US2856434A - Ochjchz - Google Patents
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- US2856434A US2856434A US2856434DA US2856434A US 2856434 A US2856434 A US 2856434A US 2856434D A US2856434D A US 2856434DA US 2856434 A US2856434 A US 2856434A
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- benzyl
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- chloride
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- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 17
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 19
- 229940073608 benzyl chloride Drugs 0.000 description 14
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 BENZYL ETHERS Chemical class 0.000 description 5
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000004851 dishwashing Methods 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 235000007686 potassium Nutrition 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- GCXHSBQTVXCWBK-UHFFFAOYSA-N 1,2-dichloroethylbenzene Chemical compound ClCC(Cl)C1=CC=CC=C1 GCXHSBQTVXCWBK-UHFFFAOYSA-N 0.000 description 1
- KTHSXIDIBJLTIB-UHFFFAOYSA-N 1-(2-chloropropan-2-yl)-2-methylbenzene Chemical compound CC1=CC=CC=C1C(C)(C)Cl KTHSXIDIBJLTIB-UHFFFAOYSA-N 0.000 description 1
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 1
- MZMVVHAHSRJOEO-UHFFFAOYSA-N 1-chloropropylbenzene Chemical compound CCC(Cl)C1=CC=CC=C1 MZMVVHAHSRJOEO-UHFFFAOYSA-N 0.000 description 1
- PVPAMCTVDFXDNB-UHFFFAOYSA-N 2-chlorobutan-2-ylbenzene Chemical compound CCC(C)(Cl)C1=CC=CC=C1 PVPAMCTVDFXDNB-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001522296 Erithacus rubecula Species 0.000 description 1
- 241000630665 Hada Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FYAUQRPGUUXFLL-UHFFFAOYSA-N [bromo(chloro)methyl]benzene Chemical compound ClC(Br)C1=CC=CC=C1 FYAUQRPGUUXFLL-UHFFFAOYSA-N 0.000 description 1
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
Definitions
- This invention relates to low-foaming non-ionic surface-active compositions. It also relates to a process by which these compositions are prepared.
- the compounds of the present invention are represented by the formula nw CH2OH2),.O ontotm wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty.
- the process by which these compounds are prepared comprises reacting a compound of the formula in which R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, with benzyl chloride or bromidein the presence of a strongly basic inorganic neutralizing agent.
- benzyl chloride is somewhat preferable to the use of benzyl nwomornnon wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, are.
- propylene oxide may be "substituted for a similar amount of ethylene oxide without substantially altering the identifying characteristics of the compound. Propylene oxide and ethylene oxide are equivalent to this extent.
- the formation of a benzyl ether from the abovetype compound results in a product having low-foam detergent properties superior to those of the parent compound.
- More- 2,856,434 Patented Oct. 14, 1958 attached to a benzene ring as, for example, methylbenzyl chloride, dimethylbenzyl chloride, trimethylbenzyl chloride, ethylbenzyl chloride, ethylmethylbenzyl chloride, chlorobenzyl chloride, bromobenzyl chloride, chloromethylbenzyl chloride, nitrobenzyl chloride, and the like.
- the corresponding bromides are likewise suitable.
- R has been defined as an alkyl group of eight to fifteen carbon atoms. Actually, there may be more than one alkyl substituent on the benzene ring. It is only important that the total number of carbon atoms in all of the alkyl substituents range between eight and fifteen. Suitable for this use are the octyl, nonyl, decyl, dodecyl or pentadecyl groups as single substituents for R. Two
- R groups may also be substituted for R, as, for example, an octyl and an amyl, a nonyl and an amyl, a decyl and a propyl, a decyl and an amyl, or a dodecyl and a propyl. Even three groups may be substituted for R, as, for example, three amyl substituents.
- the positions or the alkyl groups on the benzene rings are not indicated because they are not critical.
- the cloud point This is called the cloud point.
- the cloud point of the octyl compound having the lowest number of ethoxy units contemplated within this invention, that is, twelve, is less than 2 C.
- the cloud point With fifteen ethoxy units the cloud point has risen to 15 C.; with sixteen ethoxy units the cloud point is 18 C.; with seventeen ethoxy units the cloud point is 23 C.;
- the lower members are excellent detergents, while the higher members are, in addition, good emulsifiers. While all of the compounds, regardless of the number of ethoxy units, are excellent detergents with good foam 1 characteristics, the lower members give the best foam results.
- the suitable agents that may be used are the alkali metals,
- sodium and potassiums such as sodium and potassiums, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide,
- the color: of '-the-;.product was equiv'alent -to ahoute4 .on'ithe Gardner-color: scale (Standards *of 1-933).
- Example 2 There was added to 747 parts of in a flask 50 parts of sodium hydroxide. The temperature was-raised to to-.80 C- to-acceleratedhendissolution-'ofzsodium hydroxide. To the rtiixturefwas added llSzpartsof benzyl chloride "over-a peritaiddfBO-minutes and the temperature of the system was increasedtolIO to C. The mixture wasstirred for. three; hours at which time 200 parts of "water was'added and the temperature raised to the boiling point of thecontents of the flask. The mixture'wasallowed to-settle'and form layers.
- the aqueous lower layer was discarded and the product upper layer :wassteam stripped to remove benzyl alcohol and benzyl chloride.
- the product was dried; by heating to 100 C. at 20 mm. pressure; and "filtered. 'Theproduct hadga Gardner'teolor value of about 3 and a :cloud point of about 2 C.
- the yield was 811 parts (97% 'o'f theoretical) Benzyl bromide "functions in a manner similar to benzyl chloride in this reaction.
- Example 6 There were added to 1540 parts of 100 parts of potassium ethoxide and 200 parts of benzyl bromide. The temperature of the system was raised to 135 to 150 C. and maintained at that level for about two and one-half hours. Water was added to the mixture and the temperature was increased to the boiling point. The mixture was allowed to settle and separate into layers. The aqueous lower layer was discarded and the product upper layer was steam stripped to remove benzyl alcohol and benzyl bromide. The product was dried and filtered. The yield was 1549 parts (95% of theoretical).
- Benzyl chloride produces the same result as benzyl bromide.
- Example 7 There was added to a mixture of 910 parts of osnnt emanation and 50 parts of sodium hydroxide 180 parts of benzyl chloride.
- the benzyl chloride was added at a rate of about 6 parts per minute during which time the tempera ture of the system was raised to 135 to 150 C. The temperature was maintained at this level for about two hours and then water was added to the system. The mixture formed layers and the water layer was removed and discarded. The product layer was steam stripped, dried, and filtered.
- the benzyl ether product was obtained in the amount of 952 parts (95% of theoretical).
- the Gardner color value of the product was about 5 and the cloud point was 18 C.
- Detergency and foam characteristics were determined on the products obtained from the above examples. All were excellent detergents when tested under dishwashing and laundering conditions. For instance, the octyl product containing 20 ethoxy units in the amount of 10 parts, in conjunction with 90 parts of an alkaline builder which was made up of 60% sodium tripolyphosphate, 20% sodium silicate, and 20% sodium sulfate, gave a 95% detergency rating in a standard mechanical dishwashing test which is markedly superior to known commercial detergents.
- R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty.
- composition of matter the compound having the formula C7Hi1 (O CHgCHDuO CHgCuHs 3.
- a composition of matter the compound having the formula 0.1119 (0 CHzCHzhaO CHzCaHIi 4.
- ClHn OCH:CH5z0O CHmCsHs 5.
- a composition of matter the compound having the formula 00H" (OCHgCHDWO CHrC6 5 6.
- a composition of matter the compound having the formula 7.
- R and n have the same significance as above, in the presence of a strongly basic inorganic neutralizing agent at a temperature of about 50 to 200 C., and then separating the product.
Description
United States Patent 0 BENZYL ETHERS 0F ALKYLPHENUXYPOLY- ETHOXYETHANOL Warren D. Niederhauser, Hunting-don Valley, and Edwin J. Smialkowski, Philadelphia, Pa., assignors to Robin & Haas Company, Philadelphia, Pa, a corporation of Delaware No Drawing. Application March 22, 1954 Serial No. 417,939
13 Claims. (Cl. 260-613) This invention relates to low-foaming non-ionic surface-active compositions. It also relates to a process by which these compositions are prepared.
The compounds of the present invention are represented by the formula nw CH2OH2),.O ontotm wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty. The process by which these compounds are prepared comprises reacting a compound of the formula in which R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, with benzyl chloride or bromidein the presence of a strongly basic inorganic neutralizing agent. The use of benzyl chloride is somewhat preferable to the use of benzyl nwomornnon wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, are.
known and available, and usually exhibit surface activity in varying degrees of practical utility. A unit or two of propylene oxide may be "substituted for a similar amount of ethylene oxide without substantially altering the identifying characteristics of the compound. Propylene oxide and ethylene oxide are equivalent to this extent. The formation of a benzyl ether from the abovetype compound results in a product having low-foam detergent properties superior to those of the parent compound.
Although the compounds prepared by the use of benzyl chloride or bromide are considered of the greatest practical importance, satisfactorily-useful compounds may be prepared from substituted benzyl chloride or bromide. The substituents on the benzene ring should be relatively inert to the reaction components of the present invention and may include the chloro, bromo, nitro, or lower alkyl groups. Compounds that have been found to be suitable include a number having alkyl groups, chlorine or bromine atoms, nitro groups, or combinations thereof,
More- 2,856,434 Patented Oct. 14, 1958 attached to a benzene ring as, for example, methylbenzyl chloride, dimethylbenzyl chloride, trimethylbenzyl chloride, ethylbenzyl chloride, ethylmethylbenzyl chloride, chlorobenzyl chloride, bromobenzyl chloride, chloromethylbenzyl chloride, nitrobenzyl chloride, and the like. The corresponding bromides are likewise suitable.
In the formula R 0 ornom)..on
R has been defined as an alkyl group of eight to fifteen carbon atoms. Actually, there may be more than one alkyl substituent on the benzene ring. It is only important that the total number of carbon atoms in all of the alkyl substituents range between eight and fifteen. Suitable for this use are the octyl, nonyl, decyl, dodecyl or pentadecyl groups as single substituents for R. Two
groups may also be substituted for R, as, for example, an octyl and an amyl, a nonyl and an amyl, a decyl and a propyl, a decyl and an amyl, or a dodecyl and a propyl. Even three groups may be substituted for R, as, for example, three amyl substituents. The positions or the alkyl groups on the benzene rings are not indicated because they are not critical. t
The number of ethoxy units employed may be varied,
as desired, within the range of twelve to forty. The
presence of twelve ethoxy units gives the compound a hydrophilic trait sufficient to assure water solubility when the alkyl substituent is an octyl group. The presence of additional ethoxy units tends to increase the water solubility of the present compounds which is particularly desirable as the alkyl substituent approaches the limit of fifteen carbon atoms. Compounds of the subject type exhibit the property of inverse solubility. That is, for
instance, as the temperature of an aqueous 1% solution is increased a point is reached where a turbidity appears. I
This is called the cloud point. As the number of ethoxy units is increased the cloud point gradually rises. instance, the cloud point of the octyl compound having the lowest number of ethoxy units contemplated within this invention, that is, twelve, is less than 2 C. With fifteen ethoxy units the cloud point has risen to 15 C.; with sixteen ethoxy units the cloud point is 18 C.; with seventeen ethoxy units the cloud point is 23 C.;
with twenty ethoxy units the cloud point has increased. -to 39 C.; and with the greatest number of ethoxy units,
forty, the cloud point has reached 52 C.
Of course, in some respects, there is a gradation of chemical and physical properties in considering the gamut of ethoxy units in the compounds. Generally, for instance, the lower members are excellent detergents, while the higher members are, in addition, good emulsifiers. While all of the compounds, regardless of the number of ethoxy units, are excellent detergents with good foam 1 characteristics, the lower members give the best foam results.
In the formation of the alkylphenoxypolyethoxyethan- 01s in the range of twelve to forty ethoxy units, there is sometimes obtained a mixture of compounds having different numbers of ethoxy units. This is known and is no deterrent to the present reaction since satisfactory and useful compounds are formed from the mixture of compounds in the same way as the individual compounds.
the suitable agents that may be used are the alkali metals,
such as sodium and potassiums, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide,
For I The choice of a specificpotassium ethoxide; sodium butoxide, sodium carbonate, lithiumhydroxide;-the'alkaliearth--metal-hydroxides;-such as barium hydroxide, calcium hydroxide and strontium hydroxide, and the like. The alkali agent should be present in an amountsomewhat; greaterthanthe molar amount of the alkylphenoxypolyethoxyethauol. "This is desirable to assure the complete --'neutralization of the hydrochloric tor hydrobromic acid formed in thereaction. The exeess agent causes no interference-with the desired result and may-easily be removed at =a-eonvenient later stage.
The reaction will satisfactorily occur in the range of temperatures from about 50 "to 200 C. The preferred range is about 100 to 150, C. "The temperature. of the reaction is t not extremely -critical I and temperatures may be-usrdother-than those mentioned. Howeverfithe best results are obtained -using-thetemperature ranges set forth above.
*The *reactionqis essentially i-cornpleted at the end .of about-"one hour althougha somewha't longer reaction time is usually provided -to *assure maximumresults. *The yieldsconsistently-average 93--to -97'% of the benzylether product-based on-=the weight ofthe alcohol used.
1f desired; the-reactio11 *may -be conducted in the; presence ofa'volatileyinert'organic solvent. Suitableffor1'this use-are benzene,-xylene, toluen e -and the; like. The use of sueh solve'nts isa matter of'choice' because thereaction proceeds satisfactorily without a solvent.
:At the conclusion =of the reaction 'the excess unused reactantsare removedfrom 'the productby'standardprocedures. The-reaction mixture is--washed with-water land -the. wash'water discarded. If*desired, an inert volatile-hydrocarbon solvent such asf-benzene. toluene, or the like, may be used-to' aidintheseparation of the water layer from the product layer. 'This is-not usually necessary and, if--not-'necessary, -would -not beused because su'cha step would add the -problem of removal of the hydrocarbon solvent-from the'product' layer. Unreacted benzyl-chloride or bromide and-formed benzyl alcohol are-preferably removed by vacuum steam distillation. The-product-is finally dried, preferably under-vacuum at any convenient temperature, and filtered.
The-method offorma'tion of'the products of this inven tion is set'forth in the following illustrative examples. Parts by wei'ght are used 'throughout.
.lExample l glntovi'a. fiaslercquipped -with a stirrer aud -azthcrmometer 82tpartssof 0.10 H210 B913 H layer wasisteamastripped to'remove toluene, :benzylzchloride, and benzylyalcohol. The-:productwas dried,'by heatingto;100-C.-at5-20 pressure-and filtered. The yield f thebenzyl ether .of
immtoetumt0it was' 860 pa-rts which= represents 95% aof-thattheoretically possible. The color: of '-the-;.product= was equiv'alent -to ahoute4 .on'ithe Gardner-color: scale (Standards *of 1-933). Therproduct-ahadua. cloudapoint of. 1 5 C.
"analogous manner.
Example 2 There was added to 747 parts of in a flask 50 parts of sodium hydroxide. The temperature was-raised to to-.80 C- to-acceleratedhendissolution-'ofzsodium hydroxide. To the rtiixturefwas added llSzpartsof benzyl chloride "over-a peritaiddfBO-minutes and the temperature of the system was increasedtolIO to C. The mixture wasstirred for. three; hours at which time 200 parts of "water was'added and the temperature raised to the boiling point of thecontents of the flask. The mixture'wasallowed to-settle'and form layers. The aqueous lower layer was discarded and the product upper layer :wassteam stripped to remove benzyl alcohol and benzyl chloride. The product was dried; by heating to 100 C. at 20 mm. pressure; and "filtered. 'Theproduct hadga Gardner'teolor value of about 3 and a :cloud point of about 2 C. The yield was 811 parts (97% 'o'f theoretical) Benzyl bromide "functions in a manner similar to benzyl chloride in this reaction. Metallic sodium or potassium or calcium hydroxide-maybe used as the alkali agent to producesimilan results.
The corresponding dodecyl- -and pentadecyl"alcohols=react to form similar products'in a-waysimilar-tmthe octyl alcohol.
---Example.3
rIQQSImat-ts of 701-par-ts of potassium*-hydrox'ide'was ad'ded. 0verja period of about --3 0-minutes '180-parts of benzyl chloride was added-and the temperature of the-system was, raised to=-l25ato "C. The'mixturewasstirredfor about three hoursandthen-ZOOparts ofwater were added. The temperature of-"the system was raised' to" the-boiling point and then**th e mixture-was allowed tosettle. and formilayers. 'T-The aqueous lowerla-yer was discarded and 'the product upper layer was -steam stripped to removewoiatile components. '1' he product was -drie'd""by .hcatiugdto 100-'- to 05 ---'C. "at 22 mm. pressure anddilteretl.
. product hada Gardner colorwalue'of -"about 4 and -a"cloud point of 23 C. The yield of the benzylether was 1002 parts (96% of theoretical).
The corresponding nonyl and decyl alcohols react similarly to the octyl alcohol.
Example-.4
' To. a .mixtuteQf;1086 parts of discarded. "The upper layer-was steam strippedyand'then drie'dand-filtered. Ayield of "l'096 parts j(93'% o'fftheoretical) --was obtained. The color 'of'the pro'ductwas about' 5on the Gardner scale. It'had a cloudpoint'o'f 39C.
The corresponding Pdecylamyl --alcohol-- works satisfactorily in thisexample.
Example A 60-part portion of sodium methoxide was added to 1966 parts of I To this mixture, 175 parts of benzyl chloride was added over a period of 28 to 30 minutes. The temperature of the system was adjusted to 120 to 135 C. for a period of three hours. Water was added and a separation into layers efiected. The water layer was discarded and the product layer was steam stripped to remove volatile components. The product was dried by he'atingand then filtered. A yield of 1961 parts (95% oftheoreticallwas obtained. The benzyl ether product had a color of 4 to 5 on the Gardner color scale and a cloud point of 52 C.
Sodium or potassium hydroxide produces results similar to those produced by sodium methoxide.
Example 6 There were added to 1540 parts of 100 parts of potassium ethoxide and 200 parts of benzyl bromide. The temperature of the system was raised to 135 to 150 C. and maintained at that level for about two and one-half hours. Water was added to the mixture and the temperature was increased to the boiling point. The mixture was allowed to settle and separate into layers. The aqueous lower layer was discarded and the product upper layer was steam stripped to remove benzyl alcohol and benzyl bromide. The product was dried and filtered. The yield was 1549 parts (95% of theoretical).
Benzyl chloride produces the same result as benzyl bromide. Sodium methoxide and sodium ethoxide per form in the same manner as potassium ethoxide.
Example 7 There was added to a mixture of 910 parts of osnnt emanation and 50 parts of sodium hydroxide 180 parts of benzyl chloride. The benzyl chloride was added at a rate of about 6 parts per minute during which time the tempera ture of the system was raised to 135 to 150 C. The temperature was maintained at this level for about two hours and then water was added to the system. The mixture formed layers and the water layer was removed and discarded. The product layer was steam stripped, dried, and filtered. The benzyl ether product was obtained in the amount of 952 parts (95% of theoretical). The Gardner color value of the product was about 5 and the cloud point was 18 C.
Detergency and foam characteristics were determined on the products obtained from the above examples. All were excellent detergents when tested under dishwashing and laundering conditions. For instance, the octyl product containing 20 ethoxy units in the amount of 10 parts, in conjunction with 90 parts of an alkaline builder which was made up of 60% sodium tripolyphosphate, 20% sodium silicate, and 20% sodium sulfate, gave a 95% detergency rating in a standard mechanical dishwashing test which is markedly superior to known commercial detergents.
The foam characteristics of these compounds at 70 C. were determined under simulated mechanical dishwashing conditions. All were excellent. The following shows the foam results on the octyl compounds:
Foam heights in cm; Compound with 12 ethoxy units 0.0 Compound with 15 ethoxy units 0.0 Compound with 16 ethoxy units 0.0
Compound with 17 ethoxy units 0.0
These results indicated foam characteristics superior to those of known commercial compounds of the corresponding polyethoxy alcohol type which under identical conditions gave foam heights of 9.0 to 11.8 cm. The
wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty.
2. As a composition of matter the compound having the formula C7Hi1 (O CHgCHDuO CHgCuHs 3. As a composition of matter the compound having the formula 0.1119 (0 CHzCHzhaO CHzCaHIi 4. As a composition of matter the compound having the formula ClHn (OCH:CH5)z0O CHmCsHs 5. As a composition of matter the compound having the formula 00H" (OCHgCHDWO CHrC6 5 6. As a composition of matter the compound having the formula 7. A process for the preparation of compounds having the formula wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, comprising reacting a benzyl compound from the class consisting of benzyl bromide and benzyl chloride with an alcohol having the formula R (OOH:CHz)..OH
wherein R and n have the same significance as above, in the presence of a strongly basic inorganic neutralizing agent at a temperature of about 50 to 200 C., and then separating the product. i
8. A process as defined in claim 7 wherein R is an octyl group and n is equal to 12.
9. A process as defined in claim 7 wherein R is a nonyl group and n is equal to 15.
10. A process as defined in claim 7 wherein R is an octyl group and n is equal to 20.
11. A process as defined in claim 7 wherein R is a nonyl group and n is equal to 30.
12. A process as defined in claim 7 wherein R is an octyl group and n is equal to 40.
13. A process for the preparation of compounds having the formula wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer; from: twelve to forty, comprising reacting a benzyl compound. from. the class consisting of bromide and chloride with an alcohol having the formula,
womcmnon wherein R and n have the same significance as" above,
in the presence of'anexcessof zr-,strong-1y-basic inorganic" neutralizing agent at a-temperatureof'a-bout 50 to 200 C., then Washing the reaction mixture with Water, removing the volatile components by distillation, drying by heating up to 100' C; at" about 20 mm. pressure, and obtaining the product as the residue.
References Cited. in thefile of this patent UNITED STATES PATENTS 2,178,831
OTHER REFERENCES Schwartz et al;; Surface Active Agents 1949 pp. 18,,
LUncist'ed et aL; Journal Amer. Oil Chemists Society, vol. 285 (1951), p. 295.
Main
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,856,434 October 14, 1958 Warren D. Niederhauser et a1.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 4, lines 34 to 36, Example 3, the formula should appear as shown below instead of as in the patenta nwCHaCH2h1OH column 6, lines 21 to 23, claim 2, the formula should appear as shown below instead of as in the patent CsH1 (0CEnCHg)uOCHQOQH5 lines 41 to 43, claim 6, the formula should appear-as shown below instead of as in the patentmmQwomommo 01110511,
Signed and sealed this 20th day of January 1959.
[SEAL] Attest KARL H. AXLINE, ROBERT C. WATSON, Attesting Oficer. Gammissz'oner of Patents.
Claims (1)
1. AS COMPOSITIONS OF MATTER THE COMPOUNDS HAVING THE FORMULA
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2913416A (en) * | 1955-03-04 | 1959-11-17 | Rohm & Haas | Liquid detergent composition |
US3072515A (en) * | 1959-03-09 | 1963-01-08 | Diversey Corp | Method and composition for chemically polishing metals |
US3082172A (en) * | 1960-04-05 | 1963-03-19 | Economics Lab | Defoaming rinse composition |
US3123561A (en) * | 1961-01-04 | 1964-03-03 | Hydroxyphenyl | |
US3281475A (en) * | 1962-02-06 | 1966-10-25 | Rohm & Haas | Process for preparing olefin-terminated alkylphenoxypolyethoxyethanols |
US3293191A (en) * | 1961-06-26 | 1966-12-20 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
US3314891A (en) * | 1964-05-27 | 1967-04-18 | Wyandotte Chemicals Corp | Low foaming detergent |
US3334147A (en) * | 1962-02-28 | 1967-08-01 | Economics Lab | Defoaming and surface active compositions |
US3359205A (en) * | 1962-12-05 | 1967-12-19 | Monsanto Co | Detergent composition containing substituted benzyl ether non-ionic detergents |
US3444242A (en) * | 1968-03-04 | 1969-05-13 | Economics Lab | Surface active agents |
DE2800710A1 (en) * | 1978-01-09 | 1979-07-12 | Kuraray Co | High purity etherified polyoxyalkylene cpds. prepn. - by etherifying polyoxyalkylene which has been treated with hydrogen in presence of hydrogenating catalyst |
US4518459A (en) * | 1979-11-13 | 1985-05-21 | Economics Laboratory, Inc. | Methods of deinking secondary fibers |
US5286300A (en) * | 1991-02-13 | 1994-02-15 | Man-Gill Chemical Company | Rinse aid and lubricant |
US5417808A (en) * | 1991-08-30 | 1995-05-23 | Lion Corporation | Deinking composition for flotation and deinking method |
US5503768A (en) * | 1991-06-06 | 1996-04-02 | S.T. Chemical Co., Ltd. | Halogen scavengers |
US5583097A (en) * | 1994-04-22 | 1996-12-10 | Ppg Industries, Inc. | Deinking agent of nonionic surfactants |
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US2178831A (en) * | 1938-04-26 | 1939-11-07 | Rohm & Haas | Aromatic polyalkylene ethers |
US2233381A (en) * | 1940-03-06 | 1941-02-25 | Petrolite Corp | Flooding process for recovering oil from subterranean oil-bearing strata |
US2527506A (en) * | 1950-10-24 | Etheks | ||
US2596091A (en) * | 1950-03-28 | 1952-05-13 | Rohm & Haas | Nonionic surface-active agents |
US2609344A (en) * | 1948-08-14 | 1952-09-02 | Nat Aluminate Corp | Prevention of foaming in steam generation |
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US2527506A (en) * | 1950-10-24 | Etheks | ||
US2178831A (en) * | 1938-04-26 | 1939-11-07 | Rohm & Haas | Aromatic polyalkylene ethers |
US2233381A (en) * | 1940-03-06 | 1941-02-25 | Petrolite Corp | Flooding process for recovering oil from subterranean oil-bearing strata |
US2609344A (en) * | 1948-08-14 | 1952-09-02 | Nat Aluminate Corp | Prevention of foaming in steam generation |
US2596091A (en) * | 1950-03-28 | 1952-05-13 | Rohm & Haas | Nonionic surface-active agents |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2913416A (en) * | 1955-03-04 | 1959-11-17 | Rohm & Haas | Liquid detergent composition |
US3072515A (en) * | 1959-03-09 | 1963-01-08 | Diversey Corp | Method and composition for chemically polishing metals |
US3082172A (en) * | 1960-04-05 | 1963-03-19 | Economics Lab | Defoaming rinse composition |
US3123561A (en) * | 1961-01-04 | 1964-03-03 | Hydroxyphenyl | |
US3293191A (en) * | 1961-06-26 | 1966-12-20 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
US3281475A (en) * | 1962-02-06 | 1966-10-25 | Rohm & Haas | Process for preparing olefin-terminated alkylphenoxypolyethoxyethanols |
US3334147A (en) * | 1962-02-28 | 1967-08-01 | Economics Lab | Defoaming and surface active compositions |
US3359205A (en) * | 1962-12-05 | 1967-12-19 | Monsanto Co | Detergent composition containing substituted benzyl ether non-ionic detergents |
US3314891A (en) * | 1964-05-27 | 1967-04-18 | Wyandotte Chemicals Corp | Low foaming detergent |
US3444242A (en) * | 1968-03-04 | 1969-05-13 | Economics Lab | Surface active agents |
DE2800710A1 (en) * | 1978-01-09 | 1979-07-12 | Kuraray Co | High purity etherified polyoxyalkylene cpds. prepn. - by etherifying polyoxyalkylene which has been treated with hydrogen in presence of hydrogenating catalyst |
US4518459A (en) * | 1979-11-13 | 1985-05-21 | Economics Laboratory, Inc. | Methods of deinking secondary fibers |
US5286300A (en) * | 1991-02-13 | 1994-02-15 | Man-Gill Chemical Company | Rinse aid and lubricant |
US5503768A (en) * | 1991-06-06 | 1996-04-02 | S.T. Chemical Co., Ltd. | Halogen scavengers |
US5417808A (en) * | 1991-08-30 | 1995-05-23 | Lion Corporation | Deinking composition for flotation and deinking method |
US5583097A (en) * | 1994-04-22 | 1996-12-10 | Ppg Industries, Inc. | Deinking agent of nonionic surfactants |
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