Abstract:
Aqueous fluids are thickened with epoxide modified polyoxyalkylene diamines. The polyoxyalkylene diamines are of the formula: 
     
       H.sub.2 NCH(CH.sub.3)CH.sub.2 O(CH.sub.2 CH(R)O).sub.x CH.sub.2 
     
      CH(CH 3 )NH 2   
     wherein: 
     R is methyl or hydrogen and 
     x is a number selected to give the diamine a molecular weight of 3000 to 9000. 
     The epoxide is a hydrophobic monoepoxide, diepoxide or mixture thereof. 
     The aqueous fluid optionally incorporate ethylene glycol. They are useful for water/glycol base hydraulic fluids, cosmetics and surfactants.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention relates to epoxide modified polyoxyalkylene diamine mixtures and thickened aqueous fluids therefrom. More specifically, the invention relates to aqueous fluids thickened with a selected 3000 to 9000 molecular weight polyoxyalkylene diamine reacted with a hydrophobic epoxide. 
     The thickened fluids are useful for water/glycol based hydraulic fluids, cosmetics and surfactant solutions. 
     2. Other Thickeners in the Field 
     U.S. Pat. No. 4,396,499 to McCoy et al. discloses water-soluble salts of polymers prepared by the reaction of polyoxyalkylene diamines and diepoxides. The diamines are of the formula: H 2  NCH(CH 3 )CH 2  O(CH 2  CH(R)O) x  CH 2  CH(CH 3 )NH 2 . 
     U.S. Pat. No. 4,606,837 to McEntire et al. discloses water-glycol fluids made from polyoxyalkylene thickeners. These thickeners are prepared by the reaction of ethylene oxide with a 10 to 50 carbon atom hydrophobe such as dinonylphenol in a specified ratio. 
     U.S. Pat. Nos. 4,310,436 and 4,354,956 to Camp disclose polyethylene glycol fatty acid diesters used as thickening agents. U.S. Pat. No. 4,395,351 to Camp discloses ethylene oxide adducts of coconut fatty acid amine, coco fatty acid and oleic acid for use as thickeners. 
     U.S. Pat. No. 4,390,440 to Schwartz et al. discloses a carboxylic acid having 5 to 20 carbon atoms, a thickener which is a polyether polyol of molecular weight of 1000 to 40,000 prepared by reacting ethylene oxide with at least one active hydrogen-containing compound and at least one alpha-olefin oxide or alcohol or glycidyl ether. 
     U.S. Pat. No. 3,992,312 to Genjida et al. discloses thickeners comprising a water-soluble polymer. The polymer contains a polyamide residue bonded to an oxyalkylene chain. Suitable polyamides include the condensation product of a polycarboxylic acid and a polyamine. Examples of polycarboxylic acids include adipic acid and polymerized fatty acids (dimer acids). Suitable polyamines include aliphatic polyamines such as ethylene diamine, propylene diamine and butylene diamine. 
     SUMMARY OF THE INVENTION 
     The invention concerns water based fluids comprising an effective amount of a thickener. The thickener is the reaction product of a polyoxyalkylene diamine and a hydrophobic monoepoxide, diepoxide or mixture thereof. The diamine is of the formula: 
     
         H.sub.2 NCH(CH.sub.3)CH.sub.2 O(CH.sub.2 CH(R)O).sub.x CH.sub.2 CH(CH.sub.3)NH.sub.2. 
    
     About 1% to 30% of R is methyl with the balance being hydrogen. The number x is a value that specifies the molecular weight of the polyoxyalkylene diamine in the range of 3000 to 9000. The hydrophobic epoxide is a monoepoxide, diepoxide or mixture thereof. The ratio of amine equivalent: monoepoxide ranges from 1:1 to 1:1.9 and the ratio of amine equivalent: diepoxide ranges from 1:0.08 to 1:0.12. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The thickeners of the invention are useful for thickening water or an aqueous solution of organic solvents. These thickeners have a relatively low molecular weight for their effectiveness in thickening. Low molecular weight thickeners are more stable to shear degradation than high molecular weight thickeners. This makes them useful for thickening water and water/glycol based hydraulic fluids where resistance to thinning with use is an important consideration. 
     A variety of monoepoxides are useful for the instant thickeners. Among these are the epoxides of 8 to 22 carbon number alpha olefin oxides and 8 to 22 carbon number alkyl glycidyl ethers. Particularly preferred are the epoxides of 8 to 14 carbon number alpha olefin oxides and 8 to 14 carbon number alkyl glycidyl ethers. 
     A variety of diepoxides are useful for the instant thickeners. These include the diglycidyl ethers of 4,4&#39;-isopropylidenediphenol (bisphenol A); 4,4-isopropylidenebis (2,6-dibromophenol) (tetrabomo bisphenol A); resorcinol; neopentylglycol; 1,4-butanediol and poly(oxypropylene)gycol. The diglycidyl ethers of bisphenol A, resorcinol and 1,4-butanediol are preferred. These diepoxides are prepared by the reaction of epichlorohydrin with a hydroxyl compound. 
     Other useful diepoxides prepared by epoxidation with peracetic acid include vinylcyclohexene dioxide; 
     3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate; 
     3-(3,4-epoxycyclohexane)-8,9-epoxy-2,4-dioxaspiro[5,5]-undecane; 
     bis(2,3-epoxycyclopentyl)ether and 
     bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate. 
     Diamines used to formulate the thickeners of the invention are commercially available as Jeffamine® ED-6075, ED-6000 and ED-4000. The amine function gives the thickener reserve alkalinity and provides rust inhibition. 
     The thickener formulations are prepared by stirring the constituents in a stainless steel kettle at 60° C. to 100° C. The blends are then diluted with the desired amount of water or organic solvent to make the concentrate. The fluids are shipped as concentrates. Before use they are diluted with water and optionally ethylene glycol, typically 1 wt % to 30 wt % concentrate in water. 
     This invention is shown by way of example. 
    
    
     EXAMPLE 
     Jeffamine® ED-6075 is a 5400 molecular weight polyoxyalkylene diamine product made by Ni/Cu/Cr catalyzed reductive amination of a corresponding polyoxyalkylene diol consisting of 75% of oxyethylene units and 22% of oxypropylene units ramdomly distributed in the main segment and 3% oxypropylene units at the end of the polymer chain. The reductive amination was conducted in a 1.5 liter tubular reactor filled with 1.2 liter of Ni/Cu/Cr catalyst (described in U.S. Pat. No. 3,654,370 to Yeakey, incorporated herein by reference) maintained at 204° C. and 2000 psia pressure. The polyoxyalkylene diol, ammonia and hydrogen were fed to the reactor at respective rates of 0.43 lb/hr., 1.04 lb/hr. and 35 liter/hr. The reactor effluent was collected for the last 23 hour period of the 26 hour period. The effluent was stripped of volatiles and analyzed as followed: 0.37 meq/g total acetylable, 0.30 meq/g total amines, 0.28 meq/g primary amines and 0.05 wt % water. The melting point of this product was 30° C. 
     Jeffamine® ED-6000 is a 6350 molecular weight polyoxyalkylene diamine product made by Ni/Cu/Cr catalyzed reductive amination of a corresponding polyoxyalkylene diol consisting of mostly oxyethylene units and 3.5% of oxypropylene units at the end of the polymer chain. The reductive amination reaction was conducted in a similar manner as for ED-6075. The stripped product analyzed as followed: 0.315 meq/g total acetylable, 0.27 meq/g total amine, 0.25 meq/g primary amines and 0.05 wt % water. The melting point of the product was 57° C. 
     Jeffamine® ED-4000 is a 3846 molecular weight polyoxyalkylene diamine product made by Ni/Cu/Cr catalyzed reductive amination of a corresponding polyoxyalkylene diol consisting of mostly oxyethylene units and 3.5% of oxypropylene units at the end of the polymer chain. The reductive amination reaction was conducted in a similar manner as for ED-6075. The stripped product was analyzed as followed: 0.52 meq/g total acetylable, 0.45 meq/g total amine, 0.43 meq/g primary amine and 0.23% water. The melting point of the product was 54° C. 
     EXAMPLE I 
     General Synthesis 
     Quantities of polyoxyalkylene diamine and n-alkyl glycidyl ether were admixed in a glass vial at 60° C. and then heated to 115° C. for a period of 20 hours. No catalyst was used. However an acid or base catalyst is appropriate for some reagents. The completion of the addition of amine to epoxide was indicated when a 10% aqueous solution of the resulting product was clear at temperatures below the cloud point of the product. The results of these reactions are summarized in Table I. 
     Heloxy®WC-7 is a mixture of C 8  and C 10  linear alkyl glycidyl ethers, 3.92 meq/g epoxide. Heloxy® WC-8 is a mixture of C 12  and C 14  linear alkyl glycidyl ethers, 3.13 meq/g epoxide. Both are a product of Wilmington Chemical Co. 
     
                                           TABLE I__________________________________________________________________________                                 (a.)            (b.)                          Viscosity                                 Vis cs @ 40° C. %                                                 Wt % RequiredJeffamine ®       Amount        Amount                          cs @ 100° F.                                 aqueous ethylene glycol                                                 for 40 cs VisExampleDiamine       (gram)            Epoxide  (gram)                          10% in water                                 10%  15%  20%   @ 40°__________________________________________________________________________                                                 C.I-1. ED-6000     None          2.5 cs 2.  ED-6075     None          2.5 3.  ED-4000     None 4.  ED-6000       40.0 Heloxy ® WC-7                     4.50 12.7   14.6                                    cs                                      79.4                                         cs                                           180 cs                                                 12.0                                                     wt % 5.  ED-6000       40.0 Heloxy ® WC-7                     2.25 32.0   34.0 191  492   10.5            Heloxy ® WC-8                     2.25 6.  ED-6000       40.0 Heloxy ® WC-8                     4.50 126    52.0 278  840   9.5 7.  ED-6000       40.0 Heloxy ® WC-7                     4.80 197    42.9 174  447   10.0 8.  ED-6000       40.0 Heloxy ® WC-7                     2.40 182    38.0 215  609   10.0            Heloxy ® WC-8                     2.40 9.  ED-6000       40.0 Heloxy ® WC-8                     4.80 Jelly  435  5636 19837 5.510.  ED-6075       50.0 Heloxy ® WC-7                     6.00 9.7    14.0 40.2 134   15.011.  ED-6075       50.0 Heloxy ® WC-7                     3.00 19.3   31.2 69.4 227   11.5            Heloxy ® WC-7                     3.0012.  ED-6075       50.0 Heloxy ® WC-8                     6.00 58.4   36.5 141  396   10.513.  ED-6075       44.0 Heloxy ® WC-7                     6.00 139    33.5 170  576   10.514.  ED-6075       44.0 Heloxy ® WC-7                     3.0015.              Heloxy ® WC-8                     3.00 296    60.5 641  2003  9.516.  ED-6075       44.0 Heloxy ® WC-8                     6.00 55.6   88.5 875  3611  8.517.  ED-4000       40.0 Heloxy ® WC-8                     7.13 50.0   54.0 352  1809  9.018.  ED-4000       40.0 Heloxy ® WC-7                     7.13 64.0   24.0 96   360   11.7__________________________________________________________________________ (a.) Solution in 1:1 w/w ethylene glycol/water (b.) Solution in 1:1 w/w ethylene glycol/water formulated for a fire resistant hydraulic fluid. 
    
     EXAMPLE II 
     General Synthesis 
     Quantities of polyoxyalkylene diamine, n-alkyl glycidyl ether and diglycidyl ether were admixed in a glass vial at 60° C. and then heated to 115° C. for a period of 20 hours. No catalyst was used. However an acid or base catalyst is appropriate for some reagents. The completion of the addition of amine to epoxide was indicated when a 10% aqueous solution of the resulting product was clear at temperatures below the cloud point of the product. The results of these reactions are summarized in Table II. 
     Epon® 828 is the diglycidyl ether of bisphenol A, 5.26 meq/g. It is a product of Shell Chemical Co. 
     Heloxy® WC-67 is the diglycidyl ether of 1,4-butanediol, 8.11 meq/g epoxide. Heloxy® WC-68 is the diglycidyl ether of neopenty glycol, 7.46 meq/g epoxide. Both are a product of Wilmington Chemical Co. 
     
                                           TABLE II__________________________________________________________________________                                (a.)              (b.)                         Viscosity                                Vis cs @ 40° C., %                                                  Wt % RequiredExam-    Jeffamine ®      Amount        Amount                         cs @ 100° F.                                aqueous ethylene glycol                                                  For 40 cs Visple Diamine      (gram)           Diepoxide                    (gram)                         10% in water                                10%     15%  20%  @ 40°__________________________________________________________________________                                                  C.II-1.    ED-6000     None          2.5 2. ED-6075     None          2.5 3  ED-4000     None          2.4 4. ED-6000      23.1 Epon ® 828                    0.9  5.0    12.4  cs                                        26.5                                           cs                                             49.6                                                cs                                                  17.2                                                      wt % 5. ED-6000      22.8 Epon ® 828                    1.2  4.9    20.0    59.9 130  14.4 6. ED-6000      22.5 Epon ® 828                    1.5  Jelled *6%-32.6          6.7                                *8%-187.1 7. ED-6000      40.0 Heloxy ® WC-67                    4.2  4.35   12.8    24.7 48.6 19.0 8. ED-6000      40.0 Heloxy ® WC-67                    4.6  3.20   9.3     40.1 79.6 15.0 9. ED-6000      40.0 Heloxy ® WC-68                    4.2  3.50   9.8     17.8 29.5 24.510. ED-6000      40.0 Heloxy ® WC-68                    5.0  4.38   12.7    24.4 46.8 17.511. ED-6075      38.0 Epon ® 828                    2.0  12.3   20.1    40.6 106  14.212. ED-6075      37.5 Epon ® 828                    2.2  23.4   27.2    64.7 166  12.513. ED-6075      37.6 Epon ® 828                    2.4  59.2   43.5    139  276  9.514. ED-6075      37.4 Epon ® 828                    2.6  276    89      400  1347 7.015. ED-4000      40.0 Epon ® 828                    2.5  4.6    10.6    22.5 40.8 20.016. ED-4000      40.0 Epon ® 828                    2.8  .34    16.8    37.7 80.5 15.517. ED-4000      40.0 Epon ® 828                    3.1  10.9   20.4    48.4 103  14.018. ED-6075      40.0 Heloxy ® WC-68                    5.0  4.6    11.3    26.3 52.9 19.019. ED-6075      40.0 Heloxy ® WC-67                    4.5  6.0    32.8    71.9 161.0                                                  12.0__________________________________________________________________________ (a.) Solution in 1:1 w/w ethylene glycol/water (b.) Solution in 1:1 w/w ethylene glycol/water formulated for a fire resistant hydraulic fluid. *Vis cs @ 40° F., 6% and 8% in aqueous ethylene glycol. 
    
     EXAMPLE III 
     General Synthesis 
     Quantities of polyoxyalkylene diamine, n-alkyl glycidyl ether and diglycidyl ether were admixed in a glass vial at 60° C. and then heated to 115° C. for a period of 20 hours. No catalyst was used. However an acid or base catalyst is appropriate for some reagents. The completion of the addition of amine to epoxide was indicated when a 10% aqueous solution of the resulting product was clear at temperatures below the cloud point of the product. The results of these reactions are summarized in Table III. 
     
                                           TABLE III__________________________________________________________________________                                 (a.)            (b.)                          Viscosity                                 Vis cs @ 40° C., %                                                 Wt % RequiredJeffamine ®       Amount        Amount                          cs @ 100° F.                                 aqueous ethylene glycol                                                 For 40 cs VisExampleDiamine       (gram)            Epoxide  (gram)                          10% in water                                 10%  15%   20%  @ 40°__________________________________________________________________________                                                 C.III-1.ED-6000     None          2.4  cs 2.  ED-6075     None          2.5 3.  ED-4000     None          2.4 4.  ED-6000       40.0 Heloxy ® WC-7                     2.25 16.6   15.5                                    cs                                      46.9                                          cs                                            96.7                                               cs                                                 14.5                                                     wt %            Epon ® 828                     1.05 5.  ED-6000       40.0 Heloxy ® WC-7                     1.05 25.3   21.7 64.5  159  12.2            Heloxy ® WC-8                     1.05            Epon ® 828                     1.05 6.  ED-6000       40.0 Heloxy ® WC-8                     2.25 45.6   7.3  41.8  214.6                                                 15.0            Epon ® 828                     1.05 7.  ED-6000       50.0 Heloxy ® WC-7                     3.30 98.4   32.0 131   412  10.7            Epon ® 828                     1.65 8.  ED-6000       50.0 Heloxy ® WC-7                     1.65 849    122  957   29.0 7.5            Heloxy ® WC-8                     1.65            Epon ® 828                     1.65 9.  ED-6000       50.0 Heloxy ® WC-8                     3.30 4174   142  1040  38.1 7.5            Epon ® 828                     1.6510.  ED-6075       50.0 Heloxy ® WC-7                     3.80 82     29.0 85.7  208  9.5            Epon ® 828                     1.6511.  ED-6075       50.0 Heloxy ® WC-7                     1.65 258    52   244   594  9.0            Heloxy ® WC-8                     1.65            Epon ® 82812.  ED-6075       50.0 Heloxy ® WC-8                     3.30 232    45.3 252   743  11.5            Epon ® 828                     1.6513.  ED-6000       50.0 Heloxy ® WC-7                     1.05 43.5   28.9 104   215  12.8            Heloxy ® WC-8                     3.3014.  ED-6000       50.0 Heloxy ® WC-68                     1.15 60.6   34.2 132   308  10.5            Heloxy ® WC-8                     3.3015.  ED-6075       50.0 Heloxy ® WC-67                     1.05 39.1   26.5 63.9  312  12.5            Heloxy ® WC-8                     3.3016.  ED-6075       50.0 Heloxy ® WC-68                     1.10 38.4   35.2 146   679  10.5            Heloxy ® WC-8                     3.3017.  ED-4000       40.0 Heloxy ® WC-8                     5.8  Jelly  899  15380 3688 5.5            Epon ® 828                     1.018.  ED-4000       40.0 Heloxy ® WC-7                     5.8  75     63   332   875  8.5            Epon ® 828                     1.919.  ED-6075       50.0 Heloxy ® WC-8                     3.35 46.6   35.9 128   393  10.5            Heloxy ® WC-68                     1.2020.  ED-6075       50.0 Heloxy ® WC-8                     3.30 35.2   37.4 197   727  10.5            Heloxy ® WC-68                     1.40__________________________________________________________________________ a. Solution in 1:1 w/w ethylene glycol/water b. Solution in 1:1 w/w ethylene glycol/water formulated for a fire resistant hydraulic fluid. 
    
     While particular embodiments of the invention have been described, it is well understood that the invention is not limited thereto since modifications may be made. It is therefore contemplated to cover by the appended claims any such modifications as fall within the spirit and scope of the claims.