HK1158175A

HK1158175A - Fluorinated alcohols

Info

Publication number: HK1158175A
Application number: HK11112835.1A
Authority: HK
Inventors: Stephan J. Mclain
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2008-07-01
Filing date: 2009-06-23
Publication date: 2012-07-13

Description

Fluorinated alcohols

Background

In the past, many fluoroalkyl surfactants were based on perfluoroalkylethanols F (CF)₂CF₂)_qCH₂CH₂OH (so-called "telomer B alcohols"), wherein q is typically from about 2 to 10. The telomer B alcohols and their preparation are described by Kirchner et al in U.S. Pat. No. 5,202,506. Other telomer B alcohol-based fluoroalkyl surfactants include "two-tailed" anionic surfactants such as F (CF)₂CF₂)_q(CH₂CH₂)OCOCH₂CH(SO₃Na)COO(CH₂CH₂)(CF₂CF₂)_qF, where q is as defined above, by first reacting two moles of one or more perfluoroalkylethanols with one mole of maleic anhydride, followed by reacting the diester product with a solution of sodium bisulfite, as described, for example, in Yoshino et al, "lubricating fluorinated resins, Synthesis of anionic Surfactants, lubricating a fluorinated group of fatty alcohols in water, Journal of Fluorine Chemistry (1995), 70(2), 187-91. Examples for supercritical carbon dioxide are reported by Yoshino et al, where q is 2, 3 and 4. Yoshino et al report two-tailed surfactants in which both end groups are limited to perfluoroalkyl groups.

Nagai et al in U.S. patent application 2008/0093582 describe a compound having R_f-(CH₂)_n1-(X¹)_p1-CH(SO₃M)(X²)_q1-R_hA two-tailed surfactant of structure (la) wherein R_fIs a fluoroalkyl group which may contain an ether bond, X¹And X²Are the same or different divalent linking groups; m is H, alkaliMetal, semi-alkaline earth metal, or ammonium; r_hIs an alkyl group; n1 is an integer from 1 to 10; and p1 and q1 are each 0 or 1.

One common route for the preparation of perfluoroalkyl alcohols for such surfactants is a multi-step process using tetrafluoroethylene. Tetrafluoroethylene is a supply-limiting, hazardous and expensive intermediate. It would be desirable to provide fluorinated surfactants that use less or no tetrafluoroethylene in their preparation. It would also be desirable to provide new and improved fluorinated surfactants in which the perfluoroalkyl groups of the prior art are replaced by partially fluorinated end groups that require less tetrafluoroethylene and exhibit improved fluorine efficiency. "fluorine efficiency" refers to the ability to achieve a desired surface effect or surfactant characteristic using a minimum amount of fluorine-containing compound when applied to a substrate, or the ability to achieve better performance using the same amount of fluorine. Polymers with high fluorine efficiencies use lower amounts of fluorine, producing the same or higher degree of surface effect, than comparative polymers. The present invention provides such improved fluorinated surfactants.

Summary of The Invention

The invention also includes compounds of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)；

c is 2 to about 6; and v is 2 to about 4.

The invention also includes a process for preparing a compound of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)；

c is 2 to about 6; and v is from 2 to about 4,

the method comprises contacting a compound of formula 6 with a compound of formula 7

R_f-O-CF＝CF₂Formula 6

Wherein R is_fIs C_cF_(2c+1)And c is from 2 to about 6,

HO-(CH₂CH₂O)_v-H formula 7

Wherein v is 2 to about 4.

Detailed Description

Trademarks herein are shown in upper case.

The surfactants of the present invention have the structure of formula 1A, 1B, or 1C.

(R_a-O-CO-)₂X formula 1A

R_a-O-CO-X-CO-O-(CH₂CH₂)R_fFormula 1B

R_a-O-CO-X-CO-O-R formula 1C

Wherein

R is H or a linear or branched alkyl group C_bH_(2b+1)-, wherein b is 1 to about 18, preferably about 6 to about 18;

each R_fIndependently is C_cF_(2c+1)C is from about 2 to about 6, preferably 2 to 4, and more preferably 4;

x is a linear or branched difunctional alkylsulfonate radical

-C_eH_(2e-1)(SO₃M)-，

Wherein e is 2 or 3, preferably 3; and M is a monovalent cation which is hydrogen, ammonium, an alkali metal, or an alkaline earth metal, and is preferably Na;

R_aselected from the structures (i) to (Vi), wherein R_fAs defined above, and g is from 1 to about 4, preferably from 1 to 3, and more preferably 2:

(i)R_f(CH₂CF₂)_d-(C_gH_2g) -, wherein d is 1 to about 3, preferably 1 to 2, and more preferably 1;

(ii)R_fOCF₂CF₂-(C_gH_2g)-

(iii)R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g) -, wherein v is 1 to about 4, preferably 1 to 2, and more preferably 2;

(iv)R_fOCFHCF₂O(C_wH_2w) -, wherein w is from about 3 to about 12, preferably 4 to 6, and more preferably 4;

(v)R_fOCF(CF₃)CONH-(C_gH_2g) -; or

(vi)R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_kWherein h is 1 to about 6, preferably 1 to 3, and more preferably 1; and i, j and k are each independently 1, 2 or 3, or mixtures thereof, preferably 1 or 2, and more preferably 1; with the proviso that the total number of carbon atoms in group (vi) is from about 8 to about 22. Preferred R_aThe groups are (i), (ii), (iii) and (iv).

Preferred embodiments of formulae 1A, 1B and 1C are those below: wherein Ra is a group (i) R_f(CH₂CF₂)_d-(C_gH_2g)-，(ii)R_fOCF₂CF₂-(C_gH_2g)-，(iii)R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g) -, or (iv) R_fOCFHCF₂O(C_wH_2w) -; c is 3 or 4; and X is CH₂CH(SO₃M)、CH₂CH(CH₂SO₃M)、CH(CH₃)CH(SO₃M)、CH₂CH(SO₃M)CH₂Or CH₂CH(SO₃M)CH₂CH₂. More specifically, preferred embodiments of formulas 1A, 1B and 1C are the following: wherein d is 1, g is 1 or 2, and R_fIs C₃F₇Or C₄F₉. Also specifically preferred are compounds wherein R is_fIs C₃F₇Or C₄F₉And X is C₃H₅(SO₃Na) or CH₂CH(SO₃Na). Also preferred are compounds of formula 1B, wherein R_aIs C₄F₉CH₂CF₂CH₂CH₂Or C₃F₇CH₂CF₂CH₂CH₂And R is_fIs (CF)₂)₆F. Formula 1A (R)_aOCO-X-COOR_a) Is C₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O-CH₂CH₂CF₂-CH₂C₄F₉. A preferred embodiment of formula 1B is C₄F₉CH₂CF₂CH₂CH₂-OC(O)CH₂CH(SO₃Na)C(O)O-CH₂CH₂(CF₂)₆F. A preferred embodiment of formula 1C is C₄F₉CH₂CF₂CH₂-CH₂OC(O)CH₂CH(SO₃Na)C(O)O(CH₂)₆H。

The surfactants of formulae 1A, 1B and 1C reduce the use of tetrafluoroethylene in their preparation and provide comparable or improved properties compared to prior art surfactants derived from telomer B alcohols.

The surfactants of formulae 1A, 1B, and 1C are prepared via unsaturated intermediates of formulae 2A, 2B, and 2C according to the following reaction scheme a:

scheme A

The unsaturated intermediates used to prepare formulas 1A, 1B and 1C are compounds of formulas 2A, 2B and 2C:

(R_a-O-CO-)₂y formula 2A

R_a-O-CO-Y-CO-O-(CH₂CH₂)R_fFormula 2B

R_a-O-CO-Y-CO-O-R formula 2C

Wherein

R_aIs a group (i) R_f(CH₂CF₂)_d-(C_gH_2g)-，(ii)R_fOCF₂CF₂-(C_gH_2g)-，(iii)R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g)-，(iv)R_fOCFHCF₂O(C_wH_2w)-，(v)R_fOCF(CF₃)CONH-(C_gH_2g) -, or (vi) R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_k-

Each R_fIndependently is C_cF_(2c+1)；

c is 2 to about 6, preferably 2 to 4, more preferably 4;

d is 1 to about 3, preferably 1 to 2, more preferably 1;

g is 1 to 4, preferably 1 to 3, more preferably 2;

v is 1 to about 4, preferably 2 to 3, more preferably 2;

w is from about 3 to about 12, preferably 4 to 6, more preferably 4;

h is 1 to about 6, preferably 1 to 3, more preferably 2;

i. j and k are each independently 1, 2 or 3, or mixtures thereof, preferably 1 or 2, more preferably 1;

provided that the total number of carbon atoms in group (vi) is from about 8 to about 22;

y is a linear or branched diradical of ethylenic unsaturation having the formula: -C_eH_(2e-2)-wherein

e is 2 or 3, preferably 2; r is H or a linear or branched alkyl group C_bH_(2b+1)-; and b is from 1 to about 18, preferably from 6 to 18.

The surfactant of formula 1A was prepared as follows: two moles of formula R_a-OH fluoroalcohol (wherein R_aAs defined above) with one mole of C_eH_(2e-2)(COOH)₂Reacting an unsaturated linear or branched dibasic acid of structure (I) or an anhydride thereof of formula (D) to form an unsaturated diester of formula (2A) as an intermediate

Wherein e is 2 or 3. Carboxylic acid esterification processes are conventional, as described by Jain and Masse in "Carboxylic acid esters: synthesis from carboxylic acids and derivatives "(Science of Synthesis (2006), 20b, 711-. When reacting the free acid group with an alcohol, an acid catalyst or a dehydrating agent is preferred. An example of the acid catalyst is a toluene solution of p-toluenesulfonic acid, and an example of the dehydrating agent is a methylene chloride solution of dicyclohexylcarbodiimide. Preferred unsaturated dibasic acids and corresponding anhydrides are maleic acid, itaconic acid (itaconic acid)Methylsuccinic acid), citraconic acid (methylmaleic acid), trans-glutaconic acid (HOOCCH)₂CH ═ CHCOOH), and trans- β -hydrogenated adipic acid (HOOCCH)₂CH＝CHCH₂COOH) and acid anhydrides. The unsaturated diester of formula 2A is then reacted with an aqueous solution of sodium bisulfite to form the sulfonic acid. Sulfonation Technology is described by Roberts in "sulfonic Technology for Anionic Surfactant Manufacture" (Organic Process Research)&Development, 1998, 2, 194-. Alternatively, the above-described olefin precursor may be converted to the sulfonate salts of formulas 1A, 1B and 1C by addition of sulfur trioxide to the double bond. The free sulfonic acid can be used as a surfactant, or the sulfonic acid can be converted to an ammonium, alkali metal, or alkaline earth metal salt, and preferably to a sodium salt. Those skilled in the art will recognize that other sulfonation methods such as those described by Roberts and Sekiguchi (above) may be employed and are included in the present invention.

Addition of sulfonate groups to the double bonds of formulae 1A, 1B and 1C produces surfactants of formulae 2A, 2B and 2C resulting in the formation of stereoisomers and regioisomers. For the purposes of the present invention, all isomers are equivalent and are included in the definitions of formulae 2A, 2B and 2C.

Surfactants of formulas 1B and 1C were prepared as follows: at a relatively low temperature (between about 50 ℃ and 85 ℃), one mole of formula R_a-OH-fluoroalcohol is reacted with one mole of an unsaturated linear or branched diacid anhydride of formula D. Then at a higher temperature (between about 100 ℃ C. and 120 ℃ C.) with one mole of fluoroalcohol (preferably of formula R)_fCH₂CH₂-OH) to produce formula 2B, or with one mole of an alcohol of formula R-OH to produce formula 2C. Any of a variety of conventional fluorinated alcohols are suitable at this stage of the process. After this, it is converted into a sulfonate. In the preparation of the surfactants of formulae 1B and 1C, anhydrides are preferred. The opening of the anhydride ring via the first esterification reaction is a faster reaction than the second esterification reaction of the intermediate acid ester. As described above, in the second esterification reaction, an acid catalyst is usedOr a dehydrating agent. Thus, the use of dibasic acids tends to obtain a mixture of products. The order of use of the two alcohols in the esterification reaction can be reversed.

The surfactant of formula 1A can also be prepared using the same two-addition of alcohols and two temperature processes described for formulas 1B and 1C, and then converted to a sulfonate. However, this two-step process is not preferred.

Two moles of two or more R may be used_a-OH、R_f-CH₂CH₂-OH and R-OH alcohol to make a mixture of composition surfactants of formulas 1A, 1B and 1C. Two moles of a mixture of two or more alcohols with one mole of a surfactant having C as described above for the preparation of the surfactant of formula 1A_eH_(2e-2)(COOH)₂The structurally unsaturated linear or branched dibasic acids or anhydrides thereof (formula D) are reacted and then converted to sulfonates. Such surfactant mixtures can be used as such or separated into several components. This separation is not preferred.

Containing R useful in the present invention_f(CH₂CF₂)_d-CH₂CH₂R of (A-C)_aThe alcohols of group (i) include fluorinated telomer alcohols of formula (V):

R_f-(CH₂CF₂)_q(CH₂CH₂)_r-OH (V)

wherein R is_fIs a linear or branched perfluoroalkyl group having 2 to 6 carbon atoms, and subscripts q and r are each independently integers of 1 to 3. These telomer alcohols can be obtained via synthesis according to scheme 1, where R_fQ and r are as defined for formula (V).

Scheme 1

Vinylidene fluoride and straight or branched chain perfluoroTelomerization of fluoroalkyl iodides to give compounds having R_f(CH₂CF₂)_qA compound of structure I wherein q is 1 or greater, and R_fIs C₂To C₆A perfluoroalkyl group. See, for example, Balague et al, "Synthesis of fluorinated tetramers," part 1, "polymerization of vinylidine fluorides with perfluorinated aldehydes", J.Fluorine chem., (1995), 70(2), 215-23. The particular telomer iodides can be isolated by fractional distillation. Telomer iodides are treated with ethylene by the method described in U.S. Pat. No. 3,979,469 to obtain telomer ethylene iodides (VI in scheme 1) where r is from 1 to 3 or greater. According to the process disclosed in WO 95/11877, telomer ethylene iodides (VI in scheme 1) are treated with oleum and hydrolyzed to give the corresponding telomer alcohols (V in scheme 1). Alternatively, telomer ethylene iodides (VI in scheme 1) may be treated with N-methylformamide, followed by ethanol/acid hydrolysis.

R of formula (ii)_aRadical R_fOCF₂CF₂(C_gH_2g) Can be prepared by preparing the formula R_fOCF₂CF₂-CH₂CH₂OH fluoroalcohol obtainable by a series of reactions wherein R_fIs a straight-chain or branched C optionally interrupted by one to three oxygen atoms₂-C₆A perfluoroalkyl group, and q is an integer from 1 to 3:

scheme 2

Perfluoroalkyl ether iodides of the above formula (V in scheme 2) can be prepared according to the method described in example 8 of U.S. patent 5,481,028, which is incorporated herein by reference, which discloses a process for preparing compounds of the formula (V in scheme 2) from perfluoro-n-propyl vinyl ether. Perfluoroalkyl ether iodides (V in scheme 2) are reacted with excess ethylene at elevated temperature and pressure. When the ethylene addition reaction is carried out by heating, a suitable catalyst is preferably used. The catalyst is preferably a peroxide catalyst such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, or acetyl peroxide. More preferably, the peroxide catalyst is benzoyl peroxide. The reaction temperature is not limited, but a temperature in the range of 110 ℃ to 130 ℃ is preferred. The reaction time may vary depending on the catalyst and the reaction conditions, but 24 hours is usually sufficient. The product is purified by any method that separates unreacted starting materials from the final product, but distillation is preferred. Using about 2.7 moles of ethylene per mole of perfluoroalkylether iodide, using a temperature of 110 ℃ and autogenous pressure, a reaction time of 24 hours, and purifying the product by distillation, satisfactory yields up to 80% were obtained.

The perfluoroalkyl ether ethylene iodide (VI in scheme 2) was treated with oleum and hydrolyzed to give the corresponding alcohol (VII in scheme 2) according to the method disclosed in WO 95/11877(Elf Atochem s.a.). Alternatively, the perfluoroalkylether ethyl iodide may be treated with N-methylformamide, followed by hydrolysis with ethanol/acid. Temperatures of about 130 ℃ to 160 ℃ are preferred.

R of the formula (iii)_aRadical R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g) Can be prepared by reaction of fluorinated vinyl ethers with polyethylene glycols. The vinyl ether is generally added slowly to the ethylene glycol in a molar ratio of about 1: 1 to about 3: 1, preferably about 2: 1. The reaction is carried out in the presence of sodium hydride, which is a catalyst, having sufficient basicity to produce the balance of alkoxy anion from ethylene glycol. Other suitable basic catalysts include potassium hydride, sodium amide, lithium amide, potassium tert-butoxide, and potassium hydroxide. The reaction is carried out under an inert atmosphere such as nitrogen. Suitable solvents include dimethylformamide, dimethylacetamide, acetonitrile, tetrahydrofuran and dioxane. Dimethylformamide is preferred. Cooling is performed to maintain the reaction temperature at about 0 ℃ to about 30 ℃. The reaction is typically carried out for 1 to about 18 hours. Then theThe solvent is removed using conventional techniques such as vacuum evaporation on a rotary evaporator; or in the case where the product is water insoluble and the solvent is water soluble, adding an excess of water to the mixture, followed by layering to remove the solvent.

The reaction of perfluoropropyl vinyl ether with polyethylene glycol is not always complete. The average degree of conversion of the hydroxyl groups of the polyethylene glycol can be determined by¹H NMR spectroscopy. Typically, a mixture of unreacted polyethylene glycol, fluorinated vinyl ether product added to one end of the polyethylene glycol (e.g., structure B below), and fluorinated vinyl ether product added to both ends of the polyethylene glycol (e.g., structure A below) is obtained. The relative amounts of the components in the mixture are influenced by the ratio of reactants, the reaction conditions and the method of product separation. The high vinyl ether to ethylene glycol ratio and long reaction time are advantageous for structure a shown below. The low vinyl ether to ethylene glycol ratio and short reaction time allowed an increase in the amount of structure B and unreacted polyethylene glycol shown below. It is sometimes possible to use the difference in solubility between structure A, B and the starting ethylene glycol to perform selective solvent extraction of the mixture to obtain a sample highly enriched in structure a or B. The alcohol having structure B being a group R_a(iii) The desired composition.

R_fOCFHCF₂O-(CH₂CH₂O)_x-CF₂CHFOR_f(Structure A)

R_fOCFHCF₂O-(CH₂CH₂O)_xH (Structure B)

Suitable polyethylene glycols are commercially available from Sigma-Aldrich (Milwaukee, Wis.). The fluorinated vinyl ethers used in the above reaction can be prepared by a variety of methods. These processes comprise reacting 2-alkoxypropionyl fluoride to prepare fluorinated vinyl ethers in a fixed bed of metal carbonate (a tubular reactor filled with dry metal carbonate and equipped with helical blades moving inside the tube) or in a fluidized bed of metal carbonate. U.S. patent application 2007/0004938 describes a process for preparing fluorinated vinyl ethers in the absence of waterReacting 2-alkoxypropionyl fluoride with a metal carbonate in a stirred bed reactor at a temperature above the decarboxylation temperature of the carboxylate intermediate to produce a fluorinated vinyl ether. Examples of suitable fluorinated vinyl ethers include CF₃-O-CF＝CF₂、CF₃CF₂-O-CF＝CF₂、CF₃CF₂CF₂-O-CF＝CF₂And CF₃CF₂CF₂CF₂-O-CF＝CF₂Each of which is available from e.i. du Pont DE Nemours and Company (Wilmington, DE).

R of formula (iv)_aRadical R_fOCFHCF₂O(C_wH_2w) - (where w is from about 3 to about 12) are obtainable by reacting a perfluorocarbon vinyl ether with a glycol in the presence of an alkali metal compound. Preferred ethers include those of the formula R_f-O-CF＝CF₂Wherein R is_fIs a perfluoroalkyl group having two to six carbons. The diol is used in an amount of about 1 to about 15 moles per mole of ether, preferably about 1 to about 5 moles per mole of ether. Suitable alkali metal compounds include alkali metals, alkaline earth metals, alkali metal hydroxides, alkali metal hydrides, or alkali metal amides. Preference is given to alkali metals such as Na, K or Cs, or alkali metal hydrides such as NaH or KH. The reaction is carried out at a temperature of about 40 ℃ to about 120 ℃. The reaction may be carried out in an optional solvent such as ether or nitrile.

R of formula (v)_aRadical R_fOCF(CF₃)CONH-CH₂CH₂-can be prepared by preparing a fluorinated alcohol of formula 4:

wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 6 carbon atoms, or a mixture thereof;

X³is oxygen or X¹；

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally comprising oxygen, nitrogen, or sulfur, or a combination thereof;

g is F or CF₃(ii) a A is amide; j' is zero or a positive integer; x²Is an organic linking group; h' is zero or one; b is H; and E is hydroxy.

The compounds of formula 4 may be prepared from the reaction between a perfluorinated ester (prepared according to the methods reported in U.S. Pat. No. 6,054,615 and U.S. Pat. No. 6,376,705, each incorporated herein by reference) and a triamine or diamine alcohol, with or without the presence of a solvent. The conditions for this reaction depend on the structure of the ester. The reaction of the α, α -difluoro-substituted ester with the diamine is conducted at a temperature of from about 5 ℃ to about 35 ℃. Suitable solvents for this reaction include tetrahydrofuran, methyl isobutyl ketone, acetone, CHCl₃、CH₂Cl₂Or an ether. The reaction of the non α -fluoro substituted ester with the diamine is carried out at a temperature of from about 90 ℃ to about 160 ℃, preferably between about 100 ℃ to about 140 ℃. For this reaction, it is preferred not to use a solvent, but suitable solvents include chlorobenzene, dimethylformamide, or 2-methoxyethyl ether.

The compounds of formula 4 may also be prepared by reaction of perfluorinated acid fluorides with a diamine or amine alcohol. The reaction is carried out at a temperature of from about-30 ℃ to about 40 ℃, preferably from about 5 ℃ to about 25 ℃. Suitable solvents for this reaction include tetrahydrofuran, methyl isobutyl ketone, acetone, CHCl₃、CH₂Cl₂Or 2-methoxyethyl ether, diethyl ether.

R of the above formula (vi)_aRadical R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_kCan be prepared by preparing the formula R_f(CH₂)_h[(CF₂CF₂)_i-(CH₂CH₂)_j]_kOH fluoroalcohol, wherein R_fIs C₂-C₆A perfluoroalkyl group, subscript h is 1 to about 6, and subscripts i, j, and k are each independently 1, 2, 3, or a mixture thereof. These alcohols can be prepared from oligomeric iodides (C) by treatment with oleum and hydrolysis_nF_2n+1C₂H₄I、C_nF_2n+1CH₂I. Or C_nF_2n+1I) Where subscript n is an integer of from 1 to about 6. It has been found, for example, that reaction with oleum (15% SO) at about 60 deg.C₃) The reaction was allowed to proceed for about 1.5 hours, then ice-cold dilute K was used₂SO₃The solution was hydrolyzed and then heated at about 100 c for about 30 minutes to obtain satisfactory results. However, other reaction conditions can be used as well. After cooling to ambient room temperature, a solid precipitated, isolated and then purified. For example, the liquid is decanted and the solid is dissolved in ether and then washed with saturated aqueous NaCl, anhydrous Na₂SO₄Dried, then concentrated and dried in vacuo. Other conventional purification steps can be employed.

Alternatively, formula R as defined above_f(CH₂)_h[(CF₂CF₂)_i-(CH₂CH₂)_j]_kOH alcohol can be obtained by oligomerizing iodide R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_kI (wherein R_fAnd subscripts h, i, j, and k are as defined above for the corresponding alcohol) with N-methylformamide to about 150 ℃ and for about 19 hours. The reaction mixture was washed with water to obtain a residue. This residue was gently refluxed (at about 85 ℃ bath temperature) with a mixture of ethanol and concentrated hydrochloric acid for about 2.5 hours. The reaction mixture was washed with water, diluted with dichloromethane and dried over sodium sulfate. The dichloromethane solution was concentrated and distilled under reduced pressure to obtain the alcohol. Optionally, N-dimethylformamide is used instead of N-methylformamide. Other conventional purification methods may also be used.

Formula R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_kI iodide is preferably prepared by using a mixture of ethylene and tetrafluoroethylene from C_nF_2n+1C₂H₄I、C_nF_2n+1CH₂I. Or C_nF_2n+1I (where n is 1 to about 6). The reaction can be carried out at any temperature from room temperature to about 150 c using a suitable free radical initiator. The reaction is preferably carried out at a temperature of about 40 ° to about 100 ℃ using an initiator having a half-life in the range of about 10 hours. The conversion of the reaction can be controlled by the feed ratio of the gas phase feed, C_nF_2n+1C₂H₄I、C_nF_2n+1CH₂I or C_nF_2n+1The ratio of moles of I (wherein n is 1 to about 6) to the sum moles of ethylene and tetrafluoroethylene. The molar ratio is from about 1: 3 to about 20: 1, preferably from about 1: 2 to 10: 1, more preferably from about 1: 2 to about 5: 1. The molar ratio of ethylene to tetrafluoroethylene is from about 1: 10 to about 10: 1, preferably from about 3: 7 to about 7: 3, and more preferably from about 4: 6 to about 6: 4.

The present invention also includes unsaturated intermediates, formed prior to the addition of sulfonic acid groups, used in the preparation of the surfactants of the present invention. The unsaturated intermediates have the structure of formulae 2A, 2B, and 2C:

(R_a-O-CO-)₂y formula 2A

R_a-O-CO-Y-CO-O-(CH₂CH₂)R_fFormula 2B

R_a-O-CO-Y-CO-O-R formula 2C

Wherein R is_aIs a group (i) R_f(CH₂CF₂)_d-(C_gH_2g)-，(ii)R_fOCF₂CF₂-(C_gH_2g)-，(iii)R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g)-，(iv)R_fOCFHCF₂O(C_wH_2w)-，(v)R_fOCF(CF₃)CONH-(C_gH_2g) -, or (vi) R_f(CH₂)_h[(CF₂CF₂)_i(CH₂CH₂)_j]_k

Each R_fIndependently is C_cF_(2c+1)；

c is 2 to about 6, preferably 2 to 4, more preferably 4;

d is 1 to about 3, preferably 1 to 2, more preferably 1;

g is 1 to 4, preferably 1 to 3, more preferably 2;

v is 1 to about 4, preferably 2 to 3, more preferably 2;

w is from about 3 to about 12, preferably 4 to 6, more preferably 4;

h is 1 to about 6, preferably 1 to 3, more preferably 2;

y is a linear or branched diradical of ethylenic unsaturation having the formula:

-C_eH_(2e-2)-a structure of the structure,

wherein e is 2 or 3, preferably 2; r is H or a linear or branched alkyl group C_bH_(2b+1)-; and b is from 1 to about 18, preferably from 6 to 18.

The compounds of formulae 2A, 2B and 2C were prepared as described above for formulae 1A, 1B and 1C, except that the sulfonation step was omitted. The compounds of formulae 2A, 2B, and 2C may also be monomers that polymerize alone or in admixture with other monomers to impart soil and water repellency to the resulting polymer and to the surface to which the resulting polymer is applied.

Preferred compounds of formulae 2A, 2B and 2C are those wherein R_aIs R_f(CH₂CF₂)_d-(C_gH_2g)-、R_fOCF₂CF₂-(C_gH_2g)-、R_f-OCFHCF₂O-(CH₂CH₂O)_v-(C_gH_2g) -, or R_fOCFHCF₂O(C_wH_2wO)-(C_gH_2g) -those of (a). Also preferred is where c is 3 or 4, or where Y is CH ═ CH, CH₂C(＝CH₂)、C(CH₃)＝CH₂、CH＝CHCH₂Or CH₂CH＝CHCH₂Those compounds of formulae 2A, 2B and 2C. More preferably wherein R_aIs R_f(CH₂CF₂)_d-(C_gH_2g)-、R_fOCF₂CF₂-(C_gH_2g)-、R_fOCFHCF₂O-(CH₂CH₂O)_v-(C_gH_2g) -, or R_fOCFHCF₂O(C_wH_2wO)-(C_gH_2g) -; d is 1, g is 1, R_fIs C₃F₇Or C₄F, and Y is CH ═ CH, CH₂C(＝CH₂) Or C (CH)₃)＝CH₂Those compounds of (1). Also preferred is where R_aIs C₄F₉CH₂CF₂CH₂CH₂Or C₃F₇CH₂CF₂CH₂CH₂And R is_fIs (CF)₂)₆F, a compound of formula 2B.

The compounds of formulae 2A, 2B and 2C are useful as intermediates to prepare partially fluorinated sulfonated surfactants, in particular those having the structures of formulae 1A, 1B and 1C as defined above.

The invention also includes a method of modifying the behaviour of a surface of a liquid in a variety of applications, the method comprising adding to the liquid a compound of formulae 1A, 1B and 1C as defined above. The surfactants of formulae 1A, 1B and 1C are generally used by simply blending with or adding to water, aqueous solutions and emulsions. The surfactants of formulas 1A, 1B, and 1C generally lower the surface and interfacial tension and provide lower critical micelle concentrations. Examples of surface behavior changes include improvements in the following properties: wettability, permeability, spreadability, leveling, flowability, emulsifiability, stability of the dispersion in a liquid, repellency, releasability, lubricity, etching, and adhesion.

Examples of such applications where low surface tension is desired include coating compositions and aqueous and non-aqueous cleaning products for the following materials, respectively: glass, wood, metal, brick, concrete, cement, natural and synthetic stone, tile, synthetic flooring, laminates, paper, textile materials, linoleum and other plastics, resins, natural and synthetic rubbers, fibers and fabrics, and coatings; a polymer; and waxes, finishes, leveling agents and glossing agents for use in flooring, furniture, footwear, inks and automotive care. Wetting agent applications include wetting agents comprising compositions of herbicides, fungicides, herbicides, hormone growth regulators, insect repellents, insecticides, bactericides, nematicides, microbicides, defoliants or fertilizers, therapeutic agents, antimicrobials, fluorochemical blood substitutes, textile treatment baths, and fiber spin finishes. Applications in the form of personal care products include shampoos, conditioners, pomades, skin cosmetic products (such as therapeutic or protective creams and lotions, oil-and water-repellent cosmetic powders, deodorants and antiperspirants), nail polish, lipstick, and toothpaste. Other applications include fabric care products (such as stain pretreaters and/or stain removers for garments, carpets, and upholstery) and laundry detergents. Other applications include rinse aids (for car washes and for automatic dishwashing), well treatment agents (including drilling muds and additives to improve tertiary oil well recovery), extreme pressure lubricants, lubricating cutting oils to improve penetration times, inks, printing inks, photographic developing solutions, emulsions for fighting forest fires, dry powder extinguishants, aerosol extinguishants, thickeners to form gels to solidify or encapsulate medical waste, photoresists, developers, cleaning solutions, etching compositions, developers, polishes, and solder resist inks in the manufacture, processing, and handling of semiconductors and electronics. The surfactant of the present invention can be incorporated into products used as antifogging agents for glass surfaces and films, antistatic agents for magnetic tapes, phonograph records, floppy disks, disk drives, rubber compositions, PVC, polyester films and films, and surface-treating agents for optical members such as glass, plastics or ceramics. Other applications are in the form of: emulsifiers, foaming agents, release agents, repellency agents, flow modifiers, film evaporation inhibitors, wetting agents, penetrants, cleaning agents, abrasives, plating agents, corrosion inhibitors, soldering agents, dispersion aids, microbial agents, pulping aids, rinse aids, polishing agents, drying agents, antistatic agents, anti-blocking agents, adhesives, and oilfield chemicals.

The compounds of the invention are also useful as foam control agents in polyurethane foams, spray-type oven cleaners, kitchen and bathroom foaming cleaners and disinfectants, in aerosol shave foams and in textile treatment baths. The surfactants of the invention are useful as polymerization (especially fluoromonomer polymerization) emulsifiers, as latex stabilizers, as mold release agents for silicones, photographic latex stabilizers, inorganic particles, and pigments. Such fluorosurfactants are also useful in supercritical carbon dioxide emulsions and dispersions of nanoparticles or pigments in water.

Low concentrations of compounds of formula 1A, 1B or 1C of less than about 0.1% by weight, preferably less than about 0.01% by weight, in the liquid are effective. Thus, the surfactants of formulas 1A, 1B and 1C can be used in a variety of end-use applications.

The invention also includes compounds of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)；

c is 2 to about 6, preferably 2 to 4, more preferably 4; and is

v is 2 to about 4, preferably 2 to 3, more preferably 2.

Preferred compounds of formula 5 are those wherein c is 3 or 4, g is 2, and v is 2 or 3. The compounds of formula 5 are useful as intermediates in the preparation of partially fluorinated sulfonated surfactants. In particular, the compounds of formula 5 are useful in the preparation of surfactants of formulae 1A, 1B and 1C as previously defined.

The invention also includes a process for preparing a compound of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)(ii) a c is 2 to about 6; and v is from 2 to about 4,

R_f-O-CF＝CF₂Formula 6

Wherein R is_fIs C_cF_(2c+1)And c is from 2 to about 6,

HO-(CH₂CH₂O)_v-H formula 7

Wherein v is 2 to about 4.

In the process of the present invention, the compound of formula 5 is prepared by the reaction of a perfluorocarbon vinyl ether with a glycol in the presence of an alkali metal compound. Preferred ethers include those of the formula R_f-O-CF＝CF₂Wherein R is_fIs a perfluoroalkyl group having one to six carbons. Preferred diols include diethylene glycol. The diol is used in an amount of about 1 to about 15 moles per mole of ether, preferably about 1 to about 5 moles per mole of ether. Suitable alkali metallizationThe compound includes an alkali metal, an alkaline earth metal, an alkali metal hydroxide, an alkali metal hydride, or an alkali metal amide. Preference is given to alkali metals such as sodium, potassium or cesium, or alkali metal hydrides such as NaH or KH. The reaction is carried out at a temperature of from about ambient temperature to about 120 c, preferably from about 40 c to about 120 c. The reaction may be carried out in an optional solvent such as ether or nitrile. The process is useful for preparing alcohols of formula 5, which are useful for preparing derivatives such as surfactants.

In many cases, the surfactants of formulas 1A, 1B and 1C of the present invention require less tetrafluoroethylene in their preparation when compared to conventional fluorosurfactants prepared from telomer B alcohols. Although when R is_aIs (ii) R_fOCF₂CF₂-(C_gH_2g)-，(iii)R_fOCFHCF₂O(CH₂CH₂O)_v-(C_gH_2g)-，(iv)R_fOCFHCF₂O(C_wH_2w) -, or (v) R_fOCF(CF₃)CONH-(C_gH_2g) When tetrafluoroethylene is used for R_aR of-OH alcohol precursor_fIn part, but otherwise, tetrafluoroethylene is not used in the preparation of a compound of formula 1A, 1B, or 1C or a compound of formula 2A, 2B, or 2C. In contrast to typical perfluoroalkyl groups having 1 to 20 carbons in surfactants prepared from conventional telomer B alcohols, a portion of the fluorine in the surfactants of the invention is replaced by other atoms or monomers. Thus, in the presence of R_a(i) And (vi) groups in the preparation of compounds of formulae 1A, 1B and 1C or compounds of formulae 2A, 2B and 2C, less tetrafluoroethylene is used.

In most cases, the monomer portion replacing tetrafluoroethylene also contains a lower proportion of fluorine. Thus, in many cases, the fluorine efficiency of the surfactants of the present invention is higher than many conventional surfactants. "fluorine efficiency" refers to the ability to achieve a desired surface effect or surfactant characteristic using a minimum amount of fluorine-containing compound when applied to a substrate, or the ability to achieve better performance using the same amount of fluorine.

Materials and test methods

The following materials and test methods were used in the examples herein.

All common organic and inorganic compounds were obtained from Sigma-Aldrich (Milwaukee, WI) and used without purification. These include maleic anhydride, sodium bisulfite, toluene, hexane, p-toluenesulfonic acid, itaconic anhydride, citraconic anhydride, trans-glutaconic acid, trans-beta-hydrohexadiene diacid, and other conventional compounds used in the examples.

SIMULSOL SL 8: octyl/decyl polyglucoside is obtained from Kreglinger Europe (Antwerp, Belgium).

TRITON X100: p-tert-octylphenoxypolyethyl alcohol was obtained from Sigma-Aldrich (Saint Louis, Mo.).

DOWANOL DB: 1-butoxy-2-ethoxyethane was obtained from Dow Chemical Company (Midland, MI).

SOLKANE 365MFC was 1, 1, 1, 3, 3-pentafluorobutane available from Solvay Fluorides (Thorofare, NJ).

The following fluorinated compounds were obtained from e.i. du Pont DE Nemours and Company (Wilmington, DE): perfluoro-2-methyl-3-oxahexanoyl fluoride, perfluoroiodobutane, vinylidene fluoride, perfluoropropyl vinyl ether, and perfluoroethyl iodoethane.

The following fluorinated compounds were prepared as follows:

C₄F₉CH₂CF₂i and C₄F₉(CH₂CF₂)₂I can be prepared by reacting perfluoroiodobutane with Vinylidene Fluoride, as described by Balague et al in Synthesis of Fluorinated polymers section 1 catalysis of vinylidenefluoride with Fluorinated ethylene ions, J.fluorine chem. (1995), 70(2), 215-23. The particular telomer iodides can be isolated by fractional distillation.

C₃F₇OCF₂CF₂I can be prepared by the reaction of perfluoropropyl vinyl ether with iodine chloride and hydrofluoric acid and boron trifluoride as a catalyst, as described in Viachesslav et al, US 5,481,028.

Test method 1Determination of the Critical Micelle Concentration (CMC) and the surface tension above CMC

The surface tension of the aqueous surfactant solutions was measured in mN/m at different weight percentages using a Kruss K11 tensiometer (available from Kruss USA (Charlotte, NC)). The compound with the lowest surface tension has the highest efficacy.

The Critical Micelle Concentration (CMC) is defined as the concentration at which increasing the surfactant concentration does not substantially reduce the surface tension any longer. To determine the CMC, the surface tension is determined as a function of the surfactant concentration. The surface tension (abscissa) is then plotted against the logarithm of the concentration (ordinate). The resulting curve has an almost horizontal portion at concentrations above CMC and a negative steep slope at concentrations below CMC. The CMC is the concentration at which the extrapolated steep slope intersects the extrapolated almost horizontal line. The surface tension above the CMC is the value of the flat part of the curve. The CMC should be as low as possible to provide the lowest cost to achieve effective performance.

Test method 2Spreadability on cyclohexane

Test method 2 was modified according to Stern et al, WO1997046283A1, in which a surfactant was applied to the surface of n-heptane to provide a selected rating for Advanced Fire Fighting Foam (AFFF). Cyclohexane was used in test method 2 instead of the n-heptane used by Stern et al. Test method 2 measures the ability of a surfactant solution to spread over the surface of a low density flammable liquid. When the surfactant solution is spread on the surface ("excellent" grade), a barrier layer is formed between the flammable liquid and the air. If the surfactant solution does not spread completely over the surface ("good" or "medium" grade, depending on the degree of incomplete spreading), the barrier between the air and the flammable liquid is incomplete. If the surfactant solution sinks into the flammable liquid (a "poor" grade), no barrier is formed between the air and the flammable liquid.

The surfactant solution was prepared as follows: a fluorosurfactant (0.9g/L active ingredient), hydrocarbon surfactant (SIMULSOL SL8 or TRITON X100; 2.4g/L active ingredient), butyl carbitol (DOWANOL DB; 4.2g/L active ingredient) were mixed and stirred well. The petri dish (11.5cm diameter) was filled to about half-full with 75mL of cyclohexane. After the cyclohexane surface had completely settled (about 1 minute), 100 microliters of a solution of fluorosurfactant, hydrocarbon surfactant, butyl carbitol and water was added dropwise starting from the center of the dish and extending outward along the radial line to the outer edge of the dish using a micropipette. A timer is started. For the less performing formulations, the surfactant solution "sinks immediately" under the cyclohexane. For medium performance formulations, the surfactant solution merely "floats" on the cyclohexane surface without sinking. For a well-performing formulation, the surfactant spreads on the cyclohexane surface. The time when the spreading range of the surfactant solution on the cyclohexane surface no longer increased was recorded, and the surface coverage at this time (< 100%) was recorded. For formulations with superior performance, the surfactant solution quickly spread across the cyclohexane surface. For a formulation with excellent performance, the time when the spreading range of the surfactant solution covered the entire surface for the first time (100%) was recorded.

Examples

Example 1

A mixture of ethanolamine (13g, 28mmol) and ether (30mL) was cooled to 15 ℃. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33g, 50mL in ether) was added dropwise to keep the reaction temperature below 25 ℃. After the dropwise addition, the reaction mixture was stirred at room temperature for one hour. The solids were removed by filtration and the filtrate was washed with hydrochloric acid (0.5N, 30mL), water (2 times, 30mL), sodium bicarbonate solution (0.5N, 20mL), water (30mL) and sodium chloride solution (saturated, 20 mL). Then concentrated, and dried under vacuum at room temperature overnight,35g of a white solid are obtained with a yield of 95%. By using¹The product was analyzed by HNMR and confirmed to be N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethanol C₃F₇OCF(CF₃)CONHCH₂CH₂OH。

Maleic anhydride (0.60g, 6.1mmol), C were continuously stirred under nitrogen₃F₇OCF(CF₃)CONHCH₂CH₂A mixture of OH (4.5g, 12mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.12g), and toluene (50mL) and heated to reflux. The temperature was maintained at 111 ℃ for about 22h until 90% of the water was azeotropically removed with the aid of a dean-stark trap. Liquid chromatography/mass spectrometry (LC/MS) was determined to show the completion to the diester. The solution was separated and extracted with two 5% sodium bicarbonate wash solutions. The combined organic extracts were washed with anhydrous magnesium sulfate (MgSO)₄) Dried and then toluene removed by rotary evaporation. By¹HNMR and LC/MS analysis of the yellow oil (3.12g, 61.9% yield, 90% purity) confirmed the structure C₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC-(O)CH＝CHC(O)OCH₂ CH₂NHC(O)-CF(CF₃)OC₃F₇。

Example 2

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70mL) was slowly added to 50g C₄F₉CH₂CF₂CH₂CH₂I and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na₂SO₃The reaction was quenched with aqueous solution and heated at 95 ℃ for 0.5 h. The bottom layer was separated off and washed with 10% by weight aqueous sodium acetate and distilled to give C₄F₉CH₂CF₂CH₂CH₂OH, boiling point 54-57 ℃ under 2mmHg (267 Pa).

Bis (1H, 1H, 2H, 2H, 4H, 4H-perfluorooctyl) maleate (7.76g, 95% yield, 95% purity) was prepared by the esterification method of maleic anhydride (1.07g, 11mmol) in example 1. C is to be₄F₉CH₂CF₂CH₂CH₂A solution of OH (7.13g, 22mmol, prepared as described above) and p-toluenesulfonic acid monohydrate (0.21g, 1.1mmol) in 50mL of toluene was heated at 111 ℃ for 40 h. By¹HNMR and LC/MS analysis of the light yellow product confirmed the structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)-CH＝CH-C(O)OCH₂CH₂CF₂CH₂C₄F₉。

Example 3

Ethylene (56g) was added to the charge C_4F9(CH₂CF₂)₂I (714g) and d- (+) -limonene (3.2g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated off by vacuum distillation to give C₄F₉(CH₂CF₂)₂CH₂CH₂I. C is to be₄F₉(CH₂CF₂)₂CH₂CH₂A mixture of I (10g, 0.02mol) and N-methylformamide (8.9mL, 0.15mol) was heated at 150 ℃ for 26 h. The mixture was cooled to 100 ℃ and the crude ester was then isolated by the addition of water. Ethanol (3mL) and p-toluenesulfonic acid (0.09g) were added, and the mixture was stirred at 70 ℃ for 0.25 hour. Ethyl formate and ethanol were removed by distillation to give the crude product. The crude product was dissolved in diethyl ether, washed successively with 10% by weight aqueous sodium sulfite solution, water and brine, and then dried over magnesium sulfate. Distilling to obtain a product C₄F₉(CH₂CF₂)₂CH₂CH₂OH (6.5g, yield 83%): the boiling point is 94-95 ℃ under 2mmHg (266 Pa).

Maleic anhydride (0.65g, 6.7mmol), C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OH(4.37g，1.333*10^-2mol, prepared as described above), p-toluenesulfonic acid monohydrate (0.13g, 0.67mmol) and toluene (50mL) were mixed together and heated at reflux for 48h at 110 ℃. The post-treatment was carried out according to example 1. By¹H NMR and LC/MS analysis of the resulting pale yellow liquid (2.90g, yield 51.4%, purity > 99%) confirmed the structure C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂O-C(O)CH＝CH-C(O)OCH₂CH₂CF₂CH₂CF₂CH₂C₄F₉。

Example 4

Under nitrogen atmosphere, C is₃F₇OCF₂CF₂I (100g, 0.24mol) and benzoyl peroxide (3g) were charged to a pressure vessel. A series of three evacuation/nitrogen procedures were then carried out at-50 ℃ followed by the addition of ethylene (18g, 0.64 mol). The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. The product was then collected in a bottle. The product was distilled to give 80g of C in 80% yield₃F₇OCF₂CF₂CH₂CH₂I. A boiling point of 56 to 60 ℃ at 25mmHg (3.3 kPa).

C is to be₃F₇OCF₂CF₂CH₂CH₂A mixture of I (300g, 0.68mol, prepared as described above) and N-methylformamide (300mL) was heated at 150 ℃ for 26 h. The reaction was then cooled to 100 ℃ and water was then added to isolate the crude ester. Ethanol (77mL) and p-toluenesulfonic acid (2.59g) were added to the crude ester, and the reaction was stirred at 70 ℃ for 15 minutes. Ethyl formate and ethanol were then distilled off to give the crude product. The crude product was dissolved in ether, washed successively with aqueous sodium sulfite solution, water and brine, and then dried over magnesium sulfate. Then the product is put intoThe material was distilled to give 199g of C in 85% yield₃F₇OCF₂CF₂CH₂CH₂I. A boiling point of 71 to 73 ℃ at 40mmHg (5333 Pa).

The same procedure as in example 1 was carried out. Maleic anhydride (0.66g, 6.8mmol), C₃F₇OCF₂CF₂CH₂CH₂OH (4.46g, 14mmol, prepared as described above), p-toluenesulphonic acid monohydrate (0.13g, 0.68mmol) and toluene (50mL) were mixed together and refluxed at 112 ℃ for 50 h. By¹Analysis of the pale yellow crude product by H NMR and LC/MS (4.12g, 82.4%, purity > 99%) confirmed the structure C₃F₇OCF₂CF₂-CH₂CH₂OC(O)CH＝CHC(O)OCH₂CH₂NHC(O)CF(CF₃)OC₃F₇.

Example 5

In a dry box, to a 500mL Pyrex bottle was added diethylene glycol (99%, Aldrich Chemical Company) (175mL, 1.84mole) and 80mL anhydrous tetrahydrofuran (Aldrich Sure/Seal)^TM). NaH (3.90g, 0.163 moles) was added slowly with magnetic stirring until hydrogen evolution was complete. The capped vial was removed from the dry box and the solution was transferred to a 400mL metal shaker tube inside a nitrogen-filled glove bag. The shaker tube was cooled to-18 ℃ internal temperature, shaking was started, and perfluoropropyl vinyl ether (PPVE, 41g, 0.145mole) was added from a metal cylinder. The mixture was allowed to warm to room temperature and shaken for 20 hours. The reaction mixture was mixed with a repeat reaction mixture performed in a separate 400mL shaking tube. The combined reaction mixture was added to 600mL of water and the mixture was extracted with 3X 200mL of diethyl ether in a separatory funnel. Extracting the ether extract over MgSO₄Dried, filtered and concentrated in vacuo on a rotary evaporator to give a liquid (119.0g),¹h NMR (in CD)₃OD) and gas chromatography showed a small amount of diethylene glycol. This material was dissolved in 150mL of diethyl ether and extracted with water (3X 150mL) in a separatory funnel. The ether layer was over MgSO₄Dried, filtered, and concentrated under high vacuum on a rotary evaporator under vacuum to give a liquid (99.1 g).¹H NMR(C₆D₆Ppm from TMS) showed 97 mole% of the desired mono-PPVE adduct: 1.77 (width s, OH), 3.08-3.12(m, OCH)₂CH ₂OCH ₂CH₂OH)，3.42(t，OCH₂CH₂OCH₂CH ₂OH)，3.61(t，OCH ₂CH₂OCH₂CH₂OH), 5.496 (double triplet,²J_H-F＝53Hz，³J_H-F＝3Hz OCF₂CHFOC₃F₇) And 3 mole% of the PPVE adduct: 5.470 (double triplet peak,²J_H-F＝53Hz，³J_H-F＝3Hz，C₃F₇OCHFCF₂OCH₂CH₂OCH₂CH₂OCF₂CHEOC₃F₇). The other peaks of the PPVE adduct overlap with the peaks of the PPVE adduct.

Maleic anhydride (0.59g, 6.1mmol), C₃F₇OCHFCF₂OCH₂CH₂OCH₂CH₂A mixture of OH (4.5g, 12mmol, prepared as above), p-toluenesulfonic acid monohydrate (0.12g, 0.61mmol) and toluene (50mL) was stirred together continuously and heated at reflux for 25h at 114 ℃. The reaction was confirmed to be complete by LC/MS and water was removed. Working-up was carried out according to example 1 to give a pale yellow liquid (4.48g, yield 90.0%, purity 87%). By using¹H NMR and LC/MS confirmed complete conversion to the diester and the structure was C₃F₇OCFHCF₂OCH₂CH₂-OCH₂CH₂OC(O)CH＝CHC(O)OCH₂CH₂O-CH₂CH₂OCF₂CFHOC₃F₇。

Example 6

Perfluoroethylethyl iodide (850g) was charged to a one gallon reactor. After cold emptyingEthylene and tetrafluoroethylene were added in a ratio of 27: 73 until the pressure reached 60psig (414 kPa). The reaction was then heated to 70 ℃. More ethylene and tetrahydrofuran were added in a ratio of 27: 73 until the pressure reached 160psig (1.205 MPa). Lauroyl peroxide solution (4g of lauroyl peroxide in 150g of perfluoroethyl iodoethane) was added at a flow rate of 1mL/min for 1 hour. The gas feed ratio of ethylene and tetrafluoroethylene was adjusted to 1: 1 and the pressure was maintained at 160psig (1.205 MPa). After about 67g of ethylene was added, the ethylene and tetrafluoroethylene feeds were stopped. The reaction was heated at 70 ℃ for a further 8 hours. Volatiles were removed by vacuum distillation at room temperature. Obtaining oligomer ethylene-tetrafluoroethylene iodide solid C₂F₅(CH₂)₂[(CF₂CF₂)(CH₂CH₂)]_k-I (773g) where k is a mixture of 2 and 3 in a ratio of about 2: 1.

The oligomeric iodide mixture (46.5g) prepared as described above was mixed with N-methylformamide (NMF, 273mL) without iodide isolation and heated at 150 ℃ for 19 h. The reaction mixture was washed with water (4X 500mL) to obtain a residue. A mixture of this residue, ethanol (200mL) and concentrated hydrochloric acid (1mL) was gently refluxed (85 ℃ bath temperature) for 24 h. The reaction mixture was poured into water (300 mL). The solid was washed with water (2X 75mL) and then dried under vacuum (2 torr, 267Pa) to yield 24.5g of a solid. About 2g of product sublimed. Oligo-alcohol C₂H₅(CH₂)_h[(CF₂CF₂)(CH₂CH₂)]_k-The total yield of OH was 26.5g, where k was a mixture of 2 and 3 in a ratio of about 2: 1.

Maleic anhydride (1.74g, 18mmol) and C₂F₅(CH₂)₂[(CF₂CF₂)(CH₂CH₂)]_k-A mixture of OH (6.26g) was stirred together continuously and heated to 70 ℃. The reaction was run for 45h without solvent and Gas Chromatography (GC) was measured at several intervals to observe disappearance of reactants and production of half acid/ester. C₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_k-oc (o) CH ═ chc (o) OH. The half acid/ester (4.75g, 9.7mmol), C were dissolved in toluene (50mL)₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_k-OH (3.80g, 9.7mmol), and p-toluenesulphonic acid monohydrate (0.12g, 0.97mmol) were heated at reflux for 19h at 114 ℃. By using CH₃CN (3X 100mL), extraction, concentration, extraction with tetrahydrofuran, concentration and drying isolated the product and obtained as a yellow/orange solid product (7.46g, yield 93.3%, 97%) from¹H NMR and LC/MS analysis confirmed that it has the structure C₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]kOOC(O)CH＝CHC(O)O[(CH₂CH₂)-(CF₂CF₂)]k-CH₂CH₂C₂F₅Wherein k is a mixture of 2 and 3.

Example 7

A mixture of ethanolamine (13g, 28mmol) and ether (30mL) was cooled to 15 ℃. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33g, 50mL in ether) was added dropwise to keep the reaction temperature below 25 ℃. After the dropwise addition, the reaction mixture was stirred at room temperature for one hour. The solids were removed by filtration and the filtrate was washed with hydrochloric acid (0.5N, 30mL), water (2 times, 30mL), sodium bicarbonate solution (0.5N, 20mL), water (30mL) and sodium chloride solution (saturated, 20 mL). Then concentrated and dried under vacuum at room temperature overnight to yield 35g of a white solid in 95% yield.¹H NMR and FNMR analysis showed the product to be N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethanol, C₃F₇OCF(CF₃)CONHCH₂CH₂OH。

Itaconic anhydride (0.67g, 6.0mmol), C₃F₇OCF(CF₃)CONH-CH₂CH₂OH (4.44g, 12mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.11g, 0.60mmol), and toluene (50mL) were stirred continuously and heated at 111 ℃ under reflux for 25 h. Decanting offToluene was removed leaving a viscous yellow solid. The product was first air dried and then placed in a vacuum oven for 2 h. By¹H NMR and LC/MS analysis of the product (3.62g, 72.4%, 65% purity) confirmed complete conversion and the structure was C₃F₇OCF-(CF₃)C(O)NHCH₂CH₂OC(O)CH₂C(＝CH₂)C(O)OCH₂CH₂-NHC(O)CF(CF₃)OC₃F₇。

Example 8

Itaconic anhydride (0.75g, 6.7mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.37g, 13mmol, prepared as described above), p-toluenesulphonic acid monohydrate (0.13g, 0.67mmol) and toluene (50mL) were refluxed at 113 ℃ for 19 h. By¹H NMR and LC/MS analyses of the resulting pale yellow liquid (4.53g, yield 90.6%, purity 72%) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂C(＝CH₂)C(O)OCH₂CH₂CF₂CH₂C₄F₉。

Example 9

Citraconic anhydride (0.67g, 6.0mmol), C₃F₇OCF(CF₃)CONHCH₂CH₂OH (4.44g, 12mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.11g, 0.60mmol), and toluene (50mL) were added together and heated at 111 ℃ under reflux for 40h with constant stirring. There are two distinct solid materials present in the toluene solution. The pink solid was removed and the white solid was vacuum filtered. The two materials were analyzed by LC/MS, which confirmed a pink solid as the product and a white solid as the unreacted alcohol (1.22 g). By¹The product was analyzed by H NMR and LC/MS (2.98g, yield 59.6%, purity 65%) to confirm the structure as C₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)-C(CH₃)＝CH₂C(O)OCH₂CH₂NHC(O)CF(CF₃)OC₃F₇。

Example 10

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70mL) was slowly added to 50g C₄F₉CH₂CF₂CH₂CH₂I and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na₂SO₃The reaction was quenched with aqueous solution and heated at 95 ℃ for 0.5 h. The bottom layer was separated off and washed with 10% by weight aqueous sodium acetate and distilled to give C₄F₉CH₂CF₂CH₂CH₂OH: the boiling point is 54-57 ℃ at 2mmHg (267 Pa).

Citraconic anhydride (0.75g, 6.7mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.37g, 13.3mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.13g), and toluene (50mL) were refluxed at 112 ℃ for about 46h, after which only diester was observed in LC/MS analysis. Working-up was carried out as in example 1 to give a pale yellow liquid (2.98g, yield 59.6%, purity > 99%) prepared from¹Analysis thereof by H NMR and LC/MS confirmed that the diester structure was C₄F₉CH₂CF₂CH₂CH₂OC(O)C(CH₃)＝CH₂C(O)OCH₂CH₂CF₂CH₂C₄F₉。

Example 11

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70mL) was slowly added to 50g C₄F₉CH₂CF₂CH₂CH₂I and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na₂SO₃The reaction was quenched with aqueous solution and heated to 0 ℃ at 95 ℃.For 5 hours. The bottom layer was separated off and washed with 10% by weight aqueous sodium acetate and distilled to give C₄F₉CH₂CF₂CH₂CH₂OH: the boiling point is 54-57 ℃ at 2mmHg (267 Pa).

Mixing trans-glutaconic acid (0.87g, 6.7mmol) and C₄F₉CH₂CF₂CH₂CH₂OH (4.37g, 13mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.13g, 0.67mmol), and toluene (50mL) were stirred together and heated at 111 ℃ under reflux for 24 h. The work-up was carried out according to example 1. The resulting white solid (2.52g, yield 50.4%, purity 80%) was dried in a vacuum oven and dried from¹H NMR and LC/MS analyses confirmed the structure to be C₄F₉CH₂CF₂CH₂CH₂OC(O)CH＝CHCH₂C(O)OCH₂CH₂CF₂CH₂C₄F₉。

Example 12

Ethylene (56g) was added to the charge C_4F9(CH₂CF₂)₂I (714g) and d- (+) -limonene (3.2g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated off by vacuum distillation to give C₄F₉(CH₂CF₂)₂CH₂CH₂I. C is to be₄F₉(CH₂CF₂)₂CH₂CH₂A mixture of I (10g, 0.02mol) and N-methylformamide (8.9mL, 0.15mol) was heated at 150 ℃ for 26 h. The mixture was cooled to 100 ℃ and the crude ester was then isolated by the addition of water. Ethanol (3mL) and p-toluenesulfonic acid (0.09g) were added, and the mixture was stirred at 70 ℃ for 0.25 hour. Ethyl formate and ethanol were removed by distillation to give the crude product. The crude product was dissolved in ether, washed successively with 10 wt% aqueous sodium sulfate, water and brine, and dried over magnesium sulfate. Distilling to obtain a product C₄F₉(CH₂CF₂)₂CH₂CH₂OH (6.5g, yield 83%): the boiling point is 94-95 ℃ under 2mmHg (266 Pa).

Mixing trans-glutaconic acid (0.75g, 5.8mmol) and C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OH (4.54g, 12mmol, prepared as described above), p-toluenesulfonic acid monohydrate (0.11g, 0.58mmol), and toluene (50mL) were stirred together and heated at 111 ℃ under reflux for 16 h. Progress was monitored by LC/MS and water was removed azeotropically. The orange/yellow solid was filtered off and washed with 5% sodium bicarbonate solution (50 mL). The filtrate was separated and the organic layer was washed with 5% sodium bicarbonate solution (50mL) and then deionized water (50 mL). The combined organic extracts were dried over anhydrous MgSO₄Dried and then concentrated in toluene (140.30mmHg, 67 ℃). The orange solid (4.14g, 81.5% yield, 85% purity) was dried in a vacuum oven¹HNMR and LC/MS analysis confirmed the structure to be C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CH＝CHCH₂C(O)O-CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉。

Example 13

By reacting maleic anhydride (2.00g, 20mmol) with C₄F₉CH₂CF₂CH₂CH₂OH (6.69g, 20mmol, prepared as described above) was reacted and a melt reaction was performed. The reaction was allowed to continue at 70 ℃ for 34h, during which time an aliquot was taken for GC analysis. By¹H NMR and LC/MS analysis of the white solid half acid/ester (8.02g, 92.3% yield, > 98% purity) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)CH＝CHC(O)OH。

Example 14

The maleate (6.68g, 17mmol) prepared as described in example 13, p-toluenesulfonic acid monohydrate (0.30g, 1.7mmol) and hexanol (1.60g, 17mmol) were mixed together with toluene (50 mL). The mixture was stirred together continuously and heated to reflux at 114 ℃ for 19 h. Working-up was carried out according to example 1, giving a clear liquid (7.14g, yield 89.3%, purity 98%) obtained from¹Analysis thereof by H NMR and LC/MS confirmed the structure to be C₄F₉CH₂CF₂CH₂CH₂OC(O)CH＝CHC(O)O-(CH₂)₆H。

Example 15

The maleate (4.41g, 10mmol) prepared as described in example 13, p-toluenesulfonic acid monohydrate (0.20g, 1.0mmol), and C were reacted₆F₁₃CH₂CH₂OH (3.77g, 10mmol) was added with toluene (50 mL). The contents were refluxed at 114 ℃ for 19h and worked up according to example 1. By¹H NMR and LC/MS analysis of the pale yellow liquid (5.78g, 72.3% yield, 90% purity) confirmed the formation of the mixed diester and the structure was C₄F₉CH₂CF₂CH₂CH₂OC(O)CH＝CHC(O)OCH₂CH₂(CF₂)₆F。

Example 16

The maleate ester prepared as described in example 1 (2.62g, 3.2mmol) and isopropanol (IPA, 31g) were added together at 50 ℃ and mixed for about 10 minutes until the mixture dissolved. Aqueous sodium bisulfite (0.17g, 1.6mmol) was dissolved in deionized water (8mL) and added dropwise to the isopropanol solution, which was then heated at reflux (86 ℃ C.) for 26 h. Isopropanol and water were removed by rotary evaporation and then dried in a vacuum oven at 50 ℃ to give a viscous yellow liquid (1.70g, yield 57.6%, purity 75%) prepared from¹Analysis by H NMR and LC/MS confirmed diester sulfonate, confirming the structure C₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O-CH₂CH₂NHC(O)CF(CF₃)OC₃F₇。

The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

Example 17

The maleate ester prepared as described in example 2 (7.74g, 11mmol) and isopropanol (31g) were stirred together continuously. The temperature was raised to 61 ℃ and then a solution of sodium bisulfite (1.09g, 11mmol) dissolved in deionized water (53mL) was added dropwise. The mixture was heated to reflux at an elevated temperature of 82 ℃ for 24 h. The solution was concentrated to remove the isopropanol/water solution. The remaining pale yellow liquid was dried in an oven overnight to give a white solid (6.96g, yield 78.8%, purity 98%), which was then purified from¹H NMR and LC/MS analyses confirmed the structure to be C₄F₉CH₂CF₂CH₂CH₂OC(O)-CH₂CH(SO₃Na)C(O)O-CH₂CH₂CF₂CH₂C₄F₉. The CMC and surface tension above CMC of the product were evaluated according to test method 1, the results are shown in Table 2, and in cyclohexane according to test method 2The results are shown in table 3.

Example 18

The maleate (2.88g, 3.3mmol) prepared as described in example 3 and isopropanol (31g) were stirred continuously at 82 ℃ for 28h while adding an aqueous solution of sodium bisulfite (1.54g, 15mmol) dissolved in deionized water (20 mL). White solid was collected by concentrating the isopropanol/water solution and then drying in a vacuum oven overnight (2.58g, yield 80.1%, purity > 95%). By¹The product was analyzed by HNMR and LC/MS to confirm the structure as C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O-CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 19

The maleate prepared as described in example 4 (4.10g, 5.5mmol), isopropanol (31g) and aqueous sodium bisulfite (0.28g, 2.8mmol) dissolved in deionized water (14mL) were stirred continuously at 82 ℃ for 18 h. The product was collected as a white solid (3.36g, 71.9% yield, > 95% purity) by rotary evaporation of the isopropanol/water solution and then dried in a vacuum oven. By¹Analysis of the product by H NMR and LC/MS confirmed conversion to the diester sulfonate and a structure of C₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O-CH₂CH₂CF₂CF₂OC₃F₇. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 20

The maleate (1.49g, 1.8mmol) prepared as described in example 5, isopropanol (31g) and aqueous sodium bisulfite (0.29g, 2.8mmol) dissolved in deionized water (14mL) were mixed together and refluxed at 82 ℃ for 27 h. The isopropanol was concentrated and the white solid obtained (1.46g, yield 87.1%, purity > 97%) was dried in a vacuum oven and purified from¹H NMR and LC/MS analyses confirmed the structure to be C₃F₇OCFHCF₂OCH₂CH₂OCH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O-CH₂CH₂OCH₂CH₂OCF₂CFHOC₃F₇. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 21

The maleate ester prepared as described in example 6 (7.54g, 8.7mmol) and isopropanol (31g) were heated to 50 ℃ until the solid dissolved in the solution. An aqueous solution of sodium bisulfite (0.91g, 8.7mmol) dissolved in deionized water (43mL) was transferred to the mixture and the contents were refluxed at 82 ℃ for 20 h. The isopropanol/water solution was removed by rotary evaporation to give an orange/brown solid (7.22g, yield 87.3%, purity 92%). By¹The product was analyzed by H NMR and LC/MS to confirm the structure as C₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_kOOC(O)CH＝CHC(O)O-[(CH₂CH₂)(CF₂CF₂)]_kCH₂CH₂C₂F₅Wherein k is a mixture of 2 and 3 in a ratio of 2: 1. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

Example 22

The itaconate ester prepared as described in example 7 (3.60g, 4.3mmol) and isopropanol (31g) were stirred together continuously. An aqueous solution of sodium bisulfite (0.45g, 4.3mmol) dissolved in deionized water (21mL) was slowly added to the solution and the temperature was raised to 82 ℃ for 23 h. The isopropanol/water was concentrated to leave a yellow gel-like product (3.73g, 92.1% yield, 75% purity) which was placed in a vacuum oven overnight¹H NMR and LC/MS analyses confirmed the structure to be C₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O-CH₂CH₂NHC(O)CF(CF₃)OC₃F₇. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 23

The itaconate ester prepared as described in example 8 (2.00g, 2.7mmol), isopropanol (31g) and aqueous sodium bisulfite (0.28g, 2.7mmol) dissolved in deionized water (14mL) were refluxed at 82 ℃ for 22 h. The white solid (precipitate) was filtered off and washed with deionized water (50mL) to remove unreacted NaHSO₃. By¹H NMR and LC/MS analysis of the dried white solid (2.11g, 91.5% yield, > 95% purity) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)OCH₂CH₂CF₂CH₂C₄F₉. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 24

Citraconate (2.96g, 3.5mmol) prepared as described in example 9 and isopropanol (31g) were stirred together continuously and heated toAnd (4) refluxing. An aqueous solution of sodium bisulfite (0.37g, 3.5mmol) dissolved in deionized water (18mL) was added dropwise to the mixture. The solution was kept at 82 ℃ for 23 h. The solution was concentrated and two distinct layers were observed. The minor top layer was yellow and the bottom layer was white. By¹H NMR analyzed each layer, which confirmed that the top layer was likely an impurity. The product was determined in isopropanol as well as in water, and the alcohol was also determined similarly. The results show that the product is soluble in water but insoluble in isopropanol, the opposite is true for alcohols. Thus, if the impurity layer contains a portion of alcohol, it can be removed by filtration when water is added. This does not affect the surface tension results if any starting acid is present. By¹Analysis of the bottom layer by H NMR and LC/MS (2.62g, yield 78.8%, purity 85%) confirmed the structure C₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O-CH₂CH₂NHC(O)CF(CF₃)OC₃F₇。

Example 25

Citraconate (2.70g, 3.6mmol) prepared as described in example 10 and isopropanol (31g) were mixed together at 50 ℃ for about 10 minutes until dissolved. Aqueous sodium bisulfite (1.54g, 14.8mmol) was dissolved in deionized water (15mL) and added dropwise to the isopropanol solution, which was then heated at about 82 ℃ for about 22 h. The isopropanol and water were removed by rotary evaporation and then dried in a vacuum oven at 50 ℃ to give an off-white solid (1.56g, yield 50.8%, purity: > 99%) prepared from¹Analysis thereof by H NMR and LC/MS confirmed formation of diester sulfonate and a structure of C₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)-C(O)OCH₂CH₂CF₂CH₂C₄F₉. CM of product assessed according to test method 1C and surface tension above CMC, the results are shown in table 2, and the spreadability on cyclohexane is evaluated according to test method 2, the results are shown in table 3.

Example 26

The trans-pentenedioate prepared as described in example 11 (2.52g, 3.4mmol) was added to isopropanol (31g) and heated to 60 ℃. At this point a solution of sodium bisulfite (0.31g, 3.0mmol) dissolved in deionized water (15mL) was added dropwise and the temperature was raised to 82 ℃ for 22 h. By¹Analysis of a pale yellow solid by H NMR and LC/MS (2.26g, yield 78.8%, purity 80%) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)OCH₂CH₂CF₂CH₂-C₄F₉. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

Example 27

Trans-pentenedioate prepared as described in example 12 (4.08g, 4.6mmol) was added to isopropanol (31g) and heated to 50 ℃. A solution of sodium bisulfite (0.31g, 3.0mmol) dissolved in deionized water (15mL) was added dropwise to the solution and the mixture was heated at 82 ℃ for 23 h. A yellow solid (3.94g, 86.3% yield, 90% purity) was collected by rotary evaporation of the isopropanol/water solution and purified from¹H NMR and LC/MS analyses confirmed the structure to be C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O-CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉。

Practice ofExample 28

The maleate (4.20g, 9.4mmol) prepared as described in example 13 and isopropanol (31g) were heated to about 50 ℃ to dissolve the solid in solution. An aqueous solution of sodium bisulfite (0.99g, 9.4mmol) dissolved in deionized water (47mL) was transferred to the solution and the contents were refluxed at 82 ℃ for 22 h. The isopropanol/water solution was rotary evaporated to leave a white solid (4.14g, yield 82.8%, purity 90%) prepared from¹H NMR and LC/MS analyses confirmed the structure to be C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na) C (O) OH. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

Example 29

The mixed diester prepared as described in example 14 (7.10g, 13.9mmol) and isopropanol (32g) were stirred together continuously and heated to 50 ℃ until the two liquids became miscible. An aqueous solution of sodium bisulfite (1.45g, 13.9mmol) dissolved in deionized water (70mL) was transferred to the mixture and the contents were refluxed at 82 ℃ for 22 h. The isopropanol/water solution was evaporated off and the white gel product (6.26g, yield 73.3%, purity 98%) was dried in a vacuum oven for 2 h. By¹The product was analyzed by H NMR and LC/MS to confirm the structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O(CH₂)₆H. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Example 30

The mixed diester prepared as described in example 15 (5.78g, 7.5mmol) and isopropanol (31g) were added together and heated at 60 ℃ for 10 minutes. A solution of sodium bisulfite (0.78g, 7.5mmol) dissolved in deionized water (37mL) was addedTo the solution and the mixture was heated at reflux for 20h at 82 ℃. The isopropanol/water solution was rotary evaporated to leave a colourless gel product (4.26g, 65% yield, 98% purity) as obtained from¹H NMR and LC/MS analyses confirmed the structure to be C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)OCH₂CH₂(CF₂)₆F. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

Comparative example A

Maleic anhydride (0.63g, 6.5mmol), 1H, 2H, 2H-perfluoro-1-octanol (4.74g, 13mmol), p-toluenesulfonic acid monohydrate (p-TsOH) (0.19g, 1.0mmol) and toluene (50mL) were added to the flask and heated at 111 ℃ under reflux for 96 hours. The solution was separated and extracted with two 5% sodium bicarbonate wash solutions (50mL each). The combined organic extracts were dried over anhydrous magnesium sulfate and concentrated at 140.30mmHg (18.7kPa) at 67 deg.C to remove toluene. The structure of the obtained liquid product maleic acid di (1H, 1H, 2H, 2H-perfluorooctyl ester) (4.88g, the yield is 93.4 percent, and the purity is more than 80 percent) consists of¹H NMR and LC/MS.

Maleic acid bis (1H, 2H-perfluorooctyl ester) (4.70g, 5.8mmol, prepared as described above) was added to isopropanol (isopropanol, 31g) and heated at 50 ℃ for 10 minutes while stirring was continued. A solution of sodium bisulfite (0.61g, 5.8mmol) dissolved in deionized water (10mL) was added dropwise to the solution. The mixture was refluxed at 82 ℃ for 22 h. Progress was monitored by LC/MS and additional aqueous sodium bisulfite (0.61g, 5.9mmol) was added. The mixture was refluxed for a further 70.3 h. The isopropanol/water solution was removed by rotary evaporation to give a white solid (2.70g, yield 52.2%, purity 99%). By¹H NMR and LC/MS confirmed the product composition to be the sodium salt of maleic acid bis (1H, 1H, 2H, 2H-perfluorooctyl) -2-sulfosuccinate. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 1.

Comparative example B

1H, 1H, 2H, 2H-perfluorooctanol (8.02g, 22mmol), Dicyclohexylcarbodiimide (DCC) (4.27g, 21mmol), and dichloromethane (CH)₂Cl₂35mL) was added to a flask equipped with a nitrogen inlet, an overhead stirrer, and two stoppers. The solution was cooled to 0 ℃ and citraconic acid (1.28g, 9.8mmol) in tetrahydrofuran (15mL) was added dropwise. The solution was stirred for 10 minutes, then the ice bath was removed and the solution was allowed to warm to room temperature. The mixture was allowed to stir overnight. The resulting mixture was filtered to remove traces of 1, 3-dicyclohexylurea formed as a by-product, then washed with excess tetrahydrofuran (50 mL). Concentrating tetrahydrofuran and CH at 378.14mmHg (kPa) at 46 deg.C₂Cl₂And the product was dried in a vacuum oven for 3 hours. By¹The product was analyzed by H NMR and LC/MS, which indicated conversion to the monoester. The similar process was again carried out, but one more mole of alcohol was added. Mixing alcohol (6.30g, 13mmol), DCC (2.63g, 13mmol), and CH₂Cl₂(35mL) was added to the flask and cooled to 0 ℃. The monoester prepared previously was again dissolved in tetrahydrofuran (15mL) and added dropwise to the solution. The work-up procedure was carried out and the product obtained was a pale yellow liquid (6.46g, yield 80.0%, purity 75%). By¹The product was analyzed by H NMR and LC/MS to confirm that the structure was citraconic acid bis (1H, 1H, 2H, 2H-perfluorooctyl ester).

Citraconic acid bis (1H, 1H, 2H, 2H-perfluorooctyl ester) (4.99g, 6.1mmol, prepared as described above) and isopropanol (32g) were transferred to a flask and heated at 50 ℃ for 10 minutes. An aqueous solution of sodium bisulfite (1.53g, 15mmol) dissolved in deionized water was added to the solution and heated at reflux (82 ℃) for 22 h. The white solid was dried in an oven overnight (2.98g, yield 53.0%, purity 95%). By¹H NMR and LC/MS confirmed that the product composition was the sodium salt of citraconic acid bis (1H, 1H, 2H, 2H-perfluorooctyl) -2-sulfosuccinate. The CMC and surface tension above CMC of the product were evaluated according to test method 1 and the results are shown in Table 2And spreading on cyclohexane was evaluated according to test method 2, the results are shown in table 3.

Comparative example C

Maleic anhydride (17.2g, 176mmol), 1H, 2H, 2H-perfluorohexanol (93.1g, 353mmol), p-toluenesulfonic acid (p-TsOH) (3.4g, 17.6mmol) and toluene (500mL) were heated to reflux for 8H. After refluxing for 4h, an additional amount of p-TsOH (3.4g, 17.6mmol) was added. The solution was stirred at room temperature overnight. The solution was diluted with ethyl acetate (500mL) and washed three times with brine (250 mL each). The combined extracts were washed with additional ethyl acetate (300mL) wash. The combined organics were dried over anhydrous MgSO₄Dried above and concentrated to give a colorless oil (85.8g, yield 80%, purity 98%). By¹H NMR and LC/MS confirmed that the product was bis (1H, 1H, 2H, 2H-perfluorohexyl) maleate.

Maleic acid bis (1H, 2H-perfluorohexyl ester) (1.5g, 2.5mmol, prepared as described above) was added to isopropanol (32g) and heated for 10 minutes until the two liquids became miscible. A solution of sodium bisulfite (1.5g, 14mmol) dissolved in deionized water (15mL) was transferred to the flask and the contents were heated to reflux at 82 ℃ for 22 h. The product was obtained as a white solid after removal of the isopropanol/water solution (0.98g, yield 55.8%, purity 99%). By¹H NMR and LC/MS confirmed the product composition to be the sodium salt of maleic acid bis (1H, 1H, 2H, 2H-perfluorohexyl) -2-sulfosuccinate. The CMC and surface tension above the CMC of the product were evaluated according to test method 1 and the results are shown in table 2, and the spreadability on cyclohexane was evaluated according to test method 2 and the results are shown in table 3.

Comparative example D

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70mL) was slowly added to 50g C₄F₉CH₂CF₂CH₂CH₂I and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na₂SO₃The reaction was quenched with aqueous solution and heated at 95 ℃ for 0.5 h. The bottom layer was separated, washed with 10% by weight aqueous sodium acetate solution and distilled to obtain C₄F₉CH₂CF₂CH₂CH₂OH: the boiling point is 54-57 ℃ at 2mmHg (267 Pa).

Trans-beta-hydrohexadiene diacid (0.94g, 6.5mmol), p-toluenesulfonic acid monohydrate (0.12g, 0.65mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.29g, 13mmol) and toluene were added together and the contents were heated to reflux at 111 ℃ for 25 h. The work-up was carried out according to example 1. By¹H NMR and LC/MS analysis of the white solid (3.82g, yield 76.4%, purity 95%) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂-CH＝CHCH₂C(O)OCH₂CH₂CF₂CH₂-C₄F₉。

Trans-beta-hydrohexadiene diester (3.80g, 5.0mmol) prepared as described above was added to isopropanol (31g) and heated to 60 ℃. An aqueous solution of sodium bisulfite (0.52g, 5.0mmol) was dissolved in deionized water and transferred to the mixture. The temperature was raised to 82 ℃ and maintained for 22 h. The white precipitate was collected by vacuum filtration and the filtrate was concentrated to remove the isopropanol/water solution. By¹H NMR and LC/MS analysis of the white solid (3.88g, yield 89.9%, purity 98%) confirmed the structure C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)CH₂CH₂C(O)O-CH₂CH₂CF₂CH₂C₄F₉. The CMC and superspeed of the product was assessed according to test method 1Surface tension at CMC pass; the results are shown in table 2.

Comparative example E

C is to be₃F₇OCF₂CF₂CH₂CH₂A mixture of I (300g, 0.68mol, prepared as described above) and N-methylformamide (300mL) was heated at 150 ℃ for 26 h. The reaction was then cooled to 100 ℃ and water was then added to isolate the crude ester. Ethanol (77mL) and p-toluenesulfonic acid (2.59g) were added to the crude ester, and the reaction was stirred at 70 ℃ for 15 minutes. Ethyl formate and ethanol were then distilled off to give the crude product. The crude product was dissolved in ether, washed successively with aqueous sodium sulfite solution, water and brine, and then dried over magnesium sulfate. The product was then distilled to give 199g of C in 85% yield₃F₇OCF₂CF₂CH₂CH₂I. The boiling point at 40mmHg (5.3kPa) is 71-73 ℃.

Trans-beta-hydrohexadiene diacid (0.94g, 6.5mmol), C₃F₇OCF₂CF₂CH₂CH₂OH (4.30g, 13mmol, prepared as described above), p-toluenesulphonic acid monohydrate (0.13g, 0.65mmol) and toluene (50mL) were stirred together and heated to reflux (111 ℃ C. for 25 h). After-treatment was carried out to obtain a pale yellow liquid (3.90g, yield 78.0%, purity 99%) prepared from¹Analysis thereof by H NMR and LC/MS confirmed the structure to be C₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH＝CHCH₂C(O)O-CH₂CH₂CF₂CF₂OC₃F₇。

Trans-beta-hydrohexadienoate (3.88g, 5.1mmol) prepared as described above was stirred with isopropanol (31g) at elevated temperature of 65 ℃ for 10 minutes. A solution of sodium bisulfite (0.29g, 2.8mmol) dissolved in deionized water (14mL) was added dropwise to the mixture. The temperature was raised to 82 ℃ and maintained for 22 h. The solution was concentrated to remove the isopropanol and the resulting liquid was left in a vacuum oven overnight. By¹H NMR and LC/MS analysis of the obtained white solid (3.72g, yield 84.4%, purity 87%) confirmed the structure of C₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)CH₂CH₂C(O)O-CH₂CH₂CF₂CF₂OC₃F₇. The CMC and surface tension above the CMC of the product were assessed according to test method 1; the results are shown in table 2.

TABLE 1 comparative examples and surface tension tests

TABLE 2 formula 1A, 1B and 1C and surface tension test

^*Example 28 was tested at pH 3.0. Due to R_aBeing H, the performance of the compound is sensitive to pH.

Table 2 shows that the surfactants of the invention provide low critical micelle concentrations (less than 0.1% by weight)) And a low surface tension value above the CMC (less than 20mN/m in water). Table 1 provides data for the comparative examples. R_fIs C₄F₉Comparative example C contains similar fluorine content as the inventive examples, but has a significantly higher CMC value, thereby demonstrating the superior performance of the inventive examples. Comparative examples A and B each comprise C₆F₁₃R of (A) to (B)_fThe fluorine content is higher than in the examples of the present invention. The inventive examples, although having a lower fluorine content, have similar CMC values as comparative examples a and B. Thus, the examples of the present invention have a higher degree of fluorine efficiency, providing comparable performance at lower fluorine levels. Beyond the CMC, all examples show comparable surface tensions.

TABLE 3 spreadability on cyclohexane

Table 3 shows that the surfactants of the invention spread more rapidly and more completely on cyclohexane when combined with the hydrocarbon surfactants SIMULSOL SL8 or TRITON X100 in aqueous formulations than the comparative examples B or C which all settled. The spreadability on cyclohexane predicts effective fire fighting foam. Table 3 shows that low critical micelle concentrations and low surface tension values beyond CMC are necessary but insufficient criteria for effective fire fighting foams.

Claims

1. Comprising a compound of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)；

c is 2 to about 6; and v is 2 to about 4.

2. The compound of claim 1, wherein c is 3 or 4.

3. The compound of claim 1, wherein v is 2 or 3.

4. A process for preparing a compound of formula 5

R_fOCFHCF₂O(CH₂CH₂O)_v-H formula 5

Wherein

R_fIs C_cF_(2c+1)；

c is 2 to about 6; and v is from 2 to about 4,

R_f-O-CF＝CF₂Formula 6

Wherein R is_fIs C_cF_(2c+1)And c is from 2 to about 6,

HO-(CH₂CH₂O)_v-H formula 7

Wherein v is 2 to about 4.

5. The method of claim 4, wherein c is 3 or 4.

6. The method of claim 5, wherein v is 2.

7. The method of claim 4, wherein R is during said contacting_f-O-CF＝CF₂And HO- (CH)₂CH₂O)_v-H in a molar ratio of about 1 to 15.

8. The process of claim 4, wherein the contacting is carried out in the presence of an alkali metal, an alkaline earth metal, an alkali metal hydroxide, an alkali metal hydride, or an alkali metal amide.

9. The process of claim 8, wherein the alkali metal is Na, K or Cs and the alkali metal hydride is NaH or KH.