Process for manufacturing diols and polyurethanes containing perfluoroalkyl radicals
First Claim
1. In a process for manufacturing diols containing perfluoroalkyl radicals by reacting in a 1st reaction step a compound of the formula (I)
wherein m=0 or 1 and Rf is an unsubstituted straight-chain or branched chain perfluoroalkyl radical with 1 to 18 C-atoms or a branched-chain or straight-chain perfluoroalkyl radical with 1 to 18 carbon atoms substituted by a perfluoroalkoxy radical with 2 to 6 C-atoms, E is a branched-chain or straight-chain alkylene radical with 1 to 10 carbon atoms which may be interrupted by 1 to 3 divalent groups of the formulate --NR--, --O--, --S--, --SO2, --COO--, --OOC--, --CONR--, --NRCO--, --SO2 NR-- and NRSO2 --, or a branched-chain or straight-chain alkylene radical with 1 to 10 carbon atoms having a --SO2 NR-- or a --CONR--groups at one end, whereby the radical Rf is linked with the sulphuric atom or the carbon atom of this group, and X'"'"'--H=--CON(R)H or SO2 N(R)H or --SH and R is an alkyl radical with 1 to 6 C-atoms, with a compound of the formula II
space="preserve" listing-type="equation">HO[CH.sub.2 --C(CH.sub.2 Y).sub.2 CH.sub.2 O].sub.n H (II)wherein Y=Cl, Br or I and n=1, 2 or 3 and whereby per mol equivalent Y of the formula II about 1 mol of the compound of the formula I are applied, the reaction being performed in the presence of an alkali metal carbonate whereby the alkali metal carbonate is present in an amount sufficient for the substantially complete neutralization of the resulting acid HY, the reaction being performed in an aprotic solvent at elevated temperature, whereby a reaction product of the formula III ##STR3## is obtained, wherein the improvement comprises carrying out the reaction (1st step) in an aprotic solvent which is substantially insoluble in water and in the presence of an aqueous solution of the alkali metal carbonate, subsequently removing the phase containing the aqueous salt solution, and removing the remaining residual water from the organic phase.
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Accused Products
Abstract
Diols containing perfluoroalkyl radicals are produced by reacting compounds of the formula
R.sub.f --(E).sub.m --X'"'"'--H
(Rf =perfluoroalkyl radical, E is an alkylene group optionally interrupted by certain groups and/or substituted at the end, m=0 or 1, X'"'"'--H=--CONRH, --SO2 NRH or --SH) in a first step with diols containing at least 2 halogen atoms. Preferably the obtained products are reacted in a second reaction step with polyvalent isocyanates to prepolymers with free --NCO-- or free --OH--groups and these prepolymers are reacted in a third step with compounds containing isocyanate groups and/or hydroxyl groups. The first reaction step is carried out in an aprotic solvent which is insoluble in water, in the presence of an aqueous solution of an alkali metal carbonate. Intermediate products have not to be isolated.
The obtained polyurethanes can be used in form of aqueous dispersions for the oil- and water repellent finishing of textiles.
26 Citations
21 Claims
- 1. In a process for manufacturing diols containing perfluoroalkyl radicals by reacting in a 1st reaction step a compound of the formula (I)
- space="preserve" listing-type="equation">R.sub.f --(E).sub.m --X'"'"'--H (I)
wherein m=0 or 1 and Rf is an unsubstituted straight-chain or branched chain perfluoroalkyl radical with 1 to 18 C-atoms or a branched-chain or straight-chain perfluoroalkyl radical with 1 to 18 carbon atoms substituted by a perfluoroalkoxy radical with 2 to 6 C-atoms, E is a branched-chain or straight-chain alkylene radical with 1 to 10 carbon atoms which may be interrupted by 1 to 3 divalent groups of the formulate --NR--, --O--, --S--, --SO2, --COO--, --OOC--, --CONR--, --NRCO--, --SO2 NR-- and NRSO2 --, or a branched-chain or straight-chain alkylene radical with 1 to 10 carbon atoms having a --SO2 NR-- or a --CONR--groups at one end, whereby the radical Rf is linked with the sulphuric atom or the carbon atom of this group, and X'"'"'--H=--CON(R)H or SO2 N(R)H or --SH and R is an alkyl radical with 1 to 6 C-atoms, with a compound of the formula II
space="preserve" listing-type="equation">HO[CH.sub.2 --C(CH.sub.2 Y).sub.2 CH.sub.2 O].sub.n H (II)wherein Y=Cl, Br or I and n=1, 2 or 3 and whereby per mol equivalent Y of the formula II about 1 mol of the compound of the formula I are applied, the reaction being performed in the presence of an alkali metal carbonate whereby the alkali metal carbonate is present in an amount sufficient for the substantially complete neutralization of the resulting acid HY, the reaction being performed in an aprotic solvent at elevated temperature, whereby a reaction product of the formula III ##STR3## is obtained, wherein the improvement comprises carrying out the reaction (1st step) in an aprotic solvent which is substantially insoluble in water and in the presence of an aqueous solution of the alkali metal carbonate, subsequently removing the phase containing the aqueous salt solution, and removing the remaining residual water from the organic phase. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21)
- 3. A process according to claim 1, wherein the concentration of the alkali metal carbonate in water is adjusted at least to such a value that the density of the alkali halide solution formed in the first reaction step is sufficiently high so that after termination of the 1st reaction step the aqueous phase separates as a phase below the organic phase.
- 4. A process according to claim 1, wherein potassium carbonate is used as alkali metal carbonate.
- 5. A process according to claim 1, wherein the first reaction step is carried out under increased pressure.
- 6. A process according to claim 5, wherein the first reaction step is carried out under autogenous pressure.
- 7. A process according to claim 2, wherein the same solvent is used for the 1st, 2nd and 3rd reaction step.
- 8. A process according to claim 1, wherein the solvent used for the first reaction step has a boiling point exceeding 90°
- C. at atmospheric pressure, in particular a boiling point exceeding 110°
C.
- 9. A process according to claim 1, wherein methyl isobutylketone is used as aprotic solvent.
- 10. A process according to claim 1, wherein as compound of the formula II a compound is used in which Y=Br and n=1.
- 11. A process according to claim 1, wherein in the formula I E is an alkylene radical with 2 to 6 C-atoms, X'"'"'=--S-- and m=1.
- 12. A process according to claim 1, wherein as compound IV an aliphatic diisocyanate and as compound IV'"'"' an alicyclic diisocyanate is used.
- 13. A process according to claim 12, wherein as aliphatic diisocyanate hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate and as alicyclic diisocyanate a diisocyanate derived from a dimeric fatty acid is used.
- 14. A process according to claim 2, wherein polyethoxylated N-alkyl-diethanolamines are used as chain-extending agents.
- 15. A process according to claim 2, wherein N-methyl-diethanolamine is used as chain-extending agent.
- 16. A process according to claim 2, wherein in the second reaction step a diisocyanate and such a quantity of the solution obtained after the 1st reaction step are used that this quantity contains 1.1 to 1.6 mol of a compound III per mol diisocyanate.
- 17. A process according to claim 1, wherein in the second reaction step an isocyanate of formula IV and that in the third reaction step an isocyanate of formula IV'"'"' is used and that the molar ratio of the isocyanate of the second reaction step (IV) to the isocyanate of the third reaction step (IV'"'"') is 0.3 to 1.8.
- 18. A process according to claim 2, wherein the aliphatic alicyclic or aromatic isocyanate of the 2nd step is a divalent isocyanate of the formula (IV)
- space="preserve" listing-type="equation">A(NCO).sub.2 (IV)
and wherein the aliphatic, alicyclic or aromatic isocyanate of the 3rd step is a divalent isocyanate of the formula (IV'"'"')
space="preserve" listing-type="equation">A'"'"'(NCO).sub.2 (IV'"'"')and each of A and A'"'"' being an unsubstituted or substituted aliphatic, alicyclic or aromatic divalent radical.
- C. at atmospheric pressure.
Specification
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- Resources
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Current AssigneeCIBA Specialty Chemicals
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Original AssigneeCiba-Geigy Corporation (Novartis Ag)
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InventorsLuSimpert, Mosch, Franz, Bernheim, Michael
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Primary Examiner(s)Kight, III, John
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Assistant Examiner(s)Truong, Duc
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Application NumberUS07/702,800Time in Patent Office739 DaysField of Search528/49, 528/55, 528/65, 528/63, 528/70, 528/71, 427/389.9, 427/393.4US Class Current528/49CPC Class CodesC08G 18/3812 having fluorine atomsC08G 18/3825 containing amide groups C08...C08G 18/3855 having sulfurC08G 18/3861 containing sulfonamide and/...C08G 18/387 in addition to a perfluoroa...
