Claims
- 1. In a highly viscous aqueous acid composition comprising an aqueous solution containing 70 to 99.8% by weight of an acid and 0.2 to 30% by weight of a crosslinked polymer composition, wherein the improvement comprises said polymer containing crosslink bridges of the formula --NR.sup.x --CH.dbd.N--CO-- wherein R.sup.x represents hydrogen, alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH.
- 2. A highly viscous aqueous acid composition according to claim 1 wherein the crosslinked polymer is obtained by reacting in a highly acidic aqueous medium amidocarbonyl groups of component (A) with formylamido groups of component (B), component (A) comprising a water-soluble homo- or copolymer having amidocarbonyl groups in an amount of more than 10%, calculated on the weight of the polymer and component (B) comprising a member selected from the group consisting of
- (a) a bis-acylamido-compound of the formula I ##STR67## wherein R.sup.1 and R.sup.2 represent hydrogen, alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH,
- n represents a number from 1 to 3 and
- m represents a number from 0 to 1, and
- (b) a water-soluble homo- or copolymer having formylamido groups of the formula ##STR68## wherein R.sup.9 stands for hydrogen or alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH, the amount of formylamido groups being not less than 1 mol per 500 g of the polymer.
- 3. A highly viscous aqueous acid composition according to claim 2 wherein component (A) comprises 50 to 100% by weight of entities of the formula II ##STR69## wherein R.sup.4 stands for hydrogen or methyl and of 0 to 50% by weight of entities of the formula III ##STR70## wherein R.sup.5 stands for hydrogen, alkyl having 1 to 3 carbon atoms and
- Y stands for formylamido; N-substituted formylamido where the N-substituent is methyl or hydroxymethyl; cyano; carboxyl; or the alkali or ammonium salts of carboxyl; the alkoxycarbonyl group having 1 to 6 carbon atoms; the hydroxy-alkoxycarbonyl group having 1 to 3 carbon atoms; the N-methylolamidocarbonyl group HOCH.sub.2 NH--CO--; the N-methylolamidocarbonyl group wherein the methylol group is etherified with alkanols having 1 to 4 carbon atoms; the mono- or dialkylamino group having altogether 1 to 8 carbon atoms in the alkyl radicals; the alkanoylamino group having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms which is N-substituted with methylol or alkyl having 1 to 4 carbon atoms; pyrrolidonyl-(1); phenyl; pyridinium; the sulfonic acid group; the sulfoalkylamidocarbonyl group having 1 to 4 carbon atoms; the phosphonic acid group; the alkali or ammonium salts of said sulfonic acids and phosphonic acid groups; a radical of the formula IV ##STR71## a radical of the formula V ##STR72## wherein R.sup.7 and R.sup.8 are the same or different and stand for alkyl having 1 to 4 carbon atoms and p represents a number from 1 to 4; or quaternary salts of formulas IV and V.
- 4. A highly viscous aqueous acid composition according to either claim 2 or claim 3 wherein component (B) comprises 50 to 100% by weight of entities of the formula VI ##STR73## wherein R.sup.9 stands for hydrogen, methyl or hydroxy methyl and of 0 to 50% by weight of entities of the formula VII ##STR74## wherein R.sup.11 stands for hydrogen or methyl and
- X stands for cyano; the carboxyl group; the alkali or ammonium salts of carboxyl; the alkoxycarbonyl group having 1 to 6 carbon atoms; the hydroxy-alkoxycarbonyl group having 1 to 3 carbon atoms; the N-methylolamidocarbonyl group HOCH.sub.2 NH-CO-; the N-methylolamidocarbonyl group wherein the methylol group is etherified with alkanols having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms which is N-substituted with methylol or alkyl having 1 to 4 carbon atoms; pyrrolidonyl-(1); phenyl; pyridinium; the sulfonic acid group; a sulfoalkylamidocarbonyl group having 1 to 4 carbon atoms; the phosphonic acid group; the alkali or ammonium salts of said sulfonic acids and phosphonic acid groups; a radical of the formula VIII ##STR75## wherein R.sup.12 and R.sup.13 are the same or different and stand for alkyl having 1 to 4 carbon atoms; a radical of the formula IX ##STR76## wherein p represents a number from 1 to 4; a radical of the formula X ##STR77## wherein R.sup.14 and R.sup.15 are the same or different and stand for alkyl having 1 to 4 carbon atoms and quaternary salts of formula IX and X.
- 5. A highly viscous aqueous acid composition according to claim 2 wherein components (A) and (B) are present in a ratio by weight of from 1:0.2 to 1:20.
- 6. A highly viscous aqueous acid composition according to claim 2 wherein component (A) is a water-soluble homo- or copolymer having amidocarbonyl groups and component (B) is a bis-acylamide-compound of the formula I ##STR78## wherein R.sup.1 and R.sup.2 are hydrogen, alkyl having 1 to 4 carbon atoms or CH.sub.2 OH.
- 7. A highly viscous aqueous acid composition according to claim 6 wherein component (B) is methylene-bis-formamide or bis-(N-formyl-aminomethyl)ether.
- 8. A highly viscous aqueous acid composition according to claim 2 wherein component (A) is a water-soluble homo- or copolymer having amidocarbonyl groups and component (B) is a water-soluble homo- or copolymer having formylamide groups of the formula ##STR79## wherein R.sup.9 is hydrogen or alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH.
- 9. A highly viscous aqueous acid composition according to claim 2 wherein component (B) is a homopolymer of vinyl formamide.
- 10. In the method of increasing the viscosity of aqueous acidic solutions wherein a viscosifier is added to an aqueous acidic solution the improvement comprises using as the viscosifier a crosslinked polymer composition containing crosslink bridges of the formula --NR.sup.x --CH.dbd.N--CO-- wherein R.sup.x represents hydrogen, alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH.
- 11. The method according to claim 10 wherein crosslink bridges of the formula --NR.sup.x --CH.dbd.N--CO-- are formed by the reaction in an aqueous acidic medium of at least two formylamido groups with at least two amidocarbonyl groups.
- 12. The method according to claim 10 wherein said crosslinked polymer composition is obtained by reacting in a highly acidic aqueous medium amidocarbonyl groups of component (A) with formylamido groups of component (B), component (A) comprising a water-soluble homo- or copolymer having amido-carbonyl groups in an amount of more than 10%, calculated on the weight of the polymer and component (B) comprising a member selected from the group consisting of
- (a) a bis-acylamido-compound of the formula I ##STR80## wherein R.sup.1 and R.sup.2 represent hydrogen, alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH,
- n represents a number from 1 to 3 and
- m represents a number from 0 to 1, and
- (b) a water-soluble homo- or copolymer having formylamido groups of the formula ##STR81## wherein R.sup.9 stands for hydrogen or alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH, the amount of formylamido groups being not less than 1 mol per 500 g of the polymer.
- 13. The method according to claim 12 wherein component (A) comprises 50 to 100% by weight of entities of the formula II ##STR82## wherein R.sup.4 stands for hydrogen or methyl and of 0 to 50% by weight of entities of the formula III ##STR83## wherein R.sup.5 stands for hydrogen, alkyl having 1 to 3 carbon atoms and
- Y stands for formylamido; N-substituted formylamido where the N-substituent is methyl or hydroxymethyl; cyano; carboxyl; or the alkali or ammonium salts of carboxyl; the alkoxycarbonyl group having 1 to 6 carbon atoms; the hydroxy-alkoxycarbonyl group having 1 to 3 carbon atoms; the N-methylolamidocarbonyl group HOCH.sub.2 NH-CO-; the N-methylolamidocarbonyl group wherein the methylol group is etherified with alkanols having 1 to 4 carbon atoms; the mono- or dialkylamino group having altogether 1 to 8 carbon atoms in the alkyl radicals; the alkanolyamino group having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms which is N-substituted with methylol or alkyl having 1 to 4 carbon atoms; pyrrolidonyl-(1); phenyl; pyridinium; the sulfonic acid group; the sulfoalkylamidocarbonyl group having 1 to 4 carbon atoms; the phosphonic acid group; the alkali or ammonium salts of said sulfonic acids and phosphonic acid groups; a radical of the formula IV ##STR84## a radical of the formula V ##STR85## wherein R.sup.7 and R.sup.8 are the same or different and stand for alkyl having 1 to 4 carbon atoms and p represents a number from 1 to 4; or quaternary salts of formulas IV and V.
- 14. The method according to either claim 12 or 13 wherein component (B) comprises 50 to 100% by weight of entities of the formula VI ##STR86## wherein R.sup.9 stands for hydrogen, methyl or hydroxy methyl and of 0 to 50% by weight of entities of the formula VII ##STR87## wherein R.sup.11 stands for hydrogen or methyl and
- X stands for cyano; the carboxyl group; the alkali or ammonium salts of carboxyl; the alkoxycarbonyl group having 1 to 6 carbon atoms; the hydroxy-alkoxycarbonyl group having 1 to 3 carbon atoms; the N-methylolamidocarbonyl group HOCH.sub.2 NH--CO--; the N-methylolamidocarbonyl group wherein the methylol group is etherified with alkanols having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms; the alkanoylamino group having 1 to 4 carbon atoms which is N-substituted with methylol or alkyl having 1 to 4 carbon atoms; pyrrolidonyl-(1); phenyl; pyridinium; the sulfonic acid group; a sulfoalkylamidocarbonyl group having 1 to 4 carbon atoms; the phosphonic acid group; the alkali or ammonium salts of said sulfonic acids and phosphonic acid groups; a radical of the formula VIII ##STR88## wherein R.sup.12 and R.sup.13 are the same or different and stand for alkyl having 1 to 4 carbon atoms; a radical of the formula IX ##STR89## wherein p represents a number from 1 to 4; a radical of the formula X ##STR90## wherein R.sup.14 and R.sup.15 are the same or different and stand for alkyl having 1 to 4 carbon atoms and quaternary salts of formula IX and X.
- 15. The method according to claim 12 wherein components (A) and (B) are present in a ratio by weight of from 1:0.2 to 1:20 .
- 16. The method according to claim 12 wherein component (A) is a water-soluble homo- or copolymer having amidocarbonyl groups and component (B) is a bis-acylamide-compound of the formula I ##STR91## wherein R.sup.1 and R.sup.2 are hydrogen, alkyl having 1 to 4 carbon atoms or CH.sub.2 OH.
- 17. The method according to claim 16 wherein component (B) is methylene-bis-formamide or bis-(N-formylaminomethyl)ether.
- 18. The method according to claim 12 wherein component (A) is a water-soluble homo- or copolymer having amidocarbonyl groups and component (B) is a water-soluble homo- or copolymer having formylamide groups of the formula ##STR92## wherein R.sup.9 is hydrogen or alkyl having 1 to 4 carbon atoms or --CH.sub.2 OH.
- 19. The method according to claim 12 wherein component (B) is a homopolymer of vinyl formamide.
- 20. A highly viscous aqueous acid composition according to claim 1 wherein crosslink bridges of the formula --NR.sup.x --CH.dbd.N--CO-- are formed by the reaction in an aqueous acidic medium of a compound having at least two formylamido groups with a polymer having at least two amidocarbonyl groups.
Parent Case Info
This application is a division of application Ser. No. 399,682 filed July 19, 1982, which in turn is a continuation of Ser. No. 216,672 filed Dec. 15, 1980 and now abandoned.
US Referenced Citations (20)
Foreign Referenced Citations (3)
Number |
Date |
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0023712 |
Feb 1981 |
EPX |
0044508 |
Jan 1982 |
EPX |
482897 |
Apr 1938 |
GBX |
Divisions (1)
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Number |
Date |
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Parent |
399682 |
Jul 1982 |
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Continuations (1)
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Number |
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Parent |
216672 |
Dec 1980 |
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