US2905681A - Surface-active formals - Google Patents
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- US2905681A US2905681A US685797A US68579757A US2905681A US 2905681 A US2905681 A US 2905681A US 685797 A US685797 A US 685797A US 68579757 A US68579757 A US 68579757A US 2905681 A US2905681 A US 2905681A
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- 239000000203 mixture Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- -1 or a water-soluble Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 125000005037 alkyl phenyl group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 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 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 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 3
- 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 3
- 239000001993 wax Substances 0.000 description 3
- 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 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- XCHDYWCWXAASER-UHFFFAOYSA-N chloromethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCl XCHDYWCWXAASER-UHFFFAOYSA-N 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=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 2
- 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 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 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
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZBJJDYGJCNTNTH-UHFFFAOYSA-N Betahistine mesilate Chemical group CS(O)(=O)=O.CS(O)(=O)=O.CNCCC1=CC=CC=N1 ZBJJDYGJCNTNTH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001397173 Kali <angiosperm> Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 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
- 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000755 henicosyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ILHIHKRJJMKBEE-UHFFFAOYSA-N hydroperoxyethane Chemical compound CCOO ILHIHKRJJMKBEE-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
Definitions
- the present invention concerns specific surface-active formals. It is further concerned with specific surfaceactive formals that are stable under alkaline or neutral conditions but which may be altered by acidic conditions. This alteration may take the form of changing an oilsoluble, surface-active compound toa water-soluble, surface-active compound, or a water-soluble, surface-active compound to one of lessened or substantially no surface activity. This invention also concerns a method for the preparation of the specific surface-active formals.
- the acid-sensitive, non-ionic, surface-active formals of this invention may be represented by the formula in which R represents an alkyl group of 8 to 21 carbon atoms, n is an integer from 6 to 50, and Z is an alkyl group of 8 to 18 carbon atoms, an alkenyl group of 8 to 18 carbon atoms, or an alkylphenyl group in which the alkyl portion has from 8 to 24 carbon atoms.
- R may typically be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, heptadeeyl, octadecyl, nonodecyl, heneicosyl, or the like, in any of the known spatial configurations, such as normal, iso, or tertiary.
- the integer It varies from 6 to about 50.
- n ranges from about 6 to 12
- the product is oil soluble
- n ranges from 13 to about 50
- the product is substantially water soluble.
- Z may represent an alkyl group of 8 to 18 carbon atoms, such as octyl, nonyl, decyl, dodecyl, pentadecyl, and octadecyl.
- Z may also represent an alkenyl group of 8 to 18 carbon atoms, such as octenyl, nonenyl, decenyl, dodecenyl, hexadecenyl, and octadecenyl.
- Z further may represent an alkylphenyl group in which the alkyl portion contains 8 to 24 carbon atoms and may be in the form of one or more alkyl groups as long as the restriction, as to range of carbon atoms, is ad hered to;
- Typical alkylphenyl representations of Z include octylphenyl, nonylphenyl, dodecylphenyl, octadecylphenyl, dioctylphenyl, dinonylphenyl, didodecylphenyl, and tetracosylphenyl.
- the alkyl and alkenyl representations of Z as well as the alkyl portion of the alkylphenyl representation of Z may exhibit any of the known spatial configurations, such as normal, iso, or tertiary.
- the alkenyl groups may have the double bond in any of the possible locations.
- the alkyl group or groups, as the case may be, in the alkylphenyl representation of Z, may be positioned at any of the possible loca tions on the benzene ring.
- Z Particularly useful are those representations of Z that include octyl, nonyl, dodecyl, octadeeyl, oc'tenyl, decenyl, dodecenyl, octadecenyl, octyl phenyl, nonylphenyl, dodecylphenyl, dioctylphenyl, and dinenylph y
- non-ionicsurface-active agents is known in the art, and usually these are stable in acid, basic, and neutral media In many applications, it is necessary or at least highly desirable to remove or change the surface activity of an agent at some critical point in the operation.
- an ordinary, non-ionic, surface-active agent is used to remove oils and waxes from raw wool by emulsification, there is obtained an emulsion in water which is not easily broken, either for the recovery of the oils and waxes or purposes of disposal.
- the effluent from commercial laundries sium carbonate; and the like.
- non-ionic detergents remains highly surface active, causing many troublesome problems of foaming and disposal. Further, when non-ionic, surface-active agents are used for the recovery of petroleum, there is obtained an emulsion which is not easily broken without the use of certain complex and expensive demulsifying agents.
- the present compounds can be used in all of the above situations by employing a step in which the objectionable emulsions are treated with dilute acids which, since there is an alteration in the surface-active properties of the present compounds, permits the ready and effective conclusion of the operations described heretofore.
- the subject compounds may also be used in the preparation of emulsion polymers which can Well be coagulated, if desired, in fiber form by treatment with dilute acids.
- the present compounds are useful general-purpose detergents that exhibit low foam, good detergency, and highcloud points.
- the two high molecular weight hydrophobic groups in the compounds of this invention contribute to the oilsolubility of the molecule up to-quite high molecular weights as represented by the number of oxyethylene units. For this reason, it is possible to prepare compounds which are initially oil-solubl e and water-insoluble, with sufiicient surface activity to function as emulsifying and suspending agents. Solutions of these compounds may be altered by acidic conditions in water to convert them to water-soluble, surface-active compounds. Thus, the surface activity can be transferred from the oil phase to the water phase. Another advantage of these compounds is the small amount of foam which is generated in water solutions.
- the present compounds are preferably prepared byreacting a compound having the formula II RCOCH X with one having the formula ZO CH CH O) ,,H
- alkali metals such as sodium and I potassium
- alkali metal hydroxides such as sodium hydrox1de, potassium hydroxide, or lithium hydroxide
- alkaline earth metal hydroxides such as barium hydroxide, calcium hydroxide, and strontium hydroxide
- aI-' kali metal carbonates such as sodium carbonate, potas-
- the basic agent should be present in an amount somewhat greater than an equivalent amount of the reactants in order'to'assure the complete neutralization of the hydrochloric or hydrobromic acid formed in the reaction.
- the compounds of this invention are prepared by conducting the reaction in the temperature range of about l0 to 40 C., preferably 0 to 20 C.
- the reaction is exothermic in nature. It is preferred to mix the alcohol and the halogenated compound in a solvent and then add the basic agent gradually in small amounts.
- Suitable as a solvent in this respect are benzene, toluene, xylene,'ancl the like. Reaction time is not critical but generallyiwill vary from about 30 minutes to 10 hours or more, depending largely on the individual reactants employed.
- Typical reactants that may be employed include:
- the reactants of this invention are known compounds or readily prepared by known methods. In a preparation of the ethoxy alcohol reactants having 6 to 50 ethoxy units, there is frequently obtained a mixture of compounds having different members of ethoxy units. This is known in the art 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. it is to be understood, therefore, that the integer n stands for either the number of ethoxy units in a single compound or an average value in a mixture of compounds. Likewise the reactants n i Joornx are derived from fatty acids which are obtained frequently in commercial practice as mixtures. These mixtures also lead to satisfactory and useful compounds.
- the halide salt formed as a reaction by-product is removed by filtration.
- the product is obtained as the filtrate. If a solvent has been employed, as indicated previously, it may be removed by stripping in a conventional manner. Even if a solvent has not been employed during the course of the reaction, the use of one is often advantageous in the isolation of the product in order to facilitate the removal of the inorganic halide salt formed.
- the products of this invention possess the hydrophobic-hydrophilic balance required for a substance to exhibit surface activity.
- a surface active material at one stage of a process and not have such material interfere at a later stage of the process as has been outlined heretofore.
- the present compounds may be used as valuable surfaceactive agents at one stage of a process and then chemically altered to change its surface-active characteristics at a later stage of the process as will be apparent hereinafter.
- the present compounds are quite stable in alkaline or neutral media but may be chemically altered in an acidic media, particularly at temperatures approaching about C.
- Hydrochloric acid or the like is particularly convenient and effective for use in this respect, and the change is effected usually in a matter of minutes, such as 5 or 10, depending largely on the temperatures and compounds involved.
- the present compound is split into three fragments: one, an oily, water-insoluble compound of no surface activity; two, formaldehyde; and the third, a water-soluble, surface-active compound.
- Example 1 There are introduced into a reaction vessel 25 parts of chloromethyl laurate, 60 parts of and 100 parts of benzene. The mixture is cooled to 5 C. and to it there is added gradually over a period one hour 8 parts of powdered commercial potassium hydroxide. The temperature is maintained below 10 C. during the addition of the potassium hydroxide by application of an ice-salt bath at intervals. The mixture is stirred at 10 C. for 2 hours and then allowed to come to room temperature. The reaction mixture is then filtered and the benzene is removed from the filtrate under vacuum to yield 65 parts of a light yellow oil.
- This oil is identified as octylphenoxynonaethoxymethyl laurate, C11H23COOCH2O 9C6H4C3H17.
- This product is soluble in hydrocarbon oils, and may be used to promote their emulsification with water.
- Example 2 There are introduced into a reaction vessel 50 parts of chloromethyl laurate, 116 parts of rz zs z Hz 9 The mixture is cooled to 20 C. and to it is added in portions 5 parts of powdered sodium hydroxide over a period of /5 hour. The mixture is held at 20 C. by use of an ice-bath. The mixture is stirred for one hour after, the end of the addition of the sodium hydroxide and then allowed to come to room temperature.
- composition of matter having the formula R'OCHflOCHgCHQnOZ in which R is an alkyl grotp of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is an alkyl group of 8 to l8 carbon atoms.
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
United States Patent SURFACE-ACTIVE FORMALS Peter de Bonneville and Homer J. Sims, Philadelphia, Pa, assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 24, 1957 Serial No. 685,797
9 Claims. (Cl. 260-4106) The present invention concerns specific surface-active formals. It is further concerned with specific surfaceactive formals that are stable under alkaline or neutral conditions but which may be altered by acidic conditions. This alteration may take the form of changing an oilsoluble, surface-active compound toa water-soluble, surface-active compound, or a water-soluble, surface-active compound to one of lessened or substantially no surface activity. This invention also concerns a method for the preparation of the specific surface-active formals.
The acid-sensitive, non-ionic, surface-active formals of this invention may be represented by the formula in which R represents an alkyl group of 8 to 21 carbon atoms, n is an integer from 6 to 50, and Z is an alkyl group of 8 to 18 carbon atoms, an alkenyl group of 8 to 18 carbon atoms, or an alkylphenyl group in which the alkyl portion has from 8 to 24 carbon atoms.
R may typically be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, heptadeeyl, octadecyl, nonodecyl, heneicosyl, or the like, in any of the known spatial configurations, such as normal, iso, or tertiary.
The integer It varies from 6 to about 50. When n ranges from about 6 to 12, the product is oil soluble, and when n ranges from 13 to about 50, the product is substantially water soluble.
Z may represent an alkyl group of 8 to 18 carbon atoms, such as octyl, nonyl, decyl, dodecyl, pentadecyl, and octadecyl. Z may also represent an alkenyl group of 8 to 18 carbon atoms, such as octenyl, nonenyl, decenyl, dodecenyl, hexadecenyl, and octadecenyl. Z further may represent an alkylphenyl group in which the alkyl portion contains 8 to 24 carbon atoms and may be in the form of one or more alkyl groups as long as the restriction, as to range of carbon atoms, is ad hered to; Typical alkylphenyl representations of Z include octylphenyl, nonylphenyl, dodecylphenyl, octadecylphenyl, dioctylphenyl, dinonylphenyl, didodecylphenyl, and tetracosylphenyl. The alkyl and alkenyl representations of Z as well as the alkyl portion of the alkylphenyl representation of Z may exhibit any of the known spatial configurations, such as normal, iso, or tertiary. The alkenyl groups may have the double bond in any of the possible locations. The alkyl group or groups, as the case may be, in the alkylphenyl representation of Z, may be positioned at any of the possible loca tions on the benzene ring. Particularly useful are those representations of Z that include octyl, nonyl, dodecyl, octadeeyl, oc'tenyl, decenyl, dodecenyl, octadecenyl, octyl phenyl, nonylphenyl, dodecylphenyl, dioctylphenyl, and dinenylph y A wide variety of non-ionicsurface-active agents is known in the art, and usually these are stable in acid, basic, and neutral media In many applications, it is necessary or at least highly desirable to remove or change the surface activity of an agent at some critical point in the operation. For example, if an ordinary, non-ionic, surface-active agent is used to remove oils and waxes from raw wool by emulsification, there is obtained an emulsion in water which is not easily broken, either for the recovery of the oils and waxes or purposes of disposal. Also, the effluent from commercial laundries sium carbonate; and the like.
using non-ionic detergents remains highly surface active, causing many troublesome problems of foaming and disposal. Further, when non-ionic, surface-active agents are used for the recovery of petroleum, there is obtained an emulsion which is not easily broken without the use of certain complex and expensive demulsifying agents. The present compounds can be used in all of the above situations by employing a step in which the objectionable emulsions are treated with dilute acids which, since there is an alteration in the surface-active properties of the present compounds, permits the ready and effective conclusion of the operations described heretofore. The subject compounds may also be used in the preparation of emulsion polymers which can Well be coagulated, if desired, in fiber form by treatment with dilute acids. The present compounds are useful general-purpose detergents that exhibit low foam, good detergency, and highcloud points.
The two high molecular weight hydrophobic groups in the compounds of this invention contribute to the oilsolubility of the molecule up to-quite high molecular weights as represented by the number of oxyethylene units. For this reason, it is possible to prepare compounds which are initially oil-solubl e and water-insoluble, with sufiicient surface activity to function as emulsifying and suspending agents. Solutions of these compounds may be altered by acidic conditions in water to convert them to water-soluble, surface-active compounds. Thus, the surface activity can be transferred from the oil phase to the water phase. Another advantage of these compounds is the small amount of foam which is generated in water solutions.
The present compounds are preferably prepared byreacting a compound having the formula II RCOCH X with one having the formula ZO CH CH O) ,,H
ducted in the presence of a strongly basic inorganic neutrallzmg agent. Among the basic agents that may be employed are the. alkali metals, such as sodium and I potassium; the alkali metal hydroxides, such as sodium hydrox1de, potassium hydroxide, or lithium hydroxide;
alkaline earth metal hydroxides, such as barium hydroxide, calcium hydroxide, and strontium hydroxide; aI-' kali metal carbonates, such as sodium carbonate, potas- The basic agent should be present in an amount somewhat greater than an equivalent amount of the reactants in order'to'assure the complete neutralization of the hydrochloric or hydrobromic acid formed in the reaction.
The compounds of this invention are prepared by conducting the reaction in the temperature range of about l0 to 40 C., preferably 0 to 20 C. The reaction is exothermic in nature. It is preferred to mix the alcohol and the halogenated compound in a solvent and then add the basic agent gradually in small amounts. Suitable as a solvent in this respect are benzene, toluene, xylene,'ancl the like. Reaction time is not critical but generallyiwill vary from about 30 minutes to 10 hours or more, depending largely on the individual reactants employed.
While a solvent is not required in this reaction, one is effects of the exodesirable in order to minimize the thermic nature of the reaction as previously indicated and also in order to aid in the separation of the inorganic salt by-product formed.
Typical reactants that may be employed include:
ll CsHn 0 OHQO].
ll Q mCOCHzCI ll in aGOGH Br ll 01 E3 0 0 OHQOI 018E210 OCHaCl ll oumgooomoi or any mixtures thereof,
The reactants of this invention are known compounds or readily prepared by known methods. In a preparation of the ethoxy alcohol reactants having 6 to 50 ethoxy units, there is frequently obtained a mixture of compounds having different members of ethoxy units. This is known in the art 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. it is to be understood, therefore, that the integer n stands for either the number of ethoxy units in a single compound or an average value in a mixture of compounds. Likewise the reactants n i Joornx are derived from fatty acids which are obtained frequently in commercial practice as mixtures. These mixtures also lead to satisfactory and useful compounds.
At the conclusion of the reaction, the halide salt formed as a reaction by-product is removed by filtration. The product is obtained as the filtrate. If a solvent has been employed, as indicated previously, it may be removed by stripping in a conventional manner. Even if a solvent has not been employed during the course of the reaction, the use of one is often advantageous in the isolation of the product in order to facilitate the removal of the inorganic halide salt formed.
The products of this invention, having the utilities previously stated, possess the hydrophobic-hydrophilic balance required for a substance to exhibit surface activity. As has been presented previously, it is frequently desirable to employ a surface active material at one stage of a process and not have such material interfere at a later stage of the process as has been outlined heretofore. The present compounds may be used as valuable surfaceactive agents at one stage of a process and then chemically altered to change its surface-active characteristics at a later stage of the process as will be apparent hereinafter. The present compounds are quite stable in alkaline or neutral media but may be chemically altered in an acidic media, particularly at temperatures approaching about C. Hydrochloric acid or the like is particularly convenient and effective for use in this respect, and the change is effected usually in a matter of minutes, such as 5 or 10, depending largely on the temperatures and compounds involved. The present compound is split into three fragments: one, an oily, water-insoluble compound of no surface activity; two, formaldehyde; and the third, a water-soluble, surface-active compound.
7 The compounds of this invention, as well as the methods for their preparation, may be more fully understood from the following examples which are offered by way of illustration and not by way of limitation. Parts by weight are used throughout.
Example 1 There are introduced into a reaction vessel 25 parts of chloromethyl laurate, 60 parts of and 100 parts of benzene. The mixture is cooled to 5 C. and to it there is added gradually over a period one hour 8 parts of powdered commercial potassium hydroxide. The temperature is maintained below 10 C. during the addition of the potassium hydroxide by application of an ice-salt bath at intervals. The mixture is stirred at 10 C. for 2 hours and then allowed to come to room temperature. The reaction mixture is then filtered and the benzene is removed from the filtrate under vacuum to yield 65 parts of a light yellow oil. This oil is identified as octylphenoxynonaethoxymethyl laurate, C11H23COOCH2O 9C6H4C3H17. This product is soluble in hydrocarbon oils, and may be used to promote their emulsification with water.
In like manner there are prepared emulsification.
By the same procedure there are also prepared 21 43 2 z z 5o e 4 12 25 a l'i z z z 34C6H3 12 25) z and C H COOCH O(CH CH O) C H C H which are water-soluble waxes useful as detergents and emulsifiers.
Example 2 There are introduced into a reaction vessel 50 parts of chloromethyl laurate, 116 parts of rz zs z Hz 9 The mixture is cooled to 20 C. and to it is added in portions 5 parts of powdered sodium hydroxide over a period of /5 hour. The mixture is held at 20 C. by use of an ice-bath. The mixture is stirred for one hour after, the end of the addition of the sodium hydroxide and then allowed to come to room temperature. It is filtered and the benzene is removed from the filtrate under vacuum to yield 130 parts of a clear, light yellow oil which is identified as dodecycloxynonaethoxymethyl laurate C H COOCH O (CH CH O C H In similar manner there are prepared C H COOCH O (CH CH O C H C H COOCH O CH CH O C H 21 43 2 2 z )o 1a :-1'7 and rs z'z z z z 20C18H35 We claim: 1. A composition of matter having the formula R OCH2(OCHZC 2)nOZ in which R is an alkyl group of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is a member of the class consisting of alkyl groups of 8 to 18 carbon atoms, alkenyl groups of 8 to 18 carbon atoms, and alkylphenyl groups in which the alkyl portion has from 8 to 24 carbon atoms.
2. A composition of matter having the formula R'OCHflOCHgCHQnOZ in which R is an alkyl grotp of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is an alkyl group of 8 to l8 carbon atoms.
3. A composition of matter having the formula II R 0 0CH2(O cnlomnoz in which R is an alkyl group of 8 to 21 carbon atoms, n is an integer of from 6 to 50, and Z is an alkenyl group of 8 to 18 carbon atoms.
4. A composition of matter having the formula II R 0 0 0112(0 C 2 2)n Z in which R is an alkyl group of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is an alkylphenyl group in which the alkyl portion has from 8 to 24 carbon atoms.
5. A composition of matter having the formula References Cited in the file of this patent UNITED STATES PATENTS 2,395,265 Gresham Feb. 19', 1946 2,596,091 De Benneville May 13, 1952 2,796,423 Cottle et al. June 18, 1957 FOREIGN PATENTS 888,688 German Sept. 3, 1953 OTHER REFERENCES McCutcheon: Synthetic Detergents, 1950, pp. 156- 157.
Claims (2)
1. A COMPOSITION OF MATTER HAVING THE FORMULA
2. A COMPOSITION OF MATTER HAVING THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US685797A US2905681A (en) | 1957-09-24 | 1957-09-24 | Surface-active formals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US685797A US2905681A (en) | 1957-09-24 | 1957-09-24 | Surface-active formals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2905681A true US2905681A (en) | 1959-09-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US685797A Expired - Lifetime US2905681A (en) | 1957-09-24 | 1957-09-24 | Surface-active formals |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206486A (en) * | 1962-06-15 | 1965-09-14 | Dow Chemical Co | Polyglycol esters of olefinically unsaturated higher fatty acids |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2395265A (en) * | 1942-05-20 | 1946-02-19 | Du Pont | Preparation of dioxolane polymers |
| US2596091A (en) * | 1950-03-28 | 1952-05-13 | Rohm & Haas | Nonionic surface-active agents |
| DE888688C (en) * | 1944-07-16 | 1953-09-03 | Hoechst Ag | Process for the preparation of ester-like condensation products |
| US2796423A (en) * | 1952-12-01 | 1957-06-18 | Exxon Research Engineering Co | Formals of lubricating grade |
-
1957
- 1957-09-24 US US685797A patent/US2905681A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2395265A (en) * | 1942-05-20 | 1946-02-19 | Du Pont | Preparation of dioxolane polymers |
| DE888688C (en) * | 1944-07-16 | 1953-09-03 | Hoechst Ag | Process for the preparation of ester-like condensation products |
| US2596091A (en) * | 1950-03-28 | 1952-05-13 | Rohm & Haas | Nonionic surface-active agents |
| US2796423A (en) * | 1952-12-01 | 1957-06-18 | Exxon Research Engineering Co | Formals of lubricating grade |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206486A (en) * | 1962-06-15 | 1965-09-14 | Dow Chemical Co | Polyglycol esters of olefinically unsaturated higher fatty acids |
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