MXPA98000334A - Poliols that have reduced insaturation and a process to produce - Google Patents

Abstract

The unsaturation of a hydroxyl-containing compound can be reduced by the reaction with a nitrile-oxide compound such as N, trimethylterephthalonitrile N, dioxide. The reaction of nitrile oxides with terminal unsaturation associated with the preparation of a polyol propylene oxide reduces the monol content of the poly composition

Description

POLIOLS THAT HAVE REDUCED INSATURATION AND A PROCESS TO PRODUCE THEM The present invention relates to polyols having reduced unsaturation, and to a method for preparing these polyols. Polyols are chemical products or functional hydroxy polymers that cover a wide range of molecular weight, hydroxy functionality, and composition. The predominant use of polyols such as polyols based on poly (propylene oxide / ethylene oxide) (poly (PO / EO)) and on poly (propylene oxide) (poly (PO)), is as a component in the manufacture of polyurethane or polyurethane resins. They are also useful as components and intermediates for other polymers, including polyesters and epoxy resins. In addition, a polyol can be further reacted with hydroxyl-reactive compounds such as additional alkylene oxide, unsaturated dibasic carboxylic acids or polycarboxyliates, to form a polymeric polyol for subsequent reaction. The properties of the polyol affect the properties of the polymers made using the polyol. For example, a flexible polyurethane foam is commonly made using linear or slightly branched polyols, while a rigid polyurethane foam is made using branched polyols. In addition, the polyol functionality and the primary hydroxyl content of the polyol affect its reactivity. The reactivity of a polyol to urethane-forming reagents (eg, isocyanate functional groups) is an important property that affects the properties of the resulting polymer as well as its processing. Other properties such as the viscosity, solubility, and stability of the polyols are also important. In a typical process, the polyol is prepared by contacting an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof with an active hydrogen initiator, typically a polyhydric initiator such as glycerol, generally in the presence of a catalyst such as a base, for example, potassium hydroxide, or an amine. Following the preparation, the reaction product is purified to reduce the level of catalyst and other by-products. The resulting product is a polyol with predominantly hydroxyl end groups. However, the propylene oxide can be isomerized during the reaction to give an allyl alcohol, which can additionally undergo alkoxylation (e.g., propoxylation); thus resulting in a number of capped chains with terminal unsaturation, for example, propoxylated allyl alcohol which is monofunctional and is referred to as "monol". This is particularly evident when a basic catalyst is employed. This is undesirable in the polyurethane preparation, since the unsaturation does not react with the isocyanate functionality. Unreacted, particularly terminal unsaturation is also susceptible to environmental influences, and may adversely affect properties, such as compression and tensile strengths, discoloration, flexural modulus and wet aging, of the resulting polymer. In particular, the modulus of a flexible polyurethane or polyurea foams or elastomeric polymers is reduced as the amount of unsaturation or monohydroxyl compound increases. One method reported to reduce the unsaturation in a polyol composition is to treat the reaction product of the initiator and the alkylene oxide with an acid. See, for example, Patents of the United States of North America Nos. 2,996,556, and 3,271,462. However, the acid must be removed after treatment. In yet another method for reducing propenyl polyethers in functional hydroxy polyethers, U.S. Patent No. 5,095,061 teaches contacting a neutral polyol with an acid catalyst and water to convert propenyl polyether to propionic aldehyde., contact the resulting product with an epoxy to remove the acid catalyst, and then remove the water and the propionate. In a similar manner, U.S. Patent No. 5,342,541 teaches contacting a polyether polyol with an acid and water ion exchange resin to convert the propenyl polyether into propionic aldehyde, and then contacting the product. resulting with an epoxy to reduce the acidity of the polyol. However, both processes described involve additional steps, such as acid removal. It would be desirable to reduce the unsaturation, particularly the terminal unsaturation, to reduce the monol content of a polyol composition. Accordingly, in one aspect, the present invention is a polyol composition comprising a polyol derived from a hydroxyl-containing compound having unsaturation reacted with a nitrile oxide compound. A nitrile oxide fraction is capable of reacting with a terminal or internal unsaturation, for example, propenyl. In a preferred embodiment, the unsaturation is terminal and the nitrile oxide reduces the terminal unsaturation. More preferably, the hydroxyl compound reacted with the nitrile oxide is a monol having terminal unsaturation. In the preferred embodiment, it is believed that the polyol composition comprises at least one polyol having an isoxazoline moiety. The polyol is a compound of the formula: wherein n is an integer of one or more, each R is independently hydrogen, methyl, or ethyl, with at least some R being preferably methyl; x is an integer of one or more, and R2 is a residue of a nitrile oxide compound. In a second aspect, the present invention is an improved method for preparing a polyol. In the improved method for making a polyol from the reaction of an alkylene oxide, preferably propylene oxide, with an initiator, the improvement is to react the unsaturation, preferably the terminal unsaturation, of the reaction product, with a nitrile oxide compound. Preferably, the nitrile oxide compound is a stable di (nitrile oxide) or a compound having a nitrile oxide and a hydroxyl group (-OH). The unsaturation in the reaction product reacts with the nitrile oxide without detachment or the formation of a by-product. As such, the terminal unsaturation, as well as the molecules having one or more non-hydroxyl-terminated chains, eg, monools, is substantially reduced or eliminated in the composition. For example, when the nitrile oxide is a dinitrile oxide having no hydroxyl group, the nitrile oxide compound will react with two monools to form a polyol. Alternatively, if the nitrile oxide compound is a mononitrile oxide containing a hydroxyl group, reaction of the hydroxyl group of the nitrile oxide compound with the unsaturation will directly impart an additional hydroxyl functionality to the resulting reaction product. The process of the present invention provides a more economical means for preparing polyols, since the need for careful and costly control to reduce unsaturation, particularly the terminal unsaturation that can result in monools, to negligible amounts becomes less critical. The polyol compositions are useful in the preparation of polymers formed from polyols, particularly in the subsequent preparation of polyurethane, and in another aspect, the present invention is a polyurethane formed from these polyol compositions. In the present invention, the polyol composition comprises a polyol derived from a hydroxyl-containing compound having an unsaturated group, generally a terminal unsaturation, which has been reacted with a nitrile oxide compound. In general, the polyol composition will contain other polyols that do not contain terminal unsaturation. The term "polyol" means a compound having two or more hydroxyl groups (-0H), the term "monol" being a compound having a hydroxyl group. Following the reaction with the nitrile oxide, it is believed that the polyol comprises an isoxazoline fraction. The hydroxyl-containing compound having unsaturation can be prepared by any technique. These techniques are known in the art, and reference is made thereto for the purpose of the present invention. Although the hydroxyl-containing compound can be prepared separately, it is generally formed simultaneously, usually as a by-product, with the preparation of a polyol. The techniques and reagents used in the preparation of the polyols are well known in the art, and these techniques and reagents can be employed in the practice of the present invention. Representatives of these techniques are described in Telechelic Polymers: Synthesis and Applications, edited by Goethals, E.J., CRC Press Inc., Boca Raton, Florida, published in 1989, and Polymers (PO-, and 1.2- epoxide polymers), by R.A. Newton at pages 633-645, and volume 18 of the Encyclopedia of Chemical Technology, edited by R. Kirk and D.F. Othmer, John Wiley & Sons, New York 1982. In general, polyol compositions are prepared by the reaction of an alkylene oxide with an initiator in the presence of a catalyst. Representative alkylene oxides include those of the general structural formula: wherein R can be essentially any organic group that does not interfere with the reaction of the alkylene oxide in the formation of the polyol or in the subsequent reactions, if any, of the polyol. Typically, R is hydrogen or an alkyl group having 1 to 12, preferably 1 or 2 carbon atoms. Often a mixture of one or more alkylene oxides is used in the preparation of the polyol composition. Preferably, the alkylene oxides used are an ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or more of these oxides. In the practice of the present invention, at least a portion of the alkylene oxide is propylene oxide. The initiators can be any compound having a functional group capable of reacting with the alkylene oxide. Representative initiators that can be employed in the practice of the present invention are polyhydric alkyl alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol; hydroxyl terminated polyalkylene polyethers; sorbitol; and sucrose; a polycarboxylic acid such as maleic acid, citric acid, succinic acid, and adipic acid; amines such as ethylene diamine, toluene diamine, 4,4'-diaminodiphenylmethane, and diethylenic tria. In general, glycerin, ethylene glycol, propylene glycol, sucrose, sorbitol, ethylene diamine, and toluene diamine are preferred. The hydroxyl functionality of the polyol composition depends primarily on the initiator, and is selected accordingly. More preferably, propylene glycol is used to produce a diol, and glycerin is used as an initiator to produce a triol. The catalysis can proceed by an anionic, cationic, or coordinated mechanism, depending on the type of catalyst used. The catalysts used in the reaction of the alkylene oxide with the initiator will vary depending on the reaction method being used, and the desired reaction product. For example, in the preparation of polyether polyols, an acid catalyst is commonly used to achieve the random microstructure; a basic catalyst is commonly used to achieve the head-to-tail microstructure; and a coordination catalyst is used to form a stereoregular polymer. Representative examples of the acid catalysts that can be employed in the reaction are Lewis acids such as boron trifluoride and other acids described in The Chemistry of Cationic Polymerization, by PH Plesch, Pergamon Press, Oxford, 1963, and UK Patent. Joined Number 1,323,184. Representative examples of the bases that can be used to catalyze the reaction are metal hydroxides such as potassium hydroxide (KOH), sodium hydroxide (NaOH), barium hydroxide (Ba (OH) 2) (see, for example , Patents of the United States of North America Numbers 5, 114, 619, and 5,070,125), cesium hydroxide (Cs (OH) 2), and strontium hydroxide (Sr (0H) 2); and different amines, such as trimethyl amine; with KOH or Ba (0H) 2) being a preferred basic catalyst. Representative coordination catalysts are iron chloride (FeCl3); organometallic compounds such as lithium phosphate hexafluoride; and double metal complexes (zinc (III) hexacyanoferrate, cobalt hexacyanoferrate (III)) as described in U.S. Patent Nos. 3,427,256; 3,829,505; 3,278,458; 4,472,560; and 4,477,589. Preferably, a basic catalyst is used in the preparation of the polyol composition, with KOH and Ba (OH) 2 being particularly preferred.

The alkylene oxide, the initiator, and the catalyst are reacted under conditions sufficient to form the desired polyol composition. Although the most conveniently used reaction conditions will vary depending on a variety of factors, including the specific reagents and the desired reaction product, in general, the polyol is conveniently formed in a stepwise reaction in an inert atmosphere (eg, nitrogen). The first step typically comprises forming an alkoxide (alcoholate) ion by contacting the initiator and the catalyst (e.g., potassium hydroxide), any water formed during the reaction being removed. Subsequently, the alkylene oxide is contacted with the alkoxide ion thus formed. The reaction between the alkoxide and the alkylene oxide is exothermic, the heat generated during the reaction being removed to maintain an appropriate temperature, which is typically 80 ° C to 150 ° C, depending on the desired reaction rate and composition of polyol that is being produced. The reaction is continued until the unreacted alkylene oxide reaches a desired level. Following the reaction, the product is purified to remove the catalyst, such as by neutralization, using high surface absorbers, washing with water using an organic solvent as a diluent, or other methods. For example, the catalyst can be removed from the reaction product by contacting it with an absorbent, such as a magnesium or aluminum silicate, as described in U.S. Patent Number 4,029,879; an acetic or formic acid as described in U.S. Patent Number 4,521,548; or a solid organic acid as described in U.S. Patent Number 3,000,963; or by contacting the reaction product with a phosphoric acid, followed by filtration of the insoluble salts; or ending with carbon dioxide as described in Japanese Patent Application Publication Number 55/092, 733-A. When trimethylamine or another amine is used as a catalyst, the excess catalyst can be removed by distillation. The reaction product is further purified by removing water and volatile organic compounds, and then it can be stabilized, such as by the addition of antioxidants or saturation with nitrogen. Representative polyols found in the polyol composition are polyether polyols (ie, a polyester (alkylene oxide) homo- or copolymer base structure), polyester polyols, polyether-polyester hybrids, and polyols which have a hydrocarbon base structure. Representative of the preferred polyols are polyether polyols having the general structural formula: I ((CH2-CH (R1) -0) n-H) m wherein I is an initiator residue, generally hydroxy or the residue of an organic active hydrogen initiator; R1 is hydrogen or alkyl, preferably at each presentation, independently hydrogen, methyl or ethyl; n is an integer from 1 to 200, preferably from 2 to 100, more preferably from 5 to 75; and m is an integer from 2 to 8, preferably from 2 to 4, more preferably from 3 to 4. Typically, the composition will contain a mixture of polyols, where n is not a single whole, but different integers with an average of 5. at 100, more conveniently from 10 to 75. In a preferred embodiment, the polyols are polyols having a base structure of poly (propylene oxide / ethylene oxide), or a polyol based on poly (propylene oxide) having a molecular weight of 2,500 to 8,000. The polyol compositions of the present invention generally comprise a polyol having two or more hydroxyl end groups (-0H). In general, these hydroxyl end groups are the direct result of the preparation of the polyol. In addition to the polyols having only terminal hydroxyl groups, at least a portion, generally a portion. small but not insignificant, of the polyol composition, will have unsaturation, generally terminal unsaturation, formed during the reaction. Although the specific amount of the reaction product having terminal unsaturation will vary depending on a number of factors, such as the specific reaction method, the reagents employed, and the reaction conditions, such as the reaction temperature and the concentration of the catalyst , in general, the reaction product will contain from 0.01 to 2 milliequivalents of terminal unsaturation per gram of reaction product, which generally corresponds to a monol content of 2 to 50, preferably 10 to 40 mole percent of the monol in the reaction product. The nitrile oxide that can be used to reduce the unsaturation of the hydroxyl-containing compound is a compound having a group -C = N + -0 ~. Although a compound having a single group -C = N + -0 ~ can be used to react with, and reduce, the unsaturation, the reaction of this mononitrile oxide with the unsaturation produces a capped product, which can not be additionally reactive , depending on whether the mononitrile has other reactive groups or not. In a preferred embodiment, the terminal unsaturation of the hydroxyl-containing compound is reacted with a compound having two or more, preferably two, nitrile oxide groups, or a compound having a nitrile oxide and a hydroxyl group. As used herein, the term "polynitrile oxide" includes a compound having two or more nitrile oxide groups per molecule, and includes a dinitrile oxide. The representative polynitrile oxides are of the formula: R2- (C = N + -0 ~)? wherein x is two or more, preferably from 2 to 6, more preferably from 2 to 4, and most preferably 2; and the representative mononitrile oxide hydroxyl-containing compounds are of the formula: H0-R3- (C = N + -0 ~) wherein R and R are organic fractions which may contain an aromatic group (including heteroaromatic fractions such as pyridines, furans, and thiophenes), aliphatic groups, or a combination of aromatic and aliphatic groups, including inert aliphatic or aromatic substituted groups. Preferably, R2 and R3 are aromatics or aromatically substituted fractions; cycloaliphatics, or inertly substituted cycloaliphatic moieties; or fractions that have both an aromatic and an aliphatic character. The nitrile oxide compounds suitably used in the practice of the present invention, preferably react with the terminal olefinic unsaturation, as opposed to the hydroxyl group of the polyol or water. The most conveniently used nitrile oxide compounds react with terminal olefinic unsaturation, such that, under the conditions of its reaction, the nitrile oxide compound does not react to a significant and detrimental amount with the hydroxyl group of the polyol or water. In one embodiment, the nitrile oxide is prepared separately, and added to the polyol composition. Preferably, in this case, the nitrile oxide forms stable molecules that do not react in a significant and detrimental manner to one another prior to their reaction with the terminal unsaturation of the polyol. Because the nitrile oxide groups on different molecules can be dimerized in the absence of stabilizing groups, the nitrile oxides prepared separately are conveniently compounds having the nitrile oxide groups adjacent to at least one substituent, such as a group sterically. an inhibitor, which: 1) inhibits the dimerization of the nitrile-containing compound, and 2) does not interfere with the reaction between the nitrile-oxide groups and the terminal olefinic unsaturation. In addition, the nitrile oxide group is preferably not adjacent to another group of nitrile oxide. Examples of aromatic di (nitrile oxide) include: wherein each R 'is independently hydrogen, a hydrocarbyl, or an inertly substituted hydrocarbyl group, such as an alkyl, or inertly substituted alkyl or aralkyl, or a halogen, preferably Cl, since R' is sufficient to stabilize the groups of nitrile oxide (for example, the R 'groups adjacent to each group of nitrile oxide are a sterically hindered fraction, preferably methyl or ethyl; Z and Y can be a covalent bond, -O-, -S-, alkylene ( preferably -CH2- and -CH2CH2-), alkylene oxide (preferably -CH2-0-CH2), alkylene sulfide, -CF2-, and Y may additionally be: 0 0 R O R -S-, -S-, -Si-, -P-, -? _, 0 R R wherein Ar can be an aromatic hydrocarbon or a halogenated derivative thereof. Preferably, each R 'is independently hydrogen, methyl, or ethyl, with each R1 being selected to render the nitrile oxide sufficiently stable for its intended end use; and each Z or Y is -O-, -S-, -CH2-, -CH2-CH2-, or CH2-0-CH2. The preferred aromatic di (nitrile oxides) are: wherein R1 is as previously defined herein, preferably, each R1 is independently hydrogen, methyl, or ethyl, more preferably the R 'adjacent to the nitrile oxide groups are methyl or ethyl, and the remaining R' s are either hydrogen or halogen, preferably hydrogen; and Y is as defined hereinabove, preferably a covalent bond, -CH2-, -CH2CH2-, S02, or -CH2OCH2-. The most preferred aromatic di (nitrile oxides) are N, N'-tetramethylterephthalonitrile dioxide; N, N'-dioxide of 3,3'-alkylenebis (2,4,6-trimethylbenzonitrile); N, N'-4,4'-dioxide-alkylenebis (2,4,6-trimethylbenzonitrile); l-methyl-2,6-bis (nitrile oxide) phenyl sulfonate ester; N, N'-dioxide of 3,3 '- (1,2-ethanediyl) bis (2,4,6-trimethylbenzonitrile); N, N'-3, 3 'dioxide - a 1 qu i 1 n n is (5-c 1 or o - 2, 4, 6 -tr ime ti lbenz on i tr i lo), N,' -diioxide of 2,2'-sulfonylbis (benzonitrile); and 2,7-bis (nitrile oxide) anthracene, and oligomers of these compounds; 2, 6-bis (nitrile oxide) -1,3,5-triethylbenzene being more preferred. Representative examples of aromatic hydroxyl-containing nitrile oxide compounds include: wherein R ', x, z and y are as defined above in the present; being: the preferred aromatic hydroxyl-containing nitrile compounds. The polynitrile oxide or the hydroxyl-containing nitrile oxide compound can be prepared by techniques known in the art, and reference is made thereto for the purposes of the present invention. See, for example, Grundmann and Grunanger, Nitrile Oxides, Springer, New York, pages 31-61, which is incorporated herein by reference. For example, a di (nitrile oxide) can be prepared by: (i) reacting a primary alkyl nitrate with phenyl isocyanate; or (ii) reacting an aldehyde with hydroxylic amine to form a hydroxymoyl aldehyde (aldoxime), subsequently reacting the aldoxime with chlorine (in the form of chlorine anion (or bleach in the presence of an acid or a base to form a hydroxymoyl chloride, and then reacting the hydroxymoyl chloride with base to form a nitrile oxide group (see, for example, U.S. Patent No. 3,717,560, issued February 20, 1973), which is incorporated herein by reference, or (iii) adding 2-chloroacetyl chloride to an aromatic ring by addition of Friedel-Crafts in the presence of a Lewis acid, reacting the acetyl chloride pendant with nitric acid to form a hydroxyalmoyl chloride, and reacting the hydroxymoyl chloride with base to form a nitrile oxide group (see, for example, "One-Component Sealant Based on 1, 3-Dipoles", volum in 32, J. App. Poly. Sci. 4657 (1986)), which is incorporated herein by reference. The nitrile oxides having a hydroxyl group are prepared using similar techniques.

In an alternative embodiment, the nitrile oxide can be prepared on site, that is, it can be prepared in the polyol composition, and the nitrile oxide thus prepared is reacted with terminal unsaturation. For example, a suitable di (poly) idroxyamoyl chloride or hydroxyl-containing hydroxyalloyl chloride can be added after the preparation of the polyol composition, preferably before the catalyst is removed. The basic catalyst or acid which is commonly used in the preparation of the polyol composition, can convert the hydroxymoyl chloride to a nitrile oxide for subsequent reaction with the terminal unsaturation. In this case, the nitrile oxide does not need to be, and preferably is not sterically hindered. Alternatively, a compound containing furoxane, for example, a compound of the formula C2R "2N202, that is: c wherein each R "is independently a hydrocarbyl, or an inertly substituted hydrocarbyl, or both R" together form a cyclic or bicyclic group (bridged). As described in Advances in Heterocyclic Chemistry, volume 29, pages 251-340, "Furoxans and Benzofuroxans", by A. Gaseo and AJ Boulton, particularly on pages 287-289, the furoxane ring can be thermally opened, or it can thermally dissociate to form a dinitrile oxide of the hydroxy-containing nitrile oxide. Representative examples of these groups include proxan itself, ie, C2H2N202, and camphorfuroxane. In the practice of the present invention, the hydroxyl-containing compound having unsaturation is contacted with the polynitrile oxide or the hydroxyl-containing nitrile oxide compound, in an amount and under conditions such that the nitrile reacts with the unsaturation of the hydroxyl-containing compound. In general, the hydroxyl-containing compound having unsaturation is a component of a polyol composition, and the unsaturation is a terminal unsaturation; the hydroxyl-containing compound being frequently a monol having terminal unsaturation. Although the amounts of the nitrile oxide and the most conveniently used conditions will vary depending on the specific nitrile oxide compound and the polyol composition employed, in general, the polyol composition is contacted with sufficient amounts of the nitrile oxide compound. to react the desired amount of the unsaturation with the nitrile oxide. Conveniently, the nitrile oxide is employed in an amount that provides at least one stoichiometric equivalent or a stoichiometric excess of nitrile oxide groups relative to the unsaturation. Conveniently, the nitrile oxide is employed in an amount of at least 0.8, preferably at least 0.9, and more preferably at least 0.95 equivalents of nitrile oxide groups per terminal unsaturated groups. Conveniently, the nitrile oxide is employed in an amount of less than 2, preferably less than 1.5, and more preferably less than 1.25 equivalents of nitrile oxide group per terminal unsaturated group. More preferably, the nitrile oxide compound is used in an amount such that the resulting mixture of the nitrile oxide and polyol composition comprises from 1 to 1.1 equivalents of nitrile oxide groups per unsaturated groups. The reaction of the nitrile oxide and unsaturated groups can usually take place at room temperature (eg, at 25 ° C), and the composition of nitrile oxide and polyol compound can simply be mixed at these temperatures for the reaction. However, depending on the desired reaction rate, temperatures as low as -10 ° C to 200 ° C or higher can be used, with temperatures of 10 ° C to 150 ° C being preferred. At these temperatures, the reaction is completed within a couple of seconds to 100 hours. At ambient temperatures, the reaction is substantially completed within 30 minutes to 48 hours. At an elevated temperature of 110 ° C to 150 ° C, the reaction is terminated substantially in less than 1 hour, more generally in less than 30 minutes, and preferably in less than 10 minutes. Although not bound by theory, the reaction of the nitrile oxide and the unsaturation of the polyol is believed to be represented by the reaction of a di (nitrile oxide) and a polyol having terminal unsaturation: -0 + N = C -R2-C = N + 0 ~ + 2 (CH2 = CH-C0 (CH2-CH (R)) n-0H or the reaction of a nitrile oxide hydroxide with a polyol having terminal unsaturation: ~ 0 + N = C-R 3 -OH + CH2 = CH-CC (CH2-CH (R)) p- CH wherein R, R, and R are as previously described herein. In any case, the compound formed in the reaction does not have terminal unsaturation, and preferably only has hydroxyl end groups. It is believed that the resulting polyol has isoxazoline groups (ie: Preferred polyol products have the formula: wherein R, R, x and n are as previously defined herein. The nitrile oxide and the polyol can be contacted essentially at any time following the preparation of the polyol. When the nitrile oxide is prepared at the site, it is preferably contacted with the polyol composition before removing the catalyst. Subsequent to the reaction of the nitrile oxide and the terminal unsaturation, the resulting product can be purified using conventional techniques. When a polynitrile oxide prepared separately is added to the polyol composition, the polynitrile oxide is preferably added immediately after removing the catalyst from the reaction product, more preferably after purification but before stabilization of the product. Following the reaction of the nitrile oxide with the polyol composition, the composition can be stabilized using conventional techniques, and subsequently used without further treatment. The following examples are presented for the purpose of illustration only. They should not be taken as limiting the scope of either the specification or the claims. Unless otherwise reported, all parts and percentages are by weight.

Example 1 71.13 grams (g) (0.1 moles) of a monol initiated with allyl alcohol of a copolymer of ethylene oxide and propylene oxide having an -OH content of 2.39 percent, a vinyl unsaturation of 3.58 percent ( 1.34 milliequivalents / gram), and a viscosity of 32 centipoise at 100 ° F (38 ° C), were dissolved in 25 grams of anhydrous tetrahydrofuran at room temperature in a round bottom flask equipped with a magnetic stirrer. While stirring the resulting solution, 6.10 grams (0.025 mole) of 2,6-bis (nitrile oxide) -1,3,5-triethylbenzene was added over a period of 30 seconds to 1 minute at room temperature. Then the mixture was stirred at room temperature for 3 days. At the end of this period, the Fourier Transform Infrared (FTIR) test indicated that all of the nitrile oxide had reacted. The results of this test showed the efficacy of reacting the terminal unsaturation with a dinitrile oxide. Similar results were obtained with additional allyl alcohol initiated monools of a copolymer of ethylene oxide and propylene oxide, with an hydroxy equivalent weight of 1414; butylene oxide polymers with equivalent hydroxy weights of 346, 418, or 900; and an ethylene oxide polymer with an equivalent hydroxy weight of 498.

Example 2 To 35 grams of a glycerin initiated polyol (Voranol ™ 5815 from The Dow Chemical Company) with an average molecular weight of 5,000 (corresponding to an hydroxyl equivalent weight of 1667), and 0.072 milliequivalents of monol per gram (meq / g) of polyol (measured by the degree of unsaturation), which corresponds to 27.3 mole percent of monol in a round bottom flask, was added a stoichiometrically equivalent amount of N, N'-tetramethylterephthalonitrile dioxide (0.3074 grams). The flask was placed in an oil bath maintained at 110 ° C. The solid dinitrile oxide was dissolved in 5 to 10 minutes in the polyol composition. The polyol composition was continuously stirred during the addition of the nitrile oxide and subsequently. 30 minutes after finishing the dissolution of dinitrile oxide compound, a sample was taken out of the mixture and cooled in a refrigerator at 8 ° C. This sample was then analyzed using Fourier Transform Infrared (FTIR), which indicated that the residual unsaturation was 0.012 milliequivalents / gram. Using the same analytical techniques, the samples removed at the time, at 1.5 hours, at 2 hours, at 2.5 hours, and at 3 hours after the complete dissolution of the dinitrile oxide. They show the same milliequivalents / gram of unsaturation; indicating the effectiveness of a dinitrile oxide in the reduction of unsaturation.

Example 3 Using techniques similar to those of Example 2, to 20 grams of a diol initiated with propylene glycol (VoranolMR 2140 from The Dow Chemical Company) with a molecular weight of 4,000 (a nominal hydroxyl equivalent weight of 2,000), and with 0.129 milliequivalents / gram of monol (measured by the degree of unsaturation), corresponding to 41.8 mole percent of monol, was added a stoichiometrically equivalent amount of N, N'-tetramethylterephthalonitrile dioxide (0.3148 grams). The resulting mixture was placed in an oil bath maintained at 50 ° C, and the solid dinitrile oxide is dissolved in 45 to 60 minutes. Approximately 2 hours after the dissolution of the dinitrile compound was finished, a sample was taken out of the mixture, and measured by titration with mercuric acetate, as described in ASTMD-2849-69, to have 0.064 milliequivalents / gram of unsaturation . A sample taken at 4 hours showed 0.05 milliequivalents / gram of unsaturation, and at 8 hours, 0.028 milliequivalents / gram. In a similar manner, except that the oil bath was maintained at 80 ° C, Voranol ™ 2140 was treated with a stoichiometric amount of N, N'-tetramethylterephthalonitrile dioxide. At this temperature, the dinitrile oxide dissolved in 10 minutes. It was found that a sample taken at 2 hours using the techniques described above (ASTMD-2849-69) had unsaturation of 0.024 milliequivalents / gram. After 4 hours, the unsaturation was measured at 0.017 milliequivalents / gram. In a similar manner, except that the dinitrile oxide was added over a period of 5 minutes, and the oil bath was heated to 110 ° C, the VoranolMR 2140 was treated with a stoichiometric amount of N, N'-tetramethylterephthalonitrile dioxide. . At this temperature, the dinitrile oxide was dissolved essentially immediately in the polyol composition. 15 minutes after finishing the addition of dinitrile oxide. It was found that the sample contained 0.014 milliequivalents / gram of unsaturation (ASTMD-2849-69). The polyol composition showed similar levels of unsaturation 30 and 60 minutes after the addition of the dinitrile oxide was completed. This example showed the effectiveness of dinitrile oxide to reduce unsaturation. The effectiveness of the dinitrile oxide and the speed of the reaction depended on the temperature and the contact time between the dinitrile oxide and the polyol composition.

Example 4 To a sample of 350 grams of a triol of propylene oxide initiated with glycerin capped with ethylene oxide (VoranolMR 4701 from The Dow Chemical Company), with a molecular weight of 5000 (a nominal hydroxyl equivalent weight of 1667), and 0.067 milliequivalents / gram of monol (measured by the degree of unsaturation) maintained at 105 ° C in a round bottom flask, was added, with stirring, a stoichiometrically equivalent amount of N, N'-tetramethylterephthalonitrile dioxide. in 10 equal additions of 0.286 grams each. The solid dinitrile oxide was dissolved essentially immediately upon addition in the polyol composition. 5 minutes after the dissolution of the dinitrile compound was finished, a sample of the mixture was taken out and found to contain 0.025 milliequivalents / gram of unsaturation (ASTMD-2849-69). At 15 minutes after the addition of dinitrile oxide was complete, it had been reduced to 0.20 milliequivalents / gram of unsaturation. At 30 minutes, it was found that the unsaturation was 0.016 milliequivalents / gram, and at 60 minutes, the unsaturation was 0.013 milliequivalents / gram. Using the same procedure as described above, Volanol ™ 5815 unsaturation was reduced from an initial unsaturation of 0.07 milliequivalents / gram to 0.031 milliequivalents / gram in 5 minutes, 0.022 milliequivalents / gram in 5 minutes. 0.022 milliequivalents / -gram in 15 minutes, 0.019 milliequivalents / gram in 30 minutes, and 0.016 milliequivalents / gram in 60 minutes.

Example 5 To a 700 gram sample of Voranol ™ 2140, maintained at 110 ° C under a nitrogen atmosphere, a stoichiometric amount (11.02 grams) of N, N'-tetramethylterephthalonitrile dioxide was added with continuous stirring over a period of time. 5 minutes The resulting mixture was stirred and maintained at 110 ° C for 15 minutes, and then the sample was rapidly cooled in a refrigerator at 8 ° C. It was found that the unsaturation had been reduced to 0.023 milliequivalents / gram (ASTMD-2849-69). Using the same techniques, the unsaturation of VoranolMR 4701 was reduced from 0.067 milliequivalents / gram to 0.012 milliequivalents / gram, and VoranolMR 5815 unsaturation is reduced from 0.72 milliequivalents / gram to 0.017 milliequivalents / gram.

Example 6 To a sample of 100 grams of VoranolMR 2140 (unsaturation of 0.129 milliequivalents / gram) maintained at 100 ° C, under a nitrogen atmosphere, 105 percent of the stoichiometric amount of camphor-hexane was added (1.32 grams), which dissolved essentially immediately upon addition. The resulting mixture was stirred continuously, and its temperature was maintained at 100 ° C. Samples were taken after 2, 4, and 6 hours, and were tested for unsaturation (ASTMD-2849-69). The results of this test, as well as the test results of other samples of VoranolMR 2140 treated under the same conditions, except that the mixtures were maintained at the temperature of 120 ° C and 130 ° C, are stipulated in Table I.

Table 1 Unsaturation at temperature and in Time, hours specified, meq / q 100 ° C 120 ° C 130 ° C 0 0.129 0.129 0.129 2 0.107 0.080 0.057 4 0.098 0.065 0.052 8 0.084 0.048 0.044 As indicated in Table I, camphor hexane, a compound that formed nitrile oxide at the site, reduces the unsaturation of the polyol composition. The amount and speed at which the unsaturation was reduced depended on the temperature of the polyol composition. The same procedure was repeated, but the polyol composition was maintained at 140 ° C. After 24 hours, the unsaturation was reduced to 0.048 milliequivalents / gram, and after 48 hours, it was reduced to 0.045 milliequivalents / gram. The same procedure was repeated, but 150 percent of the stoichiometric amount of the camphor roxane was added to a new sample of VoranolMR 2140 maintained at 130 ° C. After 1 hour, the unsaturation of the polyol composition dropped to 0.039 milliequivalents / gram. After 8 hours of reaction, the unsaturation dropped to 0.032 milliequivalents / gram, and after 24 hours, it dropped to 0.026 milliequivalents / gram.

Example 7 In a manner similar to that of Example 5, to a 100 gram sample of VoranolMR 4701 (unsaturation of 0.067 milliequivalents / gram) maintained at 120 ° C, under a nitrogen atmosphere, 150 percent of the stoichiometric amount (0.975 grams) of camphor roxane, which was dissolved essentially immediately upon addition. After 4 hours at this temperature, it was found that the unsaturation had been reduced to 0.036 milliequivalents / gram (ASTMD-2849-69). After 8 hours, the unsaturation was reduced to 0.029 milliequivalents / gram, and after 24 hours it was reduced to 0.027 milliequivalents / gram. In a similar way, a sample of 100 grams of VoranolMR 5815 (unsaturation of 0.072 milliequivalents / gram) maintained, under a nitrogen atmosphere, at 120 ° C, was added 150 percent of the stoichiometric amount of camphor-hexane (1.019). grams), which dissolved immediately upon addition. After 4 hours of holding at this temperature, the unsaturation was reduced to 0.028 milliequivalents / gram (ASTMD-2849-69). After 8 hours at this temperature, the unsaturation was reduced to 0.027 milliequivalents / gram, and after 24 hours, it was reduced to 0.026 milliequivalents / gram. Example 8 To 2500 grams of Voranol * 11 * 4701 (unsaturation of 0.067 milliequivalents / gram) maintained at 115 ° C, under a nitrogen atmosphere, 20.74 grams of tetramethylterephthalonitrile N, N'-dioxide (100 percent of the stoichiometric amount) were added. This mixture was stirred for 30 minutes, and an additional 1.24 grams (5 percent of the stoichiometric amount) of N, N'-tetramethylterephthalonitrile dioxide was added. The mixture was stirred for an additional 1.5 hours. At this time, it was found that the unsaturation was 0.0081 milliequivalents / gram. This example indicated that sequential addition of the nitrile oxide compound may be more effective in reducing unsaturation than a single addition of nitrile oxide. Example 9 To 500 grams of VoranolMR 4701 (unsaturation of 0.068 milliequivalents / gram) maintained at 115 ° C, under a nitrogen atmosphere, an equivalent amount (1584 grams) of 3-hydroxymethyl-2,4,6-oxide was added. -triethylbenzonitrile, a mononitrile oxide having a hydroxyl group. This solid material dissolved essentially immediately upon addition. This mixture was stirred for 3 hours. At this time, no unsaturation was found in the tested composition.

Claims (1)

1. CLAIMS. A composition comprising (a) a polyol of the formula: ((CH2-CH (R1) -O) n-H) m wherein I is a starter residue; R1 is a hydrogen or alkyl, each time it occurs; n is an integer from 1 to 200; and m is an integer from 2 to 8 and (b) a poole having a portion of isoxazoline 2 The composition of claim 1, wherein the component (b) is the reaction product of a hydroxyl-containing compound that is hydrated and a nitrile oxide 3 The composition of claim 2, wherein the component (b) is the reaction product of a propoxylated ring alcohol and a nitro oxide 4 A composition comprising (a) a polyol of ether having a base structure of poly (propylene oxide / ethylene oxide) or a base structure of poly (propylene oxide) and (b) the reaction product of a nitrile oxide with an alcohol of propoxylated allyl The composition of claim 4, wherein the nitrophoxide is a polynitropic oxide represented by the formula R2- (C = N + -O ") x or a mononitroxide oxide hydroxide represented by the formula HO -R3- (C = N + -0 ') wherein R2 and R3 are organic portions which may contain an aromatic, aliphatic or combination of aromatic and aliphatic groups, including aliphatic or aromatic groups substituted inertly; and x is from two to six. 6. The composition of claim 5, wherein the nitrite oxide is a di (nitrile oxide) of the formula: wherein R 'is independently hydrogen, hydrocarbyl, inertly substituted hydrocarbyl, aralkyl, or halo so long as the R' groups are sufficient to stabilize the nitryl oxide groups; each Z and Y is a covalent bond, -O-, -S-, alkylene, alkylene oxide, alkylene sulfide, -CF2- and Y can additionally be: OOROR -S-, -S-, -Si-, - P-, -P-, or ORR wherein Ar can be an aromatic hydrocarbon or halogenated derivative thereof. The composition of claim 6, wherein the R 'groups adjacent to the nitrile oxide group are a spherical concealing portion when the nitrile oxide is not formed in situ and each Z and Y are independently alkylene, alkylene oxide or alkylene sulfide. The composition of claim 7, wherein the R 'groups adjacent to the nitrile oxide group are methyl or ethyl and each of Y or Z is -CH2- -CH2CH2-, or -CH2-O-CH2-. 9. The composition of claim 5, wherein the nitrile oxide is a compound of the formula: -M. \ N "CR wherein each R "is independently a hydrocarbyl or inertly substituted hydrocarbyl group or both R" together form a cyclic or bicyclic ring (bridged). The composition of claim 6, wherein the aromatic di (nitrile oxide) is wherein each R 'is independently hydrogen, hydrocarbyl, inertly substituted hydrocarbyl, aralkyl or halo provided that the R' groups are sufficient to stabilize the nitroxide groups, and each Z and Y is a covalent bond, -O-, -S-, alkylene, alkylene oxide, alkylene sulfide or -CF2-11 The composition of claim 10, wherein the R 'groups adjacent to each nitrophoxide group are methyl or ethyl and each Y or Z is - CH2, -CH2CH2-, or -CH2-0-CH2- 12 The composition of claim 11, wherein the aromatic d? (Oxo of nitplo) is N, N'-d? Ox? Do of tetramethylterephthalonitplo 13. The composition of claim 4, wherein the nitrile oxide is a nitrile oxide of the formula: wherein R 'is independently hydrogen, hydrocarbyl, inertly substituted hydrocarbyl, aralkyl, or halo. The composition of claim 1, wherein the component (b) comprises a compound of the formula: The composition of claim 1, wherein the nitrophoxide is N, N'-d? Oxeta of tetramethyloterephthalonitop, N, N'-d? Oxeta of 3,3-alkylennob? , 4,6-tr? Met? Lbenzon? Tr? Lo), 1-met? L-2 sulfonate ester, 6-b? S (oxide of n? Tr? Lo) -fen? Lo, N, N'-d? Óx? Do of 3,3 '- (1,2-ethano? -? L) b ? s (2,4,6-tr? met? lbenzon? tr? lo), N, N? -d? ox? of 3,3-alk? a? b? s (5-chloro-2,4,6 -tr? met? l-benzon? tr? lo), or N, N'-d? óx? of 2,2'-sulfon? lb? s (benzon? tr? lo) 16 An improved method to prepare a polyol by reacting an alkylene oxide, at least a portion of which is propylene oxide, with an initiator, the improvement comprising reacting at least a portion of the unsaturation in the reaction product with a nitrophoxide 17 The method of claim 16 wherein the alkylene oxide unsaturation is terminal unsaturation and the nitroxide oxide is reacted with propoxylated linolenol alcohol. The method of claim 16, wherein the polyol is a polyether polyol having the general structural formula l ((CH2-CH (R1) -O) nH) m wherein I is an initiating residue R1 is a hydrogen or alkyl each time it occurs, n is an integer from 1 to 200 and m is a nu whole number from 2 to 8 The method of claim 18 wherein I is a hydroxy or the residue of an organic active hydrogen initiator each R 'independently is hydrogen, methyl or ethyl; n is from 2 to 100; and m is from 2 to 4. The method of claim 16, wherein the nitrile oxide is a polynitrile oxide represented by the formula: R2- (C = N + -O-) "or a mononitrile oxide hydroxide represented by the formula: HO-R3- (C = N + -O ") wherein R2 and R3 are organic portions which may contain an aromatic, aliphatic or combination of aromatic and aliphatic groups, including aliphatic or aromatic groups substituted inertly; is from two to six 21. The method of claim 20, wherein the nitrile oxide is a di (nitrile oxide) of the formula: wherein R 'is independently H, hydrocarbyl, inertly substituted hydrocarbyl, aralkyl, or halo so long as the R' groups are sufficient to stabilize the nitrile oxide groups; each Z and Y is a covalent bond, -O-, -S-, alkylene, alkylene oxide, alkylene sulfide, or -CF2-. 22. The method of claim 21, wherein the R 'groups adjacent to each nitrile oxide group are methyl or ethyl and each Y or Z is -CH2, -CH2CH2-, or -CH2-O-CH2-. 23. The method of claim 16, wherein the nitrile oxide is a compound of the formula: fA \ N '• CR wherein each R "is independently a hydrocarbyl or inertly substituted hydrocarbyl group or both R" together form a cyclic or bicyclic ring (bridged). The method of claim 16, wherein the di (oxime of nitrile) is N, N'-dioxido of tetramethyl-terephthalonitrile, or oxide of 2,6-b? Snitr? Lo-1,3, 5-tr? Et? Lbenceno 25. The method of claim 16, wherein the nitrile oxide is a nitrile oxide of the formula: wherein R 'is independently hydrogen, hydrocarbyl, inertly substituted hydrocarbyl, aralakyl or halo. 26. A polyol composition comprising a polyol having two or more terminal hydroxyl groups and a portion of isoxazoline. R ESU M EN The unsaturation of a hydroxyl-containing compound can be reduced by the reaction with a nitrile oxide compound such as N, N'-trimethylterephthalonitrile dioxide. The reaction of a nitrile oxide with terminal unsaturation associated with the preparation of a propylene oxide polyol reduces the monol content of the polyol composition.