The pure adduct of 2 moles of ethylene oxide (EO) and 1 mole of hydroquinone (HQ) is very crystalline and is believed to be desirable to get the best properties. However, for practical reasons, the pure adduct of 2 moles of EO and 1 mole of HQ is not available commercially. During ethoxylation of HQ with EO, due to kinetics, in addition to the desirable adduct, one also gets, mono adduct, triadducts, and higher adducts. In addition, the solvent used in the process also imparts impurities. Therefore, on a commercial scale, the HQEE grades available have 1-10% of non-desirable species and 99-90% of pure adduct (2 moles EO and 1 mole HQ). The impurities lower the final part properties and cause color instability for HQEE when HQEE is exposed to heat and/or oxygen. That is the color of HQEE goes up with time and temp. In many plants, HQEE is processed at elevated temp and there the color of HQEE goes up leading to parts, which are high in color. The color increase is very significant when light or pastel color parts are to be produced. Therefore, a practical method to stabilize the color of generally available grades of HQEE is desired and this invention provides such solution.

2. Brief Description of Art It is well known that hydroquinone hydroxyethyl ethers (HQEE) are used for manufacturing of polyurethanes. Commercial grade hydroxyethyl ethers of hydroquinone contain >90% of hydroquinone bis (2-hyroxyethyl) ether. Due to the impurities contained in the product, they have tendency to discolor especially at higher temperatures.

Hydroxyethyl ethers of hydroquinone are solids at room temperature and for application purposes are kept in molten condition. At increased temperature discoloration proceeds faster and there is a need for color stabilization to allow the use in color sensitive applications.

Color stabilization of hydroquinone hydroxyethyl ethers using phosphite type color stabilizer have been described in US Patent 3592858. According to the disclosure the phosphite molecule consists of either one or two cyclic phosphite groups attached to an aryl-or cycloalkyl ring. The result of color stabilization was not good enough to protect against discoloration for prolonged usage especially with commercial grades of hydroquinone hydroxyethyl ethers.

DETAILED DESCRIPTION OF THE INVENTION Antioxidants are known to be color stabilizers for many products and processes involving exposure to oxygen or heat. Many general mechanisms as to how the antioxidants work have been proposed in the literature. However, a variety of factors such as polymer structure, polymer processing conditions, (time, temp, pressure), and antioxidant structure, decide which antioxidant or combination of antioxidants work the best. For the current problem on hand, several chemistries were evaluated as stabilizers for hydroquinone hydroxyethyl ether products (HQEE) including: phenolic based-2,6-di-t- butyl-p-cresol, Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydroconnamate)] methane, 2,2-oxalydiamidobis [ethyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) ] propionate; acyclic phosphite based-Tris (2,4-di-t-butylphenyl) phosphite, Tris (nonylphenyl) phosphite ; cyclic phosphite based-2,4, 6 tri-t-butylphenyl 2 butyl 2 ethyl 1,3 propane diol phosphite and bis-cyclic phosphite based-Diisodecyl Pentaerythritol Diphosphite, Bis (2,4-di-t- butylphenyl) Pentaerythritol, Distearyl Pentaerythritol Diphosphite.

It has been surprisingly found, in accordance with the present invention, that phosphite compounds containing the double ring structure of bis cyclic phosphites, that are attached to the same tertiary carbon atom were very efficient in color stabilization of hydroquinone hydroxyethyl ethers and any present impurities. The phenolic-based antioxidants were found to afford no improvement in color stability and some of the products evaluated lead to an increased in color. In contrast to the prior art where the color stabilizer used was a phosphite, which had a molecule with either one cyclic phosphite group or two groups that were attached para on an aryl-or cycloalkyl ring the color stabilizer used according to the present invention have a spiro ring structure in which the two rings are attached to the same tertiary carbon atom. Color stabilization effect of the phosphite used in the previous art (US patent # 3,592, 858) was found to show a slight

improvement, but not sufficient to be used with commercial HQEE, the present inventors have surprisingly discovered that phosphite compounds containing double ring structure, which are attached to the same tertiary carbon atom in the phosphite molecule, are very efficient in color stabilization of hydroxylalkyl ethers of hydroquinone. Preferably such hydroxylalkyl ethers of hydroquinone contain >80% of pure adduct of 2 moles of EO and 1 mole of hydroquinone and most preferably contain >90% of pure adduct of 2 moles of EO and 1 mole of hydroquinone. Commercial hydroxyalkyl ethers of hydroquinone typically contain >90% of pure adduct of 2 moles of EO and 1 mole of hydroquinone and contain <10% of other species of which the triether (3 moles of EO and 1 mole of hydroquinone) is the predominant specie. Suitable phosphite compounds containing double ring structure of cyclic phosphates, which are attached to the same tertiary carbon atom in the molecule are phosphites like commercially available Weston 619F, and Doverphos 1220. The antioxidants of this type were evaluated to optimize the usage level that was determined to be between 0.2% to 3% and most preferably between 0.5 and 1.0%.

It is believed that phosphite compounds containing double ring structure of cyclic phosphites, which are attached to the same tertiary carbon atom in the molecule have the optimal chemical structure. This is because two phosphite rings attached to the same tertiary carbon atom are in sterically stressed state The color stabilizing agents disclosed here can be added during the manufacturing of hydroxyalkyl ethers of hydroquinone or could be post added. If added during the manufacturing, they can help to produce a lower initial color product. Also, the polyurethane articles produced from color stabilized HQEE display lighter initial color and enhanced color stability.

R1 and R2 can be aromatic ring with orwithoutsubstituents R, and R2 can be any akyl or cycloalkyl group R and R2 can be same ordifferent The present invention is further described in detail by means of the following Examples and Comparisons. All parts and percentages are by weight and all temperatures are degrees Celsius unless explicitly stated otherwise.

EXAMPLE 1 Experimental Procedure: Commercial HQEE with the following analysis was used to evaluate the effectiveness of antioxidants. The analysis was Diether hydroquinone (2 moles EO plus 1 mole hydroquinone) -92%, Triether of hydroquinone (3 moles of EO plus 1 mole of hydroquinone)-7%, other-1%. To 14 gram samples of this HQEE, we initially compared the antioxidants of Table 1 by adding the antioxidant in an amount of 1% based on the weight of the mixture. The mixture was heated to 150C, under nitrogen, and the colors of the mixtures were compared at 4 hours after mixing. The colors after 4 hours were compared using an approximation of the Gardner color for the molten HQEE material. The Gardner color results are given in Table 1 below.

TABLE 1 AO Chemistry CAS Form Gardner Color 4 hours at 150C Weston Flakes 1-2 GE Specialty Chemicals DiphosphiteAliphatic-Bis 0-M "Q cyclic phosphite/ 0-H/\ e-. Hd cnsj-o v Naugard BHT 6-di-t-butyl-p-cresol phenolic 128-37-0 Crompton Irganox 1010 Tetrakis [methylene (3, 5-di-t- Powder 16 Ciba butyl-4- hydroxyhydroconnamate)] meth ane Phenolic Wytox Tris (nonylphenyl) phosphite 26523-78-4 Me- (CH 2) 8 Liquid 10 Crompton Aromatic-Acyclic phosphite Me- ULo JL-0-P-O'J &num TABLE 1 - CONTINUED AO Chemistry CAS Form Gardner Color 4 hours at 150C Naugard Phenolic-organic Acyclic Not Liquid 6-7 Crompton Naugard 2, 2-oxalydiamidobisfethyl Powder 8 Crompton 3- 5-di-t-butyl-4- hydroxyphenyl) propionate I Phenolic-based Naugard Tris (2, 4-di-t- Powder >18 Crompton butylphenyl) phosphite rli Aromatic-Acyclic phosphite t-Bu .. t-bru t-Bu Doverphos 1220 Diisodecyl Pentaerythritol 26544-27-4 Liquid 1-2 Dover Diphosphite. (cyclic bis Chemicals phosphite) <iso-CioH2l)-0--P'X. O 0 0

Table 2 below shows the results. As can be seen from Table 2, the most effective agents were Weston 619F (sample 2), and Doverphos 1220 (sample 10). As can be seen, for the 4 hours reading the control shows that the color goes up from 1 Gardner to 16 and for the additives of this invention, the color ranges between 1 to 2 Gardner.

TABLE 2 Sample Antioxidant Initial HQEE HQEE Gardner Color- Gardner Color 4 hours at 150C 1 None-Control 1 16 2 Weston 619F >1 but <2 3 Naugard BHT 1 16 4 Irganox 1010 1 16 5 Wytox 312 1 10 6 Ultranox 641 1 5 7 Naugard 492 1 6-7 8 Naugard XL-1 8 9 Naugard 524 1 >18 10 Doverphos 1220 1 >1 but <2 Notes : #1 is the control sample without any antioxidant ; &num 2 and #10 are preferred examples of the invention; &num 3, &num 4, &num 5, &num 7, #8 and #9 are comparative examples. And #6 is an example from prior art patent # 3,592, 858.

HQEE Color-approximate Gardner color for molten HQEE While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims.