US2454543A - Polymeric detergents - Google Patents
Polymeric detergents Download PDFInfo
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- US2454543A US2454543A US2454543DA US2454543A US 2454543 A US2454543 A US 2454543A US 2454543D A US2454543D A US 2454543DA US 2454543 A US2454543 A US 2454543A
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- United States
- Prior art keywords
- phenol
- formaldehyde
- group
- substituted
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003599 detergent Substances 0.000 title description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 126
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 64
- 150000002989 phenols Chemical class 0.000 description 44
- 239000000047 product Substances 0.000 description 42
- 239000007859 condensation product Substances 0.000 description 38
- 125000004432 carbon atoms Chemical group C* 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000693 micelle Substances 0.000 description 28
- 229920002521 Macromolecule Polymers 0.000 description 26
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 230000004048 modification Effects 0.000 description 18
- 238000006011 modification reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 16
- 238000009833 condensation Methods 0.000 description 16
- 230000005494 condensation Effects 0.000 description 16
- 239000000344 soap Substances 0.000 description 16
- 125000002947 alkylene group Chemical group 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 229920001568 phenolic resin Polymers 0.000 description 12
- 239000000271 synthetic detergent Substances 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 150000001340 alkali metals Chemical class 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000005755 formation reaction Methods 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- -1 n-octyl Chemical group 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004900 laundering Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 210000004940 Nucleus Anatomy 0.000 description 4
- 230000002378 acidificating Effects 0.000 description 4
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 230000002209 hydrophobic Effects 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 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 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 229920001281 polyalkylene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- MQCUIYULLYRTPE-UHFFFAOYSA-N 1,4-bis(2-methylpropyl)cyclohexa-2,4-dien-1-ol Chemical class CC(C)CC1=CCC(O)(CC(C)C)C=C1 MQCUIYULLYRTPE-UHFFFAOYSA-N 0.000 description 2
- SOCLAPVGGRUYNS-UHFFFAOYSA-N 2,3-dicyclohexylphenol Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C1CCCCC1 SOCLAPVGGRUYNS-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-Dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- MOPDEMAOEMHGAS-UHFFFAOYSA-N 2-cyclohexyl-3-methylphenol Chemical compound CC1=CC=CC(O)=C1C1CCCCC1 MOPDEMAOEMHGAS-UHFFFAOYSA-N 0.000 description 2
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 2
- DLUMXTSYXVRNIP-UHFFFAOYSA-N 3,5-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(O)=CC(CC(C)C)=C1 DLUMXTSYXVRNIP-UHFFFAOYSA-N 0.000 description 2
- UEULEVKFYSYUCZ-UHFFFAOYSA-N 4-naphthalen-1-ylphenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=CC=CC=C12 UEULEVKFYSYUCZ-UHFFFAOYSA-N 0.000 description 2
- LZRRIVILFHXNLU-UHFFFAOYSA-N C(CCC)C=1C(=C(C=CC1)O)C1CCCCC1 Chemical compound C(CCC)C=1C(=C(C=CC1)O)C1CCCCC1 LZRRIVILFHXNLU-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000004297 Draba Species 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N Hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229960004011 Methenamine Drugs 0.000 description 2
- 210000002268 Wool Anatomy 0.000 description 2
- 241000933336 Ziziphus rignonii Species 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium(0) Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002153 concerted Effects 0.000 description 2
- 238000001816 cooling Methods 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
- 230000001419 dependent Effects 0.000 description 2
- 238000010790 dilution 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
- 238000004043 dyeing Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000002140 halogenating Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid 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
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
Definitions
- hydrophilic groups or portions so arranged and balanced as tobecome oriented at an interface.
- surface-active agents as, for example, alkali-metal soaps or quaternary ammonium compounds
- surface-active agents exist in water in the form of micelles. While the exact nature of such micelles is not established, there is evidence that they are. electrically charged aggregates of molecules. For example, when a sodium soap of a fatty acid is dispersed in water, it dissociates into positively charged sodium ions and into negative ions. Some of the latter apparently form aggregates with soap molecules and, as a result, negatively charged micelles are produced. Because the micelles carry a negative charge,- this type of soap is known as an anionactive detergent.
- detergents of the type of quaternary ammonium compounds yield positively charged micelles in aqueous solution and, hence, are known as cation-active soaps or agents.
- This conception of the formation of micelles is based on measurements of freezing points, vapor pressures, and electrical conductivities of aqueous dispersions of surface-active agents. It is further recognized that surface activity is related to the formation of such micelles and to the orientation of the micelles at an interface.
- the products of this invention differ fromand have advantages over -detergents known heretofore in that their effectiveness is not dependent upon the formation of loosely bound micelles.
- water-soluble macromolecules are synthesized in which all of the bonds between atoms are primary valence links and, hence, are strong and are not afiected by such factors as concentration and tempera ture.
- the synthesized macromolecules contain balanced hydrophilic and hydrophobic groups so positioned in the macromolecule that orientation can and does occur readily at an interface.
- the products of this invention may be made by condensing hydrocarbon-substituted phenols with formaldehyde to produce polymeric mate- 'rials which are in fact macromolecules and then introducing into said macromolecules hydrophilic groups.
- the hydrophilic groups which impart water solubility, may be ether-alcohol groups or esterified ether-alcohol groups and are introduced, for example, by the reaction of ethylene oxideor a propylene oxide or a butylene oxide with the macromolecule. If desired, the terminal hydroxyl of said ether-alcohol group may be converted into a salt-forming ester group of a polybasic acid.
- the resultant products may be considered to have three functional portions. Thus, they contain (a). as the hydrophobic portion, the hydrocarbon groups'attached to the phenol nucleus;
- the type of hydrocarbon group which is attached to the-phenol nucleus may vary as to kind but in every case must contain at least four carbon atoms. In reality, substituting groups of at least eight carbon atoms are much preferred. Generally, it is preferred that the substituent hydrocarbon group be a straight or branched chain acyclic group, such as n-butyl, iso-butyl, tertiary butyl, amyl, tertiary amyl, n-octyl, diisobutyl, decyl, dodecyl, hexadecyl, octadecyl, and
- phenols substituted with alicyclic groups may be used. These are typified by cyclohexyl phenol, methyl-cyclohexyl phenol, butyl-cyclohexyl phenol, and dicyclohexyl phenol. While aryl-su'bstituted phenols, such as p-phenyl phenol and p-naphthyl phenol, may be employed they are less satisfactory than those listed above unless they in turn contain an alkyl group. Thus, p-toly-l phenol is much preferred over p-phenyl phenol. Furthermore, a preference is given to the para-substituted phenols over those substituted in the ortho position. It is understood that although it is preferable to employ individual phenols, mixtures of phenols, for example, p-tert.amyland p-diisobutyl-phenols, may be employed.
- the ratio of formaldehyde should be between 0.5 and 1.0 mol per mol of phenol.
- 'I'he formaldehyde may be used in the form of a solution, such as the formalin of commerce, or in a polymeric form such as paraformaldehyde. Also, though not preferred, it may be in a form such as a formal 'or hexamethylene tetramine which will yield formaldehyde under the conditions of reaction.
- M is one equivalent of a metal, preferaibly of an alkali metal such as sodium, potassium, lithium, or a group 11 metal such as beryllium, magnesium, calcium, barium, or strontium, and a: is an integer greater than one.
- detergent products are preferably made by first reacting an alkali metal derivative of a hydrocarbon-substituted phenol-aldehyde polymer or macromolecule with a dihalogeno polyalkylene ether having the general formula, XR,-O-(RO)yR-X, in which X is a halogen, preferably chlorine, and R is an alkylene group, preferably of two to four carbon atoms,and y is zero or an integer.
- a strongly alkaline condensing agent such as sodium or potassium hydroxides
- condensation catalysts are preferred because of the ease with which the condensation may be controlled. Elevated temperatures naturally ac-- celerate the rate of reaction. Condensation of formaldehyde and substituted phenols such as are here involved does not proceed to the infusible stage and, accordingly, no limit need be imposed upon the degree of condensation. In practice, it is convenient to follow the extent of condensation by means of viscosity measurements and the condensation may be halted, at an early stage at which the molecular weight is low and the product This product is then heated with a water-soluble salt of sulfurous acid in aqueous or aqueous-alcoholic solution, and the final product has the general formula shown above.
- Theldihalogeno polyalkylene others which may be used-are typified by thefollowlng: [MY-dichlorodiethyl ether, '-dibromodipropyl ether, p49- dichlorrodiisopropyl ether, fi-chloroethoxyethylp'-chloroethyl ether, and higher homologues.
- the salts of sulfurous acid which are preferred are those of the alkali metals, especially of sodium, because these are water-soluble and most readily available.
- a polymeric condensate of a hydrocarbon-substituted phenol and formaldehyde may be condensed with 'an alkylene oxide, such as ethylene, a propylene oxide, or a butylene oxide, in the presence of an alkaline condensing agent.
- 'an alkylene oxide such as ethylene, a propylene oxide, or a butylene oxide
- an alkaline condensing agent Preferably, more than one mol of oxide per mol of phenol in said condensate isused and, in such a case, the product is a Polymeric detergents in which the hydrophilic or water-solubilizing groups are alcohols or saltforming partial esters thereof are the subjects phenoxypolyalkoxy alcohol having the general formula:
- a halogenating agent such as phosphorous penta- Step 4.-A mlxtme of 396 grams of the product chloride, phosphorous o yc lo der thionyl of step 3, M0 grams .of sodium sulflte, and 800 chloride.
- the halide is then reacted with an grams of water was heated and stirred in an inorganic sulfite salt, such as sodium sulflte, to autoclave for four hours at 160-l7d C.
- an inorganic sulfite salt such as sodium sulflte
- the products of this invention may be dewas surface-active in dilute aqueous solution. scribed as surface-active polymeric products of It had the following general formula:
- the roducts described herein on cooling, solidified to a brittle mass. 1 may be used in hard gate! or in water of mgh eti ffini'n' i 232F232 22332125 8f aliment- Theymawbeemployedunderacwic g 1 weremixed with parts of toluene and or alkaline conditions.
- Their advantage over heated at 120L135, under pressure for t synthetic detergents resides in the fact that they hours.
- the products of this invention are particularly useful when used in conjunction with other capillary-active agents, including fatty acid soaps and synthetic detergents such as those shown in United States Patents 2,115,192 and 2,143,759. Such combinations have extraordinarily high degrees of wetting and detergent properties.
- a modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing four to eighteen carbonatoms, and wherein the modification of said condensation product consists of the group 0.5 to 1.0 mol of formaldehyde and one mol of 'a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R' is a saturatethhydrocarbon substituent containing four to eighteen carbon atoms, and
- the modification of said condensation product consists of the group -(RO)'y-R,-SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula inwhich R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists of the group 1 -(RO)y--RSO3M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleous in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, 31 has a value of 0 to 19 inclusive, and M is a metal from the class con- (RO)1IRSO
- a modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to' brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of aphenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula OH v in which R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists vof the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurences is the same saturated alkylene group containing two to four carbon atoms, 11 has a value of zero to seven inclusive, and M is an alkali metal.
- a modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from'0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of orthosubstituted and para-substituted phenols, said phenol having the formula in which R'- is a saturated hydrocarbon substituent containing 4 .to 18 carbon atoms, and wherein '9 I the modification of said condensation pr'oduct consists of the group 4 r (C2H40) u Cal-I4 SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g has a value of to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.
- a modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an'oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, saidphenol having the formula in which a is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms,and wherein the modification of said condensation product consists of thegroup Y (CzHaO) y Cal-I4 SOaM in which R is a saturated hydrocarbon substitu ent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g; has a value of 0 to 19 inclusive,
- M is a metal from the group consisting of alkali and alkaline earth metals.
- a modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from-0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group (CaHaO) 1 C4Ha $03M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein y has a value of 0 to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.
- a modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and mol of a phenol having the formula and wherein the modification consists of the group (C2H4O) u C2H4 SOaNa replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein 11 has a value of 0 to 19 inclusive.
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Description
Patented Nov. 23, 1948 POLEMERIC DETERGENTS Louis B. Bock, lluntingdon Valley, and James L. Rainey, Abington, 2a., assisnors to Bohm (a Haas Company. Philadelphia, 2a., a corpora;
tionof Delaware slmllcatlon September 9, 1944, Serial No. 553,418
hydrophilic groups or portions so arranged and balanced as tobecome oriented at an interface.
It is generally recognized that surface-active agents, as, for example, alkali-metal soaps or quaternary ammonium compounds, exist in water in the form of micelles. While the exact nature of such micelles is not established, there is evidence that they are. electrically charged aggregates of molecules. For example, when a sodium soap of a fatty acid is dispersed in water, it dissociates into positively charged sodium ions and into negative ions. Some of the latter apparently form aggregates with soap molecules and, as a result, negatively charged micelles are produced. Because the micelles carry a negative charge,- this type of soap is known as an anionactive detergent. In contrast, detergents of the type of quaternary ammonium compounds yield positively charged micelles in aqueous solution and, hence, are known as cation-active soaps or agents. This conception of the formation of micelles is based on measurements of freezing points, vapor pressures, and electrical conductivities of aqueous dispersions of surface-active agents. It is further recognized that surface activity is related to the formation of such micelles and to the orientation of the micelles at an interface.
The individual molecules in colloidal micelles are held together only by physical forces or by weak seondary valences; and, as a result, the extent of micelle formation depends upon the prevailing conditions, and it is affected by such factors as the concentration of the surface-active agent, the presence of electrolytes, solvents, and other surface-active agents, and also upon the temperature. Thus, dilution of the solution, elevation of the temperature, or a change in the amount or any salts which" may also be present in solution favor the reversion of micelles into simple molecules and/or ions with the formation of true solutions. As an example, synthetic detergents known heretofore have no value at very low concentrations or in very hot water because under these conditions the micellar structure reverts, themolecules then exist in true solution, and, as a result, detergency is lost. The neces sity of using relatively high concentrationsplus the higher cost of synthetic detergents combines to make the use of such detergents uneconomical andoiten impractical. Furthermore, the materials are ineffective in many laundering operations wherein extremely hot water is used in order to accelerate the removal of soil.
The products of this invention differ fromand have advantages over -detergents known heretofore in that their effectiveness is not dependent upon the formation of loosely bound micelles. By the process of this invention, water-soluble macromolecules are synthesized in which all of the bonds between atoms are primary valence links and, hence, are strong and are not afiected by such factors as concentration and tempera ture. Furthermore, the synthesized macromolecules contain balanced hydrophilic and hydrophobic groups so positioned in the macromolecule that orientation can and does occur readily at an interface.
The products of this invention may be made by condensing hydrocarbon-substituted phenols with formaldehyde to produce polymeric mate- 'rials which are in fact macromolecules and then introducing into said macromolecules hydrophilic groups. The hydrophilic groups, which impart water solubility, may be ether-alcohol groups or esterified ether-alcohol groups and are introduced, for example, by the reaction of ethylene oxideor a propylene oxide or a butylene oxide with the macromolecule. If desired, the terminal hydroxyl of said ether-alcohol group may be converted into a salt-forming ester group of a polybasic acid.
The resultant products may be considered to have three functional portions. Thus, they contain (a). as the hydrophobic portion, the hydrocarbon groups'attached to the phenol nucleus;
(b) as the hydrophilic portion, the modified or v unmodified ether-alcohol groups, and (c) as the polymeric portion, the phenol nuclei joined by methylene bridges. The hydrocarbon groups attached to the phenol and the modified or unmodified ether-alcohol groups alsov attached to the phenol are so balanced as to assure water solubility and orientation at an interface. At the same time, the polymeric nature of the product assures such a high molecular weight that the product is in fact a macromolecule which imparts capillaryor surface-activity to a solution,
as (lo-micelles of ordinary soaps, but which is stable and is not dissociated as are the micelles of customary detergents under adverse conditions.
The above discussion is for purposes of theoretical explanation only, and it must be understood that the so-called three portions of the macromolecule are not independent of each other but are all combined inone large molecule which functions as a concerted whole.
The type of hydrocarbon group which is attached to the-phenol nucleus may vary as to kind but in every case must contain at least four carbon atoms. In reality, substituting groups of at least eight carbon atoms are much preferred. Generally, it is preferred that the substituent hydrocarbon group be a straight or branched chain acyclic group, such as n-butyl, iso-butyl, tertiary butyl, amyl, tertiary amyl, n-octyl, diisobutyl, decyl, dodecyl, hexadecyl, octadecyl, and
the like. Alternatively, phenols substituted with alicyclic groups may be used. These are typified by cyclohexyl phenol, methyl-cyclohexyl phenol, butyl-cyclohexyl phenol, and dicyclohexyl phenol. While aryl-su'bstituted phenols, such as p-phenyl phenol and p-naphthyl phenol, may be employed they are less satisfactory than those listed above unless they in turn contain an alkyl group. Thus, p-toly-l phenol is much preferred over p-phenyl phenol. Furthermore, a preference is given to the para-substituted phenols over those substituted in the ortho position. It is understood that although it is preferable to employ individual phenols, mixtures of phenols, for example, p-tert.amyland p-diisobutyl-phenols, may be employed.
The ratio of formaldehyde should be between 0.5 and 1.0 mol per mol of phenol. 'I'he formaldehyde may be used in the form of a solution, such as the formalin of commerce, or in a polymeric form such as paraformaldehyde. Also, though not preferred, it may be in a form such as a formal 'or hexamethylene tetramine which will yield formaldehyde under the conditions of reaction. I
Ordinarily, the substituted phenol and formaldehyde are reacted by condensing together in the presence of an acidic or alkaline condensation catalyst until the products have become relatively viscous. Solvents may be employed. Acidic hydrocarbon-substituted phenoxy alcohols. They have the following general formula:
three. or four carbon atoms, 3 is zero'or an integer between one and twenty and preferably between one and seven, M is one equivalent of a metal, preferaibly of an alkali metal such as sodium, potassium, lithium, or a group 11 metal such as beryllium, magnesium, calcium, barium, or strontium, and a: is an integer greater than one.
These detergent products are preferably made by first reacting an alkali metal derivative of a hydrocarbon-substituted phenol-aldehyde polymer or macromolecule with a dihalogeno polyalkylene ether having the general formula, XR,-O-(RO)yR-X, in which X is a halogen, preferably chlorine, and R is an alkylene group, preferably of two to four carbon atoms,and y is zero or an integer. The reaction is conducted in the presence of a strongly alkaline condensing agent, such as sodium or potassium hydroxides, and only one'terminal halogen reacts with the sodium derivative of the macromolecule. In this way', substituted ether halides having the following general formula are produced:
condensation catalysts are preferred because of the ease with which the condensation may be controlled. Elevated temperatures naturally ac-- celerate the rate of reaction. Condensation of formaldehyde and substituted phenols such as are here involved does not proceed to the infusible stage and, accordingly, no limit need be imposed upon the degree of condensation. In practice, it is convenient to follow the extent of condensation by means of viscosity measurements and the condensation may be halted, at an early stage at which the molecular weight is low and the product This product is then heated with a water-soluble salt of sulfurous acid in aqueous or aqueous-alcoholic solution, and the final product has the general formula shown above.
Theldihalogeno polyalkylene others which may be used-are typified by thefollowlng: [MY-dichlorodiethyl ether, '-dibromodipropyl ether, p49- dichlorrodiisopropyl ether, fi-chloroethoxyethylp'-chloroethyl ether, and higher homologues.
The salts of sulfurous acid which are preferred are those of the alkali metals, especially of sodium, because these are water-soluble and most readily available.
As an alternative method, a polymeric condensate of a hydrocarbon-substituted phenol and formaldehyde may be condensed with 'an alkylene oxide, such as ethylene, a propylene oxide, or a butylene oxide, in the presence of an alkaline condensing agent. Preferably, more than one mol of oxide per mol of phenol in said condensate isused and, in such a case, the product is a Polymeric detergents in which the hydrophilic or water-solubilizing groups are alcohols or saltforming partial esters thereof are the subjects phenoxypolyalkoxy alcohol having the general formula:
- preparation of alcoholshaving' the above general formula is discussed in application Serial No.
553,476, filed of even date. It is possible to react on a steam bath, diluted with 250 milliliters of more than one moi of alkylene oxide per mol of benzene, and then washed with two portions of phenol in the macromolecule. In fact, as many 400 milliliters each of water. The product was as sixty have been reacted. However, a maxdried with anhydrous M03, and the benzene imum of twenty is indicated as satisfactory and and toluene were stripped off. A yield of 457 between one and eight is preferred. The terminal grams was bt of a product having a h1 hydroxyl group of the compound is next 0011- rine content of 7.68% and a hydroxyl number verted to a halide, for example, by reaction with of 11.
a halogenating agent such as phosphorous penta- Step 4.-A mlxtme of 396 grams of the product chloride, phosphorous o yc lo der thionyl of step 3, M0 grams .of sodium sulflte, and 800 chloride. The halide is then reacted with an grams of water was heated and stirred in an inorganic sulfite salt, such as sodium sulflte, to autoclave for four hours at 160-l7d C. The
yield a sulfonate. product, a turbid paste, was soluble in water and when measured asa 60% solution in toluene arid,
The products of this invention may be dewas surface-active in dilute aqueous solution. scribed as surface-active polymeric products of It had the following general formula:
on, t. aHu 8311 high molecular weight containing in their chem- Although the above example is directed to the ical structure a plurality of salt-forming hydrouse of ethylene oxide, it is understood that a carbon-substituted phenoxy-alkoxy sulfonate propylene oxide or a butylene oxide may be emunits joined through the nuclei of said phenoxy ployed in a similar manner. In order to impart groups by means of methylene bridges. a given degree of water-solubility, it is advisable Following is an example which indicates the to use a greater amount of the higher oxides than preferred method of preparing the products of the amount of ethylene oxide required. Furtherthis invention. more, as the entire length of the hydrophilic Step 1. -Into a three-necked flask equipped group is increased, the product ordinarily becomes with thermometer, mechanical agitator, and remore water-soluble. It is, therefore-advisable flux condenser was charged the following: 412 to increase the hydrophobic group proportiongrams of diisobutyl phenol, 162 grams of a 37% ately. This can be done by increasing the size of aqueous solution of formaldehyde, and 27.6 grams the hydrocarbon substituent of the phenol, as of water. The mixture was agitated and heated represented by R in the above general formula. to atemperature of 90 C. At this point, 2.46 Inthis way, a balance is maintained between the grams of oxalic acid and 0.92 gram of Twitchells hydrophilic and hydrophobic portions of the reagent dissolved in ten grams of water was added. macromolecule so that the product is water- While being agitated, the reaction mixture was 40 soluble and at the same time capillary-active, in refluxed for six hours. Two hundred grams of that it becomes oriented at an interface.
water and 384 grams of toluene were added, and All of the products of this invention function refluxing was continued for an hour. Agitation as capillary-active or, surface-active agents. As was stopped and the contents of the flask were such, they become oriented at an interface, lower removed to a separatory funnel. The aqueous thesurface tension of water, and cause more rapid and re ino l y wer parated and the solwetting of surfaces such as the surfaces of fibers ventwas removed from the re ino s l yer b as measured by the standard Draves Sinking vacuum distillation. After the removal of the t Their outstanding property is their eflecsolvent, heating at areduced pressure Of 1.5 13-) tiveness as detergents In this capacity as measat temperature 9 t %5- ured by wash tests and laundering tests, they are was confirmed for four and one'half hours' e outstanding and are. far superior to soaps and condensate then had a viscosity of 4.0 poises Synthetic detergents known heretofore.
As detergents the roducts described herein on cooling, solidified to a brittle mass. 1 may be used in hard gate! or in water of mgh eti ffini'n' i 232F232 22332125 8f aliment- Theymawbeemployedunderacwic g 1 weremixed with parts of toluene and or alkaline conditions. Their advantage over heated at 120L135, under pressure for t synthetic detergents resides in the fact that they hours. This ratio corresponds to three mols 6f g'ggflffiggigg g d g rffi ggm s ggl g gfigs gi fifi i igg ff 'ffififififig 1 13333? 60 are excellent detergents at very low concentration, was further diluted to 50% solids con tions or at very high temperatures where former with toluene. Its structure may be represented Synthetic detergents failed. as r n w 1 They are uncommonly advantageous in the 1Q sHn I 21111 I Step 3.To 934 grams of a solution prepared laundering of cotton fabrics and in the securing as, in step 2 was added 213 grams of benzyldiof wool, sized. dyed, and printed fabrics in genmethylamine and grams of thlonyl chloride. eral. They may be used for preparing disper- The reaction mixture was heated for two hours sions of oil in water or dispersions of polymer izable materials prior to the polymerization thereof. Also, they serve to break water-in-oil emulsions Such as are encountered in oil-fields. And they have been found to be very satisfactory in the treatment of leather, in the dispersion of pigments, and as assistants in dyeing.
The products of this invention are particularly useful when used in conjunction with other capillary-active agents, including fatty acid soaps and synthetic detergents such as those shown in United States Patents 2,115,192 and 2,143,759. Such combinations have extraordinarily high degrees of wetting and detergent properties.
We claim:
1. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing four to eighteen carbonatoms, and wherein the modification of said condensation product consists of the group 0.5 to 1.0 mol of formaldehyde and one mol of 'a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R' is a saturatethhydrocarbon substituent containing four to eighteen carbon atoms, and
wherein the modification of said condensation product consists of the group -(RO)'y-R,-SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula inwhich R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists of the group 1 -(RO)y--RSO3M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleous in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, 31 has a value of 0 to 19 inclusive, and M is a metal from the class con- (RO)1IRSO3M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleous in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, :1; hasa value of zero to seven inclusive, and M is a metal from the class consisting of alkali and alkaline earth metals.
5. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to' brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of aphenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula OH v in which R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms, and wherein the modification of said condensation product consists vof the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurences is the same saturated alkylene group containing two to four carbon atoms, 11 has a value of zero to seven inclusive, and M is an alkali metal.
6. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from'0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of orthosubstituted and para-substituted phenols, said phenol having the formula in which R'- is a saturated hydrocarbon substituent containing 4 .to 18 carbon atoms, and wherein '9 I the modification of said condensation pr'oduct consists of the group 4 r (C2H40) u Cal-I4 SOaM replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g has a value of to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.
7. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an'oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, saidphenol having the formula in which a is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms,and wherein the modification of said condensation product consists of thegroup Y (CzHaO) y Cal-I4 SOaM in which R is a saturated hydrocarbon substitu ent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein g; has a value of 0 to 19 inclusive,
and M is a metal from the group consisting of alkali and alkaline earth metals.
9. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from-0.5 to 1.0 mol of formaldehyde and one mol of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing 4 to 18 carbon atoms, and wherein the modification of said condensation product consists of the group (CaHaO) 1 C4Ha $03M replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein y has a value of 0 to 19 inclusive, and M is a metal from the group consisting of alkali and alkaline earth metals.
10. A modified phenol-formaldehyde condensation product having surface-active properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mol of formaldehyde and mol of a phenol having the formula and wherein the modification consists of the group (C2H4O) u C2H4 SOaNa replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein 11 has a value of 0 to 19 inclusive.
LOUIS H. nocK. JAMES L. RAINEY.
REFERENCES CITED The following references are of record in the file of this patent:
I UNITED STATES PATENTS Number Name Date 2,046,318 Brubaker July 7, 1936 2,178,829 Bruson et'al. Nov. 7, 1939 2,213,477 Steindorfi et a1. Sept. 3, 194d FOREIGN PATENTS Number Country Date 576,177 Germany .1.- May 8, 1933 one - I Certificate of Correction 7 Patent No. 2,454,543. November 23, 1948.
. LOUIS H. BOOK ET AL. Y
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:
Column 4, in the formula following line 2, right-hand portion thereof, for O(RO),SO M read 0(R0),,R-S0 M; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.
. Signed and sealed this 5th day of April, A. D. 1949.
THOMAS F. MURPHY,
Assistant Commissioner of Patents.
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US2541994A (en) * | 1948-12-10 | 1951-02-20 | Petrolite Corp | Process for breaking petroleum emulsions |
US2831013A (en) * | 1953-12-30 | 1958-04-15 | Universal Oil Prod Co | Sulfo-esters of alcohols bearing a hydrophilic substituent |
US2883369A (en) * | 1956-04-19 | 1959-04-21 | Shawinigan Chem Ltd | Surface-active agents derived from acrylates and methacrylates |
US3049511A (en) * | 1959-06-15 | 1962-08-14 | Nalco Chemical Co | Sulfated oil soluble phenol formaldehyde polymers |
US3084124A (en) * | 1959-06-15 | 1963-04-02 | Nalco Chemical Co | Processes for breaking petroleum emulsions of the oil-in-water type |
US3219607A (en) * | 1961-02-21 | 1965-11-23 | Kuhlmann Ets | Aqueous dispersions of vinyl chloride-acrylic ester copolymers emulsified with sulfonated phenol aldehyde condensates |
US3502607A (en) * | 1966-10-31 | 1970-03-24 | Celanese Corp | Art of making dyeable polyacrylonitrile products |
US3934975A (en) * | 1971-12-10 | 1976-01-27 | Diamond Shamrock Corporation | Leather treating process |
US4018559A (en) * | 1974-06-14 | 1977-04-19 | Diamond Shamrock Corporation | Non-rewet leather and method of producing same |
US4374740A (en) * | 1981-01-16 | 1983-02-22 | Mobil Oil Corporation | Water soluble surfactant mobility control agent in oil recovery |
US4451623A (en) * | 1981-01-16 | 1984-05-29 | Mobil Oil Corporation | Water soluble phenolic-formaldehyde polymer which is a surfactant mobility control agent in oil recovery |
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DE576177C (en) * | 1930-11-11 | 1933-05-08 | Louis Blumer Fa | Process for the production of resinous products from phenol condensation products and polyhydric alcohols |
US2046318A (en) * | 1933-03-21 | 1936-07-07 | Du Pont | Synthetic resin |
US2178829A (en) * | 1938-02-07 | 1939-11-07 | Rohm & Haas | Condensation products |
US2213477A (en) * | 1935-12-12 | 1940-09-03 | Gen Aniline & Film Corp | Glycol and polyglycol ethers of isocyclic hydroxyl compounds |
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0
- US US2454543D patent/US2454543A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE576177C (en) * | 1930-11-11 | 1933-05-08 | Louis Blumer Fa | Process for the production of resinous products from phenol condensation products and polyhydric alcohols |
US2046318A (en) * | 1933-03-21 | 1936-07-07 | Du Pont | Synthetic resin |
US2213477A (en) * | 1935-12-12 | 1940-09-03 | Gen Aniline & Film Corp | Glycol and polyglycol ethers of isocyclic hydroxyl compounds |
US2178829A (en) * | 1938-02-07 | 1939-11-07 | Rohm & Haas | Condensation products |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US2541994A (en) * | 1948-12-10 | 1951-02-20 | Petrolite Corp | Process for breaking petroleum emulsions |
US2831013A (en) * | 1953-12-30 | 1958-04-15 | Universal Oil Prod Co | Sulfo-esters of alcohols bearing a hydrophilic substituent |
US2883369A (en) * | 1956-04-19 | 1959-04-21 | Shawinigan Chem Ltd | Surface-active agents derived from acrylates and methacrylates |
US3049511A (en) * | 1959-06-15 | 1962-08-14 | Nalco Chemical Co | Sulfated oil soluble phenol formaldehyde polymers |
US3084124A (en) * | 1959-06-15 | 1963-04-02 | Nalco Chemical Co | Processes for breaking petroleum emulsions of the oil-in-water type |
US3219607A (en) * | 1961-02-21 | 1965-11-23 | Kuhlmann Ets | Aqueous dispersions of vinyl chloride-acrylic ester copolymers emulsified with sulfonated phenol aldehyde condensates |
US3502607A (en) * | 1966-10-31 | 1970-03-24 | Celanese Corp | Art of making dyeable polyacrylonitrile products |
US3934975A (en) * | 1971-12-10 | 1976-01-27 | Diamond Shamrock Corporation | Leather treating process |
US4018559A (en) * | 1974-06-14 | 1977-04-19 | Diamond Shamrock Corporation | Non-rewet leather and method of producing same |
US4374740A (en) * | 1981-01-16 | 1983-02-22 | Mobil Oil Corporation | Water soluble surfactant mobility control agent in oil recovery |
US4451623A (en) * | 1981-01-16 | 1984-05-29 | Mobil Oil Corporation | Water soluble phenolic-formaldehyde polymer which is a surfactant mobility control agent in oil recovery |
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