding claim fiirthfir comprising addina a poiyoxyethylene-oxypropylene copolymer polyol in an amount of up to about 500 weight percent based on vegetable oil content, after mixing the isocyanate with the vegetable oil-polyol mixture. 10. The method of any preceding claim further comprising cooling the hydroxyl terminated precursor to room temperature. 11. The method of any preceding claim wherein mixing the isocyanate and the vegetable oil-polyol mixture reacts the vegetable oil-polyol mixture with the isocyanate, defining the hydroxyl terminated precursor as follows: wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group. 12. The method of any preceding claim further comprising the step of making a polyurethane product from the hydroxyl temiinated precursor by mixing a base isocyanate as an A-side reactant with B-side reactants comprising the hydroxyl terminated precursor and optional catalyst and optional additive in a weight ratio so that the isocyanato content of the isocyanate in equivalent units is between about 60:100 and 100:80 to the active hydrogen content in equivalent units of the B-side reactants, the mixing of the A-side and the B-side reactants occun^ing at a predetermined pressure and a temperature of between about 20 and 50 degrees Celsius, and defining a liquid polyurethane mixture; and reacting the polyurethane mixture in situ to form the polyurethane product. 13. The method of claim 12 wherein adding an isocyanate to the vegetable oil-polyol mixture comprises: adding up to about 5 weight percent antioxidant at room temperature; adding up to about 40 weight percent polypropylene glycol at room temperature defining the polyol. adding up to about 40 weight' percent vegetable oil at room temperature; mixing the antioxidant, polyol, and the vegetable oil to define the vegetable oil-polyol mixture; and adding up to about 40 weight percent of the isocyanate, the isocyanate being 1,1'-methylenebis[isocyanatobenzene] at room temperature to the vegetable oil-polyol mixture. 14. The method of claims 12 or 13 wherein the predetermined pressure is up to about 203 kPa (2 atm). 15. The method of claims 12 or 13 wherein the predetermined pressure is between about 10.3 MPa (1500 psi) and 20.7 MPa (3000 psi). 16. A compound of formula A

Full Text

FIELD OF THE INVENTION
[0001] The present invention relates to hydroxyl terminated precursors and
methods of making hydroxyl terminated precursors.
BACKGROUND OF THE INVENTION
[0002] Due to their widely ranging mechanical properties and their ability to be
relatively easily machined and formed, plastic foams and elastomers have found
wide use in a multitude of industrial and consumer applications. In particular,
urethane foams and elastomers have been found to be well suited for many
applications. Automobiles, for instance, contain a number of components, such as
cabin interior parts, that are comprised of urethane foams and elastomers. Such
urethane foams are typically categorized as flexible, semi-rigid, or rigid foams with
flexible foams generally being softer, less dense, more pliable, and more subject to
structural rebound subsequent to loading than rigid foams.
[0003] Urethanes (or more accurately for polymers, polyurethanes.) are
formed when isocyanate (NCO) groups (or A-side reactants) react with hydroxyl
(OH) and other active hydrogen groups (or B-side reactants). Specifically, a
carbamate linkage (or urethane bond) is formed upon the reaction between an
isocyanate group and a hydroxyl group. The polyurethane polymer-forming reaction
occurs between substances with more than one isocyanate group per molecule (or
A-side reactants) and substances with more than one hydroxyl or other active
hydrogen group per molecule (B-side reactants). The most common method of
polyurethane production is via the reaction of a polyol (a B-side reactant) and an

isocyanate (an A-side reactant) which forms the backbone urethane group. A cross-
linking agent may also be added. Depending on the desired qualities of the final
polyurethane product, the precise formulation may be varied. VariaWes in the
formulation include the type and amounts of each of the reactants.
[0004] Although vegetable-based polyurethane foams have been used in
various polyurethane foam markets, the use of vegetable-based polyurethane foam has not gain acceptance in industries, such as the automotive industry. For example, vegetable-based polyurethanes have not been able to meet specification requirements for use in automotive interior components.
[0005] Thus, there is a need to provide a high quality polyurethane product
made from a relatively high level of bio-based raw materials.
BRIEF SUMMARY OF THE INVENTION [0006] The present Invention generally provides a hydroxyl terminated
precursor to be used In making a relatively high quality polyurethane product. The
hydroxyl terminated precursor is made from a relatively high level of bio-based raw
materials. The hydroxy! terminated precursor may be then used as the B-side
reactant and reacted with an A-side reactant from standard petrochemical
isocyanates to produce a relatively high quality polyurethane product or foam.
Depending on the choice of isocyanate and polyols, the polyurethane is suitable for
a number of applications ranging from automotive seating to rigid strtrctural urethane
parts, it is to be understood that the terms "isocyanate group" and "isocyanate
group" are used interchangeably in this application.
[0007] In one aspect, the present invention provides a method of making a
hydroxyl terminated precursor for polyurethane. The method comprises heating a

vegetable oil-polyol mixture of modified vegetable oil cwntaining about two or more hydroxy! groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. The mixture has a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol. The method further comprises mixing for at least about 10 minutes an isocyanate containing about two or more isocyanato groups per molecule at least about 25 degrees Celsius to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate. This reacts the isocyanate with the mixture to form the hydroxyl terminated precursor.
[0008] In another aspect, the isocyanate is at least one of 1,1'-methylenebis[isocyanatobenzene], polymethylenepolyphenylene isocyanate, and any isomer or isomer ratio of tolylene diisocyanate.
[0009] In another aspect, the method comprises the step of adding and mixing additional polyol to the isocyanate and the vegetable oil-polyol mixture. [0010] In another aspect, the vegetable oil-polyol mixture has a temperature of between about 35 and 50 degrees Celsius.
[0011] In another aspect, the method comprises cooling the hydroxyl terminated precursor to room temperature.
[0012] In another aspect, mixing reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows:

wherein (HO)n—R—OH represents polyether polyo!, HO—R'—(OH)m represents
oxidized polymerized soybean oil, and OCN—Ar—NCO represents 1,1'-
methylenebis[isocyanatobenzene].
[0013] In another aspect, the method comprises adding about 0.3 weight
percent based on vegetable oil content of antioxidant at room temperature to the
mixture.
[0014] In another aspect, the method comprises adding a catalyst in an amount
of about 0.05 weight percent based on vegetable oil content, the catalyst comprising
about 33% weight triethylene diamine of the catalyst and about 67% weight
dipropyleneglycol of the catalyst at room temperature.
[0015] In another aspect, the method comprises adding a polyoxyethylene-
oxypropylene copolymer polyol in an amount of up to about 500 weight percent
based on vegetable oil content, after mixing the isocyanate with the vegetable oil-
polyol mixture.
[0016] In another aspect, the method comprises cooling the hydroxy! terminated
precursor to room temperature.
[0017] In another aspect, mixing the isocyanate and the vegetable oil-polyol
mixture reacts the vegetable oil-polyol mixture with the isocyanate, defining the
hydroxyl terminated precursor as follows:

wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group. [0018] In another aspect, the method comprises making a polyurethane product
from the hydroxyl terminated precursor by mixing a base isocyanate as an A-side
reactant with B-side reactants comprising the hydroxyl temninated precursor and
optional catalyst and optional additive in a weight ratio so that the isocyanato content
of the isocyanate in equivalent units is between about 60:100 and 100:80 to the
active hydrogen content in equivalent units of the B-side reactants, the mixing of the
A-side and the B-side reactants occurring at a predetermined pressure and a
temperature of between about 20 and 50 degrees Celsius, and defining a liquid
polyurethane mixture; and reacting the polyurethane mixture in situ to form the
polyurethane product,
[00191 In another aspect, adding an isocyanate to the vegetable oil-polyol
mixture comprises adding up to about 5 weight percent antioxidant at room
temperature; adding up to about 40 weight percent polypropylene glycol at room
temperature defining the polyol; adding up to about 40 weight percent vegetable oil
at room temperature; mixing the antioxidant, polyol, and the vegetable oil to define
the vegetable oil-polyol mixture; and adding up to about 40 weight percent of the
isocyanate, the isocyanate being 1,1'-mefriylenebis[isocyanatobenzene] at room
temperature to the vegetable oil-polyol mixture.
[0020] In another aspect, the predetemnined pressure is up to about 203 kPa (2
atm).
[0021] In another aspect, the predetermined pressure is t>etween about 10.3
MPa (1500 psi) and 20.7 MPa (3000 psi).

[0026] Further aspects, features, and advantages of the invention will become apparent from consideration of the following description and the appended claims when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
lOO^^j Figure ia is a micrograph of a prior crt pclyurethane foam; and
[0028] Figure 1 b is a micrograph of a polyurethane foam made by reacting B-side reactants in a mixture containing a hydroxyl terminated precursor in accordance with one example of the present invention.

DETAILED DESCRIPTION OF THE INVENTION [0029] Examples of the present invention provide a tiydroxyl terminated
precureor, methods of making a hydroxyl terminated precursor for polyurethane, and
methods of making a polyurethane foam from a hydroxyl terminated precursor. In
one example, hydroxyl groups (-0H) on two precureor substances react with
isocyanato groups (-NCO) on a third precursor substance to fomn carbamate
linkages (-NHCOO-). The hydroxyl-containing precursor substances are used in
excess so that molecules of the hydroxyl terminated precursor (a new chemical
substance) contain, on average, two carbamate groups and at least two hydroxyl
groups.
[0030] In accordance with one example, the present invention provides a
method of making a hydroxyl terminated precursor for polyurethane. The method
comprises providing a modified vegetable oil comprising hydroxyl groups. For
example, the modified vegetable oil may be any suitable oil having hydroxyl groups,
or modified to contain hydroxyl group, such as a modified soybean oil (polymerized,
oxidized), palm oil, canola oil, rapeseed oil, castor oil, or olive oil. Any other
modified non-petroleum based oil may be used without falling beyond the scope or
spirit of the present invention.
[00311 In this example, the modified vegetable oil is a modified soybean oil
(polymerized, oxidized). Soybean oil, and other plant based oils, is a mixture of
triglycerides, i.e., triesters of glycerol and fatty acids. A triglyceride may have the
general structure as follows:

where R\ R^, and R' can have any of a number of structures. A naturally occumng
triglyceride typically exists as a mixture of different structures in which R\ R^, and R^
vary from structure to structure.
[0032] A fatty acid is a carboxylic acid and may have a general formula of
HO2CR, where R is usually an unbranched aliphatic chain attached to a carboxyl
group. The chain may contain double or triple bonds. Other functional groups may
also be present, such as hydroxyl groups, as in ricinoleic acid.
[0033] The most common R groups in vegetable oils are listed in Table 1 below

[0034] It is to be noted that Table 1 Is not exhaustive and that a number of other
fatty acids may be present in triglycerides without falling beyond the scope or spirit
of the present invention.
[0035] When a plant based oil is exposed to oxidizing agents, especially with
added heat or ultraviolet light, the R groups can react to form a number of other
staictures. The positions of double bonds may change, and polymerization may
occur via free radical, ionic, or electrocyclic reactions. Hydroxyl groups may also be
introduced into the molecule.
[0036] The chemical structure of oxidized, polymerized soybean oil may be
generally described as follows:

where R\ R^, and R^ are groups derived from the original R groups of the starting triglyceride; A\ A^, and A^ are chemically bonded to R\ R^, and R^ and may be hydroxyl or other triglyceride moieties whose R groups themselves may have undergone similar reactions to those undergone by R\ R^, and R^; and x, y, and z may be any whole number 0 or above, but will usually be 0,1, or 2. Ntoreover, if x is 2 or greatfir A^ may represent two or more different groups, for example, a hydroxyl group and a triglyceride moiety, or a triglyceride moiety that contains hydroxyl groups. Furthermore, the same is for y and z.

[00371 Examples of structures generally having the above description include as follows, but are not limited to:

[0038] More specifically, the modified soybean oil (polymerized, oxidized) may be Soyol™ R2-052, a di-functional, 52 hydroxy! number biobased polyol suitable for urethane applications and manufactured by Urethane Soy Systems Company of Volga, SD.

[0039] The method further comprises providing a poiyol, preferably a polyether polyol. For example, a general description of a polyether poiyol that may be used in accordance with an example of the present invention includes polymers formed by the addition of alkylene oxide monomers to an initiator compound containing two or more active hydrogen atoms. That is, the active hydrogen compound in the presence of a catalyst initiates a ring opening and an oxide addition, which continue until the desired molecular weight is obtained. In one example, the preferred alkylene oxides are propylene oxide and ethylene oxide. Polymers may be formed from one or more of the following or similar initiators: water, ethylene glycol, propylene glycol, dipropylene glycol, glycerine, trimethylolpropane, ethylene diamine, pentaerythritol, diethylene triamine, sorbitol, and sucrose. Example of some trade names for the polyols described above and useful in this invention are: Dow Chemical's Voranol™ 5815, Voractiv™ DW6340, Voranol™ 4240; Bayer MaterialScience's Multranol™ 3901 and BASF's Pluracol™ 1596. Furthermore, graft (or "filled") copolymer polyol produced by free radical polymerization of styrene and acrylonitrile ("SAN") in situ with a polyether polyol have proven to be useful in this invention; Dow Chemical's Specflex™ NC701 and BASF Pluracol™ 1528 are examples of these type of polyols. Another class of copolymer polyol suitable in this

tolylene diisbcyanate or alkanolamine with an isocyanate in the presence of a
polyether polyol; an example of the former is Bayer MaterialScience's Multranol™
9151.
[0040] The polyol used herein may be an ethylene oxide-propylene oxide
copolymer polyether polyol with average functionality (number of hydroxyl groups

per molecule) greater than 1 and less than about 5. The molecular weight may be between about 200 and about 6500. Preferably, the polyol is a polypropylene glycol (diol or triol) with a molecular weight between about 400 and 3000. For example, polyols with a tradename of Pluracol™ P410R by BASF, Pluracol™ PI 010 by BASF, Voranol™ 220-110 by Dow, and Voranol™ 230-238 by Dow may be used. [0041] The modified vegetable oil containing about two or more hydroxyl groups per molecule is then mixed with the polyol having about two or more hydroxyl groups per molecule to define a vegetable oil-polyol mixture. In this example, the mixture has a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol. Preferably, the vegetable oil-polyol mixture is heated to a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere. More preferably, the vegetable oil-polyol mixture is heated to a temperature of between about 35 and 50 degrees Celsius.
[0042] The method further comprises providing an isocyanate containing about two or more isocyanato groups per molecule. In one embodiment, the isocyanate may be any suitable isocyanate such as one of 1,1'-methylenebis[isocyanatobenzene] (MDI), polymethylenepolyphenylene isocyanate (polymeric MDI), and all isomers and isomer ratios of toluene diisocyanate (TDI).

present invention. The isocyanate is heated to a temperature of at least about 25 degrees Celsius, preferably between about 25 and 60 degrees Celsius, and more preferably between about 35 and 50 degrees Celsius at a pressure of preferably about 1 atmosphere.

[0043] The isocyanate is added to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate. The isocyanate is then mixed with the vegetable oil-polyol mixture for at least about 10 minutes to react the isocyanate with the mixture, thereby forming the hydroxyl terminated precursor. The mixing of the isocyanate and the vegetable oil-polyol mixture reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows:

wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group.
[0044] Additional polyol may then be added and mixed with the vegetable oil-polyol mixture and isocyanate. In this example, up to about 500 weight percent based on vegetable oil content of a polyoxyethylene-oxypropylene copolymer polyol may be added after mixing the isocyanate with the mixture. However, other polyols may be used as provided above without falling beyond the scope or spirit of the present invention.
[0045] Catalyst(s) may then be added in accordance with one example of the present invention. The catalysts added may include tertiary amines such as

triethyiamine, tributylamine, N-methylmorpho!ine, N-ethylmorpholine, N-
cocomorpholine, N.N.N'.N'-tetramethyl-ethylenediamine, 1,4-clia2abicyclo-(2,2,2)-
octane (DABCO), N-methyl-N'-dimethylaminoethylpiperazine, N.N-dimethyl-
benzylamine, bis-(N,N-cliethylaminoethyl)aclipate, N.N-diethylbenzylamine,
pentamethyl diethylenetriamine, N.N-dimethylcyclohexylamine, N.N.N'.N'-
tetramethyl-1,3-butanecliamine, N.N-dimethyl-p-phenylethylamine, 1,2-
dimethylimidazole, 2-methylimidazole, 3-(2-(dimethylamino)ethoxy]-N,N-
dimethylpropylamine, N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine), 2,4,6-
tris(dimethylaminomethyl)phenol, 1,3-bis(dimethylamino)-2-propanol,
diazabicyclo[5.4.0]undec-7-ene (DBU) and the like.
[0046] Also useful are commercially available delayed action catalysts such as
1-(2-hydroxypropyl)imidazole fomnic acid salt; 2-[[2-
(dimethylamino)ethyl]methylamino]ethanol fomnic acid salt; bis(2-dimethylaminoethyl) ether diformate; N,N,N',N'-tetramethyl-1,2-ethanediamine formic acid salt; 1,8-diazabicyclo[6.4.0]undec-7-ene 2-ethylhexanoic acid salt; 1,8-diazabicyclo[5.4.0]undec-7-ene phenol salt; and the like. Mannich bases known per se obtained from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols such as phenol nnnyiphfinol or bisphenol may also be used as catialysts. Examples of catalysts which include tertiary amines having hydrogen atoms reactive with isocyanate groups include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine and their reaction products with alkylene oxides such as propylene oxide and/or ethylene oxide.

[0047] Basic nitrogen compounds such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium phenolate and alkali metal alcoholates such as sodium methylate may also be used as catalysts. Hexahydrotriazines are also suitable catalysts.
[0048] Organic metal compounds may also be used as catalysts according to the invention, in particular organic tin compounds. The organic tin compounds used are preferably tin(ll) salts such as tin(ll) acetate, tin(ll) octoate, tin(ll) ethyl hexoate and tin(ll) laurate; and tin(IV) compounds such as dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurylmercaptide, dibutyl tin maleate dioctyl tin diacetate, dimethyl tin dichloride, dimethyl tin dilaurate, or dimethyl tin dilauryl mercaptide. All the above-mentioned catalysts may, of course, be used as mixtures.
[0049] Salts of other metals may also be used as catalysts, in particular, organobismuth compounds such as bismuth 2-ethylhexanoate. bismuth neodecanoate and the like, organozirconium compounds such as tetrakis(2,4-pentanedionato)zirconium and the like, or organomercury compounds such as phenyl mercuric neodecanoate and the like.
[0050] Further examples of catalysts that may be used in accordance with one exdiiiplc of the present invention are described 'n KunRtstoff-Handbuch, Volume VII. published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 96 to 102, each of which are incorporated herein by reference in its entirety. [0051] The catalysts, when used, are generally used in a quantity of between about 0.001 and 10%, by weight, based on the quantity of reactants. Any other suitable catalyst may be used. For example, catalysts are listed in U.S. patent

numbers 5,229,427 and 7,211,616, each of which is incorporated herein by reference in its entirety.
[0052] In another example, about 0.05 weight percent based on vegetable oil content of catalyst may be added. In this example, the catalyst comprises about 33% weight triethylene diamine of the catalyst and about 67% weight dipropyleneglycol of the catalyst at room temperature. Optionally, the method may further comprise adding about 0.2 weight percent based on vegetable oil content of antioxidant at room temperature to the mixture.
[0053] As discussed in greater detail below, the hydroxyl terminated precursor may be then used as the B-side reactant alone or blended with additional polyol(s), catalyst(s) and additives as B-side reactants and then mixed with an A-side reactant using standard petrochemical isocyanates. It has been found that this produces a relatively high quality polyurethane foam. Depending on the choice of isocyanate, and other B-side reactants, the foam is suitable for a number of applications ranging from automotive seating to rigid structural urethane parts.
[0054] A compound in accordance with one example of the present invention include formula A as follows:

[0058] In another example, the present invention provides a method of making a polyurethane product from a hydroxyl terminated precursor. As mentioned above, polyurethane foam may be prepared by reacting what is known as an A-side reactant (or A-side reactants) with what is known as a B-side reactant (or B-side reactants). The A-side reactant is generally considered to include at least one isocyanate. The B-side reactant may comprise the hydroxyl terminated precursor alone but generally Is a solution or mixture of an isocyanate-reactive component, such as a polyol and optionally catalyst(s) and/or additive(s). [0059] The method comprises forming the hydroxyl terminated precursor as described herein. The hydroxyl terminated precursor may be used as the B-side reactant. The method further comprises mixing a base isocyanate with a catalyst (mentioned above) and optionally any additive to define an isocyanate mixture. In this example, catalysts may or may not be added to the isocyanate except for isocyanato terminated prepolymers where catalysts are frequently used in their preparation. The catalysts to accelerate the polyurethane reaction may be added to

the B-side reactants which will include hydroxyl terminated precursor for one example of the present invention and optionally additional polyol(s), optionally additive(s) (such as crosslinkers or chain extenders, surfactants, water, blowing agents, pigments, etc.) and optionally catalyst(s). The isocyanate mixture may be used as the A-side reactant. It is to be noted that isocyanate mixtures are mixtures or solutions of different types of isocyanates or isomers. Optionally, some A-side reactants may contain surfactants, flame-retardants, special additives or dilulents or in some cases additional catalyst may be added. The isocyanate mixture (A-side reactants) may have a weight ratio with the hydroxyl terminated precursor and optionally other B-side reactants so that the isocyanato content of the isocyanate mixture in equivalent units is between about 100:80 and 60:100 to the active hydrogen content in equivalent units in the hydroxyl temninated prwursor and optionally other B-side reactants.
[0060] In this example, the isocyanate, A-side reactant, (or reactants) is (are) then mixed with the B-side reactants containing the hydroxyl terminated precursor plus optionally additional polyol(s), catalyst(s) and additive(s) at a predetennined pressure and a temperature of between about 20 and 50 degrees Celsius, defining a liquid polyurethane mixture. In one example, the predetermined pressure may be up ly about 2 atmospheres, depending on the gpnaratus. However, in another example, the predetermined pressure may be between about 1500 and 3000 pounds per square inch gauge.
[0061] The liquid polyurethane mixture may then be injected or poured in a cavity of a mold. The polyurethane mixture reacts in situ to form the polyurethane product. That is, in the cavity, the liquid polyurethane mixture reacts and for foam

formulations rises to fill the cavity and form the polyurethane product in situ. For non-foam formulations, the liquid polyurethane mixture fills the cavity to the volume injected or poured and then cures to a solid to form the polyurethane product in situ. In this example, the mold may be made of aluminum, polymeric material, or steel, or any other suitable material. After a defined period of time, the polyurethane product is removed from the mold, thereby retaining the predetermined shape. [0062] Figures 1a and 1b illustrate a comparison betv^een a prior art polyurethane foam and a polyurethane foam made in accordance with an example of the present invention. Figure la depicts a prior art polyurethane foam made from made from a TDI based isocyanate. More specifically, the prior art polyurethane foam of Figure la was made by reacting B-side reactants containing about 7% polymerized, oxidized soybean oil based on the total B-side reactants in a mixture of standard petrochemical based molding polyether polyols, catalysts and additives with A-side reactants of 80/20% 2,4-, 2,6-tolylenedilsocyanate. As shown, the cell stmcture of the prior art polyurethane foam is relatively coarse and highly in^egular. Moreover, the foam tends to have a "tight" and "dead" feel. [0063] Figure lb shows a polyurethane foam made from the hydnoxyl terminated precursor in accordance with one example of the present invention, morc spccificnlly, the polyurethgne foam of Finurft lb was made by reactinq B-side reactants in a mixture containing a hydroxyl terminated precursor in accordance with one example of the present invention, petrochemical based molding polyether polyols, catalysts and additives with A-side reactants of 80/20% 2,4-, 2,6-tolylenediisocyanate. The hydroxyl terminated precursor in the foam depicted by Figure lb contains about 7% polymerized, oxidized soybean oil based on the total B-

side reactants. As depicted, the cell structure of the polyurethane foam is relatively fine and significantly more consistent. Additionally, the foam tends to have an open and resilient "flexible" feel.
[0064] Furthermore, it is understood that the hydroxyl terminated precursor may be used alone as the B-side reactant.
EXAMPLE [0065] This example provides a method of making a hydroxyl terminated precursor to be used in making a polyurethane product. About 1 weight percent of polypropylene glycol (Pluracol™ P-1010 by BASF) mixture with about 0.04 weight percent antioxidant (Irganox™ 245 by Ciba Specialty Chemicals) was predispersed in a separate mixing container to define a polypropylene glycol-antioxidant blend. The polypropylene glycol-antioxidant blend was heated to about 65 degrees Celsius. [0066] About 16 weight percent of a modified soybean oil (polymerized, oxidized), Soyol™ R2-052, from Urethane Soy Systems Company of Volga, SD was weighed and loaded into a lined, open reactor vessel equipped with a band style heater and a Patterson™ mixer. The mixer was turned on low and the batch heated to about 25 degrees Celsius. About 7 weight percent of polypropylene glycol (Pluracol™ P-1010 by BASF) at room temperature was added to the batch. [0067] The noiynronyienfi glycol-antioxidant blend was then added to the batch, and the batch was mixed and heated to between about 39 and 44 degrees Celsius. The batch was maintained at a temperature no higher than about 45 degrees Celsius. As mixing continued, about 1.452 weight percent of 1,1'-methylenebis[isocyanatobenzene] (MDI) labeled MONDUR IVIL™ by Bayer MaterialScience was charged to the batch. About 5 minutes after the MDI was

added, about 0.008 weight percent triethylene diamine catalyst dispersed in
dipropyleneglycol (Dabco™ 33LV by Air Products) was added to the batch. For
about 20 to 30 minutes, the batch was continuously mixed and held at a batch
temperature of between about 45 and 51 degrees Celsius. The batch temperature
did not exceed 55 degrees Celsius and the reaction time did not exceed about 40
minutes.
[0068] Then, about 74.5 weight percent polyoxyethylene-polyoxypropylene
copolymer polyol, Dow DVV6340™ by Dow Chemical, was added to the batch.
Heating was stopped and mixing was continued for about 60 minutes.
[0069] The reaction batch containing the hydroxy! terminated precursor was
cooled to room temperature and was then was sealed in a storage container. The
hydroxy! terminated precursor was ready to be used in malting a polyurethane
product.
[0070] While the present invention has been described in terms of preferred
embodiments, it will be understood, of course, that the invention is not limited thereto
since modifications may be made to those s! foregoing teachings.

CLAIMS
1. A method of making a hydroxyl terminated precursor for polyurethane,
the method comprising:
heating a vegetable oil-polyol mixture of modified vegetable oil containing about two or more hydroxyl groups per molecule and a polyether polyol having about two or more hydroxyl groups per molecule at a temperature of at least about 25 degrees Celsius and at a pressure of about 1 atmosphere, the mixture having a hydroxyl equivalent ratio of about 1:1 vegetable oil to polyol; and
adding an isocyanate at a temperature of at least 25 degrees Celsius and containing about two or more isocyanato groups per molecule to the vegetable oil-polyol mixture at a molar equivalent ratio of at least 2:1 vegetable oil-polyol mixture to isocyanate, and mixing to react the isocyanate with the vegetable oil-polyol mixture for at least about 10 minutes to form the hydroxyl terminated precursor.
2. The method of claim 1 wherein the isocyanate is at least one of 1,1'-methylenebis[isocyanatobenzene], polymethylenepolyphenylene isocyanate, and any isomer or isomer ratio of tolylene diisocyanate.
3. The method of any preceding claim further comprising the step of adding and mixing additional polyol to the isocyanate ddci liie vegetabie oii-pciyo! mixture.
4. The method of any preceding claim wherein the vegetable oil-polyol mixture has a temperature of between about 35 and 50 degrees Celsius.

5. The method of any preceding claim 1 further comprising cooling the hydroxyl terminated precursor to room temperature.
6. The method of any preceding claim wherein mixing reacts the isocyanate with the vegetable oil-polyol mixture to define the hydroxyl terminated precursor in a reaction as follows:

wherein (HO)n—R—OH represents polyether polyol, HO—R'—(OH)m represents oxidized polymerized soybean oil, and OCN—^Ar—NCO represents 1,1'-methylenebis[isocyanatobenzene].
7. The method of any preceding claim further comprising adding about 0.3 weight percent based on vegetable oil content of antioxidant at room temperature to the mixture.
8. The method of any preceding claim further comprising adding a catalyst in an amount of about 0.05 weight percent based on vegetable oil content, the catalyst comprising about 33% weight triethylene diamine of the catalyst and about 67% weight dipropyleneglycol of the catalyst at room temperature.
3. The method of any preceding claim fiirthfir comprising addina a poiyoxyethylene-oxypropylene copolymer polyol in an amount of up to about 500 weight percent based on vegetable oil content, after mixing the isocyanate with the vegetable oil-polyol mixture.

10. The method of any preceding claim further comprising cooling the hydroxyl terminated precursor to room temperature.
11. The method of any preceding claim wherein mixing the isocyanate and the vegetable oil-polyol mixture reacts the vegetable oil-polyol mixture with the isocyanate, defining the hydroxyl terminated precursor as follows:

wherein R is a polyoxypropylene polymer or polyoxyethylene-polyoxypropylene polymer group; R' is a modified vegetable oil group; and Ar is a bisphenyl methylene or methylbenzene group.
12. The method of any preceding claim further comprising the step of
making a polyurethane product from the hydroxyl temiinated precursor by mixing a
base isocyanate as an A-side reactant with B-side reactants comprising the hydroxyl
terminated precursor and optional catalyst and optional additive in a weight ratio so
that the isocyanato content of the isocyanate in equivalent units is between about
60:100 and 100:80 to the active hydrogen content in equivalent units of the B-side
reactants, the mixing of the A-side and the B-side reactants occun^ing at a
predetermined pressure and a temperature of between about 20 and 50 degrees
Celsius, and defining a liquid polyurethane mixture; and reacting the polyurethane
mixture in situ to form the polyurethane product.

13. The method of claim 12 wherein adding an isocyanate to the vegetable
oil-polyol mixture comprises:
adding up to about 5 weight percent antioxidant at room temperature;
adding up to about 40 weight percent polypropylene glycol at room temperature defining the polyol.
adding up to about 40 weight' percent vegetable oil at room temperature;
mixing the antioxidant, polyol, and the vegetable oil to define the vegetable oil-polyol mixture; and
adding up to about 40 weight percent of the isocyanate, the isocyanate being 1,1'-methylenebis[isocyanatobenzene] at room temperature to the vegetable oil-polyol mixture.
14. The method of claims 12 or 13 wherein the predetermined pressure is
up to about 203 kPa (2 atm).
15. The method of claims 12 or 13 wherein the predetermined pressure is between about 10.3 MPa (1500 psi) and 20.7 MPa (3000 psi).
16. A compound of formula A

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Patent Number

278875

Indian Patent Application Number

967/CHENP/2010

PG Journal Number

01/2017

Publication Date

06-Jan-2017

Grant Date

02-Jan-2017

Date of Filing

19-Feb-2010

Name of Patentee

LEAR CORPORATION

Applicant Address

21557 TELEGRAPH ROAD, SOUTHFIELD, MICHIGAN 48033

Inventors:

#	Inventor's Name	Inventor's Address
1	MADAJ, EDMUND J.	9212 SHARON HILLS LANE, MANCHESTER, MICHIGAN-48158
2	JONES, THOMAS N.	8722 COYLE DRIVE, PINCKNEY, MICHIGAN-48169

PCT International Classification Number

C08G18/12

PCT International Application Number

PCT/US2008/073836

PCT International Filing date

2008-08-21

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	11/842,903	2007-08-21	U.S.A.