KR20060136432A - Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers - Google Patents

Abstract

There is provided a method and system for preparing a system comprising reacting a halogenated compound, dehalogenating the compound, reacting an alcohol, reacting an olefin and a saturated compound, and reacting a reactant having at least two —CF ₃ groups with a reactant having a ring group. do. R _F -intermediates, R _F -surfactants, R _F -monomers, R _F -monomer units, R _F -metal complexes, R _F -phosphate esters, R _F -glycols, R _F -urethanes and / or R _F -foams R _F -compositions such as stabilizers.

The R _F -moiety may comprise at least two -CF ₃ groups, at least three -CF ₃ groups, and / or at least two -CF ₃ groups and at least two -CH ₂ -groups. Detergents, emulsifiers, paints, adhesives, inks, wetting agents, foaming agents, and antifoaming agents comprising the R _F -surfactant composition are provided. Provided are acrylic products, resins, and polymers comprising an R _F -monomer unit. There is provided a composition comprising a substrate having a R _F -composition thereon. R _F - surfactant and / or R _F - is prepared, which may include a foam stabilizer, water-based film-forming foaming agent ( "AFFF") water is provided.

Surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film-forming blowing agents, foam stabilizers.

Description

Production methods and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming blowing agents, and foam stabilizers AQUEOUS FILM FORMING FOAMS, AND FOAM STABILIZERS}

This application is incorporated by reference in U.S. Provisional Patent Application No. 60 / 540,612 entitled, "Fluorofunctional group, fluorine composition, method for preparing fluorine composition, and material treatment" of Jan. 30, 2004, which is incorporated herein by reference in its entirety. Claim priority.

The present invention relates to the field of halogenated compositions, methods of making halogenated compositions, and more particularly, fluorinated compositions, methods of making fluorinated compositions and methods of treating substrates with fluorinated compositions.

Compositions such as surfactants and polymers contained fluorine to affect the performance of the composition, for example, when the composition is used as a treatment of the material and when the composition is used to enhance the performance of the material. For example, it can be used as a fire extinguishing agent alone or as a preparation such as an aqueous film forming blowing agent (AFFF) containing a fluorinated functional group. Conventional fluorosurfactants such as perfluoro-octyl sulfonate derivatives (PFOS) have a linear perfluorinated moiety.

Polymer conjugated fluorine was used to treat the material. Examples of fluorination treatments include compositions such as Scotchguard®.

summary

A method and system are provided comprising a reactor having at least one inner sidewall comprising glass; Reacting the halogenated compound with an allyl-comprising compound in the presence of water to form a halogenated intermediate; A portion of the heterohalogenated alcohol is dehalogenated with a heterohalogenated alcohol comprising at least two —CF ₃ groups and at least one halogen that is not fluorine to form a homohalogenated alcohol; Reacting the alcohol with an alcohol comprising at least two —CF ₃ groups and a ring group to form an acrylate; Reacting the olefin with a saturated compound to form a saturated product, at least two -CF ₃ Along with an olefin comprising a group, the saturated compound comprises at least two different -CF ₃ groups, and the saturated product contains the -CF ₃ of the olefin. Both a group and a —CF ₃ group of a saturated compound; And / or at least two -CF ₃ The first reactant comprising the group is reacted with the second reactant comprising the ring group to form a compound comprising two -CF ₃ groups and a ring group.

R _F -intermediates, R _F -surfactants, R _F -monomers, R _F -monomer units, R _F -metal complexes, R _F -phosphate esters, R _F -glycols, R _F -urethanes, and / or R _F- R _F compositions, such as foam stabilizers. The R _F moiety may comprise at least two -CF ₃ groups, at least three -CF ₃ groups, and / or at least two -CF ₃ groups and at least two -CH ₂ -groups.

R _F portion with a greater affinity than the Qs portion with respect to the first part of the system having at least two portions in the surfactant composition, and better than _F R portion with respect to the second part of the system - R _F and R _F of -Qs Qs with great affinity are provided. Detergents, emulsifiers, paints, adhesives, inks, wetting agents, foaming agents, and antifoaming agents comprising the R _F -surfactant composition are provided.

A first compound, said first compound comprising at least two -CF ₃ group and two hydrogen, and R _F - providing a portion of the first compound that R _F portion of the surface active agent was added and the Qs portion of the part R _F To provide an R _F -surfactant. A process is provided for changing the surface tension of a portion of a system having at least two portions, including adding an R _F -surfactant.

For example, R _F with R _F portion containing pendant groups of the monomer units are acrylic products, resins, and polymers is provided which comprises a monomer unit. There is provided a composition comprising a substrate having a R _F -composition thereon.

R _F - and R _F monomer provides - a production method which can comprise the formation of a oligomer, a combination of a monomer and another monomer is provided. Examples of oligomers may include R _F -monomer units.

R _F, which is the ligand may comprise a metal and a ligand containing R _F -QMc - the metal complexes are provided. The Q _MC moiety, for example, coordinates with the metal of the complex.

R _F -Q _PE R _F, which may include-phosphate esters are provided, the Q _PE portion comprises a portion of the ester.

R _F, which may include R _F -Q _h - is provided with a glycol, and Q _h comprises the hydroxyl portion of the glycol.

R _F, such as R _F -Q _U - and urethane are also provided, Q _U is a partial remainder of the polyurethane.

R _F - surfactant and / or R _F - is prepared, which may include a foam stabilizer, water-based film-forming foaming agent ( "AFFF") water is provided.

Embodiments are described below with reference to the accompanying drawings.

1 is a general view of a representative R _F -composition.

2 is an illustration of a system for preparing a composition according to an embodiment.

3 is an illustration of a system for preparing a composition according to an embodiment.

4 is an illustration of a system for preparing a composition according to an embodiment.

5 is an illustration of a system for preparing a composition according to an embodiment.

6 is an illustration of a system for preparing a composition according to an embodiment.

7 is an illustration of a system for preparing a composition according to an embodiment.

8 is an illustration of a system for preparing a composition according to an embodiment.

details

Representative R _F -compositions and manufacturing systems are described with reference to FIGS. 1-8. Referring to FIG. 1, a general view of a representative R _F -composition is shown. R _F -compositions include, but are not limited to, R _F -surfactants, R _F -monomers, R _F -monomer units, R _F -metal complexes, R _F -phosphate esters, R _F -glycols, R _F- Urethanes, and or R _F -foam stabilizers. In an exemplary embodiment, the poly-anhydride, acrylic, urethane, metal complex, polyene, and / or phosphate esters may also comprise an R _F moiety.

The R _F -composition comprises a composition having an R _F moiety and / or an R _F moiety. R _F moieties can be R _F moieties such as pendant groups and / or moieties of the composition. The R _F moiety may comprise at least two —CF ₃ groups and the —CF ₃ groups may be terminal. The R _F moiety may also include both —CF ₃ groups and additional groups containing fluorine, such as —CF ₂ — groups.

In an exemplary embodiment, the R _F moiety may comprise up to two -CF ₂ -groups to -CF ₃ groups, such as (CF ₃ ) ₂ CF—groups. The R _F moiety may also include hydrogen. For example, the R _F moiety may comprise two -CF ₃ groups and a hydrogen such as (CF ₃ ) ₂ CH- group. In other embodiments the R _F moiety may comprise two —CF ₃ groups and —CH ₂ — groups. The R _F moiety may comprise at least three -CF ₃ groups, such as two (CF ₃ ) ₂ CF- groups. In an exemplary embodiment, the R _F moiety may comprise a ring group such as an aromatic group. The R _F moiety may comprise at least two -CF ₃ groups and at least four carbons, for example one of the four carbons comprises a -CH ₂ -group.

In practice examples, the R _F -compositions may exhibit desirable surface energies that shape the surface tension of the solution being exposed and / or affect the environmental resistance of the materials to which they are applied and / or incorporated. Examples of compositions include, but are not limited to, substrates having R _F -compositions thereon and / or liquids having R _F -compositions therein. The RF moiety can be incorporated into compositions such as polymers, acrylate monomers and polymers, glycols, fluorosurfactants, and / or AFFF formulations. These compositions are used as dispersants or substrates such as garments, wallpaper, paper bags, cardboard boxes, porous clays, building materials such as bricks, stones, wood, concrete, ceramics, tiles, glass, stucco, gypsum, drywall, particles It can be used to process boards, chipboards, carpets, drapery, upholstery materials, automobiles, awnings, and raincoats as well as textile tissues, textile yarns, leather, paper, plastics, sheeting, wood, ceramic clay. R _F -compositions can be prepared from R _F -intermediates.

R _F R _F part - can be a starting material for a composition - R _F through the intermediate-composition may be in conjugation, and / or R _F. At least one functional part of which forms a composition as well as, comprises a part R _F described above - R _F - R _F are examples of the intermediates was conjugated to R _F part in the composition. The functional moiety is for example halogen (eg iodine), mercaptan, thiocyanate, sulfonyl chloride, acid, acid halide, hydroxyl, cyano, acetate, allyl, epoxide, acrylic ester, ether, Sulfate, thiol, phosphate, and / or amines. Without inclusions and / or reactions, the R _F -intermediate may comprise, for example, an R _F -composition, such as an R _F -monomer and / or ligand of the R _F -metal complex.

R _F - R _F represents the intermediate part R _F and Qg, for example, -Qg R _F, and / or indicating the functional part, and as another example, may comprise an element periodic table of the elements. In an exemplary embodiment, Qg is not a proton, methyl, and / or methylene group. Examples of R _F -intermediates include, but are not limited to, those in Table 1 below.

R _F -Intermediate is also

및/또는

중 하나 또는 둘다를 포함할 수 있고, 이때 R₁은 적어도 하나의 탄소 원자, 예를 들어 이를테면 -CH₂-를 포함한다. 대표적인 구체예에서, n 은 적어도 1이 될 수 있고 다른 구체예에서 n 은 적어도 2가 될 수 있고 R_F-중간체는

And / or

May comprise one or both, wherein R ₁ comprises at least one carbon atom, such as —CH ₂ —. In an exemplary embodiment, n can be at least 1 and in other embodiments n can be at least 2 and the R _F -intermediate is

It may include one or more of.

(4-요오도-2-(트리플루오로메틸)- 1,1, 1, 2-테트라플루오로부테인)을 예를 들어, Matrix Scientific, P. O. Box 25067, Columbia, SC 92994-5067에서 얻을 수 있다.R _F -Intermediate

(4-iodo-2- (trifluoromethyl) -1,1,1,2-tetrafluorobutane) can be obtained, for example, from Matrix Scientific, PO Box 25067, Columbia, SC 92994-5067 have.

(1,1,1-트리플루오로-2-트리플루오로메틸- 2, 4-펜타디엔)은 본원에 참조에 의해 포함된 J.Org. Chem. , Vol. 35, No. 6,1970, pp. 2096-2099에 따르는 대표적인 관점에서 제조될 수 있다. 1,1, 1-트리플루오로-2-트리플루오로메틸-2, 4-펜타디엔은 하기 실시예에 따라 또한 제조할 수 있다.R _F -Intermediate

(1,1,1-trifluoro-2-trifluoromethyl-2, 4-pentadiene) is described in J. Org. Chem. , Vol. 35, No. 6,1970, pp. It may be prepared from an exemplary aspect according to 2096-2099. 1,1, 1-trifluoro-2-trifluoromethyl-2, 4-pentadiene can also be prepared according to the following examples.

1,1, 1-trifluoro-2-trifluoromethyl-2, 4-pentadiene can be prepared according to the following schematic diagram (1).

Referring to the schematic diagram (1), pentane (300 mL) can be placed in a 500 mL three neck flask and cooled down to -30 ° C. To the pentane hexafluoroacetone (59 grams, 0.36 mole), propylene (16.2 grams, 0.38 mole), and anhydrous aluminum trichloride (0.77 g, 0.006 mole) can be added to form a mixture. This mixture can be stirred and the temperature can be warmed to room temperature over 3 hours. 15% (wt / wt) aqueous HCl solution (20 mL) can be added to the mixture and the mixture can be washed three times with H ₂ O. The aqueous layer can, after washing, pour out the supernatant and dry the organic layers (pentane and propylene) with MgSO ₄ . The remaining pentane and propylene were suddenly evaporated at 60 ° C. to give 54.4 grams (70% area percent by gas chromatography) of isomer 1,1-bis (trifluoromethyl) -3-penten-1-ol. Can be.

Crude 1,1-bis (trifluoromethyl) -3-penten-1-ol (54 grams) was placed in a 250 mL three neck flask and 125 mL of concentrated H ₂ S0 ₄ was added to form a mixture, which was stirred and 95 Can be slowly heated to < RTI ID = 0.0 > C (< / RTI > The prepared 1,1, 1-trifluoro-2-trifluoromethyl-2, 4-pentadiene (15.6 grams, 45.5% yield) can be separated from the mixture as a gas between 70 ° C and 74 ° C.

Representative R _F -intermediates can be prepared from reactant 2-iodoheptafluoropropane. In an exemplary embodiment, a halogenated compound such as 2-iodoheptafluoropropane can be prepared with reference to FIG. 2. Referring to FIG. 2, a system 20 is shown that includes a reactor 22 connected to an alkyl reactant reservoir 24, a halogenating agent reservoir 26, and a halogenated compound reservoir 28. According to an exemplary embodiment, system 20 may be used to halogenate alkyl reactants with halogenating agents in reactor 22 to form halogenated compounds. The alkyl reactant in the alkyl reactant reservoir 24 may comprise olefins such as fluoro-olefins such as hexafluoropropene. The halogenating agent in the halogenating agent reservoir 26 may comprise a mixture of salts and diatomic halogens such as KF and I ₂ , KF and Br ₂ , and for example salts such as ammonium salts.

In an exemplary embodiment, reactor 22 may be lined with glass and / or hastelloy®, such as hastelloye® C. According to another embodiment, the conduit 29 may be configured to provide the contents of the reservoirs 24 and 26 to the reactor 22 and / or to provide the contents of the reactor 22 to the reservoir 28. have. Conduit 29 may be lined with glass and / or hastelloy®, such as hastelloy® C. Both conduit 29 and reactor 22 may be lined with glass and / or hastelloy®, such as hastelloy® C.

In an exemplary embodiment, the halogenating agent can be provided to the reactor 22 with a polar, nonpolar solvent comprising a reactant medium such as, for example, acetonitrile and / or dimethyl formamide (DMF). The reactant medium is added simultaneously with the halogenating agent through another conduit (not shown) or through reservoir 26. Together, the halogenating agent and reactant medium may form a mixture in which the alkyl reactant may be added in reactor 22 to form another mixture comprising the agent, the medium, and the reactant. The alkyl reactant can react in this mixture to form a halogenated compound. In an exemplary embodiment, the reactant medium may be liquid when the alkyl reactant reacts in the mixture. The mixture may also be stirred when the alkyl reactant reacts, for example the mixture may also be heated. In an exemplary embodiment, hexafluoropropene may be provided in a reactor 22 having KF, I ₂ , and acetonitrile therein, wherein a portion of the contents of the reactor 22 is at least about 90 ° C., and / or about Heated to 90 ° C. to about 135 ° C. to form 2-iodoheptafluoropropane. Hexafluoropropene was fed into the reactor 22 with KF, I2, and acetonitrile therein in a reactor 22 with a pressure of about 446 kPa to 929 kPa to yield 2-iodoheptafluoropropane. Can be formed.

Halogenated compounds may also be removed from reactor 22 to reservoir 28 via conduit 29. In an exemplary embodiment, conduit 29 between reservoir 28 and reactor 22 may include a condenser (not shown). A portion of the halogenated compound formed in the reactor 22 may be converted to a gas, the gas may be transferred to a condenser, the condenser may return the gas to a liquid, and the liquid may be removed from the condenser to store the reservoir 28 Can be moved to. In an exemplary embodiment, the conduit 29 between the reactors 22 and 28 that is configured to include a condenser may be referred to as a distillation apparatus.

Halogenated compounds such as the 2-iodoheptafluoropropane described above can be removed from the reactor 22 by heating at least a portion of the 2-iodoheptafluoropropane to at least about 40 ° C.

(1,1, 1,2-테트라플루오로-2-(트리플루오로메틸)-4-요오도부테인)를 제조하는데 사용될 수 있다. 예를 들어, 오직 예로서, 105.14 그램의 2-요오도헵타플루오로프로페인과 10 그램의 에틸렌이 800mL Parr 반응기에 첨가될 수 있다. 반응기는 약 180℃로 약 6시간동안 가열할 수 있다. 반응기는 그후 냉각될 수 있고 제거된 내용물의 일부분은 약 86% 순수한 (가스 크로마토그래피에 의해 결정될때) 약 105.99 그램의 R_F-중간체 1,1, 1,2-테트라플루오로-2-(트리플루오로메틸)-4- 요오도부테인을 제공한다. 1,1, 1,2-테트라플루오로-2-(트리플루오로메틸)-4-요오도부테인은 56℃/96 Torr에서 증류될 수 있다. 1,1, 1,2-테트라플루오로-2-(트리플루오로메틸)-4-요오도부테인은 또한 Matrix Scientific (카탈로그 번호 1104)로부터 구입할 수 있다.Representative halogenated compounds described above are R _F -intermediates such as

(1,1, 1,2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane) can be used. For example, by way of example only 105.14 grams of 2-iodoheptafluoropropane and 10 grams of ethylene can be added to an 800 mL Parr reactor. The reactor may be heated to about 180 ° C. for about 6 hours. The reactor can then be cooled and a portion of the content removed is approximately 86% pure (as determined by gas chromatography) of about 105.99 grams of R _F -intermediate 1,1, 1,2-tetrafluoro-2- (tree Fluoromethyl) -4-iodobutane. 1,1, 1,2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane can be distilled at 56 ° C / 96 Torr. 1,1, 1,2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane can also be purchased from Matrix Scientific (Catalog No. 1104).

Halogenated compounds can also be used to prepare R _F -intermediates such as heterohalogenated intermediates 7,8,8,8-tetrafluoro-7 (trifluoromethyl) -5-iodooct-1-ene. R _F -intermediates can be prepared and then dehalogenated according to the following schematic (2) to form another R _F -intermediate.

Referring to the schematic (2) above, 2-iodoheptafluoropropane (231.3 grams, 0.782 mole), 1,5-hexadiene (126.6 g, 0.767 mole), and 2,2'-azobisisobuty Ronitrile (AIBN) (13.6 g, 0.083 mole) is equipped with a burst, disc, thermocouple, heater band, electronic temperature controller, dip-tube with needle valve, gas outlet with needle valve, pressure gauge, and stirrer It can be filled into a clean, dry 750 mL stainless steel autoclave device. The device can then be sealed and heated slowly to about 60 ° C. where exotherm can be observed and slowly raised to about 80 ° C. The device contents may be maintained at 80 ° C. for about 72 hours to provide about 337 g of crude material. The contents were vacuum distilled (53 ° C./5.0 Torr) to give R _F -intermediate 7,8,8,8-tetrafluoro-7 (trifluoromethyl) of about 125 g 99.6% area percent purity (by gas chromatography). -5-iodooct-1-ene may be provided (m / z 377.7 (M +), 251 (MI)), IR stack: (w) at 3082 cm ⁻¹ Olefins CH stretch, (w) C = C stretch in the fingerprint, and 729,1149, 1224, and 1293 cm ^-1 band at 1643cm ^{-1, 1} HNMR, ¹⁹ F NMR, ¹³ C NMR, using a, high resolution MS 7 , 8, 8,8-tetrafluoro-7 (trifluoromethyl) -5-iodooct-1-ene may also be determined.

Referring back to the schematic (2), 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -5-iodooct-1-ene (36.1 grams, 0.095 mole) is reflux condensed. It can be added to a 100 mL three necked round bottom flask equipped with a device, heating mantle, thermocouple, electronic thermal controller, and stirrer and heated to 75 ° C. Tributyltin hydride (34.6 grams, 0.119 mole) can be added dropwise over 3 hours through an addition funnel to form a mixture. Exotherm may be observed during the addition. The mixture was vacuum distilled (25 ° C./5. Torr) to a clean solution having about 99.8% area percent purity (by gas chromatography) of 15.6 grams of R _F -intermediate 7,8,8,8-tetrafluoro -7 (trifluoromethyl) oct-1-ene and 5.5 g of lower purity 7,8,8,8-tetrafluoro-7 (trifluoromethyl) oct-1-ene can be provided. (m / z 252 (M < + >), 183 (M ⁺ -CF ₃ ), 69 (M ⁺ -C ₈ H ₁₁ F ₄ ), 55 (M ⁺ -C ₅ H ₄ F ₇ )); IR: (w) olefin CH stretch at 3087 cm ^-1 , (w) at 1644 cm ^-1 C = C stretch, and 720,1135, 1223, and 1315cm ^- fingerprint band in the ^{first; _{1 H NMR (CDC1 3, 300MHz}} ) δ1.40-1. 50 (m, 2H), 1.54-1. 65 (m, 2 H), 1.95-2. 14 (m, 2 H), 4.95-5. 06 (m, 2 H), 5.72-5. 85 (ddt, J = 17. 10. 2, 6. 7, 1H); ¹⁹ F NMR (CDC1 ₃ , CFC1 ₃ , 282 MHz) δ-76. 57 (d, J = 7.9, 7F), -183.2 (m, 'F)).

Referring to FIG. 3, a system 30 is shown that includes a reactor 32 configured to receive a halogenated compound, such as the 2-iodoheptafluoropropane described above, from a halogenated compound reservoir 33. Halogenated compounds are for example at least two CF ₃ -groups; At least one (CF ₃ ) ₂ CF- group; And / or at least two CF ₃ -groups and halogen other than fluorine. Reactor 32 may also be configured to receive allyl-comprising compound from allyl-comprising compound reservoir 34 and water from water reservoir 35. The allyl-comprising compound can include, for example, an ester such as allyl acetate. Allyl containing compounds may also include alcohols such as allyl alcohol as another example.

Reactor 32 may be configured to react halogenated compounds with allyl-comprising compounds in the presence of water to form R _F -intermediates and provide RF-intermediates to intermediate reservoir 36. Halogenated compounds, allyl-comprising compounds and water can be combined in reactor 32 to form a mixture. Salts, such as Na ₂ S ₂ 0 ₅ , can be added to water, for example, before forming the mixture to form an aqueous solution. The salt can be as much as 30% (wt / wt) of solution.

In an exemplary embodiment, the halogenated compound comprises 2-iodoheptafluoropropane; Allyl-comprising compounds include allyl acetate; The aqueous solution may comprise Na ₂ S ₂ 0 ₅ and the R _F -intermediate may comprise 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate . Reacting 2-iodoheptafluoropropane with allyl acetate in the presence of a solution results in at least a portion of the mixture in reactor 32 having at least about 80 ° C., about 65 ° C. to about 100 ° C., and / or about 80 ° C. to Heating to about 90 ° C.

In another exemplary embodiment, the halogenated compound comprises 2-iodoheptafluoropropane; Allyl-comprising compounds include allyl alcohol; The solution comprises Na ₂ S ₂ 0 ₅ , and the R _F -intermediate may comprise 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol Can be. Reacting 2-iodoheptafluoropropane with allyl alcohol causes at least a portion of the mixture in reactor 32 in the presence of a solution to at least about 80 ° C, about 65 ° C to about 100 ° C, and / or about 80 ° C. To about 90 ° C.

An initiator can also be provided in the reactor 32 to facilitate the reaction of the halogenated compound with the allyl-comprising compound. Representative initiators can include AIBN. Reactor 32 may contain about 0.01% (wt / wt) to about 10% (wt / wt), and / or about 0.1% (wt / wt) to 5% (wt / wt) of the initiator.

According to an exemplary embodiment, the R _F -intermediates may be provided to the intermediate reservoir 36 when formed in the reactor 32. Providing the R _F -intermediate includes a process for separating the RF-intermediate from the remaining contents of the reactor, the contents comprising reactants and / or byproducts. Representative methods for providing R _F -intermediates to reservoir 36 may include liquid / liquid separation and / or distillation.

The R _F -intermediates formed above may also react to form additional intermediates, including additional R _F -intermediates. For example, a portion of the intermediate may be unsaturated to form an R _F -intermediate comprising a halogenated olefin. In an exemplary embodiment, not saturating the intermediate may comprise exposing the intermediate to a reducing agent. The reducing agent may include, for example, Zn and / or a mixture of Zn and diethylene glycol. R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate is unsaturated according to one embodiment to R _F -intermediate 4,5, 5,5 -Tetrafluoro-4- (trifluoromethyl) pent-1-ene can be formed. R _F -Intermediate 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate is combined with a mixture of Zn and diethylene glycol, for example, to form another mixture. And the remaining other mixture may be heated to at least about 120 ° C. to form R _F -intermediate 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene.

As another example, R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be used, for example, as a mixture of Zn and diethylene glycol. Reaction in the presence of a reducing agent may form an RF-intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene.

According to another embodiment, the reducing agent may comprise POCI ₃ pyridine, and / or a mixture of POCI ₃ and pyridine. For example, R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol is reacted in the presence of a mixture of POCI ₃ and pyridine R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene may be formed. This reaction can be carried out, for example, while maintaining the temperature of the mixture between about 0 ° C and about 5 ° C.

(4,5, 5,5-테트라플루오로-4-(트리플루오로메틸)펜트-1-엔)은 또한 본원에 참고문헌으로 포함되는 Synthesis and Characterization of a New Class of Perfluorinated Alkanes : Tetrabis ( 퍼플루오로알킬 ) alkan 예를 들어 Gambaretto et al., Journal of Florine Chemistry, 5892 (2003) pgs 1-7 및 Knell et.al.의 미국 특허 3,843, 735에 따라 예시적 관점에서 제조할 수 있다. 예를 들어 하기 개략도 (3)에 따라 4,5, 5, 5-테트라플루오로-4-(트리플루오로메틸)펜트-1-엔을 또한 제조할 수 있다. R _F -Intermediate

(4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene) is also incorporated herein by reference the Synthesis and Characterization of a New Class of Perfluorinated Alkanes : Tetrabis ( perfluoroalkyl ) alkan For example, it can be prepared according to Gambaretto et al., Journal of Florine Chemistry, 5892 (2003) pgs 1-7 and Knell et. Al. US Pat. For example, 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can also be produced according to the following schematic diagram (3).

Referring to the schematic diagram (3), AIBN (9.2 g, 0.06 mole), 1,1, 1,2, 3,3,3-heptafluoro-2-iodopropane (1651 g, 5.6 mole), And 293 g of 30% (wt / wt) aqueous Na ₂ S ₂ 0 ₅ can be placed in a 2 L pressure reactor to form a mixture. The reactor can be sealed and heated to 80 ° C. under endogenous pressure. Allyl acetate (587 g, 5.9 mole) can be added slowly to this mixture and the mixture can be stirred for an additional 4 hours. After stirring, the organic layer was observed, removed, washed twice with H ₂ O, dried over MgSO ₄ and 2212 g of 94% (area percent by gas chromatography) R _F -Intermediate 4,5, 5,5-tetra Fluoro-4- (trifluoromethyl)-2-iodopentyl acetate was provided.

Diethylene glycol (2944 g) and zinc powder (1330 g) can be placed in a 5 L five-necked flask equipped with a simple distillation apparatus to form a mixture. The mixture can be stirred and heated to 120 ° C. and 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate (4149 g) can be added slowly. When 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate is added, R _F -intermediate 4,5, 5, 5-tetrafluoro-4- (Trifluoromethyl) pent-1-ene (2075 grams) can be flashed off and collected in a 1 L ice trap. The contents of the ice trap were distilled to give 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene> 99.5% (area percent by gas chromatography) (bp54 ° C.) can do.

R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can be prepared according to the following schematic (4).

Referring to schematic diagram (4) above, about 10.3 grams of 2-iodoheptafluoropropane can be added to the glass pressure tube. The tube is sealed with a septum, heated to about 75 ° C. and 1.9 mL of 30% (wt / wt) aqueous Na ₂ S ₂ 0 ₅ can be added via a syringe to the tube through a septum to form a mixture in the tube. . The mixture may be heated to about 80 ° C. and 0.07 grams of AIBN may be dissolved in allyl alcohol to form a solution. This solution can be added slowly through the septum into the tube to form another mixture. This other mixture can be stirred and maintained at a temperature of about 80 ° C. for 3 hours. The mixture can then be cooled and 11.2 grams of 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be removed as an organic layer upon separation. have. R _F -Intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can have as much as 93% (area percent by gas chromatography) have.

About 11 g of R _F -intermediate 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol may be added to the glass pressure tube and about 13 grams 30% (wt / wt) of aqueous acetic acid can be added to other tubes to form a mixture. The mixture can be heated to about 80 ° C. and 4 grams of powdered zinc can be added slowly through a solid addition system. The mixture can be phase separated by stirring for an additional 2 hours before cooling and adding 2 mL of 1.5 N HCl. 3 grams of R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pentane- which can be decanted to 75.14% (area percent by gas chromatography) over the organic layer You can get 1-yen.

As another example, about 254 grams of diethylene glycol and 127.5 grams of Zn powder can be added into a 1000 mL three neck round bottom flask equipped with a Dean-Stark apparatus, thermometer, and dip tube to form a mixture. The mixture can be heated to 120 ° C. with stirring and about 213.81 grams of R _F -intermediate 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol It can be slowly pumped into the mixture below the surface. Collect about 111.4 grams of RF-intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pentane-1-ene, which can be 88% (area percent by gas chromatography). .

R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can be prepared according to the following schematic (5).

Referring to the schematic diagram (5) above, RF-intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be prepared as described above. And converted according to the following schematic (6).

Referring to the schematic diagram (6), 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol (11.42 g, 0.032 mole) and pyridine (84.17 g, 1.06 mole) was added to a 250 mL two-necked round bottom flask equipped with a 50 mL pressure equalization addition funnel containing thermocouple, magnetic stir bar, heating mantle, and phosphorus oxychloride (2.23 g, 0.015 mole) Mixtures may be formed. The mixture can be cooled to between 0 ° C.-5 ° C. and POC1 ₃ can be added dropwise over 25 minutes. Color change and exotherm can be observed from yellow to dark red of the reaction mixture. The mixture can be warmed to room temperature and then maintained overnight. Portions of the compound can be combined, washed with H ₂ O, dried over MgSO ₄ and then analyzed by gas chromatography and / or gas chromatography / mass spectrometry.

Gas chromatography, gas chromatography / mass spectrometry and ¹ H NMR can be used to determine 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene.

R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can also be used to prepare other RF-intermediates. For example, by way of example only, according to the following schematic (7), 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene is halogenated to provide at least two CF ₃ − R _F -intermediates, such as R _F -intermediates 5-bromo-1,1, 1,2-tetrafluoro-2- (trifluoromethyl) pentane, can be formed comprising groups and non-fluorine halogens.

Referring to schematic (7) above, about 45 g (0.214 mole) of 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can be loaded onto a 50 mL auto syringe Evaporated in the heated coil before feeding into the quartz tube via the Claisen adapter, which was terminated into a 250 mL two-necked round bottom flask equipped with HBr scrubber containing 10% (wt / wt) KOH solution. The quartz tube is equipped with an internal thermocouple and dry ice and acetone reflux condenser and can be surrounded by an ultraviolet light (254 nm) carousel. Simultaneously with the addition of 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene, anhydrous HBr can be fed into the quartz tube from the regulated tank via the same Claisen adapter. The feed rates for HBr and 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can be set to 39.3 g / hour and 13.4 g / hour, respectively. About 53.94 g (0.19 mole) of product can be collected, washed with NaHCO ₃ , then washed with H20 and dried over the mole. Samples of the product can be collected for gas chromatography / mass spectrometry analysis (m / z 290.8 (M < + >), 209.0 (M + -HBr), 189.1 (M + -101. 9)).

As another example, R _F -intermediate 7,8,8,8-tetrafluoro-7- (trifluoromethyl) oct-1-ene, prepared as described above, can be, for example, ) May be used to prepare another R _F -intermediate comprising an RF-intermediate such as 8-bromo-1, 1,1,2-tetrafluoro-2- (trifluoromethyl) octane.

Referring to the schematic diagram (8), 67.06 grams (0.266 mole) of R _F -intermediate 7,8, into a 250 mL pressure tube equipped with a 9 inch Pen-Ray® Hg lamp, pressure gauge, stirrer, and dip tube. 8,8-tetrafluoro-7- (trifluoromethyl) oct-1-ene may be added. The tube was sealed, gaseous anhydrous HBr was bubbled into the system, and the pressure was maintained at about 184 kPa. The tube was irradiated for 3 hours, the mixture in the tube was washed with NaHCO ₃ , then washed twice with water and dried over a mole sieve to about 68.89 grams (0.21 mole) of RF-intermediate 8-bromo-1,1, 1, 2-tetrafluoro-2- (trifluoromethyl) octane can be obtained.

R _F -intermediates with alcohol functionality can be used as starting material to produce additional RF-intermediates. For example, by way of example only, a portion of the RF-intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol described above is dehalohydrogenated. Can be. For example, a heterohalogenated compound 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) -2-io including R _F -intermediates such as at least two CF 3-groups and a halogen other than fluorine Dofentan-1-ol may be dehalohydrogenated to form homohalogenated alcohols. Dehalohydrogenation can include, for example, exposing the intermediate to tributyltin hydride. According to an exemplary embodiment, the R _F -intermediate may comprise 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol, for example According to the schematic diagram (9) below

을 포함할 수 있다. Alcohol

It may include.

According to the schematic diagram (9), it can be a 500 mL two necked round bottom flask equipped with a thermocouple, a stirrer, and a heating mantle. About 212.1 g (0.599 mole) 4,5, 5, 5-tetrafluoro-4 (trifluoromethyl) -2-iodopentan-1-ol (212.1 g, 0.599 mole) is added to the flask and about 60 Heating to ° C to 70 ° C. From the 100 mL pressure equalization addition funnel, about 196.4 g (0.66 mole) tributyltin hydride is added dropwise over 4 hours followed by 2 hours of continued heating and stirring. R _F -intermediate 4,5, 5,5-tetrafluoro-4 (trifluoromethyl) pentan-1-ol can be obtained via vacuum distillation and confirmed by gas chromatography / mass spectrometry (m / z 228 (M ⁺ ), 211 (M ⁺ -OH), 159 (M ⁺ -CF 3)).

Still another RF-intermediate, for example, 2,3, 4,5, 5, 5-, in accordance with the process detailed in US Pat. Nos. 3,467, 247, described in Scheme 10 below and hereby incorporated by reference Hexafluoro-2, 4-bis (trifluoromethyl) pentanol can be prepared.

는 상기와 하기 개략도 (11)에 따라 R_F-중간체 1,1, 1,3, 3,3- 헥사플루오로프로판-2-올을 3-브로모프로프-1-엔과 반응시킴으로써 제조될 수 있다. According to an exemplary embodiment of the disclosure, R _F -intermediates with alcohol functionality such as 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol and / or 2, described above 3, 4,5, 5, 5-hexafluoro-2, 4-bis (trifluoromethyl) pentan-1-ol reacts with halogenated olefins to form another R _F -intermediate such as allyl-ether compound Can be. As described above, the R _F -intermediate comprises at least two CF ₃ -groups; At least one (CF ₃ ) ₂ CF- group; And / or at least three CF ₃ -groups. Representative halogenated olefins include olefins comprising halogens other than fluorine such as, for example, bromine. 3-bromoprop-1-ene may be used as the halogenated olefin. Halogenated olefins can be exposed to alcohol in the presence of a basic solution, such as an aqueous KOH solution. In an exemplary embodiment, a mixture of alcohol, halogenated olefins, and reactant media comprising a phase transfer catalyst such as tetrabutylammonium hydrogen sulphate can be prepared, and basic solution is added to the mixture while maintaining the mixture below at least 10 ° C. Can be added. R _F -Intermediates Containing Allyl Ether Compounds

Can be prepared by reacting R _F -intermediate 1,1, 1,3, 3,3-hexafluoropropan-2-ol with 3-bromoprop-1-ene according to the above and the following schematic (11). have.

을 수득할 수 있다. 미정제 생성물은 증류되어 83.5℃의 끓는 점을 갖는 99.94% (가스 크로마토그래피에 의한 면적 퍼센트)3-(1,1,1,3,3,3-헥사플루오로프로판-2-일옥시) 프로프-1-엔을 수득할 수 있다. Referring to the schematic (11), the 500mL three-necked flask may be equipped with a thermometer, a stirrer, and a condenser. About 40.86 g of NaOH can be dissolved in 120 g of deionized H 2 O to form a mixture. About 170.1 grams of hexafluoroisopropan-2-ol can be added to the mixture. After about 15 minutes, 100.5 grams of 3-bromoprop-1-ene can be added to the mixture at room temperature. The mixture can be stirred for about 2 days. The mixture was then phase separated to yield about 178.6 g of crude product which was about 92.4% area percent pure (by gas chromatography) with 3.2% area percent allyl bromide.

Can be obtained. The crude product was distilled to 99.94% (area percent by gas chromatography) with a boiling point of 83.5 ° C. 3- (1,1,1,3,3,3-hexafluoropropan-2-yloxy) pro P-1-ene can be obtained.

As another example, halogenated intermediates comprising allyl-ether compounds

는 하기 개략도 (9)와 개략도 (12)에 따라서 R_F-중간체 1,2, 3,4, 4, 4-헵타플루오로-2,4-비스-(트리플루오로메틸) 펜테인-1-올을 3-브로모프로프-1-엔과 반응시킴으로써 제조될 수 있다.

R _F -intermediate 1,2,3,4,4,4-heptafluoro-2,4-bis- (trifluoromethyl) pentane-1- according to the following schematic (9) and schematic (12) It can be prepared by reacting ol with 3-bromoprop-1-ene.

Referring to schematic 12 above, 2,3, 4,5, 5, 5-hexafluoro-2, 4-bis (trifluoromethyl) pentan-1-ol (551 g, 1.66 mole), allyl bromide (221.2 g, 1.83 mole) and tetrabutylammonium hydrogen sulphate (5 mole%) can be added to form a mixture. The mixture can be cooled to about 10 ° C. and 50% (wt / wt) KOH (400 grams) can be added over 2 hours. The mixture can then be stirred at 10 ° C. for about 72 hours. After 72 hours, an additional 100 mL of 33% (wt / wt) KOH can be added and the mixture can be stirred for an additional 12 hours. The reaction can be monitored by removing portions and analyzing using gas chromatography, 2,3, 4,5, 5,5-hexafluoro-2, 4-bis (trifluoromethyl) pentane-1- after the non-detection of all, once the mixture is washed with H ₂ 0, washed twice with 10% (wt / wt) HCl, and may be washed one or more times with H ₂ O. The combined organic layers were dried over MgSO ₄ and 20.04 grams of 2,3, 4,5, 5, 5-hexafluoro-2, 4-bis (28.21 grams with 28.21% (area percent by gas chromatography)). About 516 grams of material containing trifluoromethyl) pentyl allyl ether can be obtained.

According to another embodiment of the disclosure, an R _F -intermediate comprising the homohalogenated alcohols described above, such as 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol May react to form acrylates. Homohalogenated alcohols can be exposed to acryloyl compounds, for example to form acrylates. In an exemplary embodiment, the homohalogenated alcohol may comprise 1,1, 1,3, 3, 3-hexafluoropropan-2-ol and the acryloyl compound may comprise acryloyl chloride. For example, 1,1,1,3,3,3-hexafluoropropan-2-ol is prepared with acryl chloride in the presence of a basic solution while maintaining the temperature of the solution at about 0 ° C. according to the following schematic (13). React with work to form R _F -intermediate 1,1, 1,3, 3,3-hexafluoropropan-2-yl acrylate,

Referring to schematic 13 above, a 1000 mL three-necked flask may be equipped with a thermometer, agitator, and a dropping funnel with a dip tube. About 130.6 grams of acryloyl chloride, 168.8 grams 1,1, 1,3, 3,3-hexafluoropropan-2-ol, and 1 gram of 2, 6-di-tert-butyl-4- in the flask Methylphenol can be added to form a mixture. About 30% (wt / wt) oil may then be added to the mixture while maintaining the mixture at 60 ° C-75 ° C through a dip tube. After addition, the mixture can be maintained at 60 ° C.-70 ° C. for about 4 hours. Single step vacuum distillation of the mixture yields 183 grams of crude product 1,1, 1,3, 3, 3-hexafluoropropan-2-yl acrylate which is about 95.7% (area percent by gas chromatography). can do. Crude 1,1, 1,3, 3,3-hexafluoropropan-2-yl may be further distilled to increase the purity to 99.7% (area percent by gas chromatography).

을 형성할 수 있다. As another example, halogenated intermediates comprising homohalogenated alcohols, such as 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol, as described above may react with acryl The rate can be formed. 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol was exposed to acryloyl chloride according to the following schematic (14)

Can be formed.

Referring to the schematic (14) above, 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol (2.59 g, 0.011 mole) and triethylamine (1.3 g, 0.013) mole) may be added to a 15 mL three neck round bottom flask equipped with a water cooled reflux condenser, thermocouple, stirrer, and addition funnel to form a mixture. The mixture may be maintained at about 0 ° C. using an ice water bath. Acryloyl chloride (1.38 grams, 0.015 mole) may be added dropwise to the mixture over about 15 minutes via an addition funnel. After holding about 1 hour, 10 mL H ₂ 0 can be added to the flask, two phases are observed, and the organic phase is separated. The organic phase can be analyzed and peak observed and identified by gas chromatography / mass spectrometry to have an m / z of 283.

를 포함한다. 예를 들어, 오직 예로서, 200mL 의 CH₂CI₂ 및 25 그램의 3,5-비스 (트리플루오로메틸) 벤질 알코올을 500mL 플라스크에 넣고 혼합물을 형성할 수 있다. 혼합물을 교반하면서, 약 13.8 그램의 트리에틸아민을 혼합물에 첨가할 수 있다. 혼합물은 그후 얼음 조에서 냉각될 수 있고 10.5mL 염화아크릴로일을 혼합물에 천천히 첨가할 수 있다. 혼합물을 약 1 시간 동안 교반하고 그후 수성 HCl 용액로 식혔다. 혼합물을 상 분리시키고 유기층을 포화된 KCI 용액으로 세척하고 MgS0₄위에서 건조시킬 수 있다. 유기용매를 증발에 의해 제거할 수 있고 남아있는 25.16 그램의 고체

는 > 98% (가스 크로마토그래피에 의한 면적 퍼센트)이 될 수 있다. As another example, an R _F -intermediate can be prepared by reacting an alcohol having at least two CF ₃ -groups and a ring group such as 3,5-bis (trifluoromethyl) benzyl alcohol to form an acrylate. The alcohol may react with the acryloyl compound such as acryloyl chloride to form the acrylate. In an exemplary embodiment, the acrylate is

It includes. For example, by way of example only 200 mL of CH ₂ CI ₂ and 25 grams of 3,5-bis (trifluoromethyl) benzyl alcohol can be placed in a 500 mL flask to form a mixture. While stirring the mixture, about 13.8 grams of triethylamine can be added to the mixture. The mixture can then be cooled in an ice bath and 10.5 mL acryloyl chloride can be slowly added to the mixture. The mixture was stirred for about 1 hour and then cooled to aqueous HCl solution. The mixture can be phase separated and the organic layer can be washed with saturated KCI solution and dried over MgSO ₄ . 25.16 grams of solid that can be removed by evaporation of organic solvent

Can be> 98% (area percent by gas chromatography).

R _F -intermediates with ring groups can also be prepared. According to exemplary embodiments, at least two CF ₃ - one reactant such heteroaryl halide intermediate containing an another reaction, such as phenol and reaction by at least 2 CF ₃ which comprises a ring - R comprising a group and ring _F Can form intermediates. One reactant may comprise an alcohol such as 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol prepared above. For example, by way of example only, R _F -intermediates can be prepared according to the following schematic (15).

의 수율은 42%이 될 수 있다. (m/z 320.1(M⁺), 94(M⁺-226)). Referring to the schematic diagram (15), about 3.9 grams (0.04 mole) of phenol and 5.5 grams (0.05 mole) of triethylamine were added to the stirrer, thermocouple, heating mantle, and 4.7 grams (0.042 mole) 4,5, 5, In a clean, dry 25 mL two-necked round bottom flask equipped with a 50 mL pressure equalization funnel containing 5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol To form a mixture. The mixture may be gradually warmed to 68 ° C. and then dropwise added 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol over 30 minutes.

The yield of can be 42%. (m / z 320.1 (M ⁺ ), 94 (M ⁺ -226)).

As another example, an R _F -intermediate can be prepared that is heterohalogenated and contains ring groups according to the following schematic (16).

Referring to schematic 16 above, about 13.7 grams (0.079 mole) of 4-bromophenol and 9.0 grams (0.089 mole) of triethylamine are equipped with a thermocouple, stirrer, heating mantle, and a 50 mL pressure equalization addition funnel To a prepared 50 mL two-neck round bottom flask. The contents of the round bottom flask were gradually heated to 93 ° C. and then 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentane-1 over 15 minutes using an addition funnel. -Ol (23.1 g, 0.065 mole) can be added dropwise. The contents can then be refluxed for 1 hour and then sampled and analyzed by gas chromatography. Yield by gas chromatography crystals will be 43% for 2- (4-bromophenoxy) -4, 5,5, 5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol Can be.

According to another embodiment of the disclosure, bicyclic halogenated intermediates can be prepared according to the following schematics (17A and B).

Referring to schematic 17A above, a three-necked 500 mL flask equipped with a stirrer, an inlet for starting material addition, and a top packed column, reflux distillation head, thermocouple, and collection flask was weighed at 60.40 g in 150 mL of deionized water. KOH (0.917 mole), 5.86 g of methyltributylammonium chloride (alicot 175, -5 wt%) can be filled to form a solution. The resulting solution can be heated to 97 ° C. and 110 g (0.281 mole) 1,1, 1,2, 5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane Can be added and pumped over the course of 2 hours through a syringe below the surface. During this addition, the resulting product can be collected in an overhead collection flask and the reaction can be continued to heat until the overhead temperature reaches 94 ° C. The collected material may be dried over magnesium sulfate to give 74.18 g of crude reaction product, thereby continuing GC analysis in the primary product and starting material. The crude reaction material was distilled to give 42.6 g of (E) -1, 1,1, 4,5, 5,5-heptafluoro-4- (trifluoromethyl) pent-2-ene (57.5 % Isolated yield). _{^{(1 H-NMR (CDCI 3}} ): □ 6.45 (d, J = 12 Hz, 1 H), 6.45 (dhep, 1 H) 13 C-NMR (CDCI 3):. 90.5 (dhep, J = 27,202 Hz, CFCH), 120 (qd, 27,287 Hz, CF3CF), 121.6 (q, J = 220 Hz, CHCF 3), 124.4 (m, CHCF), 128.2 (qd, J = 21,36 Hz, CHCF 3). 19 F -NMR (CDC1 ₃ w / CCI ₃ F): □ -66.4 (d, JH-F = 3 Hz, CF ₃ CH), -76.9 (d, JF-F = 8 Hz, CF ₃ CF) ,-186.9 (m, CF 3 CF).

Referring to the schematic diagram 17B, 5.26 grams (0.08 mole) cyclopentadiene and 14, 67 grams (0.06 mole) (E, Z) -1, 1,1, 4,5, 5,5-heptafluoro 4- (trifluoromethyl) pent-2-ene can be added to form a mixture in a stainless steel autoclave that can be equipped with a 6.9 x 10 ³ kPa burst disk, agitator, external thermocouple, valve, and pressure gauge. have. The mixture may be maintained at about 140 ° C. to 250 ° C. for about 4 to 72 hours under endogenous pressure. 5- (trifluoromethyl) -6- (perfluoropropan-2-yl) bicycle [2.2. 1] Hept-2-ene yield can be greater than 12 (percent area by gas chromatography). Reaction samples can also be analyzed by gas chromatography / mass spectrometry. (m / z 330 (M ⁺ ), 261 (M ⁺ -CF ₃ ), 161 (M +-(CF ₃ ) ₂ CF)).

Referring to FIG. 4, system 40 includes a taxogen 42, telogen 44, and initiator 46 to provide a reagent such as reactor 48 to form a product such as telomer 49. R _F -is shown to prepare intermediates. In an exemplary embodiment, system 40 performs a telomerization process. According to an embodiment, the taxogen 42 is exposed to telogen 44 to form telomer 49. According to another embodiment, the taxogen 42 may be exposed to the telogen 44 in the presence of the initiator 46. Reactor 48 may also be configured to provide heat to the reagents during exposure.

The taxogen 42 may comprise at least one CF ₃ -comprising compound. The CF ₃ -comprising compound may have a C-2 group having at least one pendant CF ₃ -group. In an exemplary embodiment, the taxogen 42 may comprise an olefin such as trifluoropropene. Taxogens 42 may also be used, for example, 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) phen-1-ten and / or 6,7, 7, 7-tetrafluoro- 6- (trifluoromethyl) hept-1-ene.

Telogen 44 may include halogens such as fluorine and / or chlorine. Telogen 44 may comprise at least four fluorine atoms and may be represented as R _F -Q and / or R _CI -Q. R _F may be as described above and may include at least four fluorine atoms, and the Q group may include one or more atoms of the periodic table of elements. The Q group can be H or I and for example the R _F group is (CF ₃ ) ₂ CF- and / or -C ₆ F ₁₃ . R _F -Q can be, for example, 2-iodofluoropropane. The R _CI group may comprise at least one —COs group. Representative telogens may include the halogenated compounds described above, such as (CF ₃ ) ₂ CFI, C ₆ F ₁₃ I, and / or trichloromethane. In an exemplary embodiment, the taxogen 42 may comprise trifluoropropene and the telogen 44 may comprise (CF ₃ ) ₂ CFI, and the taxogen 42 to telogen 44 The molar ratio of is from about 0.2: 1 to about 10: 1, about 1: 1 to about 5: 1, and / or about 2: 1 to about 4: 1. The taxogens 42 are 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) phen-1-ten and / or 6,7, 7, 7-tetrafluoro-6- (tri Fluoromethyl) hept-1-ene and telogen 44 may comprise, for example, (CF ₃ ) ₂ CFI.

Reactor 48 may be any lab-scale or industrial-scale reactor, and in certain embodiments, reactor 48 may be configured to control the temperature of reagents therein. According to an exemplary embodiment the reactor 48 may be used to provide a temperature during exposure of the reagent to about 90 ° C. to about 180 ° C., 60 ° C. to about 220 ° C. and / or 130 ° C. to about 150 ° C. According to this, the reactor 48 may be configured to maintain the temperature of the reagent at about 90 ° C.

와 같은 적어도 하나의 -CF₃ 기를 포함하는 펜단트 기를 갖는 적어도 하나의 C-2 기를 포함할 수 있다. The telomer 49, prepared when exposing the taxogen 42 to telogen 44, may comprise R _F (R _T ) nQ and / or R _CI (R _T ) nH. R _T creeper

It may include at least one C-2 group having a pendant group comprising at least one -CF ₃ group, such as.

Representative telomers (49)

And / or

중 하나 또는 둘다를 포함할 수 있고, 예를 들어 R_F는 -CH₂-와 같은 적어도 하나의 탄소 원자를 포함한다. 대표적인 구체예에서, n은 적어도 1이 될 수 있고 다른 구체예에서 n은 적어도 2가 될 수 있고 생성물은 다음

May comprise one or both, for example R _F comprises at least one carbon atom, such as —CH ₂ —. In an exemplary embodiment, n can be at least 1 and in other embodiments n can be at least 2 and the product is

One or more of which Z is, for example, H, Br, and / or Cl.

In an exemplary embodiment, the taxogentrifluoropropene is exposed to telogen (CF ₃ ) ₂ CFI to telomer

를 형성할 수 있고, 또다른 예로서, 트리플루오로프로펜은 텔로겐 C₆F₁₃I에 노출되어 텔로머

를 형성할 수 있다.

And as another example, trifluoropropene is exposed to telogen C ₆ F ₁₃ I to telomer

Can be formed.

를 형성할 수 있다. 텔로겐과 비교하여 초과량의 탁소젠을 이용할때 적어도 2인 n을 갖는 생성물이 형성될 수 있다. 적어도 2인 n을 갖는 생성물을 얻기 위해 예를 들어, 탁소젠 대 텔로겐의 적어도 2: 1 몰비가 이용될 수 있다. 예를 들어, 오직 예로서, 적어도 2개의 몰의 탁소젠트리플루오로프로펜은 적어도 1 몰의 텔로겐 (CF₃)₂CFI 에 노출되어 텔로머 According to another embodiment, the taxoxentrifluoropropene is also exposed to telogen CCl ₃ H to telomer

Can be formed. A product with n being at least 2 can be formed when using an excess of taxogen compared to telogen. For example, at least a 2: 1 molar ratio of taxogen to telogen can be used to obtain a product having n of at least 2. For example, by way of example only, at least two moles of taxogentrifluoropropene may be exposed to at least one mole of telogen (CF ₃ ) ₂ CFI to telomer

및

중 하나 또는 둘다를 형성할 수 있다.

And

May form one or both.

In further embodiments, initiator 46 may be provided to the reactor 48 during the exposure of the reagents. The initiator 46 may include, for example, thermal, photochemical (UV), radical, and / or metal complexes, including peroxides, such as di-tert-butyl peroxide. Initiator 66 may also include a catalyst, such as Cu. The initiator 46 and the taxogen 42 may be provided to the reactor 48 in a molar ratio of initiator 46 to taxogen 42, for example, from about 0.001 to about 0.05 and / or from about 0.01 to about 0.03. . The initiator 46 and the taxogen 42 can be provided to the reactor 48 in a molar ratio of initiator 46 to taxogen 42, for example, from about 0.001 to about 0.05 and / or from about 0.01 to about 0.03. .

According to an exemplary embodiment, various initiators 46 and telogen 44 may be used to telomerize the taxogen 42 as referenced in Table 2 below. Telomerization using photochemical and / or metal-complexing initiators 46 may be carried out in batch conditions using Carius tube reactors 48. Telomerization with thermal, peroxide and / or metal complex initiators 46 can be performed in 160 mL and / or 500 mL Hastelloye ^® reactor 48. Telogen 44 (pure and / or as a peroxide solution) may be provided as a gas at a temperature of about 60 ° C. to about 180 ° C. and the telogen 44 [T] ₀ / taxen 42 (Tx) _{The zero} initial molar ratio R ₀ can vary from 0.25 to 3.0 and the reaction time can range from 2 to 22 hours. The product mixture can be analyzed by gas chromatography and / or the product can be distilled to other small portions and analyzed by ¹ H and ¹⁹ F NMR and / or ¹³ C NMR. Mono-adduct (n = 1) and di-adduct (n = 2) products can be recognized as shown in Table 2 below.

a) The telogen can be C6F13I in run numbers 1-9 and (CF3) 2CFI in run numbers 10-13.

b) R ₀ = [T] ₀ / [Tx] ₀ ; C ₀ = [In] ₀ / [Tx] ₀

c) Heavy TFP telomers (n> 2) may constitute the remainder of the product.

d) the initiator is Perk. 16s (t-butyl cyclohexyl dicarbonate); AIBN; Trig. 101 (2,5-bis- (t-butyl peroxy) -2,5-dimethylhexane); And DTBP.

For example, by way of example only, taxogen trifluoropropene may be combined with telogen 2-iodofluoropropane according to the following schematic (18) to telomer 1,1, 1,2, 5,5, 5 -Heptafluoro-2- (trifluoromethyl) -4-iodopentane can be formed.

As another example, telogen 1,1, 1,2, 2,3, 3,4, 4,5, 5,6, 6-tridecafluoro-6-iodohex according to the following schematic diagram (19) Sein is combined with teloxentrifluoropropene telomer 1,1, 1,2, 2,3, 3,4, 4,5, 5,6, 6,9, 9,9-hexadecafluoro- 8-iodononeine may be formed.

As another example, taxenes comprising at least two CF ₃ -groups such as R _F -intermediate 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) phen- in accordance with the schematic 20 below 1-ten and / or 6,7, 7,7-tetrafluoro-6- (trifluoromethyl) hept-1-ene is combined with telogen comprising a saturated compound having at least two CF ₃ -groups To form a telomer comprising a saturated compound.

Referring to the schematic (20) above, 3-perfluoroisopropyl-1-propene (20 grams, 0.095 mole) and 2-iodoheptafluoropropene (28.18 grams, 0.095 mole) were added to a glass pressure tube. Can be provided to form a mixture. AIBN (0.51 grams) can be added to this mixture and the mixture can be heated and maintained at 85 ° C. for 24 hours. During heating, additional AIBN can be added (0.11 gram after 3 hours and another 0.1 gram after 21 hours). The mixture can then be washed twice with H ₂ 0 and analyzed via gas chromatography to obtain 56% area percent purity.

Referring to schematic 21 above, 30.4 grams (0.121 mole) 6,7, in a 250 mL stainless steel autoclave equipped with sealed and emptied dip tubes and valves, pressure gauges, bursting discs, outlet valves, agitators, and thermocouples, 7,7-tetrafluoro-6- (trifluoromethyl) hept-1-ene, 41.32 grams (0.140 mole) heptafluoro-2-iodopropane, and 0.209 grams (0.0013 mole) 2, 2'-azobisisobutyronitrile may be added to form a mixture. The mixture can then be slowly heated to 90 ° C. and maintained for 24 hours. After the retention period, the sample can be drawn and analyzed by gas chromatography and gas chromatography / mass spectrometry. (GC-HP-5 column (RT: 15.9 min), GC / MS (m / z 421 (M ⁺ -I), 211 (M ⁺ -C ₆ H ₅ F ₇ I), 127 (I ⁺ )).

According to a further embodiment, the R _F -intermediates comprising telomers can be further modified to form additional R _F -intermediates. For example, by way of example only, R _F -intermediate 1,1, 1,2, 5,5, 5-heptafluoro-2- (trifluoromethyl) -4-iodopentane is shown in the following schematic (22) Can be prepared as described below.

Referring to the schematic 22 above, a 500 mL three-necked flask may be equipped with an agitator, thermocouple, reflux condenser, and partition wall. About 483 grams (1.23 mole) 1,1, 1,2, 5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane can be added to the flask. About 12.4 grams (0.08 mole) AIBN can be added to a syringe pump containing about 123 grams (1.23 mole) allyl acetate to form a mixture. The syringe pump may be connected to the flask via a Teflon tube supplied through the septum. 1,1, 1,2, 5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane may be maintained at about 80 ° C to 90 ° C. The allyl acetate and AIBN mixture in the syringe pump can be filled (supplied) into the flask at a rate of 15 mL per hour. The mixture was sampled and analyzed by gas chromatography to obtain 6,7, 7, 7-tetrafluoro-4, 6-bis (trifluoromethyl) -2-iodoheptyl acetate having about 78.3% area percent purity. You can find it.

Referring to schematic 23 above, a three neck 250 mL flask may be equipped with a thermocouple, agitator, 50 mL pressure equalization funnel, and a short path distillation apparatus. About 150 grams of diethylene glycol and 26.01 grams (0.4 mole) zinc can be added to the flask to form a mixture. The mixture may be maintained at about 50 ° C. to 65 ° C. and the vacuum may be maintained at about 5.3 kPa to 8.7 kPa. Add about 33 grams (0.067 mole) 6,7, 7, 7-tetrafluoro-4, 6-bis (trifluoromethyl) -2-iodoheptyl acetate into a 50 mL addition funnel and add dropwise over about 1 hour can do. Approximately 6,7, 7,7-tetrafluoro-4 in coordination with the addition of 6,7, 7, 7-tetrafluoro-4, 6-bis (trifluoromethyl) -2-iodoheptyl acetate , 6-bis (trifluoromethyl) hept-1-ene can be distilled by reaction and collected in a 50 mL receiver flask. A total of about 39.7 grams of crude R _F -intermediate 6,7, 7,7-tetrafluoro-4, 6-bis (trifluoromethyl) hept-1-ene with 53% area percent purity by gas chromatography Can be collected.

와 같은 위에서 기술된 텔로머 (49)를 포함하는 R_F-중간체를 포함할 수 있다. 에스테르 (54)는 알릴-포함 화합물 이를테면 알릴 아세테이트를 포함할 수 있다. Referring to FIG. 5, a system 50 is shown that can be used to prepare telomers comprising ester functional groups. System 50 may include a reactor 56 configured to receive reagents such as ester 54 and telomer 52, in other embodiments, initiator 59 as well. The telomer 52 may be fluorinated and may be represented by the general formula Q ₁ (R _T ) nQ ₂ . The Q ₁ and Q ₂ groups may comprise one or more atoms of the periodic table of elements comprising Q and / or Qg and, according to exemplary embodiments, Q ₁ and Q ₂ The flags do not need to be different or the same. The Q ₁ group may, in an exemplary embodiment, comprise at least two —CF ₃ groups and in other embodiments, at least two —CF ₃ groups. The Q ₁ group may in one embodiment also comprise a —CF (CF ₃ ) ₂ group and in other embodiments a —C ₆ F ₁₃ group. The Q ₂ group may comprise halogen in certain embodiments and hydrogen in other embodiments. The telomer 52 is for example

R _F -intermediates comprising the telomer 49 described above, such as. Ester (54) may comprise allyl-comprising compounds such as allyl acetate.

According to a further embodiment, the initiator 59 may be used in the reactor 46 while the ester 54 is exposed to the telomer 52. The initiator (29) is a compound such as azobisisobutyronitrile (AIBN), a peroxide such as dibenzoyl peroxide, tert-amylperoxy pivalate, tert-butyl peroxy pivalate, DTBP (di-tert-butyl peroxide) And / or metal complexes such as copper chloride, ferric chloride, palladium and / or ruthenium complexes may also be used.

는 에스테르 알릴 아세테이트에 노출되어 에스테르-포함 텔로머

를 형성할 수 있다. 대표적인 구체예에서, 시약을 노출하는 동안 반응기 (56) 내에서 시약을 대략 10 시간동안 적어도 82℃로 가열할 수 있다. 시약을 또한 예를 들어 동일한 양의 시간동안 동일한 온도에서 AIBN의 존재하에서 노출할 수 있다. Ester 54 may be exposed to telomer 52 to form ester-containing telomer 58. The ester-containing telomer 58 may comprise the composition Q ₁ (R _T ) nR _E , wherein the R _E groups comprise at least one ester group and / or Qg, such as an acetate group. In an exemplary embodiment, telomer 52 may comprise formula R _F (R _T ) nQ ₂ , wherein the R _F group comprises at least one fluorine atom such as —CF ₃ group and / or as described above . R _F (R _T ) nQ ₂ may be exposed to ester 54 to form an ester-containing telomer 58 such as R _F (R _T ) R _E. According to an embodiment, the telomer

Are ester-containing telomers exposed to ester allyl acetate

Can be formed. In an exemplary embodiment, the reagent may be heated to at least 82 ° C. for approximately 10 hours in reactor 56 while exposing the reagent. Reagents may also be exposed, for example, in the presence of AIBN at the same temperature for the same amount of time.

In some embodiments, the process of system 50 can be exothermic and the initiator can prevent achieving a temperature that can degrade and / or rearrange the product. For example, when the temperature of the contents of the reactor is higher than 90 ° C. and dibenzoyl peroxide initiator is used, the reaction temperature of the ester and telomer can be raised to about 160 ° C.-180 ° C., and the ester obtained at such a high temperature For example, thermal rearrangements can undergo R _F CH ₂ CH (OAc) CH ₂ I. AIBN can be used as initiator and can be added stepwise to avoid such rearrangements and provide product yields up to 80-82% (by gas chromatography) or 75% (by distillation).

를 포함할 수 있다. Referring to FIG. 6, system 60 includes a reactor 62 configured to receive reagents such as telomer 64 and reducing agent 66 and to form allyl-comprising telomer 68. The telomer 64 may comprise the R _F -intermediates such as ester-containing telomer 58 described above. For example, telomer 64 is Q ₁ (R _T ) nR _E , such as

It may include.

는 MeOH 용액중에 2-배 과잉량의 활성화 Zn 더스트를 함유하는 반응기 (62)에 첨가될 수 있다. 반응기(62)가 텔로머(64)의 첨가 동안 및/또는 후에 그 용액을 교반 및/또는 더욱 격렬하게 교반하도록 구성될 수 있다. 일부 구체예에 따르면, 텔로머(64)의 첨가 시에, 텔로머(64)의 작용제 (66)와 반응은 발열일 수 있고 만일 원한다면, 발열을 제어하기 위해 MeOH의 환류하에서 텔로머(64)을 적가할 수 있다. 텔로머(64)의 전환은 정량이 될 수 있고 예를 들어, 증류후에 전반적인 수율의 알릴-포함 텔로머 (68)이 대략 75% 이다. The reducing agent 66 may comprise one or more reagents, such as a mixture of activated zinc and methanol. Other reducing agents may be used. Reactor 62 may be configured to expose agent 66 to telomer 64 at approximately 65 ° C. and reflux these materials for approximately three hours, plus or minus two hours. For example, by way of example only, telomer 64, such as

Can be added to reactor 62 containing a 2-fold excess of activated Zn dust in MeOH solution. Reactor 62 may be configured to stir and / or more vigorously stir the solution during and / or after addition of telomer 64. According to some embodiments, upon addition of the telomer 64, the reaction with the agent 66 of the telomer 64 may be exothermic and if desired, the telomer 64 under reflux of MeOH to control the exotherm Can be added dropwise. The conversion of telomer 64 can be quantitative, for example, after distillation, the overall yield of allyl-comprising telomer 68 is approximately 75%.

에 노출되어 알릴-포함텔로머

를 형성할 수 있다. 알릴-포함 텔로머(68)는 예를 들어, 폴리머의 형성에서 모노머로서 사용될 수 있다. In an exemplary embodiment, the allyl-comprising telomer 68 may comprise Q ₁ (R _T ) nR _A , wherein the R _A group comprises a Qg and / or at least one allyl group as described above. Allyl-comprising telomer 68 may comprise R _F (R _T ) nR _A , and as such, may include at least one fluorine atom. For example only by way of example, the agents zinc and methanol are telomers.

Allyl-containing telomers exposed to

Can be formed. Allyl-comprising telomer 68 can be used, for example, as a monomer in the formation of a polymer.

을 포함할 수 있고, n은 적어도 1이다. In an exemplary embodiment, when referring to FIGS. 4, 5, and 6 in order, systems 40, 50, and 60 are allyl-containing telomers from taxogens 42 and telogen 44. (68) can be arranged to produce sequentially. In this alignment, telomer 49 made in system 40 may be used as telomer 52 in system 50, and telomer 58 made in system 50 may be used as system 60. It can be used as a telomer 64 in. As such, allyl-comprising telomer 68 may comprise a fluoromonomer comprising a telomer of trifluoropropene. Telomers (49), (52), (64), and (68)

And n is at least 1.

For example, by way of example only, referring to Table 3 below, telomers, esters, and monomers having the recited properties can be prepared.

* GC analysis: column OV1 (3% silicon grease in chromosob G); 2m length, 1/8 "diameter, 50-200 ℃ ramp.

According to another embodiment of the disclosure, the R _F -intermediates comprising the telomers described above can be modified according to the following schematic (24).

According to the schematic diagram 24, the 150 mL three-neck round bottom flask is a 150 mL pressure which may contain 70 mL of allyl magnesium bromide in a reflux condenser, stirrer, thermocouple, heating mantle, and diethyl ether of 1. OM solution. Equalization addition funnels may be provided. About 27.64 grams (0.07 mole) of 1,1, 1,2, 5,5, 5-heptafluoro-2- (trifluoromethyl) -4-iodopentane can be added to the flask. Allylmagnesium bromide solution can be slowly added to the flask where an exotherm can be observed with a color change from orange to colorless. Allylmagnesium bromide can be added over a period of 2.5 hours and the reaction mixture can then be maintained at room temperature overnight. After the holding period, the reaction mixture can be washed in water to wash any unreacted allylmagnesium bromide, to observe the organic layer, to decant the supernatant and to dry over MgSO ₄ . Samples of the dried organic layer can be analyzed by gas chromatography / mass spectrometry. (m / z 306 (M ⁺ ), 237 (M ⁺ -CF ₃ )).

According to another embodiment of the disclosure, the R _F -intermediates comprising the telomers described above can be altered to form additional R _F -intermediates. For example, by way of example only, R _F -intermediates 1,1, 1,2, 6,7, 7, 7-octafluoro-2, 6-bis (trifluoromethyl) -4-iodoheptane Modified according to Scheme 25 below, R _F -intermediate 6,7, 7,7-tetrafluoro-4- (2, 3,3, 3-tetrafluoro-2- (trifluoromethyl) propyl ) -6- (trifluoromethyl) hept-1-ene may be formed.

(488 그램) 및 무수에테르 (306mLI)으로 채워져서 혼합물을 형성할 수 있다. 혼합물은 얼음/물 조로 0℃로 냉각될 수 있고 에테르 (976mL)중의 1M 알릴마그네슘 브롬화물이 첨가될 수 있고 혼합물 실온으로 밤새 데웠다. Referring to schematic 25 above, the dried flask is

(488 grams) and anhydrous ether (306mLI) to form a mixture. The mixture can be cooled to 0 ° C. with an ice / water bath and 1M allylmagnesium bromide in ether (976 mL) can be added and the mixture warmed to room temperature overnight.

을 수득할 수 있다.Saturated ammonium chloride (500 mL) can then be added dropwise to the mixture at a rate that maintains the temperature of the mixture at <5 ° C., and deionized water (250 mL) can be added to help dissolve the salt and form a biphasic mixture. The organic layer was separated from and dried over magnesium sulfate, filtered and distilled at 5 Torr 41 ° C.-43 ° C. to give a clear liquid (361 g, 84.2%). Boil out the rest of the ether, as determined by NMR, 359.6 grams

Can be obtained.

As another example, in a dry 500 mL round bottom flask equipped with an addition funnel, 120 grams (0.24 moles) of (1,1, 1,2, 6,7, 7,7-octafluoro-2, 6- Bis (trifluoromethyl) -4-iodoheptane) to 150 mL of anhydrous THF can be added to form a mixture. Under N ₂ atmosphere, the mixture can be cooled to 0 ° C. with vigorous stirring. To this mixture, a 2M solution of allylmagnesium bromide in 120 mL of THF can be added at a rate to maintain the temperature of the mixture below about 5 ° C. After addition of the allyl magnesium bromide solution, the flask can be slowly warmed to room temperature.

White powder suspension can be formed during the reaction and removed by suction filtration to form a filter cake. The filter cake may be washed with 100 mL of THF, the filtrate collected and 3 to 5 mL of water added to destroy any remaining allylmagnesium bromide. THF can be distilled off and the remaining solution can be washed with water. Dry with organic layer (90.7 grams) MgS0 ₄ and about 63 grams of 63.5% (area percent by gas chromatography) at 40 ° C-41 ° C / 5 Torr R _F -Intermediate 6, 7,7,7-tetrafluoro- 4- (2,3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) hept-1-ene may be separated.

As further disclosed in schematic 25 above, 6,7, 7,7-tetrafluoro-4- (2, 3,3, 3-tetrafluoro-2- (trifluoromethyl) propyl)- 6- (trifluoromethyl) hept-1-ene may be altered to produce another R _F -intermediate. Referring to the schematic above, 60 grams (0.14 moles) of 6,7, 7,7-tetrafluoro- into a 100 mL pressure tube equipped with a 9 inch Pen-Ray® Hg lamp, pressure gauge, stirrer, and dip tube 4- (2, 3,3, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) hept-1-ene may be added. The tube can be sealed and gaseous anhydrous HBr bubbled into the system to maintain a pressure between 101.37 kPa and 308.27 kPa. The tube can be illuminated with a Pen-Ray lamp until the pressure stops decreasing. The mixture can then be washed once with water and once with 10% aqueous sodium bicarbonate. The organic layer can be analyzed as high as 92.7% (area percent by gas chromatography), dried over MgSO ₄ and distilled at 73 ° C-74 ° C / 3.1 Torr.

Referring to schematic diagram 26, 71.05 grams (0.13 mole) of R _F -intermediate 1,1, 1,2, 8,9, in a 250 mL three neck round bottom flask equipped with a thermocouple, agitator, and reflux condenser 9, 9-octafluoro-2, 8-bis (trifluoromethyl) -4-iodooctane can be added and then cooled to 0 ° C. in an ice bath. Over a period of 3 hours, about 121.37 grams (0.14 mole) of 1.0 M allylmagnesium bromide in diethyl ether can be added dropwise with a 150 mL pressure equalized addition funnel. After addition, the solution can gradually warm to room temperature and hold for 48 hours. The mixture is then cooled with deionized water and the organic layer supernatant decanted and MgS0 ₄ It can be dried in the stomach. Crude R _F -Intermediate 8,9, 9,9-tetrafluoro-4- (2, 3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -8- (trifluoro Methyl) non-1-ene can be evaluated by mass spectrometry (m / z 462 (M ⁺ ), 420.1 (M ⁺ -42), 279.1 (M ⁺ -183)).

According to a further embodiment, 1,1, 1,2, 2,3, 3,4, 4,5, 5,6, 6,9, 9, 9-hexadecafluoro-8-iodononene and The R _F -intermediates, including the telomers described above, can be modified according to the following schematic (27).

Specific examples of the disclosed examples R _F R _F containing a part described above - to provide a surfactant composition. Representative R _F -surfactant compositions may be referred to as R _F -Qs. In a system having at least two parts, R _F may have a greater affinity than Qs for the first part of the system and Qs may have a greater affinity for the second part of the system than R _F. The system can include a liquid / liquid system, a liquid / gas system, a liquid / solid system, and / or a gas / solid system. The liquid / liquid system may include, for example, a system having at least one portion comprising water and another liquid portion which is hydrophobic relative to the portion comprising water. Liquid / liquid systems may also include systems where water is not part of the system, such as hydrocarbon liquid systems. In an exemplary embodiment, R _F may be hydrophobic relative to Q and / or Qs may be hydrophilic relative to R _F. R _F can be hydrophobic and Qs can be hydrophilic, for example. The hydrophobic portion may be called the tail of the R _F -surfactant, and the hydrophilic portion may be called the head of the R _F -surfactant. R _F -surfactants may include such surfactants having tails or hydrophobic moieties containing fluorine. The R _F -surfactant tail or hydrophobic portion may be referred to as the R _F portion and the R _F -surfactant head or hydrophilic portion may be referred to as the Qs portion. Examples of R _F -surfactants include those of Table 4 below.

R _F -surfactants may also include

NMR: ¹ H (D6-DMSO, 300 MHz) δ 1.8 (m, 2H), 2.6 (m, 2H), 3.0 (m, 2H), 3.1 (bs, 6H), 3.6 (m, 2H), 3.9 ( m, 4H), 7.9 (bs, 1H); ¹³ C (D6-DMSO, 75 MHz) δ 22.6, 22.9, 23.1, 43.1, 50.0, 60.8, 64.4, 88-93 (ds), 114.5-126. 5 (qd); And ¹⁹ F (CFC13, D6-DMSO, 282 MHz) δ-76. 4 (d, 6.95 Hz, 6F), -183. 4 (m, 1 F)

According to an embodiment of the disclosure, a method for preparing an R _F -surfactant is provided. Representative R _F - includes providing an intermediate-surfactant production method R _F - R _F having such intermediate at least two -CF ₃ groups described above. Representative R _F - The intermediates may include -Qg R _F and R _F is Qg, for example - is designed to be attached later to the Qs portion of the surfactant. Representative methods for preparing surfactants are both described in German Offen. 1,924, 264 and US Pat. Nos. 3,721,706. Representative methods for preparing R _F -surfactants are described below.

Referring to Figure 7, R _F - intermediates for example, it reacted with RF- intermediate containing at least one fluorine atom R _F - system that may be configured to perform a process including the formation of a surface active agent ( 70) appears. System 70 includes reactors 71 and 75. Reactor 71 may be configured to expose R _F -intermediate 72 to radical reagent 73. In an exemplary embodiment, the R _F -intermediate 72 may comprise an R _F moiety, such as those described above.

Reagent 73 may include, for example, HSCH ₂ CO ₂ H. R _F -intermediate 72 is exposed to reagent 73 in the presence of a radical initiator, such as AIBN, for example R _F -intermediate 74 such as R _F -C ₃ H ₆ -S-CH ₂ CO ₂ H Can be prepared.

In an exemplary embodiment, reactor 75 is R _F - may be configured to produce a surface active agent (77) - R _F by combining the intermediate 74 and the reagent 76. Reagent 76 may comprise HO (CH ₂ CH ₂ 0) n-CH ₃ and R _F -surfactant 77 may be, for example, R _F -C ₃ H ₆ -S-CH where n is at least 1. ₂ C (O) (CH ₂ CH ₂ ) nCH ₃ .

As another example, the reagent 73 may comprise a radical initiator and / or ethylene (CH ₂ = CH ₂ ). When exposing the R _F -intermediate 72 to the reagent 73 in the reactor 71, for example R _F -Intermediate 74, such as R _F -CH ₂ CH ₂ I ⁺ N (CH ₃ ) ₃ Can be prepared. Reactor 72 is R _F - exposing the intermediate (74) to the reagent (76) R _F - may be arranged to form a surface active agent (67). Reagent 76 may include, for example, pyridine. RF- surfactants 77 may comprise a surface active agent such as R _F RF- -Qs, Qs, for example, quaternary ammonium ions such as ^{_{-CH 2 CH 2 N + (CH}} 3) 3 I - including can do.

According to yet another embodiment, the heteroaryl halide R _F - an intermediate such as iodine RF- intermediates, for example, by reaction with potassium thiocyanate R _F - intermediate thiocyanate RF- intermediates for instance be converted to the R _F -SCN Can be. The reaction can be carried out in anhydrous ethanol using acetic acid as a catalyst. More than 30% molar excess of KSCN can be used compared to the R _F -intermediate. Ethanol, acetic acid, R _F -intermediate, and KSCN can be charged to the reaction vessel, heated to reflux and maintained there until the reaction is complete. The reaction progress can be monitored by analyzing the reaction mixture for R _F -intermediates by gas chromatography. Upon completion of the reaction, the KI formed can filter the reaction mixture, evaporate ethanol and the thiocyanate R _F -intermediate can be washed twice with hot water (70 ° C.). Reagent 73 comprises a mixture of KSCN, ethanol and acetic acid described above. The R _F -intermediate can be exposed to the mixture at a temperature of about 83 ° C. and / or at reflux to produce the intermediate 74, such as R _F -SCN.

R _F -intermediate 74 may then be exposed to reagent 76 to form intermediate 77. Exemplary reaction sequence (28) as shown below: R _F - intermediate (74), such as R _F R _F is -SCN treated wet chlorine-sulfonyl chloride to give the intermediates.

2R _F -SCN + 8H ₂ O + 9Cl _2- > 2R _F -SO ₂ Cl + 2CO ₂ + N ₂ + 16HCl (28)

R _F -SCN, water, and acetic acid can be charged to the reactor 75 as a solvent. Chlorine may be added to the reaction vessel in 30 minute increments while the temperature of the mixture in reactor 75 is maintained at 20 ° C to 30 ° C. At the end of each 30 minutes of chlorine addition, 0.314 grams of water may be added to reactor 75. For each gram of chlorine added, 4.5 moles per mole of R _F -SCN can be added. When this amount is added, the mixture in reactor 75 can be sampled and analyzed for R _F -SCN by gas chromatography. When the reaction is complete, the mixture in reactor 75 is diluted with 65% (wt / wt) R _F -S0 ₂ Cl with chloroform, heated to about 40 ° C and washed twice with its volume of 40 ° C water. Can be. After washing, the washed mixture can be dried by azeotropic distillation of water using Dean Stark traps. Karl Fischer titration can be used to determine the amount of water. The water content can be less than 0.1%. As described above, reagent 76 may comprise a mixture of Cl ₂ , H ₂ O, and acetic acid. R _F - intermediate (74) is exposed to the mixture at a temperature of about 30 ℃ to 40 ℃ R _F - may be prepared for intermediate 67, such as a R _F -S0 ₂ Cl.

In 8, a more specific example, R _F - intermediates, for example, those prepared from the system 70, such as a R _F - the system is configured to produce a surface active agent (- R _F from Intermediate 77 80) is shown. System 80 may include reactors 81 and 82. Reactor 81 is R _F - is an intermediate 77, may be configured to expose the reagent (84) intermediate (83), such as a R _F described above. R _F -intermediate 83 can have, for example, the general formula R _F -SO ₂ Cl described above. In an exemplary embodiment, exposing the R _F -intermediate 83 to the reagent 84 can esterify the intermediate 83 to form an RF-intermediate 85, which can include sulfonamidoamine. Dimethylaminopropylamine (H ₂ N (CH ₂ ) ₃ N (CH ₃ ) ₂ , DMAPA) can be used to esterify intermediate 83 as shown in Representative Reaction Schematic (29) and described below.

R _F -S0 ₂ Cl + H ₂ N (CH ₂ ) ₃ N (CH ₃ ) _2- > R _F -S02NH (CH ₂ ) ₃ N (CH ₃ ) ₂ + HCl (29)

The esterification can be carried out in chloroform solution at reflux. The solvent and reactants can be dried with at least 0.1% by weight water. DMAPA can be dissolved 1.5 times in its volume in chloroform in the reactor 81 which can be immersed in a cooling bath. The reactor 81 can be added 65% (wt / wt) R _F -SO ₂ Cl of DMAPA molar equivalents in chloroform solution while maintaining the temperature of the contents of the reactor 81 at less than 50 ° C. When the addition is complete, the temperature of the contents can be raised to reflux and maintained at reflux for 5 hours. Reactor 81 contents may then be cooled to 60 ° C. and washed three times with the same volume of 60 ° C. water. The remaining chloroform can be removed under vacuum and the pure product can be washed twice with 90 ° C. water. The washed pure product can be sampled and analyzed for free DMAPA using wet chemistry specific to the primary amine.

와 같은 RF-중간체(85)를 제조할 수 있다. 또다른 예로서, 시약(84)은 2-아미노아세트산 및 CHCl₃의 혼합물을 포함할 수 있고 중간체(83)는 약 30℃-65℃ 사이의 온도에서 혼합물에 노출되어

와 같은 R_F-중간체(85)를 제조할 수 있다. 시약(84)은 또한 2-(메틸아미노) 아세트산과 CHCl₃의 혼합물을 포함할 수 있고 중간체(83)은 약30℃-65℃ 사이의 온도에서 혼합물에 노출되어

와 같은 중간체(85)를 제조할 수 있다. According to an exemplary embodiment, reagent 84 may comprise a mixture of DMAPA and CHCl 3. Intermediate 83 is exposed to the mixture at a temperature of about 30 ° C.-65 ° C., for example

RF-intermediates 85 can be prepared. As another example, reagent 84 may comprise a mixture of 2-aminoacetic acid and CHCl ₃ and intermediate 83 is exposed to the mixture at a temperature between about 30 ° C.-65 ° C.

R _F -intermediate 85 such as can be prepared. Reagent 84 may also include a mixture of 2- (methylamino) acetic acid and CHCl ₃ and intermediate 83 is exposed to the mixture at a temperature between about 30 ° C.-65 ° C.

Intermediate 85 such as can be prepared.

Intermediate 85 is then betained with an acetate reagent such as, for example, sodium monochloroacetate, in a reactor 82, as described below in a representative reaction sequence 30, and described as R _F -surfactant (87). ), Such as a positive R _F -surfactant R _F -SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ (CH ₂ CO ₂ Na).

Sulfonamide may be dissolved in sufficient anhydrous ethanol to provide a 40% (wt / wt) solution. The same molar amount of sodium monochloroacetate can be added to reactor 82 containing a 40% (wt / wt) solution to form a mixture. The mixture can then be refluxed for 8 hours and then sampled and titrated against free OH-. If OH- is greater than 1.5 x 10 ^-3 eq., The mixture is refluxed and reanalyzed for additional time. This sequence can be repeated until free OH is less than 1.5 × 10 ⁻³ eq. If there is no decrease in OH ⁻ in two subsequent samplings, additional sodium monochloroacetate can be added and the amount is calculated as the amount needed to lower OH ⁻ to a value of less than 1.5 × 10 ⁻³ eq. By-product NaCl can be filtered and sufficient water added to provide a solution that can be poured at ambient temperature.

과 같은 중간체 (85)를 시약(86)에 노출되어 R_F-계면활성제 (87)를 형성하도록 구성될 수 있다. 대표적인 구체예에 따르면, 시약(86)은

과 에탄올의 혼합물을 포함할 수 있다. Reactor 82

Such an intermediate 85 may be configured to expose the reagent 86 to form an R _F -surfactant 87. According to an exemplary embodiment, the reagent 86 is

And a mixture of ethanol.

와 같은 R_F- 계면활성제(87)를 제조하는 동안 중간체(83)은 혼합물에 노출될 수 있다.The mixture is refluxed, for example

Intermediate 83 may be exposed to the mixture while preparing R _F -surfactant 87, such as.

과 같은 중간체(83)의 혼합물을 포함할 수 있고, 예를 들어, 약 35℃ 의 온도에서 혼합물에 노출되어

과 같은 R_F-계면활성제(87)를 제조할 수 있다. 시약(86)은 1-(클로로메틸) 벤젠, 및 EMI54.6과 같은 중간체 (85)를 포함할 수 있고, 1-(클로로메틸) 벤젠에 노출시켜

와 같은 R_F-계면활성제(87)를 제조할 수 있다. As another example, the reagent 86 may be mixed with 50% (wt / wt) H ₂ 0 ₂ / H ₂ 0.

A mixture of intermediates 83, such as, for example, exposed to the mixture at a temperature of about 35 ° C

R _F -surfactant (87) such as can be prepared. Reagent 86 may include 1- (chloromethyl) benzene, and intermediates 85 such as EMI54.6, and may be exposed to 1- (chloromethyl) benzene

R _F -surfactant (87) such as can be prepared.

According to another embodiment, the reagent 86 is 1- (bromomethyl) benzene, and

과 같은 중간체(85)를 포함할 수 있고, 1-(브로모메틸) 벤젠에 노출되어

와 같은 R_F-계면활성제 (87)를 생산할 수 있다. 또다른 예로서, 시약(86)은 브로모메테인 및

Intermediate 85, such as, and exposed to 1- (bromomethyl) benzene

Such as R _F -surfactant (87) can be produced. As another example, reagent 86 may comprise bromomethane and

와 같은 중간체(85)를 포함할 수 있고, 브로모메테인에 노출되어

Intermediate 85, such as, and exposed to bromomethane

와 같은 R_F-계면활성제(87)를 제조할 수 있다.

R _F -surfactant (87) such as can be prepared.

Reagent 86 also contains chloromethane and

와 같은 중간체(85)를 포함할 수 있고

May comprise an intermediate 85 such as

와 같은 R_F-계면활성제(87)를 제조할 수 있다. Exposed to chloromethane

R _F -surfactant (87) such as can be prepared.

와 같은 중간체(85)를 포함할 수 있고,According to another embodiment, the reagent 86 is also combined with a basic solution such as NaOH.

May comprise an intermediate 85 such as

Exposed to solution

과 같은 R_F-계면활성제(87)를 제조할 수 있다.

R _F -surfactant (87) such as can be prepared.

Systems 70 and 80 were combined in order to produce an R _F -surfactant according to the following schematics (31)-(45). Where LC / MS can be used to identify the compound, Table 5 of the following LC / MS parameters can be used.

According to the schematic (31) above, a mixture of 1,1, 1, 2-tetrafluoro-4-iodo-2-trifluoromethyl-butane (100 grams) and potassium thiocyanate (39 grams) It can be dissolved in 55 mL of ethanol and 1 mL of acetic acid and heated to reflux, where it can be refluxed for several days. The mixture can be cooled to room temperature and concentrated to dryness under vacuum. Deionized water (100 mL) can be added to the dry solid and the resulting oil is decanted and 1,1, 1, 2-tetrafluoro-4- thiocyanate-2-trifluoromethyl- by NMR analysis. Butane (69.9 grams, 88.4%).

A mixture of 1,1, 1, 2-tetrafluoro-4-thiocyanate-2-trifluoromethyl-butane (25.5 grams) in 25 mL acetic acid containing 2 mL of water was intermittent It may be sparged with chlorine gas for several days at 40 ° C. with heating to form a heterogeneous mixture. The mixture can be cooled to room temperature and diluted with chloroform (50 mL). The organic portion can be washed twice with water, dried over sodium sulphate, filtered and concentrated in vacuo. The resulting yellow oil may contain large amounts of residual acetic acid by NMR analysis. The yellow oil can be dissolved in chloroform and washed twice with water (25 mL / each), dried over sodium sulfate, filtered and concentrated in vacuo and 4,4, 4, 3-tetrafluoro-4 by NMR analysis Trifluoromethyl-butanesulfonyl chloride (23.8 grams, 80%).

4,4, 4, 3-tetrafluoro-4-trifluoromethyl-butanesulfonyl chloride (23.8 grams) is dissolved in 50 mL of ether and dimethylaminopropylamine (8.2 g) over 20 minutes at ambient And 11.2 mL of a solution of triethylamine (TEA) can be added dropwise to form a mixture. The mixture can be partitioned between ethyl acetate (100 mL) and water (150 mL). The organic layer can be separated and washed with saturated bicarbonate solution (50 mL) and brine (50 mL), dried over sodium sulphate, filtered and concentrated to a yellow semi solid under vacuum. NMR and LC / MS analysis may indicate that the yellow semisolid can be a mixture of mono and bis sulfonate materials. The semi solid is powdered in hexane, and the filtered solid is 3,4, 4, 4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) by NMR analysis. ) -Amide (9.9 grams).

를 수득할 수 있다. 생성물을 60 ℃ 및 0.1 Torr에서 Kugelrohr에 놓고 엷은 황색 발포 유사 고체 (10 그램, 84%)를 수득할 수 있다. 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) -amide (10 grams) contains 50 grams containing 3.2 grams of sodium chloroacetate. It can be dissolved in mL of ethanol to form a mixture and refluxed overnight. The mixture is filtered, concentrated in vacuo, distilled twice with chloroform by NMR analysis

Can be obtained. The product can be placed in Kugelrohr at 60 ° C. and 0.1 Torr to give a pale yellow foaming like solid (10 grams, 84%).

20 mL of 3,4, 4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) -amide (9 g) according to the schematic diagram (32) above It can be dissolved in ethanol and 3.5 mL of water and treated with 5.9 mL of 50% (wt / wt) hydrogen peroxide. The resulting mixture can be heated to 35 ° C. overnight and the reaction can be determined to be complete by LC / MS analysis.

로 확인될 수 있다. 백색 고체는 Kugelrohr에서 45℃ 및 0.1 Torr에서 건조되어 NMR 분석에 의해 8.7 그램 (92%) 생성물을 제공할 수 있다.Nolet, bleached carbon (4 grams) can be added to the mixture, stirred for 30 minutes and filtered through celite. Additional carbon (4 grams) was added, the mixture was heated to 50 ° C., filtered again through the heated mixture celite, the resulting filter cake washed with ethanol and the combined filtrates concentrated in vacuo to a white solid. You can leave White solids were analyzed by NMR and LC / MS analysis.

It can be confirmed as. The white solid can be dried at 45 ° C. and 0.1 Torr in Kugelrohr to give 8.7 grams (92%) product by NMR analysis.

를 수득할 수 있다. According to the schematic (33) above, 5.0 grams of 3,4, 4, 4-tetrafluoro-3-trifluoromethyl butane-1-sulfonic acid- (3-dimethylamino-propyl) amide are stirred bar, reflux Dissolve in 15 mL of t-butyl methyl ether in a three-necked, 100 mL round bottom flask equipped with a condenser and thermocouple. 1.75 grams of benzyl chloride can be added to the flask to form a mixture and the mixture can be heated to reflux (56 ° C.) and stirred. White precipitate can form when the temperature reaches 56 ° C. The mixture can be cooled to room temperature after 3 hours. The solids can be collected by filtration, washed with chloroform and air dried to find 2.83 grams of NMR.

Can be obtained.

을 수득할 수 있다. According to the schematic (34) above, 5.0 grams of 3,4, 4, 4-tetrafluoro-3-trifluoromethylbutane-1-sulfonic acid- (3-dimethylamino-propyl) amide were stirred in a stir bar, reflux It can be dissolved in 15.0 mL of t-butyl methyl ether in a three-necked, 100 mL round bottom flask equipped with a condenser and thermocouple. Benzyl bromide (2.36 grams) can be added to the flask to form a mixture and the mixture can be heated to reflux (56 ° C.) and stirred for 2 hours. White precipitate can form when the temperature of the mixture reaches 56 ° C. The mixture may be too thick for 2 hours and unable to stir. The mixture can be cooled to room temperature and the solids collected by filtration and dried in a vacuum oven overnight at 45 ° C. to 6.24 grams (99.6%) by NMR.

Can be obtained.

으로 확인될 수 있다. Teflon lined cap of 10.0 grams of 3,4, 4, 4-tetrafluoro-3-trifluoromethyl butane-1-sulfonic acid- (3-dimethylamino-propyl) amide according to schematic diagram 35 above The mixture can be formed by dissolving in 13.8 mL of a 2.0 M solution of bromomethane in diethyl ether in a 25 × 250 mm culture tube with. The mixture can be heated to 45 ° C. for 4 hours to form a thick precipitate. The mixture can be cooled to room temperature and dried under vacuum and solid collected by filtration to give a white solid which is 7.46 grams (59.9%) by LC / MS

It can be confirmed.

According to the schematic (36) above, 5.0 grams of 3,4, 4, 4-tetrafluoro-3-trifluoromethyl butane-1-sulfonic acid- (3-dimethylamino-propyl) amide were added to a stirring bar, reflux The mixture can be formed by dissolving in 13.8 mL of a 1.OM solution of chloromethane in t-butyl methyl ether in a three-necked, 100 mL round bottom flask equipped with a condenser and thermocouple. The mixture is heated to reflux (56 ° C.) and stirred for 4 hours to form a heavier precipitate which is filtered to give 0.56 grams of

을 수득하고 이것을 NMR에 의해 확인할 수 있다. R_F-계면활성제는 또한 하기 개략도 (37)에 따라 제조될 수 있다

Can be obtained and confirmed by NMR. R _F -surfactants may also be prepared according to the following schematic (37).

According to the schematic (38) above, 9.68 grams of glycine benzyl ester hydrochloride can be partitioned between 100 mL of methylene chloride and 200 mL of 1: 1 solution of 15% (wt / wt) aqueous sodium carbonate and saline. The layers can be separated and the bottom organic layer can be washed with 200 mL of a 1: 1 solution of 15% (wt / wt) aqueous sodium carbonate and brine. The layers can be separated again, dried over organic sodium sulfate, filtered and concentrated in vacuo to yield 5.42 grams (68.3%) of a light yellow oil identified as benzyl glycinate by NMR.

A solution of 5.421 grams of benzyl glycinate as demonstrated above in 15.0 mL of methylene chloride in a three-necked, 100 mL round bottom flask with a stir bar, addition funnel with nitrogen inlet and thermocouple was prepared at 0 ° C- in an ice bath. Can be cooled to 5 ° C. Another solution of 4.75 grams of 3,4, 4,4-tetrafluoro-3-trifluoromethylbutane-1-sulfonyl chloride as demonstrated above in 15.0 mL of methylene chloride was added at reaction temperature < The mixture may be added dropwise under nitrogen at a rate to maintain 5 ° C., (15 min., T max = 3.5 ° C.). The mixture can be stirred at <5 ° C. for 1 hour. The mixture can be filtered and the solid can be washed three times with 25 mL of methylene chloride. The solid can be identified by NMR as 3,4, 4,4-tetrafluoro-3-trifluoromethyl-1-butane-sulfonylamino) -acetic acid benzyl ester.

으로 확인될 수 있다. 3,4,4,4-tetrafluoro-3-trifluoromethyl-1-butane sulfonylamino) -acetic acid benzyl ester (1.0 grams) can be dissolved in 10 mL of ethanol in a 250 mL Parr bottle . Palladium on carbon (10% (wt / wt), 50% (wt / wt) water Degussa type E101, 0.2 grams), can be added to the bottle to form a mixture. The bottle was placed in a Parr shaker at 418 kPa and shaken overnight. The mixture can be sparged with nitrogen and filtered through a thin pad of celite. Rinse the celite three times with 20 mL of ethanol and 1.18 mL of aqueous 2N sodium hydroxide solution can be added to the combined filtrate and stirred. The filtrate was concentrated in vacuo and dried to afford 0.803 grams (95.7%) of white solid desired product which was obtained by NMR.

It can be confirmed.

According to the schematic (39) above, sarcosine ethyl ester hydrochloride (7.68 grams) was partitioned between 100 mL of methylene chloride and 200 mL of 15% (wt / wt) aqueous sodium carbonate and 1: 1 solution of saline. Can be. The layers can be separated and the bottom organic layer can be washed with 200 mL of a 1: 1 solution of 15% (wt / wt) aqueous sodium carbonate and brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to yield 5.45 grams (93.0%) of a colorless oil which could be identified as sarcosine ethyl ester by NMR.

3.45 grams of a solution of sarcosine ethyl ester in 20.0 mL of methylene chloride in a 3-necked, 100 mL round bottom flask with a nitrogen inlet, and a thermocouple with a stir bar, addition funnel, was cooled to 0 ° C.-5 ° C. in an ice bath. You can. A solution of 6.91 grams of 3,4, 4,4-tetrafluoro-3-trifluoromethyl butane-1-sulfonyl chloride as described above in 20.0 mL of methylene chloride is added and the reaction temperature <5 The mixture may be added dropwise under nitrogen at a rate to maintain C, (45 min., T _max = 2.1 ° C.). The mixture can be stirred for 3 h at <5 ° C. (Tmax = 3.7 ° C.) and washed twice with 20 mL of 5% (wt / wt) aqueous HCl solution and once with brine. The organic layer was recovered, dried over sodium sulfate, filtered and concentrated in vacuo to yield 7.78 grams of a light yellow oil which was placed on Kugelrohr and heated to 50 ° C., 0.01 Torr to remove low boiling impurities and [Methyl- It can be identified as (3, 4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonyl) -amino] -acet ethyl ester (> 96%).

A solution of 6.8 grams of [methyl- (3, 4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonyl) -amino] -acet ethyl ester in 25.0 mL of ethanol The mixture can be formed by treating with 1 equivalent of 2N sodium hydroxide (9.OmL) in a single sphere, 100mL round bottom flask. The mixture was stirred at rt overnight, concentrated in vacuo, placed in Kugelrohr for 30 min at 50 ° C., 0.01 Torr and 6.21 grams by NMR.

을 수득할 수 있다.

Can be obtained.

을 수득할 수 있다. According to the schematic 40, a solution of (876 grams) and potassium thiocyanate (255 grams) prepared according to the schematic 24 is dissolved in ethanol (880 mL) and acetic acid (35 mL) and heated to reflux, It can then be refluxed for about 2.5 hours to form a heterogeneous mixture which can be cooled to room temperature and concentrated to a yellow semi-solid under vacuum. The semi-solid can be partitioned between methylene chloride (1 L) and deionized water (1 L) and the aqueous phase is extracted with methylene chloride (500 mL) and the organic layers combined, dried over magnesium sulfate, filtered and yellow under vacuum Concentrate to oil. Yellow oil was briefly placed in Kugelrohr at room temperature and 0.1 Torr and 97% of 828.3 grams (99.3%) by NMR

Can be obtained.

(828.3 그램)은 아세트산 (828mL)에 용해하여 혼합물을 형성할 수 있다. 혼합물은 33mL 탈이온수로 처리하고 염소로 살포하고 물의 추가 처리와 함께 40℃로 밤새 가열할 수 있다. 혼합물의 온도는 50℃로 증가될 수 있고 염소 살포와 함께 추가의 몇일동안 계속해서 가열하여 대략 80% 완료를 달성될 수 있다. 혼합물을 실온으로 냉각될 수 있고 염화메틸렌 (2L) 및 탈이온수 (2L)를 사용하여 식힐 수 있다. 유기층을 탈이온수 (1L 각각)로 세번 세척할 수 있다. 유기층은 그후 황산 마그네슘 위에서 밤새 건조할 수 있다. 건조된 유기 층을 여과할 수 있고 진공하에서 무색의 오일 (862.4 그램)로 농축시키고, 오일을 아세트산(850mL)중에 용해하여 혼합물을 형성할 수 있다. 이 혼합물을 염소 살포와함께 50℃ 로 가열할 수 있고, 일단 반응이 50℃에 도달하면 탈이온수 (33mL)을 첨가할 수 있다. 혼합물은 실온으로 냉각시키고 염화메틸렌 (2L) 및 탈이온수 (1L)를 사용하여 식힐 수 있다. 유기층을 탈이온수(1L 각각)로 세번 세척할 수 있고 그후 황산 마그네슘 위에서 밤새 건조할 수 있다. 건조된 유기 층을 여과할 수 있고 진공하에서 무색의 오일로(859.6 그램, 95.4%) 농축시킬 수 있고 NMR 및 가스 크로마토그래피 분석은 (97%, 면적 퍼센트)

을 나타낼 수 있다.

(828.3 grams) may be dissolved in acetic acid (828 mL) to form a mixture. The mixture can be treated with 33 mL deionized water, sparged with chlorine and heated to 40 ° C. overnight with further treatment of water. The temperature of the mixture can be increased to 50 ° C. and approximately 80% complete can be achieved by continuing heating for additional days with chlorine sparging. The mixture can be cooled to room temperature and cooled using methylene chloride (2 L) and deionized water (2 L). The organic layer can be washed three times with deionized water (1 L each). The organic layer can then be dried over magnesium sulfate overnight. The dried organic layer can be filtered and concentrated in vacuo to a colorless oil (862.4 grams) and the oil can be dissolved in acetic acid (850 mL) to form a mixture. The mixture can be heated to 50 ° C. with chlorine sparging and deionized water (33 mL) can be added once the reaction reaches 50 ° C. The mixture can be cooled to room temperature and cooled using methylene chloride (2 L) and deionized water (1 L). The organic layer can be washed three times with deionized water (1 L each) and then dried over magnesium sulfate overnight. The dried organic layer can be filtered and concentrated in vacuo to a colorless oil (859.6 grams, 95.4%) and NMR and gas chromatography analysis (97%, area percent)

Can be represented.

Dimethylaminopropylamine (568 mL) and chloroform (4 L) were combined to form a mixture and cooled to 0 ° C. using an ice / acetone bath and

(839 그램)을 클로로포름 (4L)에 용해하고 혼합물에 4시간에 걸쳐 적가하고 온도 < 0℃에서 혼합물을 유지할 수 있다. 반응은 한 시간 적가후에 완료되어 황색 용액을 형성할 수 있다. 균질 황색 반응 용액은 포화된 중탄산염 (8L), 탈이온수 (8L), 및 식염수 (8L)으로 세척하고 유기층 황산 마그네슘 위에서 건조하여, 여과하고, 진공에서 백색 고체로 농축시킬 수 있다. 백색 고체를 1시간동안 진공하에서 35℃에서 건조하여 NMR에 의해 899.7(95.2%, 영역 퍼센트)의

(839 grams) can be dissolved in chloroform (4 L) and added dropwise to the mixture over 4 hours and the mixture is maintained at a temperature <0 ° C. The reaction can be completed after one hour dropping to form a yellow solution. The homogeneous yellow reaction solution can be washed with saturated bicarbonate (8 L), deionized water (8 L), and brine (8 L) and dried over organic layer magnesium sulfate, filtered and concentrated to a white solid in vacuo. The white solid was dried at 35 ° C. under vacuum for 1 hour to give 899.7 (95.2%, area percent) by NMR.

를 수득할 수 있다.

Can be obtained.

(600 그램)을 50% (wt/wt) 과산화수소(241 mL)와 함께 에탄올 (820mL) 및 물(130mL)에 용해하여 혼합물을 형성하고 35℃로 가열할 수 있다. t_max=49.3℃를 갖는 발열이 관찰될 수 있다. 반응이 NMR 분석에 의해 결정될때, 혼합물을 가열한 후 한 시간에 완료될 수 있지만, LC/MS 분석에 의하면 미량의 출발 재료가 관찰될 수 있다. 혼합물을 35℃에서 2시간동안 다시 가열하여 반응을 완료할 수 있다. 탈색 카본 (135 그램) 및 에탄올 (820mL)을 혼합물에 부분으로 나누어 첨가할 수 있고 혼합물을 50℃로 가열할 수 있다. 발열이 관찰될 수 있다. 혼합물을 주위 온도에서 밤새 교반시킬 수 있다. 반응을 KI 전분 테스트 스트립을 사용하여 과산화물에 대해서 테스트할 수 있고, 만일 포지티브라면, 혼합물을 50℃까지 1.5 시간동안 또는 네거티브가 될 때까지 가열할 수 있다. 혼합물을 그후 셀라이트를 통해 여과할 수 있고 셀라이트 패드를 1L 에탄올을 사용하여 세척하였다. 여과액은 백색 고체로 농축시킬 수 있고 백색 고체는 30 분동안 0.1 Torr 및 50℃에서 Kugelrohr에 놓는다. 백색 고체는 그후 50℃에서 4시간동안 진공하에서 건조하여 NMR 및/또는 LC/MS에 의해 593.8 그램 (96.6%)의 6,7, 7,7-테트라플루오로-4-(2,3,3,3-테트라플루오로-2-트리플루오로메틸-프로필)-6-트리플루오로메틸-헵탄-1-술포닐 아민을 수득할 수 있다.

(600 grams) may be dissolved in 50% (wt / wt) hydrogen peroxide (241 mL) in ethanol (820 mL) and water (130 mL) to form a mixture and heated to 35 ° C. An exotherm with t _max = 49.3 ° C. can be observed. When the reaction is determined by NMR analysis, it can be completed one hour after heating the mixture, but traces of starting material can be observed by LC / MS analysis. The mixture can be heated again at 35 ° C. for 2 hours to complete the reaction. Decolorized carbon (135 grams) and ethanol (820 mL) can be added in portions to the mixture and the mixture can be heated to 50 ° C. Exotherm may be observed. The mixture can be stirred overnight at ambient temperature. The reaction can be tested for peroxide using a KI starch test strip, and if positive, the mixture can be heated to 50 ° C. for 1.5 hours or until it is negative. The mixture can then be filtered through celite and the celite pad washed with 1 L ethanol. The filtrate can be concentrated to a white solid and the white solid is placed in Kugelrohr at 0.1 Torr and 50 ° C. for 30 minutes. The white solid was then dried under vacuum at 50 ° C. for 4 hours to give 593.8 grams (96.6%) of 6,7, 7,7-tetrafluoro-4- (2,3,3) by NMR and / or LC / MS. , 3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptane-1-sulfonyl amine can be obtained.

을 수득할 수 있다. 6,7, 7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptan-1-sulfonyl Amine (319 grams), ethanol (1290 mL), and sodium chloroacetate (63.5 grams) were combined to form a mixture and the mixture was refluxed for 48 hours. After 48 hours, NMR analysis may indicate that no starting material is present, but LC / MS analysis may show product ions. The mixture can be filtered and the filter cake can be washed with ethanol (1 L). The filtrate can be concentrated in vacuo with an orange blowing agent and the orange blowing agent placed on Kugelrohr for 1 hour at 0.1 Torr and 50 ° C. Orange foam-like solids were dried overnight under vacuum at 50 ° C. to 344.4 grams (98.2%) as evidenced by NMR.

Can be obtained.

According to the schematic diagram 41, 6,7, 7,7-tetrafluoro-4- (2,3, 3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoro Methyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.2 grams) can be dissolved in 25 mL of ethanol containing 1.23 grams of sodium chloroacetate to form a solution. The solution can be heated to reflux and refluxed overnight. After refluxing for approximately 2 days, the solution can be cooled, filtered and the solvent of the filtrate can be removed overnight in vacuo (50 ° C., 1 Torr). Remaining solids are determined by NMR

으로서 확인될 수 있다.

Can be identified as

With reference to schematic 42 above, 6,7, 7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl described above in 125 mL dichloromethane A solution of -propyl) -6-trifluoromethyl heptane-1-sulfonyl chloride (25 grams) was added to a cooled solution of ethanolamine (17.6 grams) in dichloromethane (125 mL) (0 ° C.-5 ° C.) Mixtures may be formed. The mixture can be stirred, warmed to room temperature and diluted with dichloromethane (250 mL). The diluted mixture can be washed with deionized water (250 mL), 5% (wt / wt) HCl (250 mL), and saturated bicarbonate solution (250 mL). The organic layer was separated, dried over sodium sulphate, filtered and concentrated in vacuo, followed by NMR analysis with 6,7, 7,7-tetrafluoro-4- (2, 3,3, 3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptane-1-sulfonic acid (2-hydroxy-ethyl) -amide (5.0 grams) can be provided.

6,7, 7,7-tetrafluoro-4- (2, 3,3, 3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptane-1-sulfonic acid ( A solution of 2-hydroxy-ethyl) -amide (5.0 grams) and 2-chloro- [1,3,2] dioxaphospholane-2-oxide (0.87 mL) was dissolved in anhydrous ether (30 mL) and iced / The bath can be used to cool to 0 ° C. Triethylamine (0.55 mL) can be added dropwise to the solution to form a white precipitate. The solution can be warmed to room temperature, filtered and concentrated in vacuo. It can be seen that the reaction decomposes after 6 hours. The bulk solution can be filtered and concentrated in vacuo to yellow oil (3. 3 grams) and this is determined by NMR and / or LC / MS analysis.

You can check with

According to the schematic diagram 43, 5-bromo-1,1,1,2-tetrafluoro-2-trifluoromethyl-pentane (25 grams) is dissolved in 25 mL of ethanol and 0.2 mL of acetic acid. And 10.9 grams potassium thiocyanate can be added to form a mixture. The mixture can be heated to reflux and cooled to room temperature after about 1 to 2.5 hours and concentrated in vacuo. The condensate can be partitioned between methylene chloride (100 mL) and water (50 mL). The aqueous phase is extracted with methylene chloride (50 mL), the organic layers combined, dried over magnesium sulfate, filtered and concentrated in vacuo to give a yellow oil which is determined by NMR analysis of 1,1, 1,2-tetrafluoro Rho-5-thiocyanato-2-trifluoromethyl-pentane (21.7 grams, 93.9%).

1,1,1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane is dissolved in 10 mL of acetic acid and 0.4 mL of water, heated to 40 ° C. and sparged with chlorine. Can be. Every two hours three additional water (.4 mL) treatments can be added and a bright temperature exotherm is noted after each addition. The mixture may be sparged and additional water treatment may be added for several days resulting in an exogenous mixture. The heterogeneous mixture can be partitioned between methylene chloride (100 mL) and water (25 mL), dried over organic magnesium sulfate, filtered and concentrated in vacuo. NMR analysis may reveal 7. 1 gram (74.1%) of 4,5, 5, 5-tetrafluoro-4-trifluoromethyl-pentanesulfonyl chloride.

4,5, 5, 5-tetrafluoro-4-trifluoromethyl-pentanesulfonyl chloride (7.1 grams) was dissolved in 40 mL of chloroform and 8.6 mL of 3-dimethylaminopropyl in 40 mL of chloroform. To the solution of amine can be added dropwise at 0 ° C-5 ° C over 45 minutes (Tmax = 5 ° C) to form a mixture. The mixture can be washed successively with saturated bicarbonate solution (80 mL), water (80 mL), and brine (80 mL). The organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuo to give 8 grams (93%) of 4,5,515-tetrafluoro-4-trifluoromethyl-pentane by NMR and LC / MS analysis. -1-sulfonic acid (3-dimethylamino-propyl) -amide may be provided.

4,5, 5, 5-tetrafluoro-4-trifluoromethyl-pentane-1-sulfonic acid (3-dimethylamino-propyl) -amide (8 grams) was added to 3 mL of water and 5.1 mL of 50% It can be dissolved in 25 mL of ethanol containing (wt / wt) hydrogen peroxide and the resulting solution can be heated at 35 ° C. for 30 minutes. The reaction can then be cooled to room temperature overnight. Nolet, bleached carbon (10 grams) and ethanol (20 mL) can be added and the mixture can be heated to 50 ° C. for 3 hours. The mixture can be filtered through celite and the filter cake washed with 90% (wt / wt) ethanol / 10% (wt / wt) water (60 mL), the filtrate was concentrated in vacuo and distilled with methanol And 7.1 grams (89.9%) by NMR and LCMS analysis by Kugelrohr

Can be provided.

1.9 g of 4,5, 5, 5-tetrafluoro-4-trifluoromethyl-pentane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 g) according to the schematic diagram 44 above It can be dissolved in 25 mL of ethanol containing sodium chloroacetate. The resulting solution can be heated to reflux and refluxed for two consecutive nights. After reflux for approximately 45 hours, the reaction is stopped, filtered, the salt is rinsed and discarded and the solvent in the filtrate is removed by NMR.

(3.6 grams).

According to the schematic (45) above, 8-bromo-1,1,1,2-tetrafluoro-2-trifluoromethyl-octane (20 grams) containing 7.6 grams potassium thiocyanate 30 Soluble in mL of ethanol. Acetic acid (0.2 mL) can be added to form a mixture and the mixture can be heated to reflux for 4 hours. The mixture can be cooled to room temperature overnight, concentrated in vacuo and partitioned between methylene chloride (200 mL) and water (100 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo to give 18.2 grams (97%) 1,1, 1, 2-tetrafluoro-8- thiocyanato-2-trifluoromethyl- by NMR analysis. Octane may be provided.

Dissolve 1,1,1,2-tetrafluoro-8-thiocyanato-2-trifluoromethyl-octane (18.2 grams) in 25 mL of acetic acid to form a mixture and form the mixture with chlorine sparge 40 Heating to ° C. Initially, 0.8 mL of water can be added to the mixture. 3 Additional water treatment (0.8 mL / each) can be added to the mixture every 2 hours, heated with chlorine sparging continued overnight and an additional 0.8 mL of water is added, the mixture is cooled and methylene chloride (200 mL) and water Can be divided between (100 mL). The aqueous layer can be extracted with methylene chloride (100 mL). The organic layers were combined, washed three times with water (100 mL / each), dried over magnesium sulfate, filtered and concentrated to 19.5 grams (94.5%) of 7,8,8,8-tetrafluoro by NMR analysis. -7-trifluoromethyl-octanesulfonyl chloride can be obtained.

7,8,8,8-tetrafluoro-7-trifluoromethyl-octanesulfonyl chloride (19.5 grams) is dissolved in 100 mL of chloroform and 100 mL of chloroform over 1 hour at 0 ° C.-5 C. To 20.9 mL of dimethylaminopropylamine in water to form a mixture. When the addition is complete, the mixture can be warmed to room temperature and stirred for 1 hour at ambient. The mixture can be washed twice with saturated bicarbonate solution (100 mL / each), deionized water (200 mL), and brine (200 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo to afford a yellow oil which was obtained by NMR with 7,8, 8,8-tetrafluoro-7-trifluoromethyl-octane-1-sulfonic acid ( 3-dimethylamino-propyl) -amide (24.09 grams, 95.97%).

7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7 grams) is 2.3 mL of water and 4.0 mL of 50% It can be dissolved in 25 mL of ethanol containing (wt / wt) hydrogen peroxide and the resulting solution can be heated at 35 ° C. overnight. Decolorized carbon (8 grams) and ethanol (15 mL) can be added to the solution and the solution is heated to 50 ° C. for 3 hours. The solution can then be cooled to room temperature, filtered through celite, the filter cake washed with 90% (wt / wt) ethanol / deionized water (50 mL) and concentrated to a waxy solid under filtrate vacuum. Can be. The solid was distilled twice with ethanol to give a yellow oil which was added to Kugelrohr for 2 hours at 40 ° C. and 0.1 Torr of white solid (5.9 grams, 79.9%) by NMR analysis.

Can be obtained.

According to the schematic (46) above, 1.6 grams of 7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 grams) Soluble in 25 mL ethanol containing sodium chloroacetate. The resulting solution can be heated to reflux, refluxed and stirred over 40 hours. The solution can be cooled, filtered, the solvent removed and placed in the resulting solid drying oven (50 ° C., 1 Torr) overnight. Remaining solids are determined by NMR

Can be identified as

According to the schematic diagram 47, 2- (3-bromo-propoxy) -1, 1,1, 3,3,3-hexafluoro-propane (19 grams) and potassium thiocyanate (8.3 grams) ) Can be dissolved in 30 mL of ethanol containing 0.2 mL of acetic acid and heated to reflux. After 2.5 hours at reflux, the reaction mixture can be cooled to room temperature and concentrated to a semi solid under vacuum. The semi solid can be partitioned between ether (100 mL) and deionized water (100 mL). The organic layer can be dried over sodium sulphate, filtered and concentrated in vacuo to afford a yellow oil (16.88 grams, 90.3%). Yellow oil can be identified as 1, 1, 1,3, 3,3-hexafluoro-2- (3-thiocyanato-propoxy) -propane by NMR.

The mixture was dissolved by dissolving 1,1,1,3,3,3-hexafluoro-2- (3-thiocyanato-propoxy) -propane (16.9 grams) in 30 mL of acetic acid and 0.8 mL of water. Can be formed. The mixture can be heated to 40 ° C. and sparged with chlorine. The mixture can then be treated three times with deionized water (0.8 mL) every 2 hours and the mixture can be heated to 40 ° C. for about 48 hours under chlorine sparging. The mixture was cooled to room temperature, partitioned between methylene chloride (100 mL) and deionized water (100 mL), the organic layer was separated and washed three times with deionized water (100 mL / each), dried over magnesium sulfate, filtered and NMR Can be concentrated under vacuum to a colorless oil 3- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonyl chloride (18.4 grams, 99.3%). have.

3- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonyl chloride (18.4 grams) is dissolved in 100 mL of chloroform and 0 ° C. over 1 hour. It can be added to 22.5 mL of dimethylaminopropylamine in 100 mL of chloroform at −5 ° C. to form a mixture. When the addition is complete the mixture can be warmed to room temperature and stirred for 1 hour at ambient. The mixture can be washed with saturated bicarbonate solution (200 mL), deionized water (200 mL), and brine (200 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo to afford a yellow oil which was placed at Kugelrohr for 15 min at ambient temperature and 0.1 Torr and was subjected to 3- (2,2,2-trifluoro-1 by NMR. Trifluoromethyl-ethoxy) -propane-1-sulfonic acid (3-dimethylamino-propyl) -amide (20.88 g (92.8%)) can be obtained.

3- (2, 2, 2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonic acid (3dimethylamino-propyl) -amide (7 grams) in 2.6 mL of water and 4.4 It can be dissolved in 25 mL of ethanol containing 50% (wt / wt) hydrogen peroxide to form a mixture and the mixture can be heated at 35 ° C. overnight. Decolorized carbon (8 grams) and ethanol (15 mL) can be added to the mixture, the mixture is heated to 50 ° C. for 3 hours, filtered through celite and the filter cake 90% (wt / wt) ethanol / water (50 mL) and the filtrate can be concentrated in vacuo to yield a white semi-solid. The solid was refluxed twice in ethanol before being added to Kugelrohr for 1 hour at 40 ° C. and 0.1 Torr by NMR.

(6.66 grams (90.0%)) can be obtained.

According to the schematic diagram 48 above, 3- (2, 2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 Gram) can be dissolved in 25 mL of ethanol containing 1.9 grams of sodium chloroacetate. The resulting solution can be refluxed and stirred for 40 hours, the reaction is cooled and filtered. Remove the solvent and place the resulting solid overnight in a drying oven (50 ° C, 1 Torr) by NMR

Can be obtained.

According to the schematic diagram 49, a solution of 3,5-bis (trifluoromethyl) benzyl bromide (25 g) and 11.9 grams potassium thiocyanate is dissolved in 40 mL of ethanol and 0.2 mL of acetic acid and Heated to reflux, refluxed for 3 hours, cooled to room temperature and concentrated in vacuo to yield a white solid. The solid can be partitioned between ether (150 mL) and deionized water (150 mL). The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to give 1,1, 1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (23.1 grams, 98.8) by NMR analysis. %) Can be obtained.

Dissolve 1,1, 1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (23.1 grams) in 33 mL acet and heat to 40 ° C. overnight with chlorine sparging to obtain a white precipitate. Can be obtained. The heterogeneous mixture can be cooled to room temperature and partitioned between deionized water (150 mL) and methylene chloride (150 mL). The organic layer is washed three times with deionized water (100 mL), dried over magnesium sulphate, filtered and concentrated in vacuo to give a white solid which can be placed in Kugelrohr at 0.1 Torr and at 40 ° C. for 30 minutes. NMR analysis can reveal 3,5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (18.52 grams, 70. 1%).

3, 5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (18.5 grams) is dissolved in 100 mL of chloroform and cooled to 0 ° C-5 ° C, then 20 mL of 3-dimethyl over 1 hour Aminopropylamine can be added dropwise to 100 mL of chloroform.

The mixture can be warmed to room temperature and stirred at ambient temperature for 3 hours. The reaction can then be washed with saturated bicarbonate solution (200 mL), deionized water (200 mL), and brine (200 mL). The organic layer can be separated, dried over magnesium sulfate and concentrated to a yellow solid (20.0 grams) under vacuum.

NMR analysis may indicate that the yellow oil is a 1: 1 mono and bis sulfonyl amine product.

According to the schematic 50 above, mono and bis sulfonyl amine starting materials (10 grams) can be dissolved in 30 mL ethanol, deionized water (3.7 mL) and 50% (wt / wt) hydrogen peroxide (4.7 mL). The heterogeneous mixture can be stirred at ambient temperature over 2 days and bleached carbon (7 grams) and ethanol (15 mL) can be added to the mixture. The mixture can be stirred at room temperature over 2 days, monitored for peroxide, filtered through bulk reaction celite, the filter cake washed with 90% (wt / wt) ethanol, water (50 mL), The filtrate can be concentrated in vacuo to afford a yellow solid (7.07 grams). Yellow solids can be identified as 1: 1 mono / bis products by NMR and / or LC / MS analysis.

According to the schematic diagram 51, a solution of 3,5-bis (trifluoromethyl) benzyl bromide (25 grams) and 11.9 grams potassium thiocyanate is suspended in 40 mL of ethanol and 0.2 mL of acetic acid and heated Reflux, reflux for 3 hours, cool to room temperature and then concentrate in vacuo to afford a white solid. The white solid can be partitioned between ether (100 mL) and deionized water (100 mL). The organic layer was separated, dried over sodium sulfate, filtered and concentrated in vacuo to give 1,1, 1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (22.58 grams, 96.6% ) Can be obtained, which can be confirmed by NMR.

1,1, 1, 2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (22.5 grams) can be dissolved in 32 mL acetic acid and heated to 50 ° C. overnight with chlorine sparging. . The reaction mixture is cooled to room temperature, partitioned between methylene chloride (100 mL) and deionized water (100 mL), and the organic layer is washed three times with deionized water (100 mL / each), dried over magnesium sulfate, filtered and under vacuum Concentration can yield a white solid of 3,5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (22.94 grams, 89.1%), which can be determined by NMR.

3, 5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (5 grams) is dissolved in 25 mL of chloroform and cooled (0) of 4.4 mL of 3-dimethylaminopropylamine in 25 mL of chloroform. ° C-5 ° C) can be added dropwise over 1 hour and then warmed to room temperature after the addition is complete. The homogeneous solution can be washed with saturated bicarbonate solution (50 mL), deionized water (50 mL), and brine (50 mL). The organic layer can be separated, dried over magnesium sulphate, filtered and concentrated in vacuo to yield a yellow solid (5.26 grams, 87.7%), which is analyzed by NMR analysis where 90% C- ( 3, 5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide.

According to the schematic (52) above, C- (3, 5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide (6 grams) was added to 20 mL of ethanol, It can be dissolved in deionized water (2.2 mL) and 50% (wt / wt) hydrogen peroxide (3.6 mL) and the heterogeneous mixture can be stirred overnight at ambient temperature. The mixture can then be cooled and bleached carbon (5 grams) and ethanol (1 5 mL) are added, heated to 50 ° C. for 2 hours, monitored for peroxides, cooled to room temperature and filtered through celite Can be. The filter cake was washed with 90% (wet) ethanol, 10% (wt / wt) water (50 mL) and the filtrate was concentrated in vacuo to give C- (3, 5-bis-trifluoromethyl- by NMR analysis. Phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide can be obtained.

Referring to the schematic diagram 53, C- (3, 5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide (2 grams) was added to ethanol (20 mL). ), And sodium chloroacetate (0.59 grams) and refluxed overnight, the reaction can be cooled to room temperature, filtered and the filtrate can be concentrated in vacuo to a white solid. The white solid can be placed in Kugelrohr at 0.1 Torr and at 50 ° C. for 1 hour to give 2.1 grams (91.3%) by NMR analysis.

를 그후 THF (70 mL)에 넣고 혼합물에 적가할 수 있다. 혼합물을 0℃에서 30분동안 교반하고, 그후 실온으로 데우고 1 시간동안 교반할 수 있다. 혼합물을 그후 40℃로 가열하고 밤새 교반하여 깨끗한 밝은 황갈색 용액을 형성하고, 이것은 소량의 부유된 고체 물질을 가질 수 있고, 이것은 HCl (5%(wt/wt), 135 mL)으로 pH=3까지 산성화시킬 수 있다. 고체를 pH=9에서 용액 안에 용해할 수 있고 혼합물은 깨끗한 황색으로 변했다. 2상 용액을 분리시키고, 수성 층을 유보해두고, 유기층을 Na₂SO₄ 위에서 건조하고, 여과하고, 용매를 제거할 수 있다. 결과의 황색 오일을 Kugelrohr(40℃, 0.1 Torr, 15 분)에 놓고 나머지 용매를 제거할 수 있다. 이종의 황색 오일(8.1 그램)의 ¹HNMR 분석은 출발 재료 및 PEG의 혼합물로서 확인될 수 있지만, LC/MS가 암시할 수 있듯이, 원하는 생성물은 아니다. 황색 오일은 Kugelrohr에서 증류되고 나머지는 NMR 및/또는 LC/MS에 의해 원하는 생성물 (1.8 그램)로 결정될 수 있다. Referring to the schematic diagram 54, a solution of polyethylene glycol (PEG) (12.01 grams) in THF (70 mL) was cooled (0 ° C.) in a nitrogen atmosphere and lithium bis (trimethylsilyl) amide (33.0 mL) was added to Mixtures may be formed. The mixture can be stirred at 0 ° C. for 15 minutes. R _F -Intermediate

Can then be added to THF (70 mL) and added dropwise to the mixture. The mixture can be stirred at 0 ° C. for 30 minutes, then warmed to room temperature and stirred for 1 hour. The mixture is then heated to 40 ° C. and stirred overnight to form a clean light tan solution, which may have a small amount of suspended solid material, which is pH = 3 with HCl (5% (wt / wt), 135 mL) It can be acidified. The solid could be dissolved in solution at pH = 9 and the mixture turned a clear yellow. The biphasic solution can be separated off and the aqueous layer left, the organic layer can be dried over Na ₂ SO ₄ , filtered and the solvent removed. The resulting yellow oil can be placed in Kugelrohr (40 ° C., 0.1 Torr, 15 minutes) to remove the remaining solvent. ¹ HNMR analysis of heterogeneous yellow oil (8.1 grams) can be identified as a mixture of starting material and PEG, but as LC / MS can suggest, this is not the desired product. The yellow oil can be distilled in Kugelrohr and the remainder can be determined by NMR and / or LC / MS to the desired product (1.8 grams).

는 에탄올 (25 mL)중의 티오유리아 (0.68 그램)와 조합될 수 있고 밤새 가열하여 환류될 수 있다. 22 시간의 환류 후에, 반응 시스템을 해체할 수 있고, 에탄올을 제거하고, 남아있는 오일을 Kugelrohr (0.01 mmHg, 20 min, 60℃)에 놓고 NMR 및/또는 LC/MS 분석에 의해 결정될 수 있는 7,8, 8,8-테트라플루오로-7-트리플루오로메틸-옥테인-1-티올 (3.4 그램)을 수득할 수 있다. Referring to the schematic diagram 55 above, the R _F -intermediate

Can be combined with thiouria (0.68 grams) in ethanol (25 mL) and heated to reflux overnight. After 22 hours of reflux, the reaction system can be disassembled, ethanol removed and the remaining oil placed in Kugelrohr (0.01 mmHg, 20 min, 60 ° C.) 7 which can be determined by NMR and / or LC / MS analysis. , 8, 8,8-tetrafluoro-7-trifluoromethyl-octane-1-thiol (3.4 grams) can be obtained.

7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-thiol can be placed in a flask, cooled to 0 ° C. and NaH (0.08 grams) added to form a mixture. The mixture can be cooled to -78 ° C, flushed with nitrogen, condensed in ethylene oxide (1.6 grams), warmed to room temperature and then placed in a 65 ° C oil bath overnight. Ethyl acetate (20 mL) and HCl (1N, 10 mL) can be added to the mixture, the layers can be separated, and the aqueous layer can be extracted with ethyl acetate (20 mL, 5 times). All organic layers were combined, dried over Na ₂ SO ₄ , filtered, solvent removed and the resulting brown oil (2.2 grams) can be characterized by LC / MS analysis.

칼륨 티오시아네이트 (8.7 그램), 에탄올 (40mL), 및 아세트산 (0.2mL)의 용액은 조합될 수 있고 환류시키고, 3시간동안 환류하고, 이종의 혼합물을 실온으로 냉각시키고 진공하에서 농축시켜 백색/황색 반-고체를 수득할 수 있다. 반-고체를 에테르(100mL)와 탈이온수(100mL) 사이에서 분할할 수 있다. 유기층을 분리시키고, 황산나트륨 위에서 건조시키고, 여과하고, 진공하에서 농축시켜 오렌지 오일 (21.19 그램, 97.2%)을 수득하고 이것은 NMR 및 가스 크로마토그래피 분석에 의해 1,1, 1,2-테트라플루오로-7-티오시아나토-2, 4-비스트리플루오로메틸-헵탄(> 95% 순수한)으로서 확인될 수 있다. With reference to the schematic diagram 56 above, the R _F -intermediate

A solution of potassium thiocyanate (8.7 grams), ethanol (40 mL), and acetic acid (0.2 mL) can be combined and refluxed, refluxed for 3 hours, the heterogeneous mixture cooled to room temperature and concentrated in vacuo to give white / A yellow semi-solid can be obtained. The semi-solid can be partitioned between ether (100 mL) and deionized water (100 mL). The organic layer was separated, dried over sodium sulphate, filtered and concentrated in vacuo to give an orange oil (21.19 grams, 97.2%), which was analyzed by NMR and gas chromatography analysis with 1,1, 1,2-tetrafluoro- 7-thiocyanato-2, 4-bistrifluoromethyl-heptane (> 95% pure).

1,1, 1, 2-tetrafluoro-7-thiocyanato-2, 4-bistrifluoromethyl-heptane can be dissolved in 30 mL acetic acid and heated to 40 ° C. overnight with chlorine sparging. The temperature of the mixture can be increased to 50 ° C. for 6 hours and cooled to room temperature. The mixture was partitioned between methylene chloride (100 mL) and deionized water (100 mL), the organic layer was separated, washed three times with deionized water (10 mL each), dried over magnesium sulfate, filtered and filtered to a colorless oil under vacuum. Can be concentrated. The oil can be placed in Kugelrohr for 30 minutes at 0.1 Torr and 40 ° C. to yield a yellow oil (13.4 grams, 57.3%), which is> 94% 6,7, 7,7- by NMR and gas chromatography analysis. Tetrafluoro-4, 6-bis-trifluoromethyl-heptane chloride sulfonyl.

Dimethylaminopropyl amine (11.6 mL) can be dissolved in chloroform (75 mL) and cooled to 0 ° C. 6,7, 7,7-tetrafluoro-4, 6-bis-trifluoromethyl-heptanesulfonyl chloride (13.4 grams) can be dissolved in chloroform (75 mL) and added dropwise to the cooled solution to form a mixture. have. Once the addition is complete, the mixture can be warmed to room temperature and washed with saturated bicarbonate solution (150 mL), deionized water (150 mL), and brine (150 mL). The organic layer can be separated, dried over magnesium sulfate, filtered and concentrated in vacuo to yield an orange oil (14.94 grams, 96.0%). Orange oil can be found as 6,7, 7,7-tetrafluoro-4, 6-bis-trifluoromethyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide by NMR analysis .

으로 확인될 수 있다. Referring to the schematic diagram 57, 6,7, 7, 7-tetrafluoro-4,6-bis-trifluoromethyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7.5 g) ) Can be dissolved in 25 mL ethanol, deionized water (30 mL) and 50% (wt / wt) hydrogen peroxide (3.7 mL). The homogeneous mixture can be stirred overnight at ambient temperature. Decolorized carbon (5 g) and ethanol (15 mL) can be added to the mixture and the mixture can be heated to 50 ° C. for 2.5 hours while monitoring for peroxide. The reaction mixture can then be cooled to room temperature and filtered through celite. The filter cake was washed with 90% (wt / wt) ethanol, 10% (wt / wt) water (50 mL), the filtrate was concentrated in vacuo and the resulting oil was purified by NMR.

It can be confirmed.

로서 확인될 수 있다. Referring to the schematic diagram 58, 6,7, 7,7-tetrafluoro-4, 6-bis-trifluoromethyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7.5 grams) ) Can be dissolved in ethanol (40 mL), and sodium chloroacetate (1.85 grams) to form a mixture. The mixture can be refluxed overnight. The heterogeneous mixture can be cooled to room temperature and concentrated under filtrate vacuum to yield an orange oil. Orange oil can be dried in Kugelrohr at 0.1 Torr and 50 ° C. for 1 hour to give an amber solid (7.85 grams, 93.1%). Amber solids by NMR analysis

Can be identified as

According to yet other embodiments, the mercaptan R _F - intermediates were also as described in U.S. Patent 3,544, 663 which is included by reference herein, iodine R _F - the intermediate is reacted with thio urea to iodonium salt in iso tiwoo Can be prepared and treated with sodium hydroxide to give mercaptan R _F -intermediate plus sodium iodide.

In an exemplary aspect of the disclosure, the mercaptan R _F -intermediate is a group 2-acrylamido, available from Lubrizol. As AMPS 2403 as described in US Pat. No. 4,000, 188, generally incorporated by reference herein. May be attached to 2-methyl-1 propane sulfonic acid.

Aminooxides of R _F -surfactants can be prepared according to processes including those generally described in US Pat. Nos. 4,983, 769, incorporated herein by reference.

Thus, sulfoamidoamine can be combined with ethanol and water and 70% (wt / wt) hydrogen peroxide and heated to at least 35 ° C. for 24 hours. Activated carbon can then be added to the mixture and refluxed for about 2 hours. The reaction mixture can be filtered and the filtrate can be evaporated to dryness to provide the aminoxide of the R _F -surfactant.

According to another embodiment of the disclosure, a process is provided that can be used to change the surface tension of a portion of a system having at least two portions. The system may include a liquid / solid system, a liquid / gas system, a gas / solid system, and / or a liquid / liquid system. In an exemplary embodiment, the liquid / liquid system may have one portion that includes water and another portion that includes a relatively hydrophobic liquid when compared to water. According to another embodiment, the liquid / liquid system may contain one portion that is relatively hydrophobic when compared to water and / or relatively hydrophobic when compared to another portion of the system. R _F -surfactants can be used to change the surface tension of portions of the system, for example, by adding R _F -surfactants to the system.

R _F -surfactants can be used in relatively pure solutions or in mixtures with other components. For example, by way of example only, R _F − surfactant may be added to the system and the surface tension of the system is determined by the Wilhelmy plate method and / or by using the Kruss Tensiometer method.

Depending on the concentration in plot # 1 below,

The surface tension of the solution of can be determined.

As another example,

pH 7 and pH5 at various concentrations

The surface tension of can be determined and the data is shown in plot # 2 below.

As another example, at various concentrations

의 표면 장력은

Surface tension of the

Can be determined and the data is shown in plot # 3 below.

As another example,

의 표면 장력을 결정할 수 있고 데이타는 하기 플롯 #4 에서 표시되어 있다.

The surface tension of can be determined and the data is shown in plot # 4 below.

의 표면 장력을 결정할 수 있고 데이타는 하기 플롯 #5 에서 표시되어 있다. As another example, at various concentrations

The surface tension of can be determined and the data is shown in plot # 5 below.

의 표면 장력을 결정할 수 있고 데이타는 하기 플롯 #6 에 표시되어 있다. As another example, at various concentrations

The surface tension of can be determined and the data is shown in plot # 6 below.

의 표면 장력을 결정할 수 있고 데이타는 하기 플롯 #7 에 표시되어 있다. As another example, at various concentrations

The surface tension of can be determined and the data is shown in plot # 7 below.

및 pH 5.0

에서

의 표면 장력을 결정할 수 있고 데이타는 하기 플롯 #8에 표시되어 있다. As another example, pH 6.2-6.8

And pH 5.0

in

The surface tension of can be determined and the data is shown in plot # 8 below.

The corresponding surface tensions and concentrations of the R _F -surfactants are shown in Table 6 below.

The R _F -surfactants described above can be incorporated into, for example, detergents, emulsifiers, paints, adhesives, inks, wetting agents, foaming agents, and / or antifoams.

R _F -surfactants may be incorporated into AFFF formulations and these formulations may be used as fire extinguishing agents to prevent combustion and / or extinguish. Representative uses of AFFF comprising R _F -surfactants include the addition of AFFF to high pressure misting systems, where the misting systems are used to prevent and / or extinguish combustion. AFFF formulations can be provided, for example, on a substrate. The substrate may comprise a liquid and / or a solid composition. AFFF formulations may be dispersed into an atmosphere that includes a gaseous atmosphere, such as air, to prevent and / or extinguish combustion.

The formulation may include other components such as a water soluble solvent. These solvents can promote solubilization of R _F -surfactants and other surfactants. These solvents may also act as foam stabilizers and / or cryoprotectant agents. Representative solvents include ethylene glycol, diethylene glycol, glycerol, ethyl Cellusolve ^® , butyl Carbitole ^® , Dowanol DPM ^® , Dowanol TPM ^® , Dowanoi PTB ^® , propylene glycol, and / or hexylene glycol. Additional components for the formulation, such as polymer stabilizers and thickeners, may be incorporated into the formulation to enhance the foaming stability made from the aeration of the aqueous solution of the formulation. Representative polymer stabilizers and thickeners are partially hydrolyzed proteins, starch, polyvinyl resins such as polyvinyl alcohol, polyacrylamide, carboxyvinyl polymer, and / or poly (oxyethylene) glycols. Polysaccharide resins, such as xanthan gum, may be included in the formulation as foam stabilizers in formulations for use in preventing or extinguishing polar solvent combustion, such as, for example, alcohol, ketone, and / or ether combustion. Formulations may also include buffers that adjust the pH of the formulation, such as tris (2-hydroxyethyl) amine or sodium acetate, and corrosion inhibitors such as toluoltriazole or sodium nitrite. Aqueous electrolytes such as magnesium sulphate may be included and may improve the membrane-spreading properties of the formulation.

By way of example only, the following formulations can be prepared using R _F -surfactants. The formulations recited in the table below can be prepared and applied to the indicated substrates.

From Table 7 above, a 3% (wt / wt) premixed solution of Formulation # 1 in water can be used for the film in the substrate heptane.

From Table 8 a 3% (wt / wt) premixed solution of Formulation # 2 in water can be used to coat the film in substrate heptane.

Third formulation comprising 3% (wt / wt) mixed formulation of Table 9 above

And 0.1% (wt / wt) of

가 기판 헵탄 및 사이클로헥세인에 막을 형성할 수 있다.

A film can be formed on the substrate heptane and cyclohexane.

3% (wt / wt) of the mixed formulation of Table 9 and 0.15% (wt / wt)

을 포함하는 네번째 조제물은 기판 헵탄과 사이클로헥세인 위에 막을 형성할 수 있다.

A fourth preparation comprising can form a film on the substrate heptane and cyclohexane.

Formulations 5 and 6 of Table 10 may be used at 3% (wt / wt) concentrations to foam and form films on the substrate heptane. R _F -surfactants may also contain other surfactants such as alkyl sulfates, alkyl ether sulfates, alpha olefin sulfonates, alkyl sulfobetaines, alkyl polyglycerides, alkyl amidopropyl betaines, alkyl imidazoline dicarboxylates, Preparations comprising 2-alkylthiopropionamido-2 methyl-propanesulfonic acid sodium salt, alkyliminodipropinates, alkylsulfonates, ethoxylated alkylphenols, dialkylsulfosuccinates, and / or alkyltrimethyl ammonium chlorides It can be useful in water.

 Variations of the acronym for AFFF, ARAFFF, alcohol resistant aqueous film forming blowing agent (s) may be used to evolve flames involving water-soluble solvents such as acetone and isopropanol, in which AFFF blowing agents are used and conventional AFFF blowing agents may not evolve. In a more identical manner that can be used, it can be used to extinguish a hydrocarbon flame.

ARAFFF formulations may contain the same ingredients as conventional AFFF formulations plus polysaccharides such as xanthan gum. In some formulations, polymer foam stabilizers. Polymer foam stabilizers are provided by DuPont ^® and Dynax ^® Inc. A representative DuPont product, Forafac® 1268, is a water soluble acrylic polymer. A representative Dynax product, DX5011 ^® is an ethyleneimine polymer. Xanthan rubber is offered by several suppliers, including Kelco CP (Keizan) and Rhodia North America (Rhodopol).

Polysaccharides alone may be sufficient to make ARAFFF formulation alcohol resistance, but produce foam concentrates in which the required amount can be quite viscous. The amount of polymer foam stabilizer may allow a reduction in the amount of polysaccharides needed to provide useful alcohol resistance.

Because of the possibility of microbial attack on the polysaccharide solution, the ARAFFF concentrate may contain an effective amount of biocide such as Kathon CG ICP manufactured by Rohm & Haas. Many other biocides such as Acticide, Nipacide and Dowicil may also be effective.

Some ARAFFF formulations may be designed to be assigned at different percentages depending, for example, on whether the substrate to be evolved is a hydrocarbon or alcohol type substrate. The alcohol type may include any fuel having hydroxyl groups.

Representative ARAFFF formulations using R _F surfactants (3% (wt / wt) x 3% (wt / wt)) are described in Tables 11-14 as follows. In all cases described in Table 11-14, water is the remainder of the formulation.

For example, R _F containing an above-described R _F - a foam stabilizer such as a stabilizing agent can be produced. The R _F -stabilizer may comprise an R _F -Q _FS composition. Q _FS may include a moiety having greater hydrophilicity than R _F.

Representative R _F -foam stabilizers include, but are not limited to, those of Table 15 below.

은 Q_FS 부분이 될 수 있다. R_F 안정화제는 하기 개략도 (59)에 따라 제조될 수 있다. For example only as an example,

May be part of the Q _FS . R _F stabilizers can be prepared according to the following schematic (59).

Referring to the schematic diagram 59, potassium carbonate (2.37 grams), methioglycolate (1.82 grams) and dimethylformamide (DMF) (20 mL) can be added and the mixture can be heated to 50 ° C. for 3 hours. have. The mixture can be stirred overnight at room temperature to form a yellow slurry which is added to water (50 mL) and ethyl acetate (50 mL), the organic layers combined, dried over Na ₂ SO ₄ , filtered and the solvent removed.

In a nitrogen atmosphere, thioester (4.0 grams) and polyethyleneimine (PEI, mw = 1200) (5.3 grams) can be placed in isopropanol (5 mL) and stirred until dissolved to form a mixture. Sodium methoxide (0.15 grams) and sodium protecting hydride (0.04 grams) can be added to the mixture and the mixture can be heated to 115 ° C. for 15 hours and stirred at room temperature for 2 days. Removal of remaining isopropanal can be difficult. A solution of sodium chloroacetate (10.52 grams) in water (25 mL) can be added dropwise to the mixture and the temperature kept below 55 ° C. and the mixture can then be heated to 70 ° C. for 2 hours.

NaOH (1.23 grams of NaOH and 50% (wt / wt) solution of water) may be added to raise the pH of the mixture from a starting pH of approximately 6 to at least 7.5. The mixture can then continue to stir at 70 ° C. for an additional 2 hours, after which heat is removed and the resulting

(4.4 그램, 82% 수율)을 특징부여하였다(¹HNMR 분석).

(4.4 grams, 82% yield) was characterized ( ¹ HNMR analysis).

은 하기 표 16-19에 따라 다른 발포 안정제와 비교될 수 있다. Manufactured

Can be compared with other foam stabilizers according to Tables 16-19 below.

R _F R _F, such as the port summing -QMC part R _F-metal complex is also provided. The R _F moiety can be combined, for example, as an acid halide or carboxylic acid with an acid halide including, for example, an acid fluoride. The R _F -metal complex is an R _F -intermediate and, as such, Qg may be interchangeable with Q _MC . Q _MC may comprise, for example, a portion of a ligand of a metal complex coordinated with a complexed metal. Representative R _F -metal complexes include, but are not limited to, those in Table 20 below.

Representative methods for the preparation of R _F -metal complexes are described above, for example, by reacting sulfuric acid with fuming R _F -intermediates having a halogen functional group, having a Qg of 1, for example an R _F -intermediate having an acid fluoride functional group. It involves doing. The R _F -metal complex can be prepared with reference to the schematic diagram 60 below.

Acid fluoride R _F -intermediates can be reacted with amino acids such as glycine to produce amine esters. The amine esters can then be reacted with chromium chloride in alcohols such as methanol or isopropanol to produce representative R _F -metal complexes such as R ^F chromium complexes. Representative acid R _F -intermediates for use in the preparation of R _F metal complexes may include ethylene carboxylic acid R _F -intermediates and / or mixtures of ethylene carboxylic acid R _F -intermediates and carboxylic acid R _F -intermediates. have. Representative preparations can be performed according to US Pat. Nos. 3,351, 643,3, 574,518, 3,907, 576,6, 525,127, and 6,294, 107, incorporated herein by reference. The R _F -metal complex may comprise a ligand having an R _F moiety and a Q _MC moiety associated with the metal of the complex. In an exemplary embodiment, the Q _MC moiety may have a greater affinity for the metal of the complex than the R _F moiety. R _F -metal complexes can be used to process substrates such as paper, leather, textiles, yarns, tissues, glass, ceramic products, and / or metals. In some cases, treating the substrate with a complex makes the substrate less permeable to water and / or oil.

Embodiments of the present invention also provide incorporation of the R _F moiety into the phosphate esters, which may be used to treat a substrate and / or as a dispersant during the manufacture of a polymer. Representative R _F - phosphate ester is an R _F -Q _{PE, PE} Q this part R _F - is the phosphate portion of the composition. R _F -phosphate esters include, but are not limited to, those of Table 21 below.

Representative R _F -phosphate esters can be prepared with reference to the following schematics (61) and (62).

Referring to the schematic diagram 61 above, an R _F -intermediate having a hydroxyl functional group (Qg = OH) can be obtained by reacting an iodine R _F -intermediate (Qg = I) with a strong base such as KOH. According to US Pat. Nos. 2,559, 749 2,597, 702, incorporated herein by reference, which generally describe the conversion of hydroxyl compounds to phosphate esters using P ₂ 0 ₅ or POC1 ₃ to provide partial esters, Iodine R _F -intermediates in the presence of metal (M) P ₂ 0 ₅ or POC1 ₃ May be reacted with to give a representative R _F -phosphate ester or R _F -pyrophosphate. These reactions can also be carried out as HCl receptors in the presence of pyridine. Monoalkyl phosphates can also be prepared by treating phosphorus pentoxide P ₂ 0 ₅ with more than molar hydroxyl R _F -intermediates followed by hydrolysis of the resulting R _F -pyrophosphate. The product can then be separated or precipitated as an ammonium salt by adding ammonia to the reaction mixture. As an alternative, a solution of salts of mixed mono- and di-esters can be prepared by neutralizing the mixture of acids with aqueous ammonia and amines or alkali metal hydroxides.

R _F -dialkyl phosphates can also be prepared by reacting excess molar R _F -intermediates with phosphorus pentoxide (not shown). Instead of hydrolysis, however, RF-pyrophosphate intermediates can be heated at low pressures. As an alternative, the R _F -phosphate ester is prepared by treating the hydroxyl R _F -intermediate with phosphorus pentoxide and neutralizing the resulting mixed acid phosphate with aqueous ammonia, and an amine such as a tetraalkyl ammonium base or an alkali metal hydroxide It can be separated to provide a solution that can include amines or metal salts of esters (not shown). The salt of the ester can be dissolved in toluene and washed with ammonia to precipitate a mixture of salts of the corresponding ester. Unreacted hydroxyl R _F, such as a trialkyl phosphate-intermediates and by-products is prepared a composition having the general formula R _F AOPORp as described in U.S. Patent 4,145, 382 incorporated by reference herein, R _F and the corresponding toluene It can remove by filtration. As used in this general formula, R _F is an R _F moiety, A may be present in an amount as high as 3 and as low as 0 from other methylene groups or phosphate esters, and Rp is hydrogen alkali metal ammonium or substituted Ammonium, such as ethanol amine, is the corresponding salt for phosphate.

R _F -phosphates may be used as dispersants in the manufacture of polymers or they may be diluted by conventional means, such as, for example, padding, dipping, impregnation, spraying, and the like, and used to treat the substrate material in an aqueous bath. These compositions can be used in materials such as textile articles, textile yarns, leather, paper, plastics, sheeting, wood, ceramic clays, as well as articles made from garment articles, wallpaper, paper bags, cardboard boxes, porous clays, and the like. May be incorporated or used to process them. US Patent 3,112, 241 describes a method for treating materials using phosphate esters and is incorporated herein by reference.

With reference to schematic 62 above, R _F -epoxide intermediates and / or R _F -diol intermediates can be prepared as generally described in US Pat. Nos. 3,919, 361, incorporated herein by reference. R _F -epoxide and diol intermediates can be reacted with phosphoric acid to obtain R _F -phosphate esters. R _F -phosphate esters may be dissolved in solution and applied to a substrate such as paper to increase resistance to environmental materials such as oil and water. R _F -phosphate esters may also be present as salts, such as alkyl amines, including ethanol amines as described in US Pat. No. 4,145,382, incorporated herein by reference.

R _F -phosphate esters can be used to treat substrates such as wood pulp products, including paper products such as packaged products including food packaged products.

Specific examples including -Qh R _F R _F - and R _F comprises a part in conjugation glycols such as glycol, where Qh represents a hydroxyl functionality as shown ether before the ether portion of the glycol, or bonded after the bonding. Representative R _F -glycols include, but are not limited to, those of Table 22 below.

R _F -glycol can be incorporated into polymers, membranes and coatings, such as, for example, urethanes including polyurethane elastomers. R _F -glycol may also be converted to phosphoric acid or to phosphate esters of such glycols. Referring to schematic diagram 63 below, the R _F moiety can be incorporated into a glycol.

Methods for preparing glycols are described in US Pat. Nos. 4,898, 981, US Pat. Nos. 4,491, 261, US Pat. Nos. 5,091, 550, and US Pat. Nos. 5,132, 445, all of which are incorporated herein by reference. For example, by way of example only, R _F -intermediates (Qg = SH) are reacted with sulfide diol or 2,6 diox-asspiro (3,3) heptane to represent a representative R _F -glycol (Qh = H ₂ CH ₂ CSH ₂ CH ₂ ...) Can be prepared. R _F -glycol can then be used directly or indirectly to prepare R _F condensation products such as polyesters, polyureas, polycarbonates, and polyurethanes. Iglycol functional groups can also be incorporated into the block polymer using R _F -glycol. U. S. Patents 5,491, 261 disclose several other glycols that can benefit from the RF portion of the present invention and are incorporated herein by reference.

R _F -glycol may also be converted to phosphate functional groups or phosphate esters (not shown). U.S. Patents 5,091, 550,5, 132,445, 4,898, 981, and 5,491, 261 all disclose methods for preparing diols and methods for converting diols to phosphate esters and are incorporated herein by reference. In an exemplary implementation, diols can be converted to phosphoric acid or phosphate esters by reacting diols in the presence of phosphoric acid. These compositions can be incorporated into compounds that can act as oil and grease processing for paper, as well as soil release agents for textile fibers.

According to another embodiment of the invention, for example, oligomers, polymers, copolymers, acrylics, and / or resins comprising R _F -monomer units such as R _F -Q _MUs can be prepared. The monomer unit portion, Q _MU , can be a single unit in the complex of units and the monomer unit need not be repeated in the complex. In an exemplary embodiment, the monomer unit can be a single unit in the complex or it can be one of many identical units linked together, for example homopolymers. The complex may also include block polymers and / or polyurethane resins. The R _F of the unit may comprise a pendant group of the monomer unit. The monomer unit may be associated with the complex and, for example, may be bonded to the complex and the Q _MU may comprise a portion of the monomer unit associated with the complex. The complex may be coated onto the substrate or it may be chemically bonded to the substrate. For example, the preparation of an R _F -intermediate can be provided on a substrate and the sites such as hydroxyl groups conventional on a substrate, such as cotton, form part of, or a site that, when associated with a complex, causes the R _F -intermediate to chemically bond to the substrate. Can be provided. In an exemplary embodiment, Q _MU can represent an acrylate functional group of acrylic and R _F can be a pendant group from an acrylic chain and / or backbone. Representative R _F -monomer units include, but are not limited to, those in Table 23 below.

From monomers R _F - - _F R in the exemplary embodiment may be an oligomer is prepared containing monomer units. R _F - monomers are the R _F - may comprise an intermediate, and allow their junction with the other monomers but be the same R _F - may contain a monomer is not necessarily functional. Representative R _F − monomers include, but are not limited to, those of Table 24 below.

Referring to schematic diagram 64 below, a multiple reaction sequence for the preparation of R _F -monomers having R _F groups is shown.

US Patents 3,491, 169,3, 282,905, 3,497, 575,3, 544,663, 6,566, 470, 4,147, 851,4, 366,299 and 5,439, 998 all use and manufacture of acrylic emulsion polymers that can benefit from the R _F group And is hereby incorporated by reference. Thiol R _F -intermediates, iodine R _F -intermediates, hydroxyl R _F -intermediates, and / or acetate R _F -intermediates can be converted to R _F -monomers according to the schematic (63) above and these R _F -monomers Can be used to prepare a composition containing an R _F -monomer unit.

For example, by way of example only, the R _F moiety is as described above into the R _F -monomer as described in US Pat. No. 6,566,470, denoted R _F -WXC (= 0) -C (R ₁ ) = CH ₂ . May be included together with the same R _F moiety. W is alkylene having 1 to 15 carbons, hydroxyalkylene having 3 to 15 carbons,-(C _n H _2n ) (OCmH _2m ) _q- , -S0 ₂ NR _2- (CnH _2n )-, or- CONR _2- (CnH _2n )-, where n is 1 to 12, m is 2 to 4, q is 1 to 10, and R ₁ is an alkyl group having 1 to 4 carbon atoms, for example For example, X can be O, S and / or N (R ₂ ), where R ₂ is equal to R ₁ .

For example, the R _F -monomer 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pentyl acrylate was reacted in two stages shown below as reaction schematics (65) and (66), respectively. R _F -intermediate 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene.

Referring to the schematic diagram 65, 4,4, 5, 5 in tetrahydrofuran (66.1 grams, 0.075 moles), chlorotri (triphenylphosphine) rhodium (0.37 grams), and tetrahydrofuran (158.8 grams) A 1M solution of -tetramethyl- 1,3, 2-dioxaborolane can be placed in a 500 mL three neck round bottom flask to form a mixture. 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene (18.243, 0.087 moles) can be added to the mixture over a period of 15 minutes at room temperature and over 72 hours. Can be mixed and monitored by gas chromatography up to the time at which 4,5, 5, 5-tetrafluoro-4- (trifluoromethyl) pent-1-ene is substantially consumed (for monitoring of reaction See Table 25 below).

Caution: 3.07 min peak = 4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene, 9.3 min peak = 4,4, 5,5-tetramethyl-1, 3 , 2-dioxaborolane, 16.8 min. Peak 2- (4, 5,5,5-tetrafluoro-4- (trifluoromethyl) pentyl) -4, 4,5,5-tetramethyl-1, 3,2-dioxaborolane

A 3M aqueous solution of sodium hydroxide (7.8 grams) can be added to the mixture over 15 minutes via an addition funnel and the mixture can then be cooled to 0 ° C. using an ice bath. Hydrogen peroxide (23.6 grams, 35% (wt / wt) aqueous solution) can be added dropwise to the mixture over 15 minutes and then the mixture can be washed in H ₂ 0 (three times). The organic layer was removed and transferred into a 100 mL three necked round bottom flask and distilled to 85% area percent pure (4, 5,5,5-tetrafluoro-4- (trifluoromethyl) pentane-1- by gas chromatography). Ol can be prepared.

4,5, 5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol (2.59 grams, 0.011 moles) and triethylamine (1.3 grams, 0.013 moles) were added to 15 mL three-neck RBF To form a mixture. The mixture can be cooled to 0 ° C. using an ice bath and acryloyl chloride (1.38 grams, 0.015 moles) can be added to the mixture using an addition funnel for RBF over 15 minutes. After 1 hour hold, 10 mL H ₂ 0 is added and two phases can be observed. The water is poured off from the mixture and the organic phase is removed with MgSO ₄ Drying above and analyzing by gas chromatography / mass spectrometry can identify new peaks with a mass of 283.

과 같은 대표적인 R_F-Q_M 이 용액에 제공될 수 있고 또다른

또는 또다른 화합물과 접합 및/또는 중합되어

Representative R _F -Q _M such as may be provided in the solution and another

Or conjugated and / or polymerized with another compound

를 포함할 수 있는 착체, 이를테면 올리고머를 형성할 수 있고, Q_MU는 착체의 잔여부를 나타낸다. 예를 들어 오직 예로서, R_F-모노머의 용액이 기판에 제공될 수 있고 예를 들어, 용액의 용매를 증발시켜 R_F-모노머 유닛을 포함하는 착체를 형성함으로써 착체형성할 수 있다. 이들 용액을 기판 이를테면 유리, 나일론, 및/또는 면에 제공하고 R_F-모노머가 착체의 부분이 되도록 이를테면 기판을 코팅하도록 한다.

And may form a complex, such as an oligomer, wherein Q _MU represents the remainder of the complex. For example, by way of example only, a solution of R _F -monomer can be provided to the substrate and complexed, for example, by evaporating the solvent of the solution to form a complex comprising the R _F -monomer unit. These solutions are provided to a substrate such as glass, nylon, and / or cotton and to coat the substrate such that the R _F -monomer is part of the complex.

Using the standard Fowkes method using diiodomethane and water as probe liquid and the Zisman method of surface energy analysis using octane, decane, tetradecane, and hexadecane as probe liquid, the surface energy of the complex You can decide. Using the Kruss Drop Shape Analysis System, the contact angle of droplets of Zisman probe liquids as well as Fowkes probes can be determined. Surface energy data of complexes comprising R _F -Qp monomer units are cited in Tables 26-35 below.

The R _F -monomer may be incorporated with other monomers and then incorporated into the composition of the paper material or used to treat the paper material. R _F -monomers can also be used to prepare polymer solutions. The polymer solution may be diluted with percent aqueous or non-aqueous solution and then applied to the substrate to be treated, such as a paper plate.

R _F -monomers are also comonomers such as dialkyl amino alkyl acrylates or methacrylates or acrylamides or methacrylamide monomers and amine salts thereof, as described in US Pat. No. 4,147,851, which is incorporated herein by reference. It can be incorporated into the copolymer together with the primary ammonium or amine oxide form. R _F - monomer general formula R _F q0 ₂ may be a CC (R) = CH ₂ for, and R is H or CH _3, q is 1 to 15 alkyl carbon atoms, alkylene of 3 to 15 carbon atoms, hydroxy Oxyalkylene, or C _n H _2n (OC _q H _2q ) m-, -S0 ₂ NR ₁ (C _n H _2n )-, or -CONR ₁ (C _n H _2n )-, n is 1 to 15 and , q is 2 to 4, m is 1 to 15. Monomers used to form copolymers with acrylates and R _F -monomers include those having amine functionality. These copolymers can be diluted in solution and applied or directly incorporated onto a substrate such as paper to be treated.

R _F -monomers may also be used to form acrylate polymers or other acrylate monomers consistent with those described in US Pat. No. 4,366, 299, which is incorporated herein by reference. As described, the R _F -monomer can be incorporated into or applied onto the paper product.

For example, R _F -monomers, acrylates and / or acrylics may be applied to the finished carpet or incorporated into the finished carpet fibers before it is woven into the carpet. The R _F -monomer may be applied to the carpet by a conventional fabric finishing process known as padding, in which the carpet is a R _F -monomer and, for example, latex, water, and / or other additives such as non-materials. Pass through the bath containing the wet surface. The nip roller can then be passed to control additional speeds before the carpet is then dried in a fabric roll. The R _F -monomer can also be incorporated into the fiber by reacting the fiber with an R _F -intermediate having an isocyanate functional group, for example R _F -isocyanate.

The R _F moiety may also be incorporated into the material used to treat the calcite and / or siliceous particulate material. For example, an R _F -monomer is a copolymer in which the copolymer can be used as part of a formulation for treating these materials as described in the US patents incorporated herein by reference or can be used to treat these materials alone. Can be included in.

R _F -monomers can have the general formula R _F -QAC (O) -C (R) = CH ₂ , wherein R _F is described above, R is H or CH ₃ , and A is O, S, or N (R ₁ ), wherein R ₁ is H or alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms,-(C _n H _2n ) (OCqH _2q ) m-, -SO ₂ -NR ₁ (C _n H _2n )-, or -CONR ₁ (C _n H _2n )-, where R ₁ is H or 1 to 4 carbons Is alkyl of the atom, n is 1 to 15, q is 2 to 4 and m is 1 to 15.

R _F - A mixture containing the composition and an R _F portion brick, stone, wood, concrete, ceramics, tile, glass, stucco, gypsum, a surface of the hard like building materials, such as drywall, particle board, and chipboard It can be used to process substrates that contain. These compositions and mixtures can be used alone or in combination with penetration aids such as non-ionic surfactants. These compositions may be applied to the surface of the calcite and / or siliceous building material by known methods such as soaking, impregnation, appearance, brushing, rolling, or spraying. The composition can be applied to the surface to be protected by a spray. Suitable spray equipment is commercially available. Spraying with a compressed air atomizer is a representative method of application to a particular substrate. US Patents 6,197, 382 and 5,674, 961 also describe methods of applying and using polymer solutions and are incorporated herein by reference.

In an exemplary process for producing a solution having a component with R _F, methyl-can be prepared ester (not shown) - R _F The intermediate monocarboxylic condensed with alkenyl acid unsaturated-R _F having an epoxide function have. Representative methods for preparing unsaturated esters of this kind are described in US Pat. No. 5,798,415, which is incorporated herein by reference. Additional esters can be prepared according to US Pat. No. 4,478, 975, which is incorporated herein by reference. As described in US Pat. No. 6,120, 892, incorporated herein by reference, the components of these solutions may also include dimethyl amino ethyl methacrylate, and these components may be applied to organic and inorganic solvents. R _F -monomers can be prepared in combination with other monomers or in solutions with amido and sulfur monomers, as described by US Pat. No. 5,629, 372, which is incorporated herein by reference.

R _F -intermediates with amine functionality may also be reacted with tetrachlorophthal anhydride using US Patent 4,043,923 as shown in a typical reaction schematic (not shown). US Patent 4,043,923 is incorporated herein by reference. The reaction product may be mixed with the carpet cleaning solution to provide soil repellency.

Referring to the schematic diagram 67 below, a urethane comprising an R _F moiety can be prepared from an R _F -intermediate.

R _F -intermediates (R _F -OH) can be combined with hexamethylene diisocyanate polymer (DESMODUR N-100) to prepare urethanes according to the general reaction sequence described in US Pat. No. 5,827,919, incorporated herein by reference. have. Another method for the production of polyurethane is R _F - intermediate (R _F -SCN) the epichlorohydrin by Hi gave the reaction as described in U.S. Patent 4,113, 748 (not shown) included by reference herein D. Producing “twin tailed” R _F -intermediates capable of reacting with isocyanates and / or urethane prepolymers. Urethanes with R _F groups can then be incorporated as additives to the composition, such as latex paints. US Patent 5,827, 919 describes a method for using these urethanes and is incorporated herein by reference. R _F -urethanes and polyurethanes can be used to treat substrates such as carpets, drapery, upholstery materials, automobiles, awnings, and raincoats. Representative R _F and R _F as -Qu - urethane is to, but are not limited to can include those listed in Table 36.

The R _F moiety may also be complexed as an acid of an amine with a quaternary ammonium polymer, such as US Pat. No. 6,486, 245, incorporated herein by reference (not shown).

Claims (96)

An aqueous film forming blowing agent comprising R _F -Q _S , wherein R _F has affinity greater than Q _S for the first part of the system having at least two parts; Q _S has affinity greater than R _F for the second part of this system; R _F comprises at least two —CF ₃ groups and at least two hydrogens. The formulation of claim 1, wherein R _F is hydrophobic relative to Q _S. The formulation of claim 1, wherein Q _S is hydrophilic compared to R _F. The formulation of claim 1, wherein R _F is hydrophobic and Q _S is hydrophilic. The formulation of claim 1, wherein R _F comprises at least one —CH ₂ — group. The formulation of claim 1, wherein R _F comprises at least one ring group. 7. The formulation according to claim 6, wherein the ring group comprises an aromatic group. The formulation of claim 1, wherein R _F comprises at least one (CF ₃ ) ₂ CF— group. The formulation of claim 1, wherein R _F comprises at least three —CF ₃ groups. The formulation of claim 1, wherein R _F comprises at least two (CF ₃ ) ₂ CF— groups. The formulation of claim 1, wherein R _F comprises at least four carbons, one of which comprises a —CH ₂ — group. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. The method of claim 1, wherein R _F -Q _S is

It is a formulation characterized by the above-mentioned. A method of providing an aqueous film forming blowing agent to a substrate, wherein the aqueous film forming blowing agent comprises R _F -Q _S , wherein R _F has affinity greater than Q _S for the first part of the system having at least two parts. ; Q _S has affinity greater than R _F for the second part of this system; R _F comprises at least two —CF ₃ groups and at least two hydrogens. 36. The method of claim 35, wherein R _F is hydrophobic relative to Q _S. 36. The method of claim 35, wherein Q _S is hydrophilic compared to R _F. 36. The method of claim 35, wherein R _F is hydrophobic and Q _S is hydrophilic. 36. The method of claim 35, wherein the substrate comprises a liquid. 36. The method of claim 35, wherein the substrate is part of a system. 36. The method of claim 35, wherein R _F comprises at least one -CH ₂ -group. 36. The method of claim 35, wherein R _F comprises at least one ring group. 43. The method of claim 42, wherein the ring group comprises an aromatic group. 36. The method of claim 35, wherein R _F comprises at least one (CF ₃ ) ₂ CF- group. 36. The method of claim 35, wherein R _F comprises at least three -CF ₃ groups. 36. The method of claim 35, wherein R _F comprises at least two (CF ₃ ) ₂ CF- groups. 36. The method of claim 35, wherein R _F comprises at least four carbons, wherein one of the four carbons comprises a -CH ₂ -group. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. The method of claim 35, wherein R _F -Q _S is

Method characterized in that. A foam stabilizer comprising R _F -Q _FS , wherein R _F is hydrophobic compared to Q _FS , and R _F comprises at least two —CF ₃ groups and at least two hydrogens. The stabilizer of claim 71 wherein R _F comprises at least one —CH ₂ — group. The stabilizer of claim 71 wherein R _F comprises at least one ring group. 74. The stabilizer of claim 73 wherein the ring group comprises an aromatic group. The stabilizer of claim 71 wherein R _F comprises at least one (CF ₃ ) ₂ CF— group. 72. The stabilizer of claim 71 wherein R _F comprises at least three -CF ₃ groups. The stabilizer of claim 71 wherein R _F comprises at least two (CF ₃ ) ₂ CF— groups. The stabilizer of claim 71 wherein R _F comprises at least four carbons, one of which comprises a —CH ₂ — group. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Stabilizer characterized by the above-mentioned. The method of claim 71, wherein R _F -Q _FS is

Wherein X is a halogen.

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