CA2227662A1 - Fluoroalkyl-modified hydrocarbon derivatives - Google Patents

Fluoroalkyl-modified hydrocarbon derivatives Download PDF

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CA2227662A1
CA2227662A1 CA 2227662 CA2227662A CA2227662A1 CA 2227662 A1 CA2227662 A1 CA 2227662A1 CA 2227662 CA2227662 CA 2227662 CA 2227662 A CA2227662 A CA 2227662A CA 2227662 A1 CA2227662 A1 CA 2227662A1
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acid
compound
saturated
carbon atoms
nitrogen
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Frank Wehowsky
Wolfgang Knaup
Hans-Detlev Gilsing
Roland Wagner
Dietrich Prescher
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Clariant Produkte Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/68—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/69—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/14—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines

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Abstract

Fluoroalkyl-modified hydrocarbon derivatives The invention relates to hydrocarbon derivatives which have been modified by means of long-chain fluoroalkyl groups, of the formula RF-(CH2)n-A-D
in which n is 1 to 3, RF are linear perfluoroalkyl radicals having from 6 to 20 carbon atoms, preferably having from 14 to 20 carbon atoms, A is one of the following groups: -0-C(=O)-, -O-, -0-P(=O)(CI)-, -0-(D-)P(=0)-, -O-(O=)S(=O)- or a single bond and D is D1: linear, branched or cyclic, saturated or unsaturated hydrocarbonshaving from 2 to 100 carbon atoms and optionally substituted by nitrogen, oxygen, sulfur or halogen, or is D2: molecular backbones of the type Y(R1)(R2)(R3) where Y = saturated or unsaturated cyclic hydrocarbons, having from 4 to 40 carbon atoms, which are optionally bridged or linked via a hetero atom or a C1 unit - which may be substituted by nitrogen, oxygen, halogen or halogenated alkyl radicals - or contain multiatom bridges, and R1, R2 and R3 = substituents containing oxygen-, sulfur- or nitrogen-containing, hydroxylated or nonhydroxylated hydrocarbon radicals having from 2 to 50 carbon atoms or metal ions, and having covalent or ionogenic bonds, in the 1,2- or 1,3-position on the ring or linked to the ring via two further, partially functionalized carbons, or is D3: linear, branched or cyclic, saturated or unsaturated hydrocarbon radicals having from 2 to 100 carbon atoms which have been mono- or polyhydroxylated and/or modified by alkylene oxide units and may contain nitrogen and also to a process for their preparation.

Description

Clariant GmbH HOE 97/F 008 Dr. KM/PI

Description Fluoroalkyl-rnodified hydrocarbon derivatives The invention relates to hydrocarbon derivatives which have been modified by means of long-chain fluoroalkyl groups, and to a process for their preparation.

For fluoroalc.ohols of the type CF3(CF2)m(CH2)nOH where m = 3, 5 or 7 and n = 2,derivatization with halogens, halogenated ethers or halogenated or nonhalogenated acid halides are known from A. Sismondi, P. Abenin, L. Joncheray, A. Cambon, J.
Fluorine Chem. 59 (1992) 127-32; T. Oishi, H. Morikawa, M. Fujimoto, Polym. J. 25 (1993) 41-8; M. Koden, K. Nakagawa, Y. Ishii, F. Funada, M. Matsuura and K. Awane, Mol. Cryst. Liq. Cryst., Lett. Sect. 6 (1989) 185-90; K. Waldmann DE-2128 956; Chem. Abstr. 78 (1973) 71482e; H. Bathelt, DE-2 558 711; Chem. Abstr.
87 (1977) 117598p; F. Wehowsky, DE-3 611 302; Chem. Abstr. 108 (1988) 188957t. The last three papers also discuss cases where m = 9, 11.

In addition, for shorter-chain fluoroalcohols where m = 5 or 7 and n = 2, modifications with phosphorus oxyhalides are also described, in M.-P. Kraffl, P.Vierling, J. G. Riess, Eur. J. Med. Chem. 26 (1991) 545-50; A. Milius, J. Greiner, J.
25 G. Riess, Carbohydr. Res. 129 (1992) 323 - 36; S. Gaentzler, P. Vierling, J. G.
Riess, Phosphorus, Sulfur and Silicon 77 (1993) 327; J. Greiner, F. Guillod, A.
Milius, J. G. Riess, Phosphorus, Sulfur and Silicon 77 (1993) 328; M.-P. Kraffl, F.
Giulieri and J. G. Riess, Angew. Chem. 105 (1993) 783 - 5.

30 Furthermore, fluoroalcohols where m = 5, 7 or 9 and n = 2 have been used for silanization according to T. Aoki, Y. Toyoshima, Polymer 33 (1992) 662-4; T. Aoki, Y. Toyoshirrla, E. Oikawa, Polym. J. 26 (1994) 1142-53, and transesterification with aromatic mclecular backbones according to U. Dahn, C. Erdelen, H. Ringsdorf, R.
Festag, J. H. Wendorff, P. A. Heiney, N. C. Maliszewskyj, Liq. Cryst. 19 (1995) 759 -64 and also for acylation with monoanhydrides according to R. Elbert, T. Folda, H. RingsdorF, J. Am. Chem. Soc. 106 (1984) 7687 - 92, carboxylic acids according to L.M. Wilsonl Macromolecules 28 (1995) 325-30, and amino acids according to E. M.Landau, S. (,. Wolf, M. Levanon, L. Leiserowitz, M. Lahav and J. Sagiv, J. Am.
5 Chem. Soc. 111 (1989) 143645; Y. Ishikawa, H. Kuwahara, T. Kunitake, Chem.
Lett. 1989, 1737 - 40; J. Am. Chem. Soc.116 (1994) 5579 - 91; E. Dessipri, K. H.Yeap, D. A. Tirrell, Polym. Prepr. 36 (1995) 536 - 7.

All these publications describe only reactions of short-chain fluoroalcohols in which 10 m is a maximum of 11. All of the corresponding working instructions refer to reactions in solution, which, in most cases, proceed incompletely and almost always require complex purification and separation processes. The processes are generally unsuitable for the reaction of very long-chain fluoroalcohols where, for example, m =
13, 15, 17 or 19 and n = 1, 2 or 3 because such fluoroalcohols are sparingly soluble 15 or insoluble in non-fluorinated solvents. It was thus the object to find a method for converting v~ery long-chain fluoroalcohols into surface-active products.

Surprisingly, it has been found that the generally less reactive, very long-chain fluoroalcohols of the type CF3(CF2)m(CH2)nOH where m = 13, 15, 17, 19 and n = 1,20 2, 3, which are unavoidably formed in large quantities in industrial waste processes, can be converted, by reaction with reactive substrates, either directly into surfactants, or else firstly into reactive intermediates (surfactant precursors) and then in a simple manner into surface-active substances. It is within the scope of the invention that these reactions are preferably carried out in the absence of solvents 25 by the direct action of the coreactants on the solid or liquid fluorine-containing starting materials and, surprisingly, almost always give quantitative yields.

The invention provides hydrocarbon derivatives which have been modified by means of long-chain fluoroalkyl groups, of the formula RF(cH2)n-A-D
in which n is1,:2Or3, RF are linear perfluoroalkyl radicals having from 6 to 20 carbon atoms, 5 A is a single bond or one of the groups O O O O
I

-O-C- -O- -O-P- -O-P- -0-~-Cl D O
D is (D~ linear, branched or cyclic, saturated or unsaturated hydrocarbon radicals having from 2 to 100 carbon atoms, or is (D"): molecular backbones of the type _Y(R1 )(R2)(R3), where Y = saturated or unsaturated cyclic hydrocarbons having from 4 to 40 carbon atom's which are linked or contain multiatom bridges and R1, R2 and R3 = identical or different oxygen-, sulfur- or nitrogen-containing, hydroxylated or nonhydroxylated hydrocarbon radicals having from 2 to 50 carbon atoms, or is (D s) linear, branched or cyclic, saturated or unsaturated hydrocarbon radicals having from 2 to 100 carbon atoms which have been mono- or polyhydroxylated and/or modified by alkylene oxide units and may contain nitrogen.

The following definitions may or may not apply:
(D1 ) are linear, branched or cyclic, saturated or unsaturated hydrocarbon radicals having from 2 to 100 carbon atoms which have been substituted by nitrogen, oxygen, sulfur or halogen, CA 02227662 l998-0l-2l Y are saturated or unsaturated, cyclic hydrocarbons having from 4 to 40 carbon atoms which are bridged or linked via a hetero atom or a C1 unit, which may be substituted by nitrogen, oxygen, halogen or halogenated alkyl radicals, or contain multiatom bridges, and R1, R2 and R3 are identical or different substituents containing metal ions, ammonium ions or hydrogen ions and having covalent or ionogenic bonds in the 1,2- or 1,3-position on the ring, or are hydrocarbon radicals having from 2 to 50 carbon atoms which are linked to the ring via two further, partially functionalized carbons.

The given structural elements preferably have the following meanings:
RF jS a plerfluoroalkyl having a chain length of C8 to C20, particularly C10 to C20, espec,ially C12 to C18, most especially C14 to C16 D1 is -O(CH2)nRF, where n and RF are as defined above, -CF3, -CH2CI, -CH2Br, -CH2(,H2CH2CI, -CH2CH2CH2CH2Br, -NHCH2CH2CI, -NHCH2CH2CH2CI, -NC0, -NHC6H3(CH3)NCO, -NH(CH2)kNCO, where k = 1 to 10, -CHCH2O, -CH2C;H20H, -CH2CH(OH)CH3 Y is Ll ~ \CL"

ICHl3 ~)~~~' ~' F 3C ~F3 ~"' ,~"

In the struchJres, the solid line on the ring (ring substituents) symbolizes the bond from the structural unit Y to the structural component RF(CH2)n-A. Dashed lines denote bondls from Y to the structural units R1, R2 and R3.
R1,R2 and R3 are -CO2H, -SO3H, -OH, -COO(CH2)nRF, where RF and n are as defined above, -C(=O)NHC(CH2OH)3, -C(=O)N(CH2CH2OH)2, -COO-M+, -SO3 ~ M+, where M+ = H+, Na, K, /2 Mg , /2 Ca , NR4, NHR3+, NH2R2+, NH3R+, where R = H, CH3, C2H5, C3H7, C4Hg, -CH2CH2OH, -(CHOH)UCH2OH, -CH2(CHOH)UCH2OH, where u = 3 to 5, or a radical of the formula [HOCH2CH2NH2CH2CH2NHC(=O)CH(OH)(HO)CHCH(OH)-CA 02227662 l998-0l-2l CH(OH)CH20H]+

[H2N[CH2CH2NHC(=O)CH(OH)(HO)CHCH(CH)CH(OH)CH20H]2]+ or [H2N C4H8 NHCH2CH2NHC(=O)CH(OH)(HO)CHCH(OH)CH(OH)CH20H]+

D3 is-CH(OH)CH20H,-[CH(OH)CH20]2CH2CH(OH)CH20H, -[CH(OH)CH20]3CH2CH(OH)CH20H, CH(OH)(HO)CH(HO)CHCH20H, -CH(OH)(HO)CH(HO)CHCH20H, -CH(OH)(HO)CHCH(OH)CH(OH)CH20H, -(HO)CH(HO)CHCH(OH)CH(OH)CH20H, -CH(OH)(HO)CH(HO)CHCH(OH)CH20H, -N(CH2CH20H)CH(OH)(HO)CHCH(OH)CH(OH)CH20H, N(CH3)CH(OH)(HO)CHCH(OH)CH(OH)CH2OH, -CH2N(CH2CH20H)CH(OH)(HO)CHCH(OH)CH(OH)CH20H or (-NH)CH(CH3)CH2(0CH2CH2)rOCH2CH(NH2)CH3, where r = 5 to 2000, preferably 50 to 500.

20 The CF3(CF2)m(CH2)nOH starting materials used for the structural element RF-(CH2)n- are pure substances or technical grade mixtures where m = 5,7,9,11,13, 15,17 or 19 and n = 1, 2 or 3. Preference is given to alcohols having fluorinated alkyl chains of the length C8 to C20, particularly having chain lengths of C10 to C20, especially having chain lengths of C12 to C18, most especially having chain lengths of C14 to C1~;.

The structural elements A - D are introduced by alkylation or acylation of the starting materials, the structural element D either being predetermined by the structure of the substrate for the introduction of A or resulting from derivatization of the product obtained when A is introduced.

For the alkylation or acylation, preference may be given to dihaloalkanes, halohydrins, di- and polyfunctional epoxides, phosphorus oxyhalides or sulfurylhalidles, difunctional carboxylic acids, acid halides, anhydrides or isocyanates.

The structural element D = D1 is formed if the alkylation or acylation is carried out 5 with halogenated or nonhalogenated epoxides, halogenated acid derivatives, halogenated isocyanates or diisocyanates. Examples which may be mentioned are 1,2-dibromoethane, epichlorohydrin, bromoacetyl bromide, p-toluenesulfonyl chloride, chloroacetic acid, chloroacetic anhydride, the mixed anhydride of chloro-and trifluoroacetic acid as in Stacey et al., Nature 164 (1949) 705, 2-chloroethyl isocyanate in Ulsperger and Jacobi, Fette, Seifen, Anstrichm. 64 (1962) 1093-8, tolylene 2,4-diisocyanate, chlorocarbonyl isocyanate and also the reaction with phosphoryl c:hloride according to Milius, Greiner, Riess, Carbohydr. Res. 129 (1992) 323-36.

15 The structurial element D = D2 is introduced by acylation using anhydrides ofsaturated or unsaturated tetra- or polycarboxylic acids, D2 being composed of the structural parameter Y, which characterizes the structural backbone (middle part of the dianhydride), and the structural units R1, R2 and R3, which describe the backbone functionalities. The structural parameter Y is, for example, pyromellitic 20 dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-2,3,4,5-tetracarboxylic dianhydride, cyclohexane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.1.2]heptane-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic 25 dianhydride, 2,2-hexafluoropropanediylbis(3-phthalic anhydride), 4,4'-oxydi(phthalic anhydride) or 3,3',4,4'-diphenyltetracarboxylic dianhydride. The structural parameters R1, R2 and R3 result from the liberation and neutralization of the carboxylic functions using nitrogen-containing hydroxyl compounds or low molecular weight, nonhydroxylated alkylamines or from the addition of hydrogen 30 sulfite onto unsaturated anhydrides. The reaction of the acylation products formed using dianhydrides with aqueous sodium or potassium hydroxide solution or aqueous solutions of ammonium hydroxide, tris(hydroxymethyl)aminomethane or diethanolamine may be cited by way of example.

The structural element D = D3 is introduced by alkylation or acylation of the fluorine-containing starting materials using reagents which bear hydrophilic groups or produce hydrophilic groups by reaction with the starting material, such as, for example, glycidol, glycerol and D-gluconic acid and/or by derivatization of 5 alkylation and acylation products obtained upon the introduction of A with thestructural element D1 using nitrogen-containing polyhydroxylated substrates which are obtainable by reducing sugars or are derived from sugars, such as, for example, arabitol, sorbitol, mannitol, dulcitol, D-glucamine, N-methyl- and N-(2-hydroxylethyl)-D-glucamine and also 0,O'-bis(2-aminopropyl)polyethylene 10 glycol and 0,0'-bis(2-aminopropyl)polypropylene glycol.

According to the invention, the following are working examples for producing surface-active substances from the long-chain fluoroalkyl-modified hydrocarbon derivatives:
1 ) Reaction of the fluorine-containing starting materials with suitable alkylation or acylation ,3gents to give fluoroalkyl ethers or esters (precursors) which, in the nonfluorinated part of the molecule, contain a further reactive functionality, such as, for example, halogen, hydroxyl or isocyanate, which are linked to a hydrophilic 20 component in a further reaction step. Alkylation agents which are to be regarded as advantageous are in each case biterminally monohalogenated alkanes, such as, for example, 1,2-dibromoethane, 1,3-dichloropropane and 1 ,4-dibromobutane, and epoxides such as, for example, epichlorohydrin, epibromohydrin, ethylene oxide, propylene oxide, hexene oxide, octene oxide and cyclohexene oxide.
25 Corresponding acylation agents include halogenated acids, acid halides, acid anhydrides and isocyanates, diisocyanates and also phosphorus oxyhalides and sulfurylhalid,es. Examples which may be mentioned are chloroacetic acid, 3-chloropropionyl chloride, chloracetic anhydride, 3-chloropropyl isocyanate, tolylene 2,4-diisocyanate and hexamethylene diisocyanate. Suitable hydrophilic 30 systems are mono-, di- or trisaccharides, such as, for example, glucose, maltose and raffinose, aminosaccharides, such as, for example, glucosamine, N-acetyl-D-glucosamine, D-glucamine, N-alkyl-D-glucamines and N-glucosides, saccharide-modified aminoamides as in DE-A-4 318 536 Example 11 a and Example 26a, amino-modilied ethylene and propylene glycols of different chain lengths or, generally, arnino and amido compounds having numerous polar functional groups, such as, for example, N-(2-acetamino)iminodiacetic acid and panthenol.
Depending on the structure of the nonfluorinated part of the precursor molecule,5 the solubility of the surfactant in water or oil can be enhanced by adjusting the hydrophilic c:omponent.

2) Acylation of the fluorine-containing starting materials using dianhydrides and subsequent amidation and neutralization of nonesterified carboxylic acid functions 1 0 using ammonia and optionally hydroxyl group-containing alkylannmonium compounds. Advantageous acylation agents are, in addition to low molecular weight substrates, such as, for example, pyromellitic dianhydride, also polycyclic systems, such as, for example 1,4,5,8-naphthalenetetracarboxylic dianhydride and3,4,9,10-perylenetetracarboxylic dianhydride. Suitable hydrophilic components are, 1 5 in addition to di- and triethanolamine, tris(hydroxymethyl)aminomethane and its derivatives, such as, preferably, N-tris(hydroxymethyl)methyl-3-amino-2-hydroxypropanesulfonic acid, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid, N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid and N-tris(hydroxymethyl)methylglycine, and also aminosaccharides and 20 saccharide-rnodified aminoamides as in DE-A-4 31 8 536 Example 1 1 a and Example 26a.

3) Direct alkylation and acylation of the partially fluorinated starting materials to give surfactants. The reaction with coreactants which already contain a sufficient 25 number of hydrophilic polar groups or produce such groups in a multiple reaction with the starl~ing material gives fluorinated surfactants and finishing agents in a one-stage synthesis. Preferred alkylating agents are glycerol, glycidol and its derivatives, such as, for example, ethylene glycol diglycidyl ether, tert-butyl glycidyl ether, glycidyl methacrylate, glycidyl isopropyl ether, glycidyl allyl ether and30 glycidyl phenyl ether. Advantageous acylation agents are sugar-carboxylic acids and their lactones, such as, for example, D-gluconic acid, lactobionic acid, pectic acid, mucic acid, o-gluconolactone, y-heptagluconolactone and glucopyranosyl-arabonolactone, tri- and tetracarboxylic acids of diamines, such as, for example, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid, ethylene- and propylenediaminetetraacetic acid, and other carboxylic acids or anhydrides whichbear hydrophilic groups, such as, for example, 3,6,9-trioxaundecanedioic acid, N,N-bis-(2-hydroxyethyl)glycine, N-tris-(hydroxymethyl)methylglycine, aconitic 5 anhydride or di-0-acetyl-L-tartaric anhydride. The fluorinated starting materials are reacted with alkylating or acylating agents with stirring in the absence of a solvent at atmospheric or superatmospheric pressure and temperatures of from 20~C to 200~C, preferably between 50~C and 1 50~C. Alkylation and acylation reactions are carried out in the presence of basic or acidic catalysts. Preferred basic catalysts 10 are alkalis, low molecular weight alkylamines and nitrogen heterocycles. Particular preference is given to sodium hydroxide and potassium hydroxide, triethylamine and imidazole. Suitable acidic catalysts are strong acids, such as, for example,sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoroacetic acid.

15 In the two-stage synthesis of surfactants, isolation of the intermediates formed is generally not required.

In exception,al cases, such as, for example, in the production of surfactants from phosphorylated fluoroalcohols, use of an aprotic solvent is favorable. Diethyl ether 20 and tetrahydrofuran are particularly advantageous.

Neutralization of the products obtained from fluoroalcohols and specific dianhydrides using nitrogen-containing hydroxyl compounds proceeds at a faster rate in water or lower alcohols, such as, for example, methanol and isopropanol.
The compounds according to the invention are used as surfactants and starting materials for the preparation of compounds for the oil- and soil-repellent finishing of textiles, leather, wood or paper.

30 Further details of how the reaction is carried out are given in the examples:

Example 1 OH OH
~O~O~OH

10.0 9 of fluoroalcohol where RF = C14-C20 and 3.9 9 of glycidol are heated at 140-1 50~C in the presence of 1.0 g of potassium hydroxide in a steel autoclave for 9.5 h. The resulting sticky brown mass is taken up in hot water and filtered. The heavily 10 foaming dark-brown opaque filtrate produces 7.2 g of a pale brown sticky solid when evaporated.

The surface tension of an aqueous solution of 1 g/l is 25 mN/m at 20~C.

IR (cm~1) 34()0 (br.), 2880, 1620, 1200, 1150, 550, 520 Example 2a ~~~(\

29.7 9 of fluoroalcohol where RF = C10-C2O and 13.6 9 of chloroacetic anhydride are heated at 80-90~C for 2 h. When the hot reaction solution is poured into saturated aqueous sodium hydrogencarbonate solution, 29.5 9 of a yellow, granular solid precipitate out.

1H-NMR (ppm) 2.56-2.71 (tt, J = 6.0 Hz, 2H, RFCH2CH2O), 4.19 (s, 2H, O2CCH2CI), 4.47 (t, 2H, J = 6.0 Hz, RFCH2CH2O) Example 2b H OH H H
~l RF~,/\ )~N~OH H OH OH OH

OH
10.0 9 of perfluoroalkylethyl chloroacetate and 3.5 9 of N-(2-hydroxyethyl)-D-glucamine are refluxed in 200 ml of tetrahydrofuran for a total of 6 h. Evaporation 10 of the reaction solution gives 12.5 g of a pale yellow, greasy solid.

The surface tension of an aqueous solution of 1 9/l is 30 mN/m at 20~C.

IR (cm~1) 3400 (br.), 2900, 1610, 1400 (br.), 1200, 1150, 1010, 650, 550 Example 3 RF~~~ ~CI
o 10.0 9 of fluoroalcohol where RF = C14-C20 and 2.3 9 of 2-chloroethyl isocyanateare heated at 80~C for 30 h. Cooling gives 11.1 g of a colorless solid mass which can be ground to give a powder.
1H-NMR (ppm) 2.48-2.61 (m, 2H, RFCH2CH2O), 3.39 (m, 2H, NHCH2CH2CI), 3.56 (m, 2H, NH(,H2CH2CI), 4.47 (t, 2H, J = 6.2 Hz, RFCH2CH2O), 6.89 (s, br.1 H, NH) Example 4 1~l NH2 ~O--P--Nl~ ~,O

(O~
<On ~NH2 2.0 g of monoperfluoroalkylethyl dichlorophosphate, synthesized from fluoroalcohol where RF = C14 C16 and phosphoryl chloride according to Milius, Greiner, Riess, Carbohydr. Res. 129 (1992) 323-36 and 11.7 9 of O,O'-bis(2-aminopropyl)-polyethylene glycol 1900 are refluxed in 100 ml of tetrahydrofuran for 6 h.
15 Evaporating the reaction solution gives 12.5 g of a pale brown, viscous oil which is water-soluble and foams.

The surface tension of an aqueous solution of 1 g/l is 31 mN/m at 20~C.

IR (cm~1) 34()0 (br.), 2880,1620, 1480, 1350, 1280, 1220,1100, 950, 830 Example 5 ~ I T THT T
/\~O--P--N\OH H OH OH OH
F--N~ \
H OH ~ \OH
HO H OH
H--OH

H OH
--OH

2.0 g of monoperfluoroalkylethyl dichlorophosphate (synthesized from fluoroalcohol where RF = C14-C20) and 1.3 9 of N-(2-hydroxyethyl)-D-glucamine are refluxed in 150 ml of tetrahydrofuran in the presence of 1.2 g of triethylamine for 10 h. Filtering and evaporating the reaction solution gives 2.7 g of a pale yellow solid which is 5 water-soluble and foams.

The surface tension of an aqueous solution of 1 g/l is 24 mN/m at 20~C.

IR (cm~1) 3300, 2900, 2600, 2480 (br.), 1590, 1450, 1200, 1050 (br.), 850, 800, 650, 550, 520 Example 6a O 1~l ~0 ~0 O O

22.8 g of fluoroalcohol where RF = C10-C20 and 8.4 9 of pyromellitic dianhydride are heated at 150~C in the presence of 0.3 g of triethylamine for 7 h. The colorless solid mass which remains after cooling can be ground to give 29.8 g of powder.

25 1 H-NMR (ppm) 2.73 (m, 2H, RFCH2CH2O), 4.61 (t, J = 6.2 Hz, 2H, RFCH2CH2O), 8.03 (s, 2H P~rH),10.84 (s, br. 1H, COOH) Example 6b }I~
- H2N~ C~H
O O

10 5.0 g of perfluoroalkylethyl ester anhydride and 2.0 9 of diethanolamine are refluxed in 120 ml of isopropanol for 4 h. Filtering off insoluble constituents and evaporating the filtrate gives 3.7 9 of a pale yellow, greasy paste, which is water-soluble and foams.

15 The surface tension of an aqueous solution of 5 9/l is 31 mN/m at 20~C.

IR (cm~1) 3300 (br.), 2900 (br.), 1710, 1600, 1390 (br.), 1200 (br.), 1050, 950, 800, 700, 650, 5~iO, 520 Example 7 HO
HO ~ o O ~OH

HO NH3 O ~NH OH
R ~ ~~ H3N~
o O ~ OH
OH

30 13.7 9 of of perfluoroalkylethyl ester anhydride, synthesized from fluoroalcohol where RF = C14-C16 and 6.2 9 of tris(hydroxymethyl)-aminomethane, are refluxed in 250 ml of water for 1 h. Evaporating the milky-cloudy, highly foaming aqueoussolution gives 17.5 9 of a colorless, sticky solid.

The surface tension of an aqueous solution of 5 g/l is 33 mN/m at 20~C.

IR (cm~1 ) 3400, 1700, 1610, 1 580, 1 390, 1 320, 1200 (br. ), 1 1 50, 650 Example 8 ~ ~ ' O

10.0 9 of fluoroalcohol where RF = C14-C20 and 5.7 9 of Epiclon B4400 are heated15 at 150~C in the presence of 0.1 9 of triethylamine for 7 h. The yellow-brown solid mass which r esults from cooling can be ground to give 14.0 9 of powder which iswater-soluble and foams highly.

The surface tension of an aqueous solution of 1 9/l is 18 mN/m at 20~C.
IR (cm~1) 34()0, 2980 (br.), 1850, 1760, 1720, 1620, 1200 (br.), 1150, 650

Claims (17)

1. A hydrocarbon derivative which has been modified by means of long-chain alkyl groups, of the formula RF(CH2)n-A-D
in which n is 1,2 or 3, RF is a linear perfluoroalkyl radical having from 6 to 20 carbon atoms, A is a single bond or one of the groups -O- D is (D1): a linear, branched or cyclic, saturated or unsaturated hydrocarbon radical having from 2 to 100 carbon atoms, or is (D2): a molecular backbone of the type -Y(R1)(R2)(R3) where Y = saturated or unsaturated cyclic hydrocarbons having from 4 to 40 carbon atoms which are linked or contain multiatom bridges, and R1, R2 and R3 = identical or different oxygen-, sulfur- or nitrogen-containing, hydroxylated or nonhydroxylated hydrocarbon radicals having from 2 to 50 carbon atoms, or is (D3): linear, branched or cyclic, saturated or unsaturated hydrocarbon radical having from 2 to 100 carbon atoms which has been mono- or polyhydroxylated and/or modified by alkylene oxide units and may contain nitrogen.
2. A compound as claimed in claim 1, wherein (D1) is a linear, branched or cyclic, saturated or unsaturated hydrocarbon radical having from 2 to 100 carbon atoms which has been substituted by nitrogen, oxygen, sulfur or halogen.
3. A compound as claimed in claim 1 and/or 2, wherein Y is a saturated or unsaturated, cyclic hydrocarbon having from 4 to 40 carbon atoms which is bridged or linked via a hetero atom or a C1 unit, which may be substituted by nitrogen, oxygen, halogen or a halogenated alkyl radical, or contains multiatom bridges.
4. A compound as claimed in one or more of claims 1 to 3, wherein R1, R2 and R3 are identical or different substituents containing metal ions, ammonium ions or hydrogen ions and having covalent or ionogenic bonds in the 1,2- or 1,3-position on the ring, or are hydrocarbon radicals having from 2 to 50 carbon atoms which are linked to the ring via two further, partially functionalized carbons.
5. A compound as claimed in one or more of claims 1 to 4, wherein, independently of one another, RF is a perfluoroalkyl having a chain length of C8 to C20, particularly C10 to C20, especially C12 to C18, most especially C14 to C16;

D1 is-O(CH2)nRF1,-CF3,-CH2C1,-CH2Br,-CH2CH2CH2C1, -CH2CH2CH2CH2Br, -NHCH2CH2C1, -NHCH2CH2CH2C1, -NCO, -NHC6H3(CH3)NCO, -NH(CH2)kNCO, where k= 1 to 10, -CHCH2O, -CH2CH2OH, -CH2CH(OH)CH3;

Y is in which the solid lines on the ring (ring substituents) represent the bond from the structural unit Y to the structural component RF(CH2)n-A and the dashed lines denote bonds from Y to the structural units R1, R2 and R3;

R1, R2 and R3 are -CO2H, -SO3H, -OH, -COO(CH2)nRF, -C(=O)NHC(CH2OH)3,-C(=O)N(CH2CH2OH)2, -COO-M+, -SO3 M+, where M+ = H+, Na+, K+,~ Mg2+,~ Ca2+, NR4+, NHR3+, NH2R2+, NH3R+, where R = H, CH3, C2H5, C3H7, C4H9, -CH2CH2OH, -(CHOH)uCH2OH, -CH2(CHOH)uCH2OH, where u = 3 to 5, or a radical of the formula [HOCH2CH2NH2CH2CH2NHC(=O)CH(OH)(HO)CHCH(OH)-CH(OH)CH2OH]+

[H2N[CH2CH2NHC(=O)CH(OH)(HO)CHCH(OH)CH(OH)CH2OH]2]+ or [H2N-C4H8-NHCH2CH2NHC(=O)CH(OH)(HO)CHCH(OH)-CH(OH)CH2OH]+

D3 is-CH(OH)CH2OH,-[CH(OH)CH2O]2CH2CH(OH)CH2OH, -[CH(OH)CH2O]3CH2CH(OH)CH2OH, CH(OH)(HO)CH(HO)CHCH2OH,-CH(OH)(HO)CH(HO)CHCH2OH, -CH(OH)(HO)CHCH(OH)CH(OH)CH2OH, -(HO)CH(HO)CHCH(OH)CH(OH)CH2OH, -CH(OH)(HO)CH(HO)CHCH(OH)CH2OH, -N(CH2CH2OH)CH(OH)(HO)CHCH(OH)CH(OH)CH2OH, -N(CH3)CH(OH)(HO)CHCH(OH)CH(OH)CH2OH, -CH2N(CH2CH2OH)CH(OH)(HO)CHCH(OH)CH(OH)CH2OH, (-NH)CH(CH3)CH2(OCH2CH2)rOCH2CH(NH2)CH3, where r = 5 to 2000, preferably 50 to 500.
6. A compound as claimed in one or more of claims 1 to 5, wherein the linear,branched or cyclic, saturated or unsaturated hydrocarbon, which is optionally substituted by nitrogen, oxygen, sulfur or halogen, in the structuralelement D1 is derived from a compound from the group consisting of dihaloalkanes, halohydrins, di- or higher epoxides, phosphorus oxyhalides and sulfurylhalides, halogenated carboxylic acids, halogenated acid halides, halogenated anhydrides, halogenated isocyanates and diisocyanates.
7. A compound as claimed in one or more of claims 1 to 6, wherein the linear,branched or cyclic saturated or unsaturated hydrocarbon, which may be substituted by nitrogen, oxygen, sulfur or halogen, in the structural element D1 is derived from the compounds 1,2-dibromoethane, 1,3-dichloropropane, 1,4-dibromobutane, 3-chloro-1,2-propanediol, epichlorohydrin, epibromohydrin, ethylene oxide, propylene oxide, hexene oxide, octene oxide, cyclohexene oxide, phosphoryl chloride, sulfuryl chloride, p-toluenesulfonyl chloride, chloroacetic acid, 3-chloropropionic acid, bromoacetyl bromide, 3-chloropropionyl chloride, chloroacetic anhydride, chloroacetic-trifluoroacetic anhydride, 2-chloroethyl isocyanate, 3-chloroethyl isocyanate, chlorocarbonyl isocyanate, tolylene 2,4-diisocyanate and hexamethylene diisocyanate.
8. A compound as claimed in one or more of claims 1 to 7, wherein the saturated or unsaturated cyclic hydrocarbon which is optionally bridged or linked via a hetero atom or a C1 unit which may be substituted by nitrogen, oxygen, halogen or a halogenated alkyl radical, or contains multiatom bridges, in structural unit Y of structural element D2 is derived from a compound from the group consisting of anhydrides of saturated or unsaturated tetra- or polycarboxylic acids and the substituents containing oxygen-, sulfur- or nitrogen-containing, hydroxylated or nonhydroxylated hydrocarbon radicals having from 2 to 50 carbon atoms, or containing metal, ammonium or hydrogen ions, and having covalent or ionogenic bonds, in the 1,2- or 1,3-position on the ring, or linked to the ring via two further, optionally functionalized carbons, in structural parameters R1, R2 and R3 of structural element D2 is derived from a compound from the group consisting of hydroxy-substituted alkylamines, low molecular weight, nonhydroxylated alkylamines, aminosaccharides and saccharide-modified aminoamides.
9. A compound as claimed in one or more of claims 1 to 8, wherein the saturated or unsaturated cyclic hydrocarbon which is optionally bridged or linked via a hetero atom or a C1 unit which may be substituted by nitrogen, oxygen, halogen or a halogenated alkyl radical, or contains multiatom bridges, in structural unit Y of structural element D2 is derived from the compounds pyromellitic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.1.2]heptane-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2-hexafluoro-propanediylbis(3-phthalic anhydride), 4,4'-oxydi(phthalatic anhydride) or 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1 ,4,5,8-naphthalene-tetracarboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic acid dianhydride and the substituent containing oxygen-, sulfur- or nitrogen-containing, hydroxylated or nonhydroxylated hydrocarbon radicals having from 2 to 50 carbon atoms or containing metal ions, and having covalent or ionogenic bonds, in the 1,2- or 1,3- position on the ring, or linked to the ringvia two further, optionally functionalized carbons, in structural parameters R1, R2 and R3 of structural element D2 is derived from the compounds diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane, N-tris(hydroxymethyl)methyl-3-amino-2-hydroxypropanesulfonic acid, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid, N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid and N-tris(hydroxymethyl)methylglycine, methylamines, ethylamines, propylamines and butylamines, glucosamine, N-acetyl-D-glucosamine, D-glucamine, N-methyl-D-glucamine and N-(2-hydroxyethyl)-D-glucamine.
10. A compound according to one or more of claims 1 to 9, wherein the linear, branched or cyclic, saturated or unsaturated hydrocarbon which has been mono- or polyhydroxylated and/or modified by alkylene oxide units and optionally contains nitrogen, in structural element D3 is derived from a compound from the group consisting of hydroxy-substituted epoxides and their derivatives, sugar carboxylic acids and their lactones, tri- and tetracarboxylic acids of diamines, carboxylic acids bearing hydrophilic substituents, anhydrides bearing hydrophilic substituents, pentoses and hexoses, mono-, di- and trisaccharides, aminosaccharides, amino-modified glycols and amino and amido compounds bearing hydrophilic substituents.
11. A compound as claimed in one or more of claims 1 to 10, wherein the linear, branched or cyclic, saturated or unsaturated hydrocarbon which has been mono- or polyhydroxylated and/or modified by alkylene oxide units and optionally contains nitrogen, in structural element D3 is derived from the compounds glycidol, ethylene glycol diglycidyl ether, tert-butyl glycidyl ether,glycidyl methacrylate, glycidyl isopropyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycerol, D-gluconic acid, o-gluconolactone, y-heptagluconolactone and glucopyranosylarabonolactone, lactobionic acid, pectic acid, mucic acid, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, 3,6,9-trioxaundecanedioic acid, N,N-bis-(2-hydroxyethyl)glycine, N-tris(hydroxymethyl)methylglycine, aconitic anhydride, di-O-acetyl-L-tartaric anhydride, arabitol, sorbitol, mannitol, dulcitol, glucose, maltose, raffinose, glucosamine, N-acetyl-D-glucosamine, D-glucamine, N-methyl-D-glucamine, N-(2-hydroxyethyl)-D-glucamine, O,O'-bis(2-aminopropyl)polyethylene glycol, O,O'-bis(2-aminopropyl)polypropylene glycol, N-(2-acetamino)iminodiacetic acid and panthenol.
12. A process for the preparation of a compound as claimed in one or more of claims 1 to 11, which comprises reacting a compound of the composition RF(CH2)nOH

in which RF and n are as defined above with a reactive substrate with stirring without a diluent in the absence of a solvent at 20°C to 200°C, preferably between 50°C and 150°C under atmospheric or superatmospheric pressure, optionally in the presence of a catalyst to give a reactive intermediate (surfactant precursor) or directly to give a surfactant.
13. The process as claimed in claim 12, wherein the reactive substrate used is a compound from the group consisting of dihaloalkanes, phosphorus oxyhalides and sulfurylhalides, halogenated carboxylic acids, halogenated acid halides, halogenated anhydrides, anhydrides of saturated or unsaturated tetra- or higher carboxylic acids, halogenated isocyanates, diisocyanates, hydroxy-substituted epoxides and their derivatives, sugar-carboxylic acids and their lactones, tri- and tetracarboxylic acids of diamines, carboxylic acids bearing hydrophilic substituents and anhydrides bearing hydrophilic substituents.
14. The process as claimed in claim 12 and/or 13, wherein the basic catalyst used is sodium hydroxide or potassium hydroxide, triethylamine or imidazole or the acidic catalyst used is sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid or trifluoroacetic acid.
15. The process as claimed in one or more of claims 12 to 14, wherein the reaction of a compound of the formula RF(CH2)nOH

in which RF and n are as defined above with a reactive substrate from the group consisting of dihaloalkanes, halohydrins, di- or higher epoxides, phosphorus oxy- and sulfurylhalides, halogenated carboxylic acids, halogenated acid halides, halogenated anhydrides, halogenated isocyanates, diisocyanates, anhydrides of saturated or unsaturated tetra- or higher carboxylic acids results in reactive intermediates (surfactant precursors) having functionality in the nonfluorinated part of the molecule, which are converted into surfactants by reaction with a compound from the group consisting of mono-, di- and trisaccharides, aminosaccharides, amino-modified glycols, hydroxy-substituted alkylamines, low molecular weight, nonhydroxylated alkylamines, aminosaccharides and saccharide-modified aminoamides in a second synthesis step.
16. The process as claimed in one or more of claims 12 to 15, wherein the reaction of a compound of the composition RF(CH2)nOH

in which RF and n are as defined above, with a reactive substrate from the group consisting of hydroxy-substituted epoxides and their derivatives, sugar carboxylic acids and their lactones, tri- and tetracarboxylic acids of diamines, carboxylic acids bearing hydrophilic substituents, anhydrides bearing hydrophilic substituents, anhydrides of saturated or unsaturated tetra- or higher carboxylic acids produces surfactants directly in one synthesis step.
17. The use of a compound as claimed in one or more of claims 1 to 11 as surfactants and starting materials for the preparation of compounds for the oil- and soil-repellent finishing of textiles, leather, wood or paper.
CA 2227662 1997-01-22 1998-01-21 Fluoroalkyl-modified hydrocarbon derivatives Abandoned CA2227662A1 (en)

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