Abstract:
The present invention provides a method for alkoxylating organic compounds comprising contacting an organic compound adapted to be alkoxylated with an alkylene oxide in a reaction vessel under conditions effective to alkoxylate the organic compound. The alkylene oxide is maintained in vapor form during transport to said reaction vessel, during discharge into said reaction vessel, and during contacting of the organic compound with the alkylene oxide. The result is an alkoxylated product containing less flocculant.

Description:
FIELD OF THE INVENTION  
         [0001]    The present invention is a method for alkoxylating organic compounds, preferably polyalkylene glycols, by exposing the organic compounds to alkylene oxide vapor which is not compressed into a liquid phase for purposes of transport or introduction into the reactor The method results in alkoxylation products containing less, little, or no flock.  
         BACKGROUND OF THE INVENTION  
         [0002]    A variety of organic materials react under suitable conditions with an adducting material, such as an alkylene oxide—particularly ethylene oxide or propylene oxide—to form alkoxylated organic materials. Typically, the alkylene oxide adducting material is compressed into liquid form for transport to and discharge into the reactor. Unfortunately, even if the alkylene oxide is decompressed into the vapor phase before the alkoxylation reaction begins, the previous compression of the alkylene oxide into the liquid phase tends to increase flock in the alkoxylation product. A method is needed by which to form alkoxylated products containing no, little, or less flock.  
         SUMMARY OF THE INVENTION  
         [0003]    The present invention provides a method comprising contacting an organic compound adapted to be alkoxylated with an alkylene oxide in a reaction vessel under conditions effective to alkoxylate the organic compound. The alkylene oxide is maintained in vapor form before and during transport to said reaction vessel, during discharge into the reaction vessel, and during contact with the organic compound.  
         DETAILED DESCRIPTION OF THE INVENTION  
         [0004]    The present invention provides a method for producing an alkoxylation product with no, little, or less flock According to the present method, the alkylene oxide adducting material is not compressed into liquid form in order to transport and/or to introduce the material into the alkoxylation reactor. The alkylene oxide is both transported and discharged into the reactor in the vapor phase. Without limiting the present invention to any particular theory or mechanism, it is believed that compression of ethylene oxide into the liquid phase produces minute amounts of oligomers or polymers which contribute to the formation of flock in the substrate The present invention is believed to reduce flock by avoiding the formation of these oligomers or polymers in the alkylene oxide The alkoxylation reaction, itself, takes place under standard conditions. The reaction takes place at any suitable temperature, preferably from about 10° C. to about 160° C. For practical purposes, most commercial operations will be carried out in the temperature range of from about 50° C. to about 200° C. The method is useful to alkoxylate any suitable alkoxylatable organic material Suitable materials include, but are not necessarily limited to polyhydric, unsaturated, linear or branched alcohols, saturated alcohols, alkyl phenols, polyols, aldehydes, ketones, amines, amides, organic acids, and mercaptans. Preferred organic materials are normally selected from the group consisting of  
           [0005]    (a) polyhydric alcohols containing a total of from about 2 to about 30 carbon atoms and having the general formula  
                         
 
           [0006]    wherein R 1 , R 2 , and R 3  independently are selected from the group consisting of linear and branched acyclic groups, alicyclic groups, aryl groups, cyclic groups, and hydrogen, and may contain one or more functional groups selected from the group consisting of amine groups, carboxyl groups, hydroxy groups, halogen atoms, nitro-groups, carbonyl groups, and amide groups Representative but non-exhaustive examples of various polyhydric alcohols which can be alkoxylated according to the present invention are: ethylene glycol, 1,2-propylene glycol; 1,4-butanediol; 1,6-hexanediol, 1,10-decanediol; 1,3-butylene glycol, diethylene glycol, diethylene glycol monobutyl ether; diethylene glycol monomethyl ether; diethyl glycol monoethyl ether, dipropylene glycol; dipropylene glycol monomethyl ether; ethylene glycol monomethyl ether; ethylene glycol monoethyl ether; ethylene glycol monobutyl ether; hexylene glycol; mannitol, sorbitol, pentaerythritol; dipentaerythritol, tripentaerythritol; trimethylolpropane; trimethylolethane; neopentyl glycol; diethanolamine; triethanolamine; diisopropanolamine; triisopropanolamine; 1,4-dimethylolcyclohexane; 2,2-bis(hydroxymethyl)propionic acid; 1,2-bis(hydroxymethyl)benzene; 4,5-bis(hydroxymethyl)furfural; 4,8-bis(hydroxymethyl)tricyclo-[5,2,1,0]decane; tartaric acid; 2-ethyl-1,3-hexanediol, 2-amino-2-ethyl-1,3-propanediol; triethylene glycol; tetraethylene glycol; glycerol; ascorbic acid Representative but non-exhaustive examples of various aldehydes and ketones which can be alkoxylated according to the present invention are lauryl aldehyde; benzaldehyde, 2-undecanoneacetophenone; 2,4-pentandione, acetylsalicyclic acid, ortho-chlorobenzaldehyde; para-chlorobenzaldehyde; cinnamic aldehyde; diisobutyl ketone; ethylacetoacetate; ethyl amyl ketone; camphor, para-hydroxybenzaldehyde; 2-carboxybenzaldehyde; 4-carboxybenzaldehyde, salicylaldehyde, octyl aldehyde, decyl aldehyde, p-methoxybenzaldehyde; p-aminobenzaldehyde; phenylacetaldehyde; acetoacetic acid; 2,5-dimethoxybenzaldehyde, 1-naphthyl aldehyde; terephthaldehyde;  
           [0007]    (b) aldehydes and ketones having from about 2 to about 30 carbon atoms and having the general formula  
                         
 
           [0008]    wherein R 1  and R 2  independently are selected from the group consisting of hydrogen, linear and branched acyclic groups, alicyclic groups, cyclic groups, and aryl groups, and may contain one or more functionalities selected from the group consisting of carboxyl groups, hydroxyl groups, halogen atoms, nitro-groups, amine groups, and amide groups;  
           [0009]    (c) primary, secondary and tertiary amides having from about 1 to about 30 carbon atoms and having the general formula  
                         
 
           [0010]    wherein R 1 , R 2 , and R 3  independently are selected from the group consisting of hydrogen, linear and branched acyclic groups, alicyclic groups, cyclic groups, and aryl groups, and may contain one or more functionalities selected from the group consisting of hydroxyl groups, carboxyl groups, carbonyl groups, amine groups, nitro-groups, and halogen atoms. Representative but non-exhaustive examples of amides which can be alkoxylated according to the instant invention are: formamide, benzamide; acetanilide, salicylamide; acetoacetanilide, ortho-acetoacetotoluidide; acrylamide; N,N-diethyltoluamide; N,N-dimethylacetamide; N,N-dimethylformamide; phthalimide, octylamide; decylamide; laurylamide; stearylamide; N,N-dimethylollaurylamide; N,N-dimethylacrylamide, para-chlorobenzamide; para-methoxybenzamide; para-aminobenzamide; para-hydroxybenzamide; ortho-nitrobenzamide; N-acetyl-para-aminophenol; 2-chloroacetamide, oxamide, N,N-methylene-bis-acrylamide;  
           [0011]    (d) primary, secondary, and tertiary amines having from about 1 to about 30 carbon atoms, and having the general formula  
                         
 
           [0012]    wherein R 1 , R 2 , and R 3  independently are selected from the group consisting of hydrogen, linear and branched acyclic groups, alicyclic groups, cyclic groups, and aryl groups, and may contain one or more functionalities selected from the group consisting of hydroxyl groups, carbonyl groups, halogen atoms, carboxyl groups, nitro-groups, and amide groups. Representative but non-exhaustive examples of anines which can be alkoxylated according to the present invention are: aniline; benzylamine; hexadecylamine; triphenylamine; aminoacetic acid; anthranilic acid; cyclohexylamine; tert-octylamine; ortho-phenylenediamine; meta-phenylenediamine; para-phenylenediamine; N-acetyl-para-aminophenol; 2-amino-4-chlorophenol; 2-amino-2-ethyl-1,3-propanediol; ortho-aminophenol; para-aminophenol, para-aminosalicyclic acid; benzyl-N,N-dimethylamine; tert-butylamine; 2-chloro-4-aminotoluene; 6-chloro-2-aminotoluene, meta-chloroaniline; ortho-chloroaniline; para-chloroaniline, 4-chloro-2-nitroaniline; cyclohexylamine, dibutylamine, 2,5-dichloroaniline, 3,4-dichloroaniline, dicyclohexylamine; diethanolamine; N,N-diethylethanolamine, N,N-diethyl-meta-toluidine; N,N-diethylaniline; diethylenetriamine; diisopropanolamine; N,N-dimethylethanolamine; N,N-dimethylaniline; 2,4-dinitroaniline, diphenylamine; ethyl-para-aminobenzoate; N-ethylethanolamine; N-ethyl-1-naphthylamine; N-ethyl-ortho-toluidine; N-ethylaniline, ethylenediamine; hexamethylenetetraamine; 2,4-lutidine; N-methylaniline; methyl anthranilate; p,p′-diaminodiphenyl methane; ortho-nitroaniline, para-nitroaniline; tert-octylamine; piperazine, ethanolamine; isopropanolamine, ortho-toluidine, para-toluidine, 2,4-toluenediamine; triethanolamine; tributylamine; triisopropanolamine; 2,4-dimethylxylidine; para-methoxyaniline; nitrilotriacetic acid; N-phenyl-1-naphthylamine,  
           [0013]    (e) organic acids having from about 1 to about 30 carbon atoms, and having the general formula  
                         
 
           [0014]    wherein R 1  is selected from the group consisting of hydrogen, linear and branched acyclic groups, alicyclic groups, cyclic groups, aryl groups, and may contain one or more functionalities selected from the group consisting of carbonyl groups, hydroxyl groups, halogen atoms, nitro-groups, amine groups, and amide groups. Representative but non-exhaustive examples of organic acids which can be alkoxylated according to the present invention are formic acid; acetic acid; valeric acid; heptanoic acid; 2-ethylhexanoic acid; lauric acid; stearic acid; oleic acid; tall oil acids; hydrogenated tall oil acids; benzoic acid; salicyclic acid; adipic acid; azelaic acid; fumaric acid; citric acid; acrylic acid, aminoacetic acid, para-aminosalicyclic acid; anthranilic acid; butyric acid; propionic acid; ricinoleic acid; chloroacetic acid; ortho-chlorobenzoic acid, 2,4-dichlorophenoxyacetic acid, tert-decanoic acid; para-aminobenzoic acid; abietic acid; itaconic acid, lactic acid; glycolic acid; malic acid; maleic acid; cinnamic acid; para-hydroxybenzoic acid, methacrylic acid; oxalic acid; myristic acid, palmitic acid; tert-pentanoic acid; phenylacetic acid; mandelic acid; sebacic acid; tallow fatty acids; hydrogenated tallow fatty acids; tartaric acid; trichloroacetic acid; 2,4,5-trichlorophenoxyacetic acid; undecylenic acid; crotonic acid; pelargonic acid; acetoacetic acid; para-nitrobenzoic acid; ascorbic acid; nitrilotriacetic acid; naphthenic acid, 1-naphthoic acid, trimellitic acid;  
           [0015]    (f) alkyl phenols having from about 6 to about 30 carbon atoms, and having the general formula  
                         
 
           [0016]    wherein R 1 , R 2 , R 3 , R 4 , and R 5  independently are selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, nitro-groups, carbonyl groups, linear and branched acyclic groups, alicyclic groups, cyclic groups, aryl groups, and may contain one or more functionalities selected from the group consisting of halogen atoms, ether groups, nitro-groups, carboxyl groups, carbonyl groups, amine groups, amide groups, and hydroxyl groups. Representative but non-exhaustive examples of various phenols which can be alkoxylated according to the present invention are: phenol, ortho-cresol; meta-cresol; para-cresol, 2,4-dimethylphenol; 2,5-dimethylphenol; 2,6-dimethylphenol; ortho-chlorophenol, meta-chlorophenol; para-chlorophenol; para-nitrophenol; para-methoxyphenol; salicyclic acid, meta-hydroxyacetophenone; para-aminophenol; ortho-phenylphenol; nonylphenol, octylphenol; t-butyl-para-cresol; hydroquinone; catechol, resorcinol; pyrogallol; 1-naphthol; 2-naphthol, 4,4′-isopropylidenediphenol (bisphenol A); methyl salicylate; benzyl salicylate; 4-chloro-2-nitrophenol; para-t-butylphenol; 2,4-di-t-amylphenol; 2,4-dinitrophenol; para-hydroxybenzoic acid; 8-hydroxyquinoline; methyl para-hydroxybenzoate; 2-nitro-para-cresol; ortho-nitrophenol, para-phenylphenol; phenyl salicylate; salicylaldehyde; p-hydroxy benzaldehyde, 2-amino-4-chlorophenol; ortho-aminophenol; salicylamide,  
           [0017]    (g) mercaptans of the general formula  
                         
 
           [0018]    wherein R 1 , R 2  and R 3  independently are selected from the group consisting of hydrogen, linear and branched acyclic groups, alicyclic groups, cyclic groups, and aryl groups having from about 1 to about 30 carbon atoms, and may contain one or more functionalities selected from the group consisting of carboxyl groups, hydroxyl groups, halogen atoms, nitro-groups, amine groups, and amide groups, and  
           [0019]    (h) alcohols having the general formula ROH wherein R is selected from the group consisting of a linear and branched alkyl groups having from about 1 to about 30 carbon atoms, aryl groups, cyclic groups having from about 6 to about 30 carbon atoms, and olefinic and acetylenic groups having from about 1 to about 30 carbon atoms. Representative but non-exhaustive examples of alcohols which can be alkoxylated according to the present invention are. 1-dodecanol; 1-tridecanol; 1-tetradecanol; 1-pentadecanol; 1-hexadecanol; 1-heptadecanol-1-octadecanol; 1-nonadecanol; 1-eicosanol; 1-docosanol; 2-methyl-1-undecanol; 2-propyl-1-nonanol; 2-butyl-1-octanol; 2-methyl-1-tridecanol, 2-ethyl-1-dodecanol; 2-propyl-1-undecanol; 2-butyl-1-decanol; 2-pentyl-1-nonanol; 2-hexyl-1-octanol; 2-methyl-1-pentadecanol; 2-ethyl-1-tetradecanol; 2-propyl-1-tridecanol; 2-butyl-1-dodecanol; 2-pentyl-1-undecanol; 2-hexyl-1-decanol, 2-heptyl-1-decanol; 2-hexyl-1-nonanol; 2-octyl-1-octanol; 2-methyl-1-heptadecanol; 2-ethyl-1-hexadecanol; 2-propyl-1-pentadecanol; 2-butyl-1-tetradecanol; 1-pentyl-1-tridecanol, 2-hexyl-1-dodecanol; 2-octyl-1-decanol, 2-nonyl-1-nonanol; 2-dodecanol; 3-dodecanol; 4-dodecanol; 5-dodecanol; 6-dodecanol; 2-tetradecanol; 3-tetradecanol; 4-tetradecanol, 5-tetradecanol; 6-tetradecanol; 7-tetradecanol; 2-hexadecanol; 3-hexadecanol; 4-hexadecanol; 5-hexadecanol, 6-hexadecanol; 7-hexadecanol; 8-hexadecanol; 2-octadecanol; 3-octadecanol; 4-octadecanol, 5-octadecanol, 6-octadecanol; 7-octadecanol, 8-octadecanol, 9-octadecanol; 9-octadecenol; 2,4,6-trimethyl-1-heptanol, 2,4,6,8-tetramethyl-1-nonanol; 3,5,5-trimethyl-1-hexanol; 3,5,5,7,7-pentamethyl-1-octanol; 3-butyl-1-nonanol; 3-butyl-1-undecanol; 3-hexyl-1-undecanol, 3-hexyl-1-tridecanol; 3-octyl-1-tridecanol; 2-methyl-2-undecanol; 3-methyl-3-undecanol; 4-methyl-4-undecanol; 2-methyl-2-tridecanol; 3-methyl-3-tridecanol; 4-methyl-3-tridecanol; 4-methyl-4-tridecanol, 3-ethyl-3-decanol, 3-ethyl-3-dodecanol; 2,4,6,8-tetramethyl-2-nonanol; 2-methyl-3-undecanol; 2-methyl-4-undecanol; 4-methyl-2-undecanol, 5-methyl-2-undecanol; 4-ethyl-2-decanol, 4-ethyl-3-decanol; tetracosanol, hexacosanol; octacosanol, triacontanol; dotriacontanol; hexatriacontanol; 2-decyltetradecanol; 2-dodecylhexadecanol; 2-tetradecyloctadecanol; 2-hexadecyleicosanol, and unsaturated alcohols such as 1-hexyn-3-ol; oleyl alcohol (technically cis-9-octadecene 1-ol); 2,5-dimethyl-4-octyne-3,6-diol; 2,4,7,9-tetramethyl-n-decyne-4,7-diol; 3-dodecene-1-ol; and 3 ,6-dimethyl-8-dodecene-1-ol.  
           [0020]    While the invention is effective to alkoxylate all classes of alcohols, including but not necessarily limited to saturated and unsaturated alcohols, saturated alcohols are preferred. Of these, polyalkylene glycols are preferred, with polyethylene glycol being most preferred.  
           [0021]    The alkoxylation reaction may be catalyzed using any suitable catalyst. Both basic and acidic catalysts may be used Suitable catalysts include, but are not necessarily limited to: potassium hydroxide, sodium hydroxide; alkylated aluminum fluorides, alkylated aluminum halides; organoaluminum zinc compounds; calcium, strontium and barium acetates and naphthanates; BF 3  or SiF 4  and metal alkyls or metal alkoxides; and, hydrofluoric acids and metal alkoxides.  
           [0022]    The alkoxylation may be carried out at ambient pressure or at pressures above or below ambient, as long as the alkylene oxide is maintained in the vapor phase. Normally, the pressure is from about −14 to about 30 pounds per square inch (psi). Pressures below about 20 psi are preferred. Referring to FIG. 1, in order to conduct the reaction, a suitable reactor that can hold vacuum and pressure may be modified to receive gas or vapor into the top of the reactor. The top of the stainless steel receptacle  16  containing liquid and gaseous ethylene oxide is connected with a tube, hose, or pipe  12  to the vent hole  14  on the reactor head  15 . The flow of ethylene oxide gas or vapor is controlled by the valves on the tube  12 . The tube  12  preferably includes a “tee” with two valves  18  so that the existing vent hole  14  on the reactor head  15  can be used both for charging ethylene oxide vapor into the reactor  10  through the tube  12  and for venting the reactor  10 . A more preferred alternative is to use a reactor with a separate vent hole for venting reactor pressure. Ethylene oxide vapors are allowed to diffuse from the receptacle  16  into the reactor  10  through the tube  12 . The separate vent hole is used to release residual inert atmosphere in the reactor once all of the charged ethylene oxide has reacted.  
           [0023]    Suitable alkylene oxide adducting materials are alpha and beta alkylene oxides, preferably ethylene oxide, propylene oxide or mixtures thereof, most preferably ethylene oxide The alkoxylated product may have any desired content of the alkoxy adducting material. Where an alcohol is ethoxylated, ethylene oxide will normally comprise from about 20 to about 90 wt % of the alkoxylated product.  
           [0024]    A suitable amount of catalyst for use in the reaction is from about 0.05 to about 10 0 weight percent catalyst based upon the weight of the total reaction mixture Preferred levels of catalyst are from about 0.1 to about 6.0 wt % based on the total reaction mixture weight.  
           [0025]    The invention will be better understood with reference to the following examples, which are provided to illustrate the invention, but not to limit the invention. 
       
    
    
     EXAMPLE 1  
       [0026]    After observing undesirable flock in batches of ethoxylated heavy ethylene glycol (EHEG), a series of experiments was performed to determine the cause for flocculation. No correlation could be observed between the percentage of flock and: the percentage of catalyst (in this case, KOH); the reaction temperature (100-160° C.); the oxide addition rate; or the hydroxyl number.  
       EXAMPLE2  
       [0027]    Experiments were undertaken to determine whether ethoxylation using only ethylene oxide vapors would prevent flock formation. In the following reaction, ethylene oxide vapor was allowed to diffuse through a tube into a Parr reactor and into contact with the substrate—flash heavy ethylene glycol (FHEG, a stream of PEG produced by Oxychem from which light ends were stripped out). The following reactions were performed.  
                                                                                                                                         EO       Total               Th               Rxn. #   FHEG (g)   KOH   added   Total EO   Product   Sample (g)   % H 2 O   Base # 1     Base # 1     ° F. 2     hr                                1319-147   957.03               957 03   a. 110.12   .03           230           (liq. EO)           846.91   5 (aq)           851.91                   320           846 91   1.528           848 4−   b 64.39   0 11   2.08   2 65   320   0.7           782.64   1.41   250   250   1034   c 204.1           2.01   320   0.4           628.2   1 13       200.7   829.95   d 800.01       1319-149   1029.2               1029.2       (liq EO)           1029 2   0.6           1029 8               0.262           1029 2   0.183           1029 4   a. 116 9           0.262   320   0.08           912.32   0.163   20       932.48               0.257   320   0.75       1319-151   1028.1                                   82       (EO gas or vap.)           1028.1   3           1031.1               1.31           1028.1   0.917           1029   a. 33.93   0.10   0.969   1.312   223   2 75                                   2           994.2   0.887           995.1   b. 62 91   0.06   0.985   1.312   225   1.08           931.35   0.831   20   20   952 18               1.28   267   1.08           931.35   0.831   90   110   1042.2               1.17   270   6.8           931.35   0.831   185   295   1227 2   c. 12.0           0 997   270   8?                                  
 
         [0028]    The last listed sample 1319-151 exhibited an OH# of 435.6. The samples from reaction 1319-151 remained clear without any trace of flock throughout an observation period of several months. Both 1319-147 and 1319-149 were synthesized with liquid ethylene oxide, and both developed flock.  
       EXAMPLE 3  
       [0029]    To demonstrate that using liquid ethylene oxide for ethoxylation would promote flock formation, a clear sample of PEG 200 (from a commercial vendor, similar to FHEG) was ethoxylated with liquid ethylene oxide under the following conditions:  
                                                                                                                                             Total                   Th               PEG 200 (g)   KOH   EO added   Total EO   Product   Sample (g)   % H 2 O   OH#   Base # 1     Base # 1     ° F. 2     hr                                848.3   2.5                                                   0.764               A 30.13   0.026   574.4   1.12   1.33   230   23       818.2   0.74   200   200   1018.9   B. 172.1       439.9   0.74   1.07   230   1       680   0.61       166.22   846.9   C. 96 73                   230       602 3   0 54   147.23   750.1   D. 713                                  
 
         [0030]    All samples developed flock within 24 hours.  
       EXAMPLE 4  
       [0031]    In order to confirm the results in Example 2, another reaction was conducted. The ethylene oxide vapors were added through the dip tube ( 20  in FIG. 1). The reaction is summarized below.  
                                                                                                                     Rxn. #   FHEG   KOH   Total EO   Total   Sample   % H 2 O   Base #   ° F.   hr   Appearance.                                1319-159   1001.9   2.92                                       (EO vap.)       (aq)           1001.9   0 89       1002.8   a 39 95   0 3   1.87   230   1 1   clear           961.99   0.857       962.8   b. 31 8   0.07   0.87   230   1.25   clear           930.2   0.829   286   1217   c 55 04       0.78   260       clear           887.53   0 791   272 9   1161 2   d 1121.5                   clear                  
 
         [0032]    The OH# of the sample with 930.2 FHEG was 448.7.  
         [0033]    Samples and products from all previous reactions in which ethylene oxide liquid was charged to the reactor developed flock in less than 24-48 hours. In contrast, all of the samples from reaction 13 19-159 were sparkling clear with no flock after 5 days at ambient temperature, and remained clear throughout an observation period of several months.  
       EXAMPLE5  
       [0034]    Seven more ethoxylations were conducted in Parr reactors using ethylene oxide in the vapor phase. The conditions and results are given in the following Table.  
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                   FHEG   KOH   EO add.   Total EO   Total   Sample   % H 2 O   BASE #   OH#   ° F.   hr.   Appearance                                Reaction 1319-163 (EO vapors to vapor space with about 30” of vacuum initially)            995.1   2.95                                               995 1   0 902           996   A. 58 78   0 09   0 9       230       clear       936.4   0.85           937.22   B. 41 25   0 05   0.9       230   0.5   clear       895 2   0.81   260   260   1156   C 74.67               260   2.5   sl. hazy       837.34   0.76       243 2   1081 3   D 1034 8                       sl. hazy            Reaction 1319-165 (EO vapor to vapor space with about 30” of vacuum initially)            990.4   2.85                                               990 4   0 87        991.27   A. 39.9               230   1.75   clear       950 5   0 84           951.4   B. 35.12                       clear       915.5   0.805   275   275   1191 3   C 55 93               266   2.7   clear       872.5   0.767       262.09   1135 3   D. 1109       0.63   443.8           clear            1319-167 (EO vapor to vapor phase with about 30” of vacuum initially)            995.8   2 95                                               995.8   0.902           996 7   A 25.56   0.05   0.8       230   1.25   clear       970.26   0.878           971.14   B. 32 3   0 02   0.81       230       clear       937 99   0.849   291   291   1229 8   C 52.51               230   3.38   sl. hazy       897 9   0 81       278.6   1177.3   D. 1107       0 65   437.1           sl. hazy            1319-169 (EO vapor through dip tube with about 30” of vacuum initially--the EO cylinder was       very full)            940 3   2.87                                               940 3   0 877               A. 32 33   0.1           230   1   clear       907.98   0.847           908.8   B 32.56   0.05   0.89       230   1   clear       875 45   0.817   115   115   991 3   C 64.46       0.79   522.1   230   1   clear       818.08   0.763   125   232 5   1051 3   D 64 3       0 75   456.1   230   0 75   clear       768.04   0.717       218.3   987.01   E 233 5                       clear       586.35   0.547   50   216 61   803.5   F. 740 3                       clear            Reaction 1319-171 (EO vapors via diptube with about 30” of vacuum initially)            783.3   2.4           785.7                                       0 73           784.03   a 44   0.12   0 9       230   1.1                           b 63.2   0.06   0.9       230   0 4   {overscore (pur)}ge and vac. 30”       676.2   0 63   200   200   876 8   c. 107 4               230   2.25   ?       593 4   0.556       175 5   769 4   d. 727 4           451.5           sl. flock            1319-173 (EO vapors through diptube with about 30” of vacuum initially)            805.1   2 5           807.6                                   805.1   0.76           803.36   a. 27 7   0 15   1       230   1                           b 16.2   0.07   0.95       230   1.25   N 2  purge vac. 30”       761.24   0 722   228   228   989.96   c. 110               230   1.25   EO in continuously       676.7   0.64   202.7   202.7   879.96   d. 830.1                       clear            1319-175 (EO vapors to vapor space with vacuum)            767.9   2.38           770 3                                   767.9   0.73           768.6   a. 16.83   0.18   0.9       230   1                                   6       751 1   0.71           751 8   b. 18.1   0.08   0.9       230   1   N 2 purge vac. 30”                                   6       732.99   0.694   220   220   953 7   c 106.2                       EO in intermittently       651 37   0.617       195.5   847.49   d.                       clear                  
 
         [0035]    The samples from 1319-163, -165, -167, -169, -173, and -175 largely remained clear throughout an observation period of several months. A number of the samples developed a slight flock later and appeared slightly hazy. The amounts of flock in these samples were less than those present in samples synthesized with liquid EO Also, the flock was finer and was more evenly distributed. It was believed that if the EO vapor is pulled from the EO container too fast, rapid effervescence or flash boiling of EO liquid would cause fine liquid droplets of EO to be carried into the reactor, thereby incorporating liquid EO in the reactions.  
       EXAMPLE 6  
       [0036]    An experiment (1319-177) was performed using an atomizer to discharge EP vapors into the Parr reactor. The atomizer was installed onto the diptube of one of the Parr reactors in which the length of the dip tube was shortened by cutting off about two inches In another experiment using a different reactor (1319-179), EO vapors were charged into the reactor vapor phase with an initial vacuum pressure of about 5″ mercury. The conditions and results are summarized in the following Table.  
                                                                                                                                                                                           FHEG   KOH   EO added   Total EO   Total   Sample   % H 2 O   Base #   OH#   ° F.   hr.   Appearance                                Reaction 1319-177 (EO vapor through diptube and atomizer, 30” var.)            1334   4.13           1338 1                                   1334   1.26           1335 3   a. 32.33   0 4   0 92       230   2.1   Drying without nitrogen sparge       1301.7   1.23           1302.9   b. 76.3   0.1   0.95       230   1.3       1225.5   1.16   255   1481 6                       230   3 61       1225.1   1.16   100   355   1581.6                   230   1.6       1225.1   1 16       355   1581 6   c. 1540.1           453.3           clear (4 days)            Reaction 1319-179 (EO vapors to vapor phase w/5” vacuum pressure initially)            831.7   2 43           834.13                                   831.7   0.743           832.44   a. 44 3   0.11   0.94       230   1.1       787 4   0.703           788 14   b. 45.3   0.01   0.92       230   1       742 18   0 663   134   134   874.84                   230   1.2       742.18   0.663   88   220   962 84                   230   1 2       742 18   0.663       220   962 84   c 926.7           444 7           clear (4 days                  
 
         [0037]    The products were clear initially and remained clear throughout an observation period of several months.  
       EXAMPLE 7  
       [0038]    In reaction 1319-183, liquid EO was added or charged into the reactor containing FHEG via the same atomizer used for reaction 1319-177. The resulting product had flock.  
       EXAMPLE 8  
       [0039]    The procedures of Example 2 were repeated No vacuum was used. The conditions and results are summarized in the following Table:  
                                                                                                                           FHEG   KOH   EO added   Total EO   Total   Sample   % H 2 O   Base #   ° F.   hr.   Appearance                                Reaction 1319-197 (EO vapor added to vapor space of reactor, no vacuum used)            551.5   1.61           553.11               220               551.5   0.49           551.99   a 24.18   0 095   10.6   215   2.3       527.34   0.47   48   48   575.81               265   2.1       527.34   0.47   89   137   664 81               265   6       527.34   0.47   30   167   194.81               260   2.5       527.34   0.47       167   694.81   b 38.2           260   2 5   clear                  
 
         [0040]    The samples were clear and remained clear throughout an observation period of several months.  
       EXAMPLE 9  
       [0041]    A mixture of PEG 200 and KOH flakes was charged into a Parr reactor and dried. The procedures of Example 2 then were repeated. The conditions and results are summarized in the following Table  
                                                                                                                           PEG 200   KOH   EO added   Total EO   Total   Sample   % H 2 O   Base #   ° F.   hr.   Appearance                                Reaction 1318-155 (EO vapor to reactor head space)            803.54   2 34                                           803 54   0.715               a 31.2   0.22       230   1.6                           b. 8.7   0.14       230   2.5                           c 12 3   0.19       230   1.2                           d. 16   0.16       240   1 6       735.4   0.654           736.06   e 16.8   0.23       240   1 6       718 6   0.64   122   122   841.3   f 238 9           230   2.5   clear       514.5   0.46   38   125.4   640 6   g 202 1           230   1 6   clear       352.2   0 31   32   117 8   470.3   h. 204 4           230   1.7   clear       199.1   0.18   20   86.6   285.9   i. 283           230   1.95   clear                  
 
         [0042]    The samples were clear and remained clear throughout an observation period of several months.  
       EXAMPLE 10  
       [0043]    The procedures of Example 9 were repeated using an initial vacuum of 10″ inside the reactor. The reaction (1318-157) and results are summarized in the following Table:  
                                                               PEG 200   KOH   EO added   Total EO   Total   Sample   % H 2 O   ° F.   hr                   835.33   2 43           837.76                       835.33   0.743           836.07   a. 14.7   0.06   230   5.3       820 64   0.73           821 37       820.64   0.73   128   128   949.37           230   2.2       820.64   0.73   132   260   1081.4   b. 1018.6       230   4.3                  
 
         [0044]    The samples were clear and remained clear throughout an observation period of several months.  
       EXAMPLE 11  
       [0045]    Finally, an ethoxylation with EO vapor was conducted in a 60-gallon reactor in the pilot plant. The reaction (1318-159) is summarized below.  
                                                                                                             FHEG   KOH (g)   EO added   Total EO   Sample   % H 2 O   Base #   ° F.   hr.   Appearance                                248 lb   148           a 6 oz   0.38       220   5   clear                       b. 16 oz   0.08   5927   220   7   clear               78 lb   78 lb   c. 16 oz       4685           clear               13 lb   91 lb.   d. 336 lb.       433           clear                  
 
         [0046]    All samples remained clear for at least one month.  
         [0047]    Persons of ordinary skill in the art will appreciate that many modifications may be made to the embodiments described herein without departing from the spirit of the present invention Accordingly, the embodiments described herein are illustrative only and are not intended to limit the scope of the present invention.