Patent Application
20080108785
The present invention relates to the filed of halogenated compositions, processes for manufacturing halogenated compositions and, more specifically, fluorinated compositions, processes for manufacturing fluorinated compositions and methods for treating substrates with the fluorinated compositions.
Compositions such as surfactants and polymers, for example, have incorporated fluorine to affect the performance of the composition when the composition is used as a treatment for materials and when the composition is used to enhance the performance of materials. For example, surfactants incorporating fluorinated functional groups can be used as fire extinguishants either alone or in formulations such as aqueous film forming foams (AFFF). Traditional fluorosurfactants, such as perfluoro-octyl sulfonate derivatives (PFOS), have linear perfluorinated portions.
Polymers incorporating fluorine have been used to treat materials. Exemplary fluorinated treatments include compositions such as Scotchguard®.
Compositions and methods for making compositions such as RF(RT)nQ are provided. The RF group can include at least two —CF3 groups, the RT group having at least two carbons, n can be at least 1 and the Q group can include one or more atoms of the periodic table of elements.
RF-Intermediates and methods for making same are also provided such as RF(RT)nQg, with the Qg group being one or more atoms of the periodic table of elements.
Surfactants and methods for making same are provided that can include RF(RT)nQS, with the QS, group being at least one atom of the periodic table of elements and at least a portion of the RF and RT groups are hydrophobic relative to the QS group and at least a portion of the QS group is hydrophilic relative to the RF and RT groups.
Foam stabilizers and methods for making same are provided that can include RF(RT)nQFS, with the QFS, group being at least one atom of the periodic table of elements and at least a portion of the RF and RT groups are hydrophobic relative to the QFS group and at least a portion of the QFS group is hydrophilic relative to the RF and RT groups.
Metal complexes and methods for making same are provided that can include RF(RT)nQMC, with the QMC group being at least one atom of the periodic table of elements.
Phosphate ester and methods of making same are provided that can include RF(RT)nQPE, with the QPE group being a portion of a phosphate ester group.
Polymers and methods of making same are provided that can include RF(RT)nQMU, with the QMU group being a portion of a polymer chain backbone.
Urethanes and methods of making same are provided that can include RF(RT)nQU, with the QU group being at least one atom of the periodic table of elements.
Glycols and methods of making same are provided that can include RF(RT)nQH, with the QH group being a portion of a glycol chain backbone.
Embodiments are described below with reference to the following accompanying drawings.
This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).
Exemplary RF-compositions and production methods are described with reference to
Referring to
RF-compositions include compositions that have an RF portion and/or RF portions. The RF portion can be RF groups, such as pendant groups and/or moieties of compositions. The RF portion can include at least two —CF3 groups and the —CF3 groups may be terminal. The RF groups can be —C3F6 or —C3F7, for example. The RF portion can also include both —CF3 groups and additional groups containing fluorine, such as —CF2— groups. In exemplary embodiments, the RF portion can include a ratio of —CF2— groups to —CF3— groups that is less than or equal to two, such as (CF3)2CF— groups. The RF portion can also include three pendant —CF3 groups, in other embodiments. The RF portion can include at least three pendant —CF3 groups and at least one —CF2— group. The RF portion can include at least three pendant —CF3— groups, at least one —CF2— group and at least five —CH2—, in exemplary embodiments. In exemplary embodiments, the RF portion can include a ratio of —CF2— groups to —CH2— groups that can be 0.4 to 1. The RF portion can include, in exemplary embodiments a ratio of —CF2— groups to —CF3— groups that can be 0.4 to 1. The RF portion can be a 1,1,1,2,4,4,6,6,13,13,13-undecafluoro-2,8,10-tris(trifluoromethyl)tridecyl group, for example.
The RF-compositions can include RF(RT)nQ, where the RF group has a carbon amount greater than C5 and at least one terminal and at least one pendant —CX3 group, with X being one or both of H and F, for example. The RF group can have carbon amount between C5 and C17. Example RF groups can include (CF3)2CF(CH2CF2)l—, with l being from 1 to 2; (CF3)2CF(CH2C(CF3)H)m—, with m being from 1 to 3; and/or (CF3)2CF(CH2CF2)l(CH2C(CF3)H)m—, with l being from 1 to 2 and m being from 1 to 3.
More particularly, the RF groups can be one or more of: (CF3)2CFCH2CH(CF3)—, (CF3)2CFCH2C(CF3)HCH2—, (CF3)2CFCH2C(CF3)HCH2CF2—, (CF3)3CCH2C(CF3)H—, (CF3)2CFCH2CF2—, (CF3)2CFCH2CF2CH2—, (CF3)2CFCH2CF2CH2CF2—, (CF3)2CFCH2CF2CH2CF2CH2—, (CF3)2CFCH2CF2CH2CF2CH2C(CF3)H—, (CF3)2CFCH2CF2CH2CF2CH2C(CF3)HCH2C(CF3)H—, (CF3)2CFCH2CF2CH2CF2CH2C(CF3)HCH2C(CF3)H—, and/or (CF3)2CFCH2CF2CFH2CF2CH2C(CF3)HCH2C(CF3)HCH2C(CF3)H—. According to exemplary embodiments, the RF group can further comprise at least a portion of an (RT) group or groups.
The RT group can include at least one C-2 group. The RT group can include a C-3 group and be incorporated into and form a part of RF groups via processes described herein, such as addition reactions employing a carbon nucleophile. The RT group can be —CnH2n— wherein n is at least 1, for example. The RT group can be butyl, in exemplary embodiments. The RT group can be —CH2CX2—, with X being H and/or F, for example. The RT group can be —CH2CH2— and/or —CH2CF2—. The RT group can be one or more of: —CH2CF2CH2CH(CF3)—, —CF2CH2CF2CH2CH(CF3)—, —CH2CF2CH2CF2CH2CH(CF3)—, —CF2CH2CH(CF3)CH2—, —CF2CH2CH(CF3)CH2CH(CF3)—, —CF2CH2CH(CF3)CH2CH(CF3)CH2—, and/or —CF2CH2CH(CF3)CH2CH(CF3)CH2CH(CF3)—. The RT group can repeat in units and the units can be designated as n with n being greater than 1. In example implementations these RT groups can be incorporated into and form a part of RF groups via processes described herein, such as telomerization processes.
In exemplary implementations, RF-compositions can demonstrate desirable surface energies, affect the surface tension of solutions to which they are exposed, and/or affect the environmental resistance of materials to which they are applied and/or incorporated. Exemplary compositions include, but are not limited to, substrates having RF-compositions thereover and/or liquids having RF-compositions therein. RF portions can be incorporated into compositions such as polymers, acrylate monomers and polymers, glycols, fluorosurfactants, and/or AFFF formulations. These compositions can be used as dispersing agents or to treat substrates such as textile fabric, textile yarns, leather, paper, plastic, sheeting, wood, ceramic clays, as well as, articles of apparel, wallpaper, paper bags, cardboard boxes, porous earthenware, construction materials such as brick, stone, wood, concrete, ceramics, tile, glass, stucco, gypsum, drywall, particle board, chipboard, carpet, drapery, upholstery, automotive, awning fabrics, and rainwear. RF-compositions can be prepared from RF-intermediates.
RF portions can be incorporated into RF-compositions and/or can be starting materials for RF-compositions via RF-intermediates. Exemplary RF-intermediates include an RF portion described above, as well as at least one functional portion that allows for incorporation of the RF portion into compositions to form RF-compositions. The Q group of the RF-composition can be a Qg group for RF-intermediates and this Qg group can be the functional portion. Functional portions can include halogens (e.g., iodine), mercaptan, thiocyanate, sulfonyl chloride, acid, acid halides, hydroxyl, cyano, acetate, allyl, epoxide, acrylic ester, ether, sulfate, thiol, phosphate, and/or amines, for example. Without incorporation and/or reaction, RF-intermediates can include RF-compositions, such as RF-monomers and/or ligands of RF-metal complexes, for example.
RF-intermediates can include RF-Qg with RF representing the RF portion and Qg representing, for example, the functional portion, and/or, as another example, an element of the periodic table of elements. In exemplary embodiments, Qg is not a proton, methyl, and/or a methylene group. Exemplary RF-intermediates include, but are not limited to, those in Table 1 below.
Utilizing the systems and methods to prepare starting materials and/or reaction products described in the Published International Applications, novel RF-Intermediates can be prepared according to examples 1-15 below.
RF-Compositions and methods of making RF-compositions are described with reference to
Referring to
Taxogen 2 can include at least one CF3-comprising compound. The CF3-comprising compound can have at least two carbons. In exemplary embodiments, taxogen 2 can comprise an olefin, such as 3,3,3-trifluoropropene (TFP, trifluoropropene), ethylene (ethene), 1,1-difluoroethene (VDF), 1,1,3,3,3-pentafluoropropene (PFP, pentafluropropene). In exemplary embodiments, taxogen 42 can include TFP and telogen 44 can include (CF3)2CFl with a mole ratio of taxogen 42 to telogen 44 being from about 0.2:1 to about 10:1, from about 1:1 to about 5:1, and/or from about 2:1 to about 4:1. Taxogen 2 can include 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pent-1-ene and/or 6,7,7,7-tetrafluoro-6-(trifluoromethyl)hept-1-ene and telogen 4 can include (CF3)2CFl, for example.
According to additional embodiments, taxogen 2 can include those compounds shown below in Table 2.
Telogen 4 can include halogens such as fluorine and/or chlorine. Telogen 4 can include at least 4 fluorine atoms and can be represented as RFQ and/or RClQ. The RF group can include at least four fluorine atoms and the Q group can include one or more atoms of the periodic table of elements. Exemplary RF groups can include: (CF3)2CFCH2CH(CF3)CHCF2—; (CF3)2CFCH2CF2CH2CH(CF3)—; (CF3)2CFCH2CF2CH2CF2CH2CH(CF3)CH2CH(CF3)CH2CH(CF3)—.
RF-Q can be 1,1,1,2,3,3,3-heptafluoro-2-iodopropane (2-iodoheptafluoropropane, i-C3F7I, F7I), for example. Exemplary telogens can include the halogenated compounds described above, such as (CF3)2CF—, C6F13I, trichloromethane, HP(O)(OEt)2, BrCFClCF2Br, R—SH(R being a group having at least one carbon) and/or ROH(R being a group having at least one carbon). The Q group can be H or I with the RF group being (CF3)2CF— and/or —C6F13, for example. The RCI group can include at least one —CCl3 group.
According to additional embodiments, telogen 4 can include those compounds shown below in Table 3. As exemplary implementations are shown in Table 3 below, telogens can be products of telomerizations.
In exemplary embodiments, taxogen 2 can include trifluoropropene and telogen 4 can include (CF3)2CFl, with a mole ratio of taxogen 2 to telogen 4 being from about 1:1 to about 1:10, 1:4 to about 4:1, and/or to about 2:1 to about 4:1.
Reactor 8 can be any lab-scale or industrial-scale reactor and, in certain embodiments, reactor 8 can be configured to control the temperature of the reagents therein. According to exemplary embodiments reactor 8 can be used to provide a temperature during the exposing of the reagents: of from about 90° C. to about 180° C.; of from about 60° C. to about 220° C.; and/or of from about 130° C. to about 150° C.
According to example implementations, the taxogen can be one or more of VDF, TFP, and ethylene, and the telogen can include one of C3F6(RT)nX or C3F7(RT)nX, wherein X is a halogen. The RT can be one or both of —CH2CF2— and —CH2C(CF3)H—, and n is 1 to 4. More particularly: the taxogen can be VDF and the telogen can be (CF3)2CFCH2CH(CF3)I; the taxogen can be TFP and the telogen can be (CF3)2CFCH2CF2I; the taxogen can be TFP and the telogen can be (CF3)2CFCH2CF2CH2CF2I; the taxogen can be TFP and the telogen can be (CF3)2CFCH2CF2CH2CF2CH2CH(CF3)I; the taxogen can be TFP and the telogen can be (CF3)2CFCH2CF2CH2CF2CH2CH(CF3)CH2CH(CF3)I; the taxogen can be ethylene and the telogen can be (CF3)2CFCH2CF2CH2CF2CH2CH(CF3)CH2CH(CF3)CH2CH(CF3)I; and the taxogen can be ethylene and the telogen can be (CF3)3CCH2CH(CF3)I.
Telomerization processes can also include exposing a taxogen to a telogen to form a telomer, with the taxogen comprising an olefin having greater than two carbon atoms, and the telogen comprising at least five carbon atoms and having at least two —CF3 groups. As an example, the taxogen can be one of ethylene, VDF, TFP, VDF, 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pent-1-ene and/or 6,7,7,7-tetrafluoro-6-(trifluoromethyl)hept-1-ene.
Telomer 9, produced upon exposing taxogen 2 to telogen 4, can include RF(RT)nQ and/or RCI(RT)nH. The RT group can include at least one C-2 group having a pendant —CF3 group, such as
Exemplary products include
and/or one or both of
with R1 including at least one carbon atom, such as —CH2— and/or —CF2—, for example. RT can also include —CH2—CF2—; —CH2—(CH2CF(CF3)2)CH—; and/or —CH2—CH2—. In exemplary embodiments, n can be at least 1 and in other embodiments n can be at least 2 and the product can include one or more of
for example. According to other implementations n can be 3 or even at least 4. In exemplary embodiments, n can be at least 1 and in other embodiments n can be at least 2 and the product can include one or more of
being H, Br, and/or Cl, for example
In an exemplary embodiment, the taxogen trifluoropropene can be exposed to the telogen (CF3)2CFI to form the telomer
and, by the way of another example, trifluoropropene can be exposed to the telogen C6F13I to form the telomer
In an exemplary embodiment, the taxogen trifluoropropene can be exposed to the telogen (CF3)2CFI to form the telomer
and, by the way of another example, trifluoropropene can be exposed to the telogen C6F13I to form the telomer
In accordance with another embodiment, the taxogen trifluoropropene can also be exposed to the telogen CCl3Z, (Z=H, Br, and/or Cl, for example) to form the telomer
Products having n being at least 2 can be formed when utilizing an excess of the taxogen as compared to the telogen. For example, at least a 2:1 mole ratio of the taxogen to the telogen can be utilized to obtain products having n being at least 2. For example and by the way of example only, at least two moles of the taxogen trifluoropropene can be exposed to at least one mole of the telogen (CF3)2CFI to form one or both of the telomers
According to exemplary embodiments, telomer 9 can include those compounds shown in Table 4 below. As exemplary implementations are shown in Table 4 below, telomers can also be utilized as telogens.
Heterotelomerization can also be accomplished via cotelomerization and/or oligotelomerization. As an example, at least two different taxogens may be combined with at least one telogen to facilitate the production of at least a cotelomer. As another example, telomers may be produced from a first taxogen and the product telomer my be used in a subsequent telomerization with a second taxogens different from the first taxogen.
In additional embodiments initiator 6 may be provided to reactor 8 during the exposing of the reagents. Initiator 6 can include thermal, photochemical (UV), radical, and/or metal complexes, for example, including a peroxide such as di-tert-butyl peroxide. Initiator 6 can also include catalysts, such as Cu. Initiator 6 and telogen 4 can be provided to reactor 8 at a mole ratio of initiator 6 to taxogen 2 of from between about 0.001 to about 0.05 and/or from between about 0.01 to about 0.03, for example.
According to exemplary embodiments, various initiators 6 and telogens 4 can be used to telomerize taxogen 2 as referenced in Table 5 below. Telomerizations utilizing photochemical and/or metal-complex initiators 6 can be carried out in batch conditions using Carius tube reactors 8. Telomerizations utilizing thermal and/or peroxide initiators 6 can be carried out in 160 and/or 500 cm3 Hastelloy reactors 8.
An embodiment of the disclosure provides RF-surfactant compositions that include the RF portions described above. Exemplary RF-surfactant compositions can be referred to as RF-QS. According to exemplary embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the surfactant can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QS portion of the surfactant. Exemplary RS portions include —CH2—CH2—. As an example, the surfactant composition can comprise RF(RT)nQS. The RF group can comprise at least one —CF3 group. The RT group can comprise —CF2CH2CH(CF3)—, with n being at least one. The QS group can be at least one atom of the periodic table of elements, wherein at least a portion of the RF and RT groups are hydrophobic relative to the QS group, and at least a portion of the Qs group is hydrophilic relative to the RF and RT groups.
In a system having at least two parts, RF can have a greater affinity for a first part of the system than QS, and QS can have a greater affinity for a second part of the system than RF. The system can include liquid/liquid systems, liquid/gas systems, liquid/solid systems, and/or gas/solid systems. Liquid/liquid systems, for example, can include systems having at least one liquid part that includes water and another liquid part that is hydrophobic relative to the part that includes water. Liquid/liquid systems can also include systems of which water is not a part of the system, such as hydrocarbon liquid systems. In exemplary embodiments, RF can be hydrophobic relative to QS and/or QS can be hydrophilic relative to RF. RF can be hydrophobic and QS can be hydrophilic, for example. The hydrophobic portion can be referred to as the tail of the RF-surfactant, and the hydrophilic portion can be referred to as the head of the RF-surfactant. The RF-surfactants can include those surfactants having a tail or hydrophobic portion containing fluorine. The RF-surfactant tail or hydrophobic portion can be referred to as an RF portion, and the RF-surfactant head or hydrophilic portion can be referred to as a QS portion. The RF-surfactants can be produced from RF-intermediates utilizing the methods and systems detailed in published International Patent applications: PCT/US05/03429, entitled Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers, filed Jan. 28, 2005; PCT/US05/02617, entitled Compositions, Halogenated Compositions, Chemical Production and Telomerization Processes, filed Jan. 28, 2005; PCT/US05/03433, entitled Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers, filed Jan. 28, 2005; PCT/US05/03137, entitled Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers, filed Jan. 28, 2005; and PCT/US05/03138, entitled Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers, filed Jan. 28, 2005. Exemplary RF-surfactants include those in Table 5 below.
Where LC/MS can be used to identify compounds, Table 6 of LC/MS parameters, below, can be used
According to scheme (16) above, in a flask that can be equipped with an agitator, thermocouple and a reflux condenser, 30 grams (67 mmol) of 1,1,1,2-tetrafluoro-2,4-bis(trifluoromethyl)-8-iodooctane (see, e.g. Published International Patent Applications), 35 ml of absolute ethanol, 9.8 grams of potassium thiocyanate (KSCN) and 1.4 ml of glacial acetic acid (HOAc) can be placed to form a mixture. The mixture can be heated to reflux (about 84.7 C) and maintained for overnight while stirring. The mixture can be observed as a light yellow slurry and can be concentrated in vacuo to afford a viscous yellow slurry. The slurry cab be extracted with 300 mL of diethyl ether, (decanted twice) and filtered to afford a wet cake and a filtrate. The wet cake can be washed with three 100 mL portions of diethyl ether wherein the collected washings can be combined with the filtrate and concentrated in vacuo to afford 25.28 grams (99.5% yield) of the 1,1,1,2-tetrafluoro-2,4-bis(trifluoromethyl)-8-thiocyanatooctane product that can be observed as a light yellow oil. The product structure can be confirmed by NMR and/or chromatographic analysis.
With reference to scheme (17) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and a chlorine gas dispersion tube, 25.2 grams (66.4 mmol) of 1,1,1,2-tetrafluoro-2,4-bis(trifluoromethyl)-8-thiocyanatooctane (refer to scheme (15) above) and 40 ml of glacial acetic acid (HOAc) can be placed to form a mixture and can be heated to about 60° C. The heated mixture can be sparged via a dispersion tube with chlorine gas (Cl2) to form a reaction mixture for overnight. The reaction mixture can be cooled to about 10° C. and 50 ml of water added drop-wise. The reaction mixture can be warmed to RT and 200 ml of CHCl3 and 100 ml of water added to form a multiphase mixture from which an organic phase can be separated from an aqueous phase. The aqueous phase can be collected and extracted with 200 ml of CHCl3. The organic phases can be collected, combined and washed with three 300 ml portions of water and 300 ml of brine and then dried over Na2SO4, filtered and concentrated in vacuo to afford 26.26 grams (95.3% yield) of the 7,8,8,8-tetrafluoro-5,7-bis(trifluoromethyl)octane-1-sulfonyl chloride product that can be observed as a cloudy colorless oil. The product structure can be confirmed by NMR and/or chromatographic analysis.
In accordance with scheme (18) above, in a flask that can be equipped with an agitator, thermocouple and a dry-ice/acetone bath, 17.80 grams (174.5 mmol) of N1,N1-dimethylpropane-1,3-diamine in 150 ml of CHCl3 can be placed to form a mixture. To the mixture, 26.20 grams (62.3 mmol) of 7,8,8,8-tetrafluoro-5,7-bis(trifluoromethyl)octane-1-sulfonyl chloride (refer to scheme (16) above) and 150 ml of CHCl3 can be added drop-wise over a 40 minute period to form a reaction mixture while maintaining the reaction temperature at between about 0° C. and −5° C. The reaction mixture can be allowed to warm to and maintained at RT while stirring for over the weekend. The reaction mixture can be washed by adding 300 ml of water, two 300 ml portions of bicarbonate, 300 ml of water, and 300 ml of brine wherein each step can be observed to afford a multiphase mixture from which an organic phase can be separated from an aqueous phase and the organic phase can be transferred to the next step. The washed organic phase can be dried over Na2SO4, filtered and concentrated in vacuo to afford 30.23 grams (99.8% yield) of the
product that can be observed as a light yellow liquid. The product structure can be confirmed by NMR and/or chromatographic analysis.
Referring to scheme (19) above, in a flask that can be equipped with an agitator, thermocouple and an addition funnel, A mixture of 10.0 grams (20.6 mmol) of
(refer to scheme (18) above), 50 ml of absolute ethanol (EtOH) and 2.40 grams (20.6 mmol) sodium chloroacetate can be placed to form a mixture. The mixture can be heated to reflux (about 79° C.) and stirred for a period of time to afford what can be observed as a thin white slurry. The slurry can be filtered and the filtrate concentrated in vacuo, dried at 45° C. under high vacuum to afford 11.29 grams of the
product that can be observed as a light yellow crunchy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
Referring to scheme (20) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and an addition funnel, 10.0 grams (20.6 mmol) of
(refer to scheme (18) above), 20 ml of absolute ethanol (EtOH) and 3 ml of water can be placed to form a mixture. To the mixture, at RT, 9.6 ml of a 50% (wt/wt) H2O2 in water can be added drop-wise over a 5 minute period to form a reaction mixture. The reaction mixture can be heated to 35° C. and maintained for overnight. The reaction mixture can be treated portion-wise with 6 grams of decolorizing carbon (neutral) over a 2 hour period at 35° C. to form a slurry and heated to 50° C. and maintained stirring for overnight. A sample of the slurry can be collected and filtered and tested negative with KI/Starch paper for any unquenched peroxide. The remainder of the slurry can be filtered through celite and stripped of EtOH on a rotary evaporator. Trace EtOH can be removed by co-stripping three times with CHCl3 to afford a concentrate. The concentrate can be concentrated in vacuo (2 hour under high vacuum at 45° C.) to afford 10.03 grams (97.4% yield) of the
product that can be observed as an off-white crunchy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
In conformity with scheme (21) above, in a sealable tube that can be equipped with an agitator and a thermocouple, 10.0 grams (20.6 mmol) of
(refer to scheme (18) above), 2.1 grams (41.1 mmol) of chloromethane in 25 mL of methyl-tert-butyl ether (MTBE) can be placed to form a mixture and heated to 55° C. for an extended period of time. Stirring can be halted, the bottle cooled below about 0° C., vented, and the mixture concentrated in vacuo to afford 9.81 grams (88.9% yield) of the
product that can be observed as a white waxy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
Referring to scheme (22) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and an addition funnel, 5 grams (0.01 mole) of 5,6,6,6-tetrafluoro-3-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)-5-(trifluoromethyl)hexane-1-sulfonyl chloride (see, e.g. International Patent Applications), 1.2 grams (0.01 mole) of methyl 2-(ethylamino)acetate and 10 mL of chloroform can be placed to form a mixture and chilled to 0° C. To the mixture, 3 mL of triethylamine (TEA) and 10 mL of chloroform can be added drop wise to form a reaction mixture. The peak temperature during addition can be about 3.9° C. The reaction mixture can be allowed to warm to room temperature while stirring and maintained for overnight. To the reaction mixture, 20 mL of cholorform can be added and washed with two 25 mL portions a saturated solution NaHCO3 in water, two 25 mL portions of water and 25 mL of a saturated NaCl solution in water to form multiphase mixtures from which an organic phase can be separated from an aqueous phase. The organic phase can be collected, dried and concentrated to form a concentrate. To the concentrate, 25 mL of chloroform can be added to form a diluant. To the diluant, 25 mL of a 5% (wt/wt) solution of HCl in water can be added to afford an acidified diluant. To the acidified diluant, 25 mL of a 1 N solution of NaOH can be added to form a neutral multiphase mixture from which an organic phase can be separated from an aqueous phase. The organic phase can be dried and concentrated to afford 3.45 grams of the
product that can be observed as a yellow oil (59.5% yd.). The product structure can be confirmed by NMR and/or chromatographic analysis.
In reference to scheme (23) above, in a 60 mL reactor that can be equipped with an agitator, ethane delivery apparatus and a thermocouple, 23.0 grams (50.4 mmol) of 1,1,1,2,4,4,7,7,7-nonafluoro-2-(trifluoromethyl)-6-iodoheptane (see, e.g. Published Patent Applications) and 0.95 grams (2.5 mmol) of di-(t-butylcyclohexyl) peroxydicarbamate (Akzo Nobel—Perkadox 16S) can be placed to form a mixture. The reactor can be sealed and heated to about 50° C. while stirring. To the reactor, ethylene can be added in a continuous fashion to afford and maintain a reactor pressure of about 260 psig to form a reaction mixture. After about 2 hours, the ethylene feed and heating can be discontinued, the reaction cooled to about 10° C., the agitation stopped and the reactor vented and opened. To the reaction mixture, 1.0 gram of Perkadox 16S can be added and heating continued for 3 hours. To the reaction mixture, 0.9 gram of Perkadox 16S can be added, the reactor heated to about 50° C., pressurized with ethylene to about 260 psig and maintained for about 5 hours. To the reaction mixture, additional Perkadox 16S can be added and the above reaction conditions established and maintained for overnight. The reaction mixture can be collected and placed on a Kugelrohr distillation apparatus to afford 26.05 grams of the 1,1,1,2,4,4-hexafluoro-2,6-bis(trifluoromethyl)-8-iodooctane product. The product structure can be confirmed by NMR and/or chromatographic analysis.
Conforming to scheme (24) above, in a sealable tube that can be equipped with an agitator, thermocouple, reflux condenser, and an addition funnel, 6.0 grams (11.5 mmol) of
(see, e.g. Published International Patent Applications) and 1.2 grams (23 mmol) of chloromethane (CH3Cl) in 30 mL of methyl-tert-butyl ether (tBuOMe) can be placed to form a mixture and heated to about 55° C. for an extended period of time. A thick layer can be observed to have settled on the bottom of the tube restricting the stirring. The tube can be cooled and vented, and heated to regain homogeneity. The stir bar can be replaced with a different type and the contents were cooled and charged with an additional 2.9 grams of CH3Cl. Once sealed, the heating can be resumed. A thick layer can be observed to have settled out again. The tube can be sonicated to homogenize and stirred at 55° C. for overnight. The tube can be cooled below about 0° C. and vented where the contents of the tube can be observed as a multiphase mixture wherein a liquid phase can be separated from a clear orange tar. The liquid phase can be discarded and ether added and the contents heated and sonicated to dissolve. The contents can be cooled to RT and the ether decanted from the tar that can be observed to have reformed (precipitated). The tar can be dissolved in dichloromethane, transferred and concentrated to afford to 5.41 grams (90.0% yield) of the
product that can be observed as an orange semi-solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
In reference to scheme (25) above, in a reactor that can be equipped with an agitator, thermocouple, and an ethylene addition apparatus, 23 grams (50.4 mmol) of 1,1,1,2,6,6-hexafluoro-2,4-bis (trifluoromethyl)-6-iodohexane (see, e.g. Published Patent Applications) and 0.95 grams (2.5 mmol) of di-(t-butylcyclohexyl) peroxydicarbamate (Akzo Nobel—Perkadox 16S) can be added to form a mixture. The reactor can be sealed, heated to 50° C. while stirring and continuously pressurized to about 260 psig with ethylene (reactions conditions) to form a reaction mixture. After 2 hours, the ethylene feed and heating can be discontinued, the reaction cooled to about 10° C., the agitation can be discontinued and the reactor vented and opened. To the reaction mixture, 1.0 grams of the Perkadox 16S can be added, reaction conditions restored and maintained for over a weekend. To the reaction mixture, 0.9 grams of Perkadox 16S can be added and the reaction conditions restored and maintained for from about 5 hours 24 hours wherein additional Perkadox 16S can be added. The reaction mixture can be collected and placed on a Kugelrohr distillation apparatus to 26.05 grams of the 1,1,1,2,6,6-hexafluoro-2,4-bis(trifluoromethyl)-8-iodooctane product. The product structure can be confirmed by NMR and/or chromatographic analysis.
Referring to scheme (26) above, in a sealable tube that can be equipped with an agitator and a thermocouple, 7.1 grams (13.6 mmol) 3,3,7,8,8,8-hexafluoro-5,7-bis(trifluoromethyl)octane-1-sulfonic acid(3-dimethylaminopropyl)amide (see, e.g. Published Patent Applications) and 1.4 grams (27.2 mmol) of chloromethane and 30 mL of methyl-tert-butyl ether can be placed to form a mixture. The mixture can be heated to 55° C. and maintained for an extended period of time. A thick layer can be observed to have settled on the bottom of the tube thereby restricting the stirring. The tube can be cooled and vented and heated to regain homogeneity. The agitator can be replaced with a different type and the contents cooled and charged with an additional 3.1 grams of CH3Cl. The tube can be sealed and the heating resumed. A layer can be observed to have settled out again. The tube can be sonicated to homogenize and stirred at 55° C. for overnight to form a multiphase mixture from which a liquid phase can be separated from a tar phase. The tube can be cooled to below about 0° C., vented and the liquid decanted from the tar. To the tar, ether can be added and the contents heated and sonicated to dissolve. The mixture can be cooled to RT and the liquid decanted from the tar that can be observed to have reformed. The tar can be dissolved in dichloromethane, transferred and concentrated to afford 7.0 grams (90.0% yield) of the 3,3,7,8,8,8-hexafluoro-5,7-bis(trifluoromethyl)octane-1-sulfonic acid(3-trimethylaminopropyl)amido chloride product that can be observed as an orange semi-solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
According to scheme (27) above, in a flask that can be equipped with an agitator, thermocouple and a reflux condenser, 20 grams (27 mmol) of 1,1,1,2,4,4,6,6-octafluoro-2,8,10,12-tetrakis(trifluoromethyl)-14-iodotetradecane (see, e.g. Published Patent Applications), 20 ml of absolute ethanol, 3.9 grams (40.5 mmol) of potassium thiocyanate (KSCN) and 0.5 ml of glacial acetic acid (HOAc) can be placed to form a mixture. The mixture can be heated to reflux (84.7 C) and maintained stirring for overnight. The mixture can be concentrated in vacuo to afford what can be observed as a thick yellow slurry. The slurry can be extracted with 300 ml of diethyl ether and decanted twice and filtered to afford a wet cake and a filtrate. The wet cake can be washed with three 100 ml portions of diethyl ether and the filtrates combined. The combined filtrates can be concentrated in vacuo to afford 17.12 grams (94.6% yield) of the 1,1,1,2,4,4,6,6-octafluoro-2,8,10,12-tetrakis(trifluoromethyl)-14-thiocyanatotetradecane product that can be observed as a light yellow oil. The product structure can be confirmed by NMR and/or chromatographic analysis.
Referring to scheme (28) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and a dispersion tube, A yellow solution of 17.1 grams (25.5 mmol) of 1,1,1,2,4,4,6,6-octafluoro-2,8,10,12-tetrakis(trifluoromethyl)-14-thiocyanatotetradecane (refer to scheme (23) above) and 30 ml of HOAc can be placed to form a mixture. The mixture can be heated to about 60° C. and sparged via the dispersion tube with chlorine gas (Cl2) for overnight. The flow of chlorine can be observed to have stopped overnight, causing the reaction material to back up into the trap. A portion of the mixture, what can be observed as a white liquid, can remain in the flask and can still be in contact with the thermocouple. Chlorination can be continued for about two overnight periods to afford what can be observed as a slurry. The slurry can be cooled to about 10° C. and about 40 ml of water can be added drop wise to form a reaction mixture. The reaction mixture can be warmed to room temperature (RT) and diluted with about 200 ml of chloroform (CHCl3) and about 100 ml of water to form a multiphase mixture from which an organic phase can be separated from an aqueous phase. The aqueous phase can be extracted with 200 ml of CHCl3 and the organic phases combined. The combined extracts can be washed with three 300 mL portions of water and the organic phase collected. The organic phase can be washed with 300 ml of brine and dried over Na2SO4, filtered and concentrated in vacuo to afford 16.52 grams (91.0% yield) of the 9,9,11,11,13,14,14,14-octafluoro-3,5,7,13-tetrakis(trifluoromethyl)tetradecane-1-sulfonyl chloride that can be observed as a cloudy colorless oil. The product structure can be confirmed by NMR and/or chromatographic analysis.
In reference to scheme (29) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, addition funnel and a dry-ice/acetone bath, 16.5 grams (23.1 mmol) of 9,9,11,11,13,14,14,14-octafluoro-3,5,7,13-tetrakis(trifluoromethyl)tetradecane-1-sulfonyl chloride (refer to scheme (24) above) and 50 mL of CHCl3 can be placed to form a mixture. In the addition funnel, 6.60 grams (64.9 mmol) of 3-dimethylaminopropylamine and 50 ml of CHCl3 can be added to form an addition mixture. To the mixture, the addition mixture can be added drop-wise over a 30 minute period to form a reaction mixture while maintaining the temperature at between about 0° C. and −5° C. The reaction mixture can be allowed to warm to room temperature (RT) and stir overnight. The reaction mixture can be washed with one 200 ml portion of water, two 200 ml portions of a saturated solution of bicarbonate and one 200 ml portion of brine wherein each step can be observed to form a multiphase mixture from which an organic phase can be separated from an aqueous phase. The organic phase can be collected and dried over Na2SO4, filtered and concentrated in vacuo to afford 39.30 grams (95.9% yield) of the
product that can be observed as a light yellow liquid. The product structure can be confirmed by NMR and/or chromatographic analysis.
According to scheme (30) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and an addition funnel, 5.80 grams of
(refer to scheme (26) above), 15 ml of absolute ethanol and 1.1 ml of water at RT can be placed to form a mixture. To the mixture, 3.5 ml of 50% H2O2 can be added drop-wise over a 1 minute period to form a reaction mixture. The reaction mixture can be heated to 35° C. and maintained for over the weekend. The reaction mixture can be treated portion-wise with 5 grams of decolorizing carbon (neutral) over a 1 hour period at 35° C. to form a slurry. The slurry can be heated to about 50° C. and maintained for overnight while stirring.
A sample of the slurry can be filtered and the filtrate tested negative for the presence of peroxides. The remainder of the slurry can be filtered through celite to afford a filtrate. The filtrate can be concentrated in vacuo to afford the
product that can be observed as an off-white crunchy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
In accordance with scheme (31) above, in a sealable tube that can be equipped with an agitator, 5.50 grams (7.1 mmol) of
(refer to scheme (26) above), 2.2 grams of chloromethane in 20 mL of methyl-tert-butyl ether (MTBE) can be placed to form a mixture and heated to about 55° C. for an extended period of time. Stirring can be halted and the mixture cooled to below about 0° C. and the tube vented. The mixture can be concentrated in vacuo to afford the
product that can be observed as a white waxy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
In accordance with scheme (32) above, in a flask that can be equipped with an agitator, thermocouple, reflux condenser, and an addition funnel, 5.50 grams (7.1 mmol) of
(refer to scheme (26) above), 20 mL of absolute ethanol and 0.90 grams (7.1 mmol) of sodium chloroacetate can be placed to form a mixture. The mixture can be heated to reflux (about 79° C.) and stirred for a period of about 6.5 days. The reaction mixture can be observed as a thin white slurry and can be filtered to afford a filtrate. The filtrate can be concentrated in vacuo and dried at 45° C. under high vacuum to afford 11.03 grams of the
product that can be observed as a light yellow crunchy solid. The product structure can be confirmed by NMR and/or chromatographic analysis.
According to another embodiment, a mercaptan RF-intermediate may also be produced by reacting a iodine RF-intermediate with thiourea to make the isothiuronium salt and treating the isothiuronium salt with sodium hydroxide to give the mercaptan RF-intermediate plus sodium iodide, as described in U.S. Pat. No. 3,544,663 herein incorporated by reference.
In an exemplary aspect of the disclosure, the mercaptan RF-intermediate may be attached to a QS portion such as group 2-acrylamido-2-methyl-1 propane sulfonic acid available from Lubrizol as AMPS 2403, as generally described in U.S. Pat. No. 4,000,188 herein incorporated by reference.
Aminoxides of the RF-surfactants can be produced according to processes that include those generally described in U.S. Pat. No. 4,983,769, herein incorporated by reference. Accordingly, sulfoamidoamines 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 be added and the mixture and refluxed for about 2 hours. The reaction mixture can be filtered and the filtrate evaporated to dryness to provide the amine oxide of the RF-surfactant.
In accordance with another embodiment of the disclosure, processes are provided that can be used to alter the surface tension of a part of a system having at least two parts. The system can include liquid/solid systems, liquid/gas systems, gas/solid systems, and/or liquid/liquid systems. In an exemplary embodiment, the liquid/liquid systems can have one part that includes water and another part that includes a liquid that is relatively hydrophobic when compared to water. According to another example, the liquid/liquid system can contain one part that is relatively hydrophobic when compared to water and/or relatively hydrophobic when compared to another part of the system. RF-surfactants can be used to alter the surface tension of a part of the system, for example, by adding the RF-surfactant to the system.
RF-surfactants may be used as relatively pure solutions or as mixtures with other components. For example, and by way of example only, the RF-surfactants can be added to a system and the surface tension of the system determined by the Wilhelmy plate method and/or using the Kruss Tensiometer method.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 1 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 2 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 3 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 4 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 5 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 6 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 7 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 8 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 9 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 10 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 11 below.
As another example, the surface tensions of
at various concentrations can be determined and the data as indicated in Plot # 12 below.
As another example, the surface tensions of
various concentrations can be determined and the data as indicated in Plot # 13 below.
RF-surfactants described above may be incorporated into detergents, emulsifiers, paints, adhesives, inks, wetting agents, foamers, and/or defoamers, for example.
RF-surfactants can be incorporated into AFFF formulations and these formulations can be used as fire-fighting foams, to prevent, and/or extinguish combustion. An exemplary use of AFFFs that include an RF-surfactant includes the addition of the AFFF to high pressure misting systems, the misting systems being used to prevent and/or extinguish combustion. AFFF formulations can be provided to a substrate, for example. The substrate can include liquid and/or solid compositions. The AFFF formulations can also be dispersed into an atmosphere including gaseous atmospheres, such air to prevent and/or extinguish combustion.
The formulations can include other components such as water soluble solvents. These solvents may facilitate the solubilization of the RF-surfactants and other surfactants. These solvents can also act as foam stabilizers and/or freeze protection agents. Exemplary solvents can include ethylene glycol, diethylene glycol, glycerol, ethyl Cellusolve®, butyl Carbitol®, Dowanol DPM®, Dowanol TPM®, Dowanol PTB®, propylene glycol, and/or hexylene glycol. Additional components to the formulation, such as polymeric stabilizers and thickeners, can be incorporated into the formulation to enhance the foam stability property of a foam produced from aeration of the aqueous solution of the formulation. Exemplary polymeric stabilizers and thickeners include partially hydrolyzed protein, starches, polyvinyl resins such as polyvinyl alcohol, polyacrylamides, carboxyvinyl polymers, and/or poly(oxyethylene)glycol. Polysaccharide resins, such as xanthan gum, can be included in the formulation as a foam stabilizer in formulations for use in preventing or extinguishing polar solvent combustion, such as alcohol, ketone, and/or ether combustion, for example. The formulation can also include a buffer to regulate the pH of the formulation, for example, tris(2-hydroxyethyl)amine or sodium acetate, and a corrosion inhibitor such as toluoltriazole or sodium nitrite may be included. Water soluble electrolytes such as magnesium sulphate may be included and can improve film-spreading characteristics of the formulation.
The RF-surfactants can also be useful in formulations that include other surfactants such as alkyl sulfate, alkylethersulfates, alphaolefinsulfonates, alkyl sulfobetaines, alkyl polyglycerides, alkylamidopropylbetaines, alkylimidazolinedicarboxylates, 2-alkylthiopropionamido-2 methyl-propanesulfonoic acid sodium salt, alkyliminodipropinates, alkylsulfonates, ethoxylated alkylphenols, dialkylsulfosuccinates, and/or alkyltrimethyl ammonium chloride.
A variation of AFFF, ARAFFF, an acronym for Alcohol Resistant Aqueous Film Forming Foam(s), can be used to extinguish hydrocarbon fires in much the same manner that AFFF foams are used and may also be used to extinguish fires involving water soluble solvents such as acetone and isopropanol which conventional AFFF foams will not extinguish.
ARAFFF formulations can contain the same ingredients as conventional AFFF formulations plus a polysaccharide such as xanthan gum and, in some formulations, a polymeric foam stabilizer. Polymeric foam stabilizers are offered by DuPont® and Dynax®, Inc. An exemplary DuPont product, Forafac® 1268, is a water soluble acrylic polymer. An exemplary Dynax product, DX5011®, is an ethyleneimine polymer. Xanthan gum is offered by several suppliers, including Kelco CP (Kelzan) and Rhodia North America (Rhodopol).
Polysaccharide alone can be sufficient to make ARAFFF formulations alcohol resistant, but the amount required produces a foam concentrate that can be quite viscous. The use of a polymeric foam stabilizer can permit a reduction in the amount of polysaccharide required to give useful alcohol resistance.
Because of the possibility of microbial attack on polysaccharide solutions, ARAFFF concentrates can contain an effective amount of a biocide such as Kathon CG ICP, manufactured by Rohm & Haas. Many other biocides such as Acticide, Nipacide and Dowicil can also be effective.
Some ARAFFF formulations can be designed to be proportioned at different percentages depending on whether the substrate to be extinguished is a hydrocarbon or an alcohol type substrate, for example. Alcohol type can include any fuel having a hydroxyl group.
Exemplary ARAFFF formulations utilizing the RF surfactants can be provided and/or formulated in accordance with the methods described in the Published International Applications. Foam stabilizers, such as RF-stabilizers that include RF groups described above, for example, can be prepared. RF-stabilizers can include RF-QFS compositions. Example foam stabilizer compositions can include RF(RT)nQFS. The RF group can comprise at least one —CF3 group. The RT group can comprise —CF2CH2CH(CF3)—, with n being at least 1. The QFS group can be at least one atom of the periodic table of elements, wherein at least a portion of the RF and RT groups are hydrophobic relative to the QFS group, and at least a portion of the QFS group is hydrophilic relative to the RF and RT groups.
According to exemplary embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the surfactant can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QFS portion of the surfactant. Exemplary RS portions include —CH2—CH2—QFS can include portions that have a greater hydrophilic character than RF. Exemplary QFS portions include the Qs portions described herein as well as those having polyalkoxylated amines. Exemplary RF-Foam Stabilizers include, but are not limited to those in Table 7 below.
RF-metal complexes such as RF-QMC incorporating the RF portions are also provided. The RF portions can be incorporated as acid halides or carboxylic acids, for example, with the acid halide including, but not limited to, acid fluorides, for example. According to exemplary embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the complex can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF. and/or RF(RT)n portions and the QMC portion of the complex. Exemplary RS portions include —CH2—CH2—. RF-metal complexes can include RF-intermediates and, as such, Qg can be interchangeable with QMC. QMC can include the portion of a ligand of a metal complex that is coordinated with the complexed metal, for example. Metal complexes are provided that can include RF(RT)nQMC. The RF group can include at least one —CF3 group. The RT group can include —CF2CH2CH(CF3)—, with n being at least 1. The QMC group can include a charged group configured to complex one or more metal ions. Exemplary RF-metal complexes include, but are not limited to, those in Table 8 below.
RF-metal complexes such as RF-QMC incorporating the RF portions are also provided. The RF portions can be incorporated as acid halides or carboxylic acids, for example, with the acid halide including, but not limited to, acid fluorides, for example. According to exemplary embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the complex can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QMC portion of the complex. Exemplary RS portions include —CH2—CH2—. RF-metal complexes can include RF-intermediates and, as such, Qg can be interchangeable with QMC. QMC can include the portion of a ligand of a metal complex that is coordinated with the complexed metal, for example. Exemplary RF-metal complexes can be prepared by way of the following exemplary synthetic steps.
An acid fluoride RF-intermediate can be reacted with an amino acid such as glycine (2-aminoacetic acid) to produce an amido-carboxylic acid. The amido-carboxylic acid can be reacted with chromic chloride in an alcohol such as methanol and/or isopropanol to produce an exemplary RF-metal complex such as a RF chrome complex. Exemplary acid RF-intermediates for use in preparation of RF-metal complexes can include ethylene carboxylic acid RF-intermediates and/or mixtures of ethylene carboxylic acid RF-intermediates and carboxylic acid RF-intermediates. Exemplary preparations can be performed in accordance with U.S. Pat. Nos. 3,351,643, 3,574,518, 3,907,576, 6,525,127 and 6,294,107, herein incorporated by reference. RF-metal complexes can include a ligand having a RF portion and a QMC portion associated with the metal of the complex. In exemplary embodiments the QMC portion can have a greater affinity for the metal complex than the RF portion. RF-metal complexes can be used to treat substrates such as paper, leather, textiles, yarns, fabrics, glass, ceramics, and/or metals. In some cases, treating substrates with the complexes can render the substrates less permeable to water and/or oil. The above described chrome complex solutions can be applied as a surface treatment of a variety of materials including, but not limited to, leather by the employment of the methods described in U.S. Pat. No. 3,351,643 and U.S. Pat. No. 3,948,887, herein incorporated by reference.
An embodiment of the present invention also provides for incorporation of the RF portions into phosphate ester which, in exemplary embodiments, can be used to treat substrates and/or as dispersing agents during the preparation of polymers. Exemplary RF-phosphate esters include RF-QPE, with the QPE portion being the phosphate portion of the RF-composition. According to exemplary to embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the ester can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QPE portion of the ester. Exemplary RS portions include —CH2CH2—. Phosphate esters are provided that can include RF(RT)nQPE. The RF group can include at least two —CF3 groups. The RT group can include a group having at least two carbons, with n being at least 1. The QPE group can be a portion of a phosphate ester. RF-phosphate esters, include, but are not limited to, those in Table 9 below.
RF-phosphate esters can be used as dispersing agents in the preparation of polymers or they can be diluted and used to treat substrate materials in aqueous bathes, for example, by ordinary means such as padding, dipping, impregnating, spraying, etc. These composition can be incorporated into or used to treat such materials as textile fabric, textile yarns, leather, paper, plastic, sheeting, wood, ceramic clays, as well as, manufactured articles of apparel, wallpaper, paper bags, cardboard boxes, porous earthenware, etc. U.S. Pat. No. 3,112,241 describes methods for treating materials using phosphate esters and is herein incorporated by reference. RF-phosphoric acid ester can be used to treat substrates such as wood pulp products, including paper products such as packaging products including food packaging products.
According to scheme (34) above, benzene, pyridine and phosphorous oxychloride (POCl3) can be combined to form mixture A. Mixture A can be chilled to about 7° C., from about 0° C. to about 15° C., and/or about 2° C. To mixture A, a mixture of RF(RT)n—OH, pyridine and benzene can be added to form a reaction mixture. The reaction mixture can be allowed to warm to room temperature and heated to reflux and maintained for about one hour to afford a product mixture that can comprise the mono (n=2), bis(n=1) and tris (n=0)RF-phosphate esters. To the product mixture, water can be added to provide a product mixture that can comprise the acid esters of the above acid chlorides.
An embodiment includes the RF portions incorporated into glycols, such as RF-glycols, including RF-QH, with QH representing the ether portion of the glycol after conjugation or, as hydroxyl functionality before conjugation as the ether. According to exemplary embodiments the RF portion can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the glycol can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QH portion of the glycol. Exemplary RS portions include —CH2—CH2—. Glycols are provided than can include RF(RT)nQH. The RF group can include at least one —CF3 group. The RT group can include —CF2CH2CH(CF3)—, with n being at least 1. The QH group can be a portion of a glycol chain backbone. Exemplary RF-glycols include, but are not limited to, those in Table 10 below.
RF-glycols can be incorporated into polymers such as urethanes including polyurethane elastomers, films and coatings, for example. RF-glycols can be converted to phosphoric acids or phosphate esters of those glycols as well. Referring to scheme 35 below, RF portions can be incorporated into glycols.
Methods for preparing glycols are described in U.S. Pat. No. 4,898,981, U.S. Pat. No. 5,491,261, U.S. Pat. No. 5,091,550, U.S. Pat. No. 5,132,445, and Dupau, et. al., Adv. Synth. Catal. 2002. 344. No. 3&4, Procedure B, all of which are herein incorporated by reference. For example, and by way of example only, an RF-intermediate (QG=SH) can be reacted with a sulfide diol or 2,6 diox-aspiro (3,3) heptane to produce exemplary RF-glycols (QH═H2CH2CSH2CH2—). The RF-glycol can be used directly or indirectly to prepare a RF condensation product such as polyesters, polyureas, polycarbonates and polyurethanes. The glycol functionality can be incorporated into block polymers using RF-glycols. U.S. Pat. No. 5,491,261 discloses several other glycols that can benefit from the RF portion of the present invention and is herein incorporated by reference.
RF-glycols may be converted to phosphoric acid functionality or phosphate esters (not shown). U.S. Pat. Nos. 5,091,550, 5,132,445, 4,898,981 and 5,491,261 all disclose methods of preparing diols and converting diols to phosphate esters and are herein incorporated by reference. In an exemplary implementation, the diols can be converted to phosphoric acids or phosphate esters by reacting diols in the presence of phosphoric acid. These compositions can be incorporated into compounds which can act as oil and/or grease proofing for paper, as well as, soil release agents for textile fibers.
According to scheme (35) above, pentaethylene glycol and anhydrous tetrahydrofuran (THF) can be combined to form a first mixture. The mixture can be cooled to about 0° C. in an acetone/ice bath. To the first mixture, sodium bis(trimethylsilyl)amide in THF can be added to form a second mixture. The second mixture can be stirred at about 0° C. for about 15 minutes. To the second mixture, the RF(RT)n—X, wherein X is a halogen, and THF can be added drop-wise to form a reaction mixture. The reaction mixture can be allowed to warm to room temperature and maintained for about two hours. The reaction mixture can be heated to about 40° C. and maintained for overnight. The reaction mixture can be allowed to cool to room temperature and a 5% (wt/wt) solution of HCl can be added to form a multiphase mixture having a pH of about 7, from which an organic phase can be separated from an aqueous phase. The organic layer can be concentrated in vacuo to afford the RF-glycol. The product structure can be confirmed by NMR and/or chromatographic analysis.
According to another embodiment of the present invention, oligomers, polymers, copolymers, acrylics, and/or resins, for example, can be prepared that include an RF-monomer unit, such as RF-QMU. The monomer unit portion, QMU, can be a single unit within a complex of units and the monomer unit need not repeat within the complex. In an exemplary embodiment, the monomer unit can be a single unit within the complex or it may be one of many identical units linked together, such as a homopolymer, for example. The complex can also include block polymers and/or polyurethane resins. The RF of the unit can include a pendant group of the monomer unit. The monomer unit may be associated with a complex, perhaps even bonded to the complex, for example, and QMU can include the portion of the monomer unit that is associated with the complex. The complex may be coated onto a substrate or it may be chemically bonded to the substrate. For example, a preparation of RF-intermediates can be provided to the substrate and groups such as hydroxyl groups common to substrates like cotton, may provide sites that allow the RF-intermediate to chemically bond to the substrate when forming part of, or being associated with a complex. In an exemplary embodiment, QMU can represent the acrylate functionality of an acrylic and RF can be a pendant group from the acrylics chain and/or backbone. Polymers comprising RF(RT)nQMU are provided. The RF group can include at least one —CF3 group. The RT group can include —CF2CH2CH(CF3)—, with n being at least 1. The QMU group can be a portion of a polymer chain backbone. Exemplary. RF-monomer units include but are not limited to those in Table 11 below.
In exemplary embodiments oligomers containing a RF-monomer unit can be prepared from RF-monomers. RF-monomers can include RF-intermediates above, but may contain functionality that allows for their conjugation with another monomer, but not necessarily the same RF-monomer. The monomers can include RF(RT)nQM. The RF group can include at least one —CF3 group. The RT group can include —CF2CH2CH(CF3)—, with n being at least 1. The QM group can be at least one atom of the periodic table of elements. Exemplary RF-monomers include, but are not limited to those in Table 12 below.
Referring to scheme (36) below, multiple reactions sequences are shown for the preparation of RF-monomers having the RF group.
U.S. Pat. Nos. 3,491,169, 3,282,905, 3,497,575, 3,544,663, 6,566,470, 4,147,851, 4,366,299, 4,439,329, and 5,439,998 all relate to the use and preparation of acrylic emulsion polymers that can benefit from the RF groups and, are herein incorporated by reference. Thiol RF-intermediates, iodine RF-intermediates, hydroxyl RF-intermediates, and/or acetate RF-intermediates can be converted to RF-monomers according to scheme (35) above, and these RF-monomers can be used to prepare a composition containing an RF-monomer unit.
For example, and by way of example only, the RF portion can be incorporated into a RF-monomer as described in U.S. Pat. No. 6,566,470 represented as RF—W—X—C(═O)—C(R1)═CH2, with the RF portion as described above. W can be an alkylene with 1 to 15 carbons, hydroxyalkylene with 3 to 15 carbons, —(CnH2n)(OCmH2m)q—, —SO2NR2—(CnH2n)—, or —CONR2—(CnH2n)—, with n being 1 to 12, m being 2 to 4, q being 1 to 10, and R1 being an alkyl group with 1 to 4 carbon atoms, for example, X being O, S and/or N(R2), where R2 is as R1.
According to scheme (37) and procedures set forth in the published international applications, RF-acrylates can be prepared wherein R═CH3 or H and X is a halogen. The resulting acrylates can be homopolymerized and/or copolymerized according to the general procedures listed in the published international applications. For example and by way of example only, solutions of RF-monomers can be provided to a substrate and allowed to complex, for example, via evaporating the solvent of the solution to form a complex that includes a RF-monomer unit, providing these solutions to a substrate such as glass, nylon, and/or cotton and allowing the RF-monomer to become part of a complex, such as coating the substrate.
The surface energy of the complex can be determined using the standard Fowkes method using diiodomethane and water as probe liquids, and the Zisman method of surface energy analysis using octane, decane, tetradecane, and hexadecane as probe liquids. Contact angle of drops of Zisman probe liquids, as well as the Fowkes probes, can be determined using a Kruss prop Shape Analysis System.
RF-monomers can be incorporated with other monomers and then incorporated into the construction of paper materials or used to treat paper materials. RF-monomers can also be used to prepare polymer solutions. Polymeric solutions can be diluted to a percentage aqueous or non-aqueous solution and then applied to substrates to be treated, such as paper plates.
RF-monomers can also be incorporated into copolymers with comonomers such as the dialkyl amino alkyl acrylate or methacrylate or acrylamide or methacrylamide monomer and its amine salt quaternary ammonium or amine oxide form, as described in U.S. Pat. No. 4,147,851, herein incorporated by reference. The general formula for RF-monomers can be RFqO2CC(R)═CH2, with R being H or CH3, q being an alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, or CnH2n(OCqH2q)m—, —SO2NR1(CnH2n)—, or —CONR1(CnH2n)—, n being 1 to 15, q being 2 to 4, and m being 1 to 15. Monomers used to form copolymers with acrylates and the RF-monomers include those having amine functionality. These copolymers can be diluted in a solution and applied or incorporated directly into or on substrates to be treated, such as paper.
RF-monomers can also be used to form acrylate polymers or other acrylate monomers consistent with those described in U.S. Pat. No. 4,366,299, herein incorporated by reference. As described, RF-monomers can be incorporated into paper products or applied thereon.
RF-monomers, acrylates and/or acrylics, for example, can be applied to finished carpet or incorporated into the finished carpet fiber before it is woven into carpet. RF-monomers can be applied to carpet by a normal textile finishing process known as padding, in which the carpet is passed through a bath containing the RF-monomer and, for example, latex, water, and/or other additives such as non-rewetting surfaces. The carpet can then be passed through nip rollers to control the rate of the add-on before being dried in a tenter frame.
RF-monomers may also be incorporated into the fiber by reacting the fiber with RF-intermediates having isocyanate functionality, RF-isocyanate, for example.
RF portions can also be incorporated into materials used to treat calcitic and/or siliceous particulate materials. For example, RF-monomers can be incorporated into a copolymer where the copolymer can either be part of a formulation to treat these materials or used by itself to treat these materials as described in U.S. Pat. No. 6,383,569, herein incorporated by reference. The RF-monomer can have the general formula RF-Q-A-C(O)—C(R)═CH2 wherein RF is described above, R is H or CH3, A is O, S, or N(R1), wherein R1 is H or an alkyl of from 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(CnH2n)(OCqH2q)m—, —SO2—NR1(CnH2n)—, or —CONR1(CnH2n)—, wherein R1 is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to 15.
RF-compositions and mixtures containing the RF portion can be used to treat substrates including hard surfaces like construction materials such as brick, stone, wood, concrete, ceramics, tile, glass, stucco, gypsum, drywall, particle board, and chipboard. These compositions and mixtures can be used alone or in combination with penetration assistance such as non-ionic surfactants. These compositions can be applied to the surface of calcitic and/or siliceous architectural construction material by known methods, for example, by soaking, impregnation, emersion, brushing, rolling, or spraying. The compositions can be applied to the surface to be protected by spraying. Suitable spraying equipment is commercially available. Spraying with a compressed air sprayer is an exemplary method of application to the particular substrate. U.S. Pat. Nos. 6,197,382 and 5,674,961 also describe methods for applying and using polymer solutions and are herein incorporated by reference.
In an exemplary process of producing solutions having components with RF, an RF-intermediate having a methyl-epoxide functionality may be condensed with a monocarboxylic alkenoic acid to prepare an unsaturated RF-ester (not shown). Exemplary methods for producing these kinds of unsaturated esters are described in U.S. Pat. No. 5,798,415, herein incorporated by reference. Additional esters may be prepared according to U.S. Pat. No. 4,478,975, herein incorporated by reference. Components of these solutions can also include dimethyl amino ethyl methacrylate, and these components can be applied in organic and inorganic solvents, as described in U.S. Pat. No. 6,120,892 herein incorporated by reference. RF-monomers can also be combined with other monomers to produce copolymers or in solutions with amido and sulfur monomers as described by U.S. Pat. No. 5,629,372 herein incorporated by reference.
RF-intermediates having amine functionality can also be reacted with tetrachlorophthalic anhydride using U.S. Pat. No. 4,043,923 as an exemplary reaction scheme (not shown). U.S. Pat. No. 4,043,923 is herein incorporated by reference. The reaction product can be mixed with a carpet cleaning solution to provide soil repellency.
In exemplary embodiments urethanes containing a RFQU (RF-Urethanes) can be prepared from RF-Intermediates. RF-Urethanes can include RF-intermediates above, but may contain functionality that allows for their conjugation with another RFQU compounds, but not necessarily the same RFQU compound. According to exemplary embodiments the RF portion of the urethane can at least partially include an RF(RT)n portion as described above. The RF(RT)n portion of the urethane can also include the RS portion described above. In accordance with exemplary implementations the RS portion can be incorporated to provide additional carbon between the RF and/or RF(RT)n portions and the QU portion of the urethane. Exemplary RS portions include —CH2—CH2—. Urethanes comprising RF(RT)nQU are provided. The RF group can include at least one —CF3 group. The RT group can include —CF2CH2CH(CF3)—, with n being at least 1. The QU group can be at least one atom of the periodic table of elements. Exemplary RF-urethanes, such as RF-QU, can include, but are not limited to those listed in Table 13 below.
In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.
This patent claims priority to U.S. provisional patent application 60/841,936 which was filed Sep. 1, 2006, entitled “Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams and Foam Stabilizers” and which is incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| 60841936 | Sep 2006 | US |
