MXPA06005345A - Ion conductive copolymers containing one or more hydrophobic oligomers - Google Patents

Abstract

In one aspect, the invention provides ion conductive copolymers comprising (1) a plurality of first oligomers, (2) a plurality of second oligomers, (3) ion conductive monomers and (4) linking monomers. The oligomers preferably are hydrophobic and together with the ion conductive monomers are randomly dispersed between the linking monomers. Uses of such polymeric materials include the formation of polymer electrolyte membranes (PEMs), catalyst coated membranes (CCM's) and membrane electrolyte assemblies (MEA's) which may be used in fuel cellsand the like.

Description

COPOLY EROS CONDUCTORS OF IONS CONTAINING ONE OR MORE HYDROPHOBIC OLIGOMERS TECHNICAL FIELD The present invention is concerned with ion conducting polymers which are useful for forming polymeric electrolytic membranes used in fuel cells.

BACKGROUND OF THE INVENTION Fuel cells have been projected as temporary power sources for portable electronic devices, electric vehicles and other applications due mainly to their non-polluting nature. Of the various fuel cell systems, polymer-based electrolytic membrane fuel cell technology such as direct methanol fuel cells (DMFC) have attracted much interest due to their high energy density and high conversion efficiency. Energy. The "heart" of a fuel cell based on polymeric electrolytic membrane is the so-called "membrane-electrode assembly" (MEA), which comprises a proton exchange membrane (PEM), catalyst arranged on the opposite surfaces of the PEM to form a catalyst coated membrane (CCM) and pair of electrodes (that is, an anode and a cathode) arranged to be in electrical contact with the catalytic layer. Proton conductive membranes for DMFC are known, such as Nafion® from E.I. Dupont De Nemours and Company or analogous products of Dow Chemicals. These perfluorinated hydrocarbon sulfonate ionomer products, however, have serious limitations when used at high temperature, the Nafion® fuel cell application loses conductivity when the operating temperature of the fuel cell is over 80 ° C. In addition, Nafion® has a very high methanol cross rate, which prevents its applications in DMFC. U.S. Patent 5,773,480, assigned to the Ballard Power System, describes a fluorinated proton conducting membrane of α, β, / 3-trifluorostyrene. One disadvantage of this membrane is its high manufacturing cost due to the complex synthetic processes for the monomer of α, β, β-trifluorostyrene and the deficient sulfonation capacity of poly (α, β, β-trifluorostyrene). Another disadvantage of this membrane is that it is very brittle, so it has to be incorporated into a support matrix. U.S. Patent Nos. 6,300,381 and 6,194,474 issued to Kerres, et al., Describe a combined binary acid-base polymer system for proton conductive membranes, wherein the sulfonated poly (ether sulfone) was made by post-sulfonation of the poly. (ether sulfone). M. Ueda in the Journal of Polymer Science, 31 (1993): 853, describes the use of sulfonated monomers to prepare poly sulfonated sulfone ether polymers. US Patent Application US 2002 / 0091225A1 of McGrath et al. Used this method to prepare sulphonated sulfone polymers. The need for a good membrane for the operation of the fuel cell requires the balancing of various properties of the membrane. Such properties include proton conductivity, fuel resistance, chemical stability and fuel crossing especially for high temperature applications, fast start-up of DMFCs and durability of cell performance. In addition, it is important that the membrane retain its dimensional stability in the temperature range of fuel operation. If the membrane swells significantly, it will increase the fuel crossing, resulting in degradation of the cell's performance. The dimensional changes of the membrane also stress the bonding of the membrane-catalytic electrode assembly (MEA). Frequently this results in delamination of the catalyst membrane and / or electrode after excessive swelling of the membrane. Therefore, it is necessary to maintain the dimensional stability of the membrane over a wide temperature range and to minimize swelling of the membrane.

BRIEF DESCRIPTION OF THE INVENTION The invention provides ion conducting copolymers which can be used to make proton exchange membranes (PEM), catalyst coated proton exchange membranes (CCM) and membrane electrode assemblies (MEA) which are useful in fuel cells and their application in electronic devices, energy sources and vehicles. In one aspect, the ion-conducting copolymers comprise at least one hydrophobic oligomer - (sometimes referred to as block segments or polymers) which is randomly dispersed in a fundamental structure or polymer backbone comprising one or more ion-conducting monomers. In another aspect, the ion-conducting polymer comprises at least two different hydrophobic monomers randomly dispersed in the fundamental chain of the polymer. In a preferred embodiment, a linking monomer is used to bind the oligomer and ion-conducting monomer. If two hydrophobic oligomers are used, the first oligomer preferably comprises a first monomer and a second monomer, while the second oligomer comprises third and fourth monomers. In one aspect, the oligomers are hydrophobic. In another aspect, one of the first or second oligomers is a hard polymer relative to the other. The ion-conducting monomers comprise a monomer and an ion-conducting group such as a sulfonic acid group. In some embodiments, the same monomer that does not contain an ion-conducting group can be used as the linking monomer in combination with the ion-conducting monomer to control the degree to which the copolymer contains ion-conducting groups. Alternatively, the linking monomer is structurally distinct, that is, different from the ion-conducting monomer. The relative amounts of monomers and oligomers used to synthesize the copolymer can be varied to control the relative amount of ion-conducting groups in the copolymer. Before the synthesis, each of the first oligomer, second oligomer and ion-conducting monomer contain leaving groups, such as halides, at their distant ends. The binding monomer, on the other hand, comprises two displacement groups such as phenoxide, alkoxide or sulfide associated with aromatic monomers. After the reaction of the binding monomer with each of the first oligomer, second oligomer and ion-conducting monomer, the displacement groups and the leaving groups react to form a plurality of different portions within the ion-conducting polymer. Alternatively, the first oligomer, second oligomer and ion-conducting monomer comprise displacement groups and the linking monomer comprises leaving groups.

A first hydrophobic oligomer can be represented by the formula (AB) ^ or (BA) mB. A second hydrophobic oligomer can be represented by the formula (CD) nC or (DC) nD. Each of these oligomers is randomly distributed in a fundamental chain of the ion-conducting polymer to form a copolymer which can be represented by Formula I Formula I - ((AiiXi-Ara-XsA? A-Xa) rt- Xr-ÁT2-) Ji ^ Ai ^ ^ Áis- s-Ax ^ -Xd -ÁX -X ^ wherein the first group (Ar? X? -Ar2-X2Ar3-X3) m-Ar? X? -Ar2- corresponds to (AB) ^, the second group (Ar-X4-Ar5-X5-Ar6-X6)? ? ~ Ar4-X4-Ar5- corresponds to (CD) nC, where (AB) ^ and (CD) nC can be the same or different. (Ar7-X-Ar8) is a monomer that is modified to contain an ion-conducting group and R! -Ar9-Y-Ar10-R- is a linking monomer. In a preferred embodiment, (AB) mA and (CD) nC are different. In this formula, Ari7 Ar2, Ar4, Ars, Ar7, Ar8, Ar9, Ar10, are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, substituted aryl nitrile and one or more of Ar7 and / or one or more of Ar8 comprise in addition one or more pendant ion groups, Xx and X4 are independently - (CO) - or -S (0) 2, X2, X3, X5 and Xe are independently -0- or -S-; X7 is a bond, -C (0) - or S (0) 2-. Ar3 and Ar6 are the same and different from each other and are wherein the ion conductive group comprises -S03H, -COOH, -HP03H or -S02NH- S02-RF wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the copolymer; Ri and R2 are independently -O- or -S-. where a, b and are independently between 0.01 and 0.98 and a + b + c = l, where m is of enters 1 and 12, n is between 1 and 12, and where Y is a bond -C (0) -, or -S (02) -, and Ar10 may be present or absent when Y is a link. In some embodiments using a single hydrophobic oligomer, when the ion-conducting monomer used to make the copolymer is SBisK, the binding monomer is not BisK. In some embodiments of this or other formulas herein, at least one of m or n = 1. In other embodiments m and n are each at least 2. The first oligomer - (Ar? X? -Ar2- 2Ar3- 3 )sea? ? -Ar2-; the second oligomer (Ar4-X4-Ar5-X5-Ars-X6) n-Ar4-X4-Ar5- and the ion-conducting monomer Ar7-X7-Ar8 are randomly linked via the linking monomer R? -Ar9-Y- Ar10-R2-. In other embodiments, three or more different hydrophobic oligomers are used. A particular preferred copolymer of the invention comprises formula II: Formula II where Ar is: and where A is between 0.05 and 0.2, b is between 0.01 and 0.2 and c is between 0.5 and 0.95. In a preferred embodiment, a = 0.13, b = 0.036 and c = 0.83. In another preferred embodiment, the invention comprises a copolymer of formula III. (ratio of bisphenol / 6F = 0.06 / 0.4) a = 0.13, b = 0.036, c = 0.834 Another preferred embodiment is the copolymer of formula IV.

Formula IV a = 0.13, b = 0.036, c = 0.834 Ion-conducting polymers can be used to formulate proton exchange membranes (PEM) catalyst coated membranes (CCM), membrane electrode assemblies (MEA) and fuel cells that they comprise the membrane of PEM. The above membranes find particular utility in hydrogen fuel cells, although they can be used with other fuels such as methanol fuel cells. Such fuel cells can be used in both portable and stationary electronic devices, power supplies that include auxiliary power units (APU) and locomotive power for vehicles such as automobiles, aircraft and marine vessels and APUs associated with them. same.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 demonstrates the conductivity against temperature for a PEM manufactured from the copolymer of Example 1 (block copolymer) and a random copolymer manufactured from the same components. Figure 2 illustrates fuel cell performance to use the copolymer of Example 1 under various conditions. Figure 3 demonstrates the effect of relative humidity on the cell voltage of fuel cells containing the copolymer of Example 1 as compared to Nafion® 112. Figure 4 illustrates the polarization and energy density curves for MEAs manufactured in the Examples 22, 23 and 24. MEA test conditions: 6 mg / cm2 Pt-Ru at the anode, 4 mg / cm2 Pt at cathode, cell temperature 60 ° C, stoichiometric air flow 2.5, 1M methanol fuel. Figure 5 illustrates the polarization and energy density curves for MEA 23 and 24. Test conditions of MEA: 6 mg / cm2 Pt-Ru at the anode, 4 mg / cm2 Pt at the cathode, fuel cell temperature 60 ° C, stoichiometric air flow 2.5, 1M methanol fuel. Figure 6 illustrates the polarization curves and energy densities for MEA of the Example. The MEA test conditions: 6 mg / cm2 Pt-Ru in anode, 4 mg / cm2 Pt in cathode, stoichiometric air flow 2.5, methanol fuel 1M.

DETAILED DESCRIPTION OF THE INVENTION In one aspect, the invention provides ion conducting copolymers comprising: (1) first oligomers, (2) optionally, second oligomers, (3) ion-conducting monomers and (4) linking monomers. The oligomers are preferably hydrophobic and, together with the ion-conducting monomers, are dispersed randomly between the linking monomers. When a single hydrophobic oligomer and ion-conducting monomer are randomly dispersed in a fundamental polymer, it is preferred in some embodiments that when SBisK is the ion-conducting monomer that BisK is not used in combination therewith to form the copolymer. In another aspect, one of the first or second oligomer is a hard polymer relative to the other. In general, the hardness or relative softness of one polymer against another can be determined by comparing the glass transition temperatures for each of the first and second oligomers. A higher glass transition temperature indicates that the oligomer is harder than that used by comparison. A determination of whether a particular monomer is harder or softer than another can be made by comparing the glass transition temperature of the homomonomers. Alternatively, the first monomer and the third monomer in the first and second oligomers are the same, allowing monomers 2 and 4 to be varied to compare the relative hardness of one against the other. Uses of such polymeric materials include the formation of polymer electrolyte (PEM) membranes, catalyst-coated membrane (CCM) and membrane electrolyte assemblies (MEA) that can be used in fuel cells and the like. In a preferred embodiment, the ion-conducting copolymer comprises a first oligomer comprising first and second comonomers, a second oligomer comprising third and fourth comonomers (at least one of which is different from one of the comonomers of the first oligomer) and at least one monomer comprises an ion-conducting group. Each of the oligomers, the ion-conducting monomer and a linking monomer form the ion-conducting copolymer. Some of the ion-conducting monomers comprise an ion-conducting group that facilitates the transport of ions such as H + in and through the ion-conducting copolymer. General methods for the proportion of ion-conducting copolymers are as follows. The methods include the steps of combining a first comonomer with a second comonomer to form a first oligomer and separately combine a third and fourth comonomer to form a second oligomer. The first and third comonomers have at least two leaving groups and the second and fourth comonomers have at least two displacement groups. In one aspect, the first and third comonomers are in a molar excess relative to the first comonomer, thereby forming first and second oligomers with leaving groups on the end of the first and second oligomers. The ion-conducting monomer also preferably has two leaving groups. The linking monomer has at least two displacement groups. The term "leaving group" is intended to include those functional portions that can be displaced by a nucleophilic portion commonly found in another monomer. The leaving groups are well recognized in the art and include at least halides (chloride, fluoride, iodide, bromide), tosyl, mesyl, etc. In certain embodiments, the monomer contains at least two leaving groups, which are "for" each other with respect to the aromatic monomer to which they are attached. The term "displacement group" is intended to include those functional portions which commonly act as nucleophiles, thereby displacing a leaving group of an appropriate monomer. The result is that the monomer to which the displacing group is attached is generally covalently attached to the monomer to which the leaving group was associated. The displacing group becomes Ri and R2 as summarized above. An example of this is the displacement of fluoride groups of aromatic monomers by phenoxide, alkoxide or sulfur ions associated with aromatic monomers. An example of the synthesis of a first and a second oligomer is as follows, wherein LG is a leaving group and DG a displacement group. The first oligomer is manufactured by combining: Formula VI LG-An-X? -AR2-LG + DGAr3DG? LGCArt-Xt-Ara-) -Ar? X? Ar2-LG comonomer A comonomer B oligomer (BJm When comonomer A is in excess The second oligomer is similarly manufactured: Formula VII LG-AJR4X4A 5-LG + DG-ARa-DG - * LGCAR4 AR3-X5ARtí-?) Ft-A? X4AR5- G comonomer C comonomer D oligomer (CD) mC when comonomer C is in excess. The first oligomer I, the second oligomer II and an ion-conducting monomer with two leaving groups and a linking monomer with two displacement groups are combined in a reaction vessel to form the ion-conducting copolymer. Alternatively, the outgoing groups and displacement groups may be exchanged. Either in one or the other of these methods, the copolymers can be represented by Formula I: Formula I (Ar? X? -Aß-Xi ás ^ k) m- -Xi- -} * / ((ArVX 4-At? -X -Arß- ti) Q- -X wherein Ari, Ar2, Ar4, AR5, Ar7, Ar8, Ar9 and Ar10 are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, aryl substituted nitrile and Ar7 and / or Ar8 further comprise an ion-conducting group, Xi and X4 are independently -C (O) - or S (0) 2, X2 X3 Xs Xe are independently -O- or -S-; X7 is a bond, -C (O) - or -S (0) 2-. Ar3 and Ar6 are the same or different from each other and are: x y ^ j wherein the ion-conducting group comprises -S03H, -COOH, HP03H or -S02NH-S02-RF wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the ion. copolymer; Ri and R are independently -O-, or -S- where a, b and c are independently between 0.01 and 0.98 and a + b + c = l, where m is between 1 and 12, n is between 1 and 12 , and where Y is a bond, -C (0) ~, or -S (02) and Rrxo can be present or absent when Y is a link. In a preferred embodiment, Ar3 and Ar6 are different from each other. It will be understood that the different oligomers and ion-conducting monomer can be combined head-to-tail to the binding monomer thereby introducing another level of randomness into the polymer thus formed. In these and other formulas, m and n are independently 1-12, more preferably 1-10 and more preferably 2-8, and more preferably 3-6. In a particularly preferred embodiment, m and n = 4. In some embodiments of this and other formulas in the present, at least one of m or n is 2. In others, m and n are at least 2. In some embodiments, when used SBisK as the ion-conducting monomer, BisK is not used in combination with SBisK. The mole fraction of the various components as defined by a, b and c are as follows, a is preferably between 0. 05-0.4, more preferably between 0.05-0.25 and more preferably between 0.05 and 0.15. b is preferably between 0.01-0.04, more preferably between 0.05 and 0.3 and more preferably between 0.05 and 0.2. c is preferably between 0.2-0.94 and more preferably between 0.5 and 0.94. The mole percent of ion-conducting groups in the ion-conducting copolymer is calculated as follows: c divided by a (n + 1) + b (m + 1) + c. When using this formula, the mole percent of a monomer containing a single ion-conducting group is preferably between 30 and 70%, or more preferably between 40 and 60% and more preferably between 45 and 55%. When more than one conductive group is contained within the ion-conducting monomer, such percentages are multiplied by the total number of ion-conducting groups per monomer. Thus, in the case of a monomer comprising two sulfonic acid groups, the preferred sulfonation is 60 to 140%, more preferably 80 to 120% and more preferably 90 to 110%. Alternatively, the amount of ion conducting group can be measured by the ion exchange capacity (IEC). By way of comparison, Nafion® commonly has an ion exchange capacity of 0.9 and 0.9 meq / g. In the present invention, it is preferred that the IEC be between 0.9 and 3.0 meq / g, more preferably between 1.0 and 2.5 meq / g, and more preferably between 1.6 and 2.2 meq / g. The above ranges can be easily adapted for use in the definition of other formulas contained herein. In an alternative embodiment, comonomer II and comonomer IV are in excess and produce oligomer IA and IIA as follows: Oligomer IA DG - (- (Arg-J £ fi-Ar4-X-Ars-Xs.) NAré-DG Oligomer IIA When oligomers IA and IIA are used in combination with an ion-conducting monomer comprising two displacement groups and a linking monomer comprising two leaving groups, the copolymer thus produced can be represented by formula V: Formula V . { At3 -X3-Ar? -X? A? 2X2) m-A ^ - ^ /. { -Ar6- 6-Ar- 4-Ar 5) p-Ar6 ^ b (-Ar7- 7. Ar?) Ñ-Rs- ArjY-Ario-Ka wherein each of the components are as previously described. In another embodiment, the oligomers have different hardness in comparison to each other. Formula VI is an example of such a situation: Formula VI X < rA? $) e-Rj r $ -Y-Ar? o-R2- wherein Arx, Ar2, Ar4, Ar5, Ar7, Ar8, Ar9 and ArXo are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, substituted aryl nitrile and Ar7 and / or Ar8 further comprise an ion-conducting group, x and X4 are independently -C (O) - or -S (0) 2, X2, X3, X5 and Xs are independently -O-, or -S-; X7 is a bond, -C (O) - or S (0) 2-. The monomers Ar3 are the same or different from each other and are wherein the monomers Ar6 are the same or different from each other and are wherein the ion conductive group comprises -S03H, -COOH, -HPO3H or -S02NH-S02-RF, wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the copolymer; Ri and R2 are independently -0- or -S-, where a, b and c are independently between 0.01 and 0.98 and a + b + c = l, where m is between 1 and 10, n between 1 and 10, and where Y is a bond, -C (0) -, or -S (02) -, and Ario can be present or absent when Y is a link. Similarly, Formula V can be modified such that Ar3 and Are are selected from the aromatic groups as summarized in Formula VI. The preparation of the first and second oligomers disclosed and the choice of the ion-conducting monomer and linking monomer provide flexibility in the formulation of the ion-conducting copolymer. First and second selected oligomers and monomers (both ion conductors and binders) can be combined in defined proportions to provide copolymers having a variety of physical and chemical properties. A particularly preferred embodiment is: Formula II where Ar is: where a is between 0.05 and 0.2, b is between 0.01 and 0.2 and c is between 0.5 and 0.95. In a preferred embodiment, a = 0.13, b = 0.036 and c = 0.83.

Formula III a = 0.13, b = 0.036, c = 0.834 Another preferred embodiment is the copolymer of formula IIC. Formula IV a = 0 13, b = 0. 036, c = 0. 834 In alternative embodiments, an oligomer is used in place of two or more different oligomers. Where this is the case, in some embodiments, it is preferred when SBisK is the only ion-conducting monomer that the BisK monomer is not used. In another embodiment, where only one oligomer is used, the copolymer is different than the one summarized in Examples 63-116 herein. The polymeric membranes can be manufactured by solution casting of the ion-conducting copolymer. Alternatively, the polymer membrane can be manufactured by solution casting of the ion-conducting copolymer the combination of the acidic and basic polymer. When molded to a membrane for use in a fuel cell, it is preferred that the membrane thickness be between 0.1 to 10 mils, more preferably between 1 and 6 mils, more preferably between 1.5 and 2.5 mils and it can be coated on the polymeric substrate. As used herein, a membrane is permeable to protons if the proton flux is greater than about 0.005 S / cm, more preferably greater than 0.01 S / cm, more preferably greater than 0.02 S / cm. As used herein, a membrane is substantially impermeable to methanol if the transport of methanol through a membrane having a given thickness is less than the transfer of methanol through a Nafion® membrane of the same thickness. In preferred modalities, the permeability of methanol is preferably 50% less than that of a Nafion® membrane, more preferably 75% less and more preferably greater than 80% lower compared to the Nafion® membrane. After the ion-conducting copolymer has been formed to a membrane, it can be used to produce a catalyst-coated membrane (CCM). As used herein, a CCM comprises a PEM when at least one side and preferably both of the opposite sides of the PEM are partially or completely coated with catalyst. The catalyst is preferably a layer made of catalyst and ionomer. The preferred catalysts are Pt and Pt-Ru. Preferred ionomers include Nafion® and other ion-conducting polymers. In general, anode and cathode catalysts are applied to the membrane by well-established standard techniques. For direct methanol fuel cells, the platinum / ruthenium catalyst is commonly used on the anode side, while the platinum catalyst is applied on the cathode side. For the hydrogen / air or hydrogen / oxygen fuel cells, platinum or platinum / ruthenium is generally applied on the anode side and platinum is applied on the cathode side. The catalysts can optionally be supported on carbon. The catalyst is initially dispersed in a small amount of water (approximately 100 mg of catalyst in 1 g of water). To this dispersion, a solution of 5% ionomer water / alcohol is added (0.25-0.75 g). The resulting dispersion can be painted directly on the polymer membrane. Alternatively, isopropanol (1-3 g) is added, and the dispersion is atomized directly on the membrane. The catalyst can also be applied to the membrane by transfer of decalcomania, as described in the open literature (Electrochimica, Acta, 40: 297 (1995)). The CCM is used to make MEA. As used herein, an MEA refers to an ion conducting polymeric membrane made from a CCM according to the invention in combination with the anode and cathode electrodes to be in electrical contact with the catalytic layer of the MCC. The electrodes are in electrical contact with the catalytic layer, either directly or indirectly, when they are able to complete an electric circuit that includes the CCM and a load at which the current of the fuel cell is supplied. More particularly, a first catalyst is electrocatalytically associated with the anode side of the PEM to facilitate the oxidation of hydrogen or organic fuel. Such oxidation generally results in the formation of protons, electrons and, in the case of organic fuels, carbon dioxide and water. Since the membrane is substantially impermeable to molecular hydrogen and organic fuels such as methanol, also as carbon dioxide, such components remain on the anodic side of the membrane. The electrons formed from the electrocatalytic reaction are transmitted from the cathode to the charge and then to the anode. The equilibrium of this direct electron current is the transfer of an equivalent number of protons through the membrane to the anodic compartment. There is an electrocatalytic reduction of oxygen in the presence of the transmitted protons that occurs to form water. In one embodiment, air is the source of oxygen. In another embodiment, oxygen enriched air is used.

The membrane electrode assembly is generally used to divide a fuel cell into anodic and cathodic compartments. In such fuel cell systems, a fuel such as hydrogen gas or an organic fuel such as methanol is added to the anodic compartment while an oxidant such as oxygen or room air is allowed to enter the cathode compartment. Depending on the particular use of a fuel cell, a number of cells can be combined to obtain an appropriate voltage and power output. Such applications include power sources for residential, industrial, commercial and power systems for locomotive power use such as in automobiles. Other uses to which the invention finds particular use include the use of fuel cells in portable electronic devices such as cell phones and other telecommunication devices, consumer electronic video and audio equipment, laptops, notebook computers, personal assistants digital and other computing devices, GPS devices and the like. In addition, fuel cells can be stacked to increase voltage and current capacity for use in high-energy applications such as industrial and residential sewage services used to provide locomotion to vehicles. Such fuel cell structures include those disclosed in U.S. Patent Nos. 6,416,895, 6,413,664, 6,106,964, 5,840,438, 5,773,160, 5,750,281, 5,547,776, 5,527,363, 5,521,018, 5,514,487, 5,482,680, 5,432,021, 5,382,478, 5,300,370, 5,252,410 and 5,230,966. Such CCM and MEM are generally useful in fuel cells such as those disclosed in U.S. Patent Nos. 5,945,231, 5,773,162, 5,992,008, 5,723,229, 6,057,051, 5,976,725, 5,789,093, 4,612,216, 4,407.905, 4,629,664, 4,562,123, 4,789,917, 4,446,210, 4,390,603. , 6,110,613, 5,916,699, 5,693,434, 5,688,613, 5,688,614, each of which is expressly incorporated herein by reference. The CCM and MEA of the invention can also be used in hydrogen fuel cells that are known in the art. Examples include 6,630,259; 6,617,066; 6,602,920 6,602,627; 6,568,633; 6,544,679; 6,536,551; 6,506,510 6,497,974, 6,321,145; 6,195,999; 5,984,235; 5,759,712 5,509,942; and 5,458,989, each of which is expressly incorporated herein by reference. The polymeric ion conducting membranes of the invention also find use as separators in batteries. Particularly preferred batteries are lithium ion batteries.

EXAMPLES A list of some of the monomers used for the practice of the invention are summarized in Table I. Table I. Monomers used This table also provides acronyms used for the various starting monomers, as well as the monomers as they are contained within the ion-conducting copolymers. Other acronyms include the following: Acronym: R = random copolymer, Bl = block copolymer RK = random copolymer based on Bis K and S-BisK, RS = random copolymer based on BisS02 and S-BisK B = biphenol, AF = BisAF (6F), FL = BisFL, Z = -BisZ BlK = block copolymer containing BisK in its formulation Bl = block copolymer without BisK in its formulation Abbreviations include: IEC: ion exchange capacity (meq / g), IV: inherent viscosity (dl / g) CD: conductivity (S / cm).

Example 1: BL_FL4AF4-B / 50, Oligomers Used: FL4 + AF4 Oligomer I (FL4, F-end): m or n = 4 In a three-necked round bottom flask of 500 ml, equipped with mechanical stirrer, probe thermometer connected to a nitrogen inlet and a Dean-Stark trap / concentrator, 4,4 '-difluorobenzene (BisK, 34.91 g, 0.16 mol), 9, 9-bis (4-hydroxyphenyl) fluorene (Bis FL, 42.05 g, 0.12 mol) and anhydrous potassium carbonate (19.9 g, 0.192 mol) were dissolved in a mixture of 220 ml of DMSO and 110 ml of toluene. The reaction mixture was stirred slowly under a slow stream of nitrogen. After heating at -120 ° C for 1 hour and it was raised to -140 ° C for 2 hours and finally to ~ 160 ° C for 3 hours. After cooling to ~70 ° C with continuous stirring, the solution was dripped into 1 liter of cooled methanol with vigorous stirring. The precipitates were filtered and washed with DI water four times and dried at 80 ° C overnight and then dried at 80 ° C under vacuum for 2 days. The oligomer has the following structure: Oligomer 2 (AF4, end F): m or n = 4 This oligomer was synthesized in a similar manner as described in the synthesis of oligomer 1, using the following compositions: 4,4 '-difluorobenzofone (BisK, 34.91 g), , 4 '- (hexafluoroisopropylidene) diphenol (Bis AF, 40.35 g), and anhydrous potassium carbonate (19.9 g) in a mixture of 220 ml of DMSO and 110 ml of toluene. The oligomer has the following structure: Polymerization In a 500 ml three-neck round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 3, 3 '-disulfonated-4, 4' -difluorobenzophone (S-BisK, 17.61 g), oligomer 1 (15.16 g), oligomer 2 (4.10 g), biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration) . The mixture was heated to the flow of toluene with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4 hours. The reaction mixture was precipitated from methanol to obtain the crude product and washed with DI water. The polymer was treated in 0.5 mole of H2S04 aqueous solution at 80 ° C for 1 hour to produce the proton form of the sulfonic acid group in the polymer and washed with deionized water and dried at 80 ° C overnight and then dried at 80 ° C under vacuum for 2 days. The dried polymer was dissolved in dimethylacetamide (DMAc) to make a solution (25% by weight) and molded and dried at 80 ° C to make a membrane (2.0 mils thick). The obtained membrane was treated in 1.5 moles of aqueous H2S0 solution to remove the DMAc residue and rinsed in DI water until no residue of H2SO4 was detected and dried at 80 ° C. The polymer membrane was swollen in water at room temperature and the membrane connectivity of the polymer was measured by impedance of AC. The dry membrane was swollen in boiling water for 1 hour to measure water absorption and swelling per area. This polymer has an inherent viscosity of 1.52 dl / g in DMAc (0.25 g / dl). The IEC is 1.97 meq / g. Conductivity: 0.093 S / cm (0.112 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 50%, absorption of water after boiling the membrane in water 1 hour 64%.

Example 2 Oligomers of BL_FL4 AF-B45 Used: FLA + AF4 This block polymer was synthesized and treated in a similar manner as described in Example 1: S-BisK (16.98 g), oligomer 1 (15.86 g), oligomer 2 (6.83 g), biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.11 dl / g in DMAc (0.25 g / dl). The IEC is 1.78 meq / g. Conductivity: 0.081 S / cm (0.099 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 40%, water absorption after boiling the membrane in water 1 hour: 57%.

Example 3 Oligomers of BL_FL4 AF4-B / 41 Used: FL4 + AF4 This block polymer was synthesized in a similar manner as described in Example 1: S-BisK (16.47 g), oligomer 1 (14.0 g), oligomer 2 (11.38 g), biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.30 dl / g in DMAc (0.25 g / dl). The IEC is 1.64 meq / g. Conductivity: 0.068 S / cm (0.092 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 35%, absorption of water after boiling the membrane in water 1 hour: 52%.

Example 4: Oligomers of BL_FL4 AF8-B / 48 Used: FL4 + AF4 Oligomer 3 (AF8, F-end), m or n = 8 This oligomer was synthesized in a similar manner as described in the synthesis of oligomer 1: BisK (34.91 g), Bis AF (47.07 g), and anhydrous potassium carbonate (23.22 g) in a mixture of 220 ml of DMSO and 110 ml of toluene. This structure is the same as oligomer 2 except that the AF unit is repeated 8 times instead of 4 times.

Polymerization The block copolymer was synthesized in a similar manner as described in Example 1: S-BisK (17.82 g), oligomer 1 (14.0 g), oligomer 3 (7.8 g), biphenol (9.31 g), and potassium carbonate Anhydrous (9.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.79 dl / g in DMAc (0.25 g / dl). The IEC is 1.87 meq / g.

Conductivity: 0.092 S / cm (0.100 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 45%, absorption of water after boiling the membrane in water 1 hour: 63%.

Example 5: Oligomers BL_FL4 AF4-B / 42 Used: FL4 + AF8 This block polymer was synthesized in a similar manner as described in Example 1: S-BisK (17.31 g), oligomer 1 (14.0 g), oligomer 3 ( 13.0 g), biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of approximately 20% solids). This polymer has an inherent viscosity of 1.73 dl / g in DMAc (0.25 g / dl). The IEC is 1.65 meq / g. Conductivity: 0.074 S / cm (0.100 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 38%, absorption of water after boiling the membrane in water 1 hour: 58%. Table II summarizes the properties of the polymer made in Examples 1-5 also as other oligomeric block copolymers. Table II. Properties of Oligomeric Block Membranes Example 6: Oligomers BL_FL4 S8-B / 42 Used: FL4 + S8) Oligomer 4 (S8, F-end): m or n = 8 Oligomer was synthesized in a similar manner as described in the synthesis of oligomer 1, using the following compositions: 4,4 '-difluorodiphenylsulfone (Bis S02, 40.68 g), 4,4'-thiodiphenol (Bis S, 30.56 g), and anhydrous potassium carbon (23.22 g) in a mixture of 220 ml of DMSO and 110 ml of toluene. S8 has the following structure: Polymerization This block polymer is synthesized in a similar manner as described in Example 1: S-BisK (17.31 g), oligomer 1 (14.0 g), oligomer 4 (11.14 g), biphenol (9.31 g), and potassium carbonate Anhydrous (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.36. dl / g in DMAc (0.25 g / dl). The IEC is 1.71 meq / g. Conductivity: 0.072 S / cm (0.097 S / cm, boiled in water 1 hour), swelling by water in boiled water 1 hour: 41%, absorption of water after boiling the membrane in water 1 hour: 64%.

Example 7: Oligomer of BL_FL4-B / 41 Used: FLR only This block polymer was synthesized in a similar manner as described in Example 1: S-BisK (16.47 g), oligomer 1 (25.66 g), biphenol (9.31 g) ), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.36 dl / g in DMAc (0.25 g / dl). The IEC is 1.63 meq / g. Conductivity: 0.061 S / cm (0.087 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 35%, absorption of water after boiling the membrane in water 1 hour: 49%.

Example 8 Oligomer of BLK_FL4-B50 AF50 / 42 Used: FL4 only This block polymer was synthesized in a similar manner as described in Example 1: Bis K (2.75 g), S-BisK (13.26 g), oligomer 1 ( 14.0 g), biphenol (4.66 g), Bis AF (8.41 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.45 dl / g in DMAc (0.25 g / dl). The IEC is 1.58 meq / g. Conductivity: 0.048 S / cm (0.088 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 43%, water absorption after boiling membrane in water 1 hour: 58%.

Example 9: Oligomer BLK_FL4-AF / 41 Used: FL4 only This block polymer was synthesized in a similar manner as described in Example 1: Bis K (2.4 g), S-BisK (13.51 g), oligomer 1 (16.33 g), Bis AF (16.81 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%).

This polymer has an inherent viscosity of 1.19 dl / g in DMAc (0.25 g / dl). The IEC is 1.40 meq / g.

Conductivity: 0.036 S / cm (0.080 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 44%, water absorption after boiling the membrane in water 1 hour: 59%.

Example 10: Oligomer B: _AF8-B / 45 used: AF8 (oligomer 3) only This block polymer was synthesized in a similar manner as described in Example 1: S-BisK (18.62 g), oligomer 3 (25.57 g) , biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.21 dl / g in DMAc (0.25 g / dl). The IEC is 1.78 meq / g.

Conductivity: 0.119 S / cm (0.103 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 36%, water absorption after boiling the membrane in water 1 hour: 81%.

Example 11: Oligomers of BLK_AF10-AF / 35 Used: AF10 only Oligomer 5 (AF10, F-terminal): DP = 10 This oligomer was synthesized in a similar manner as described in the synthesis of oligomer 1, using the following compositions: BisK ( 34.91 g), Bis AF (48.42 g), and anhydrous potassium carbon (23.88 g) in a mixture of 220 ml of DMSO and 100 ml of toluene.

Polymerization This block polymer was synthesized in a similar manner as described in Example 1: Bis K (2.34 g), S-BisK (14.57 g), oligomer 5 (25.74 g), BisAF (16.81 g), and potassium carbonate Anhydrous (8.29 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). This polymer has an inherent viscosity of 1.14 dl / g in DMAc (0.25 g / dl). The IEC is 1.23 meq / g. Conductivity: 0.049 S / cm (0.045 S / cm, boiled in water 1 hour), swelling per area in boiled water 1 hour: 127%, water absorption after boiling the membrane in water 1 hour: 160%. The conductivity of the membrane: 0.060 S / cm, swelling after boiling: 68% per area, water absorption: 84%.

Example 12: Synthesis of partial block polymer with unsulfonated hydrophobic segment Preparation of the fluorine end group oligomer (difluorophenyl sulfone / 4,4'-thiolbisbenzene sulfide) (segment size n = 4) In a round three-necked flask of 250 ml, equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4,4 'thiolbisbenthiol (15.0246 g), difluorophenyl sulfone (20.34 g), anhydrous potassium carbonate (11 g) were dissolved in a mixture of DMSO and toluene (concentration of solids approximately 20%). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The reaction mixture precipitates from methanol to obtain the crude product and is then washed by hot water 4 times. It is dried at 80 ° C in an oven for 1 day and in a vacuum oven at 75 ° C for 2 days.

Polymerization In a 250 ml three neck round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4,4'-thiolbisbenzothiol (12,520 g), difluorophenylsulfone (6,102 g), difluorophenyl sulfone sulfonated (901664 g), oligomer (12.672 g, n = 4, fluorine end of difluorophenylsulfone / 4,4 thylbisbencenesulfide composition), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (concentration of solids of approximately 20%). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C for 6 hours, then increasing the temperature to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. • Membrane conductivity: 0.076 S / cm. Swelling after boiling: 50% per area, water absorption: 41%.

Example 13: End oligomer F 1: DP = 4 In a 500 ml three neck round flask, equipped with mechanical stirrer, thermometer probe connected with a nitrogen inlet and Dean-Stark trap / condenser, 4, 4 ' -difluorobenzofone (BisK 34.91 g, 0.16 moles), 9, 5-bis- (4-hydroxyphenyl) fluorene (42.05 g, 0.12 moles) and anhydrous potassium carbonate (25.87 g, 0.187 moles), 220 ml of DMSO and 110 ml of toluene. The reaction mixture was stirred slowly under a slow nitrogen stream. After heating to ~ 85 ° C for 1 hour and to ~ 120 ° C for 1 hour, the reaction temperature was raised to ~ 140 ° C for 3 h and finally to ~ 170 ° C for 2 h. After cooling to ~70 ° C with continuous stirring, the solution was poured into 1 liter of methanol with vigorous stirring. The precipitates were filtered and washed with deionized water four times and dried at 80 ° C overnight and then dried at 80 ° C under vacuum for 2 days. A block copolymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4'-difluorobenzophone (BisK 6.49 g), 3,3'-disulfonated-4,4 '-difluorobenzofone ( SBisK, 13.39 g), Oligomer 7 (18.29 g), 1, 1-Bis- (4-hydroxyphenyl) cyclohexane (BisZ, 26.28 g) and anhydrous potassium carbonate (12.51 g), 216 ml of DMSO and 108 ml of toluene. The dried polymer was converted to the acid form by stirring in hot H2SO4 solution (0.5 M) for one hour, followed by washing with deionized water and drying.

Example 14 This block copolymer was synthesized in a similar manner as described in the synthesis of example 13, using the following compositions: (BisK 6.84 g), SBisK (16.76 g), Oligomer 7 (20.90 g), BisZ (21.47 g) and anhydrous potassium carbonate (14.37 g).

Example 15 This block copolymer was synthesized in a similar manner as described in the synthesis of example 13, using the following compositions: BisK (5.72 g), SBisK (17.04 g), Oligomer 7 (19.59 g), BisZ (20.12 g) and anhydrous potassium carbonate (13.48 g).

Example 16 This block copolymer was synthesized in a similar manner as described in the synthesis of example 13, using the following compositions: BisK (5.27 g), SBisK (19.80 g), Oligomer 7 (20.90 g), BisZ (21.47 g) and anhydrous potassium carbonate (14.37 g).

Example 17 This block copolymer was synthesized in a similar manner as described in the synthesis of example 13, using the following compositions: BisK (3.92 g), SBisK (13.48 g), Oligomer 7 (23.51 g), BisZ (16.10 g) and anhydrous potassium carbonate (10.78 g).

Example 18 This block copolymer was synthesized in a similar manner as described in the synthesis of example 13, using the following compositions: BisK (2.16 g), SBisK (15.48 g), Oligomer 7 (31.35 g), BisZ 16.10 g) and anhydrous potassium carbonate (10.78 g).

Table 1. Summary of ex situ data of block polymers Example 19 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (8.52 g), SBisK (13.51 g), Oligomer 7 (20.90 g), 2,2 '-biphenol ( 14.89 g) and anhydrous potassium carbonate (14.37 g).

Example 20 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (6.97 g), SBisK (12.00 g), Oligomer 7 (17.76 g), 2,2'-biphenol ( 12.66 g) and anhydrous potassium carbonate (12.22 g). • Example 21 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (7.84 g), SBisK (14.83 g), Oligomer 7 (20.90 g), 2,2 '-biphenol ( 14.89 g) and anhydrous potassium carbonate (14.89 g). Example 22 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (5.41 g), SBisK (14.13 g), Oligomer 7 (27.43 g), 2,2'-biphenol ( 13.03 g) and anhydrous potassium carbonate (12.58 g). MEA 10 contains this block copolymer.

Example 23 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (5.41 g), SBisK (12.67 g), Oligomer 7 (23.51 g), 2,2'-biphenol ( 11.17 g) and anhydrous potassium carbonate (10.78 g). MEA 11 contains this block copolymer.

Example 24 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (4.73 g), SBisK (15.43 g), Oligomer 7 (27.43 g), 2,2'-biphenol (13.03 g) and anhydrous potassium carbonate (12.58 g). MEA 12 contains this block copolymer.

Example 25 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.94 g), SBisK (12.33 g), Oligomer 7 (28.73 g), 2,2'-biphenol (10.24 g) and anhydrous potassium carbonate (9.88 g).

Example 26 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.86 g), SBisK (14.11 g), Oligomer 7 (31.35 g), 2,2'-biphenol (11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 27 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.54g), SBisK (14.74g), Oligomer 7 (31.35 g), 2,2'-biphenol (11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 28 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (1.80 g), SBisK (12.90 g), Oligomer 7 (26.12 g), 2,2 '-biphenol ( 9.31 g) and anhydrous potassium carbonate (8.98 g).

Example 29 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (1.55 g), SBisK (13.39 g), Oligomer 7 (26.12 g), 2,2 '-biphenol (9.31 g) and anhydrous potassium carbonate (8.98 g).

EXAMPLE 30 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (1.25 g), SBisK (13.96 g), Oligomer 7 (26.12 g), 2, 2'-biphenol (9.31 g) and anhydrous potassium carbonate (8.98 g).

Table 2. Summary of ex situ data of block polymers Table 3. Summary of ex situ data of block polymers Example 31 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 1, using the following compositions: BisK (4.99 g), SBisK (12.84 g), Oligomer 1 (15.67 g), bis (4-hydroxylphenyl) - 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 32 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (4.70 g), SBisK (13.40 g), Oligomer 7 (15.67 g), bis (4-hydroxylphenyl) -1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 33 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (4.38 g), SBisK (14.01 g), Oligomer 7 (15.67 g), bis (4-hydroxylphenyl) -1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 34 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (4.38 g), SBisK (14.01 g), Oligomer 7 (15.67 g), bis (4-hydroxylphenyl) -1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 35 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.89 g), SBisK (15.48 g), Oligomer 7 (23.51 g), bis (4-hydroxylfenyl) - 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g). MEA 23 contains this block polymer.

Example 36 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.49 g), SBisK (16.27 g), Oligomer 7 (23.51 g), bis (4-hydroxylphenyl) - 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g). MEA 24 contains this block copolymer.

Example 37 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (1.23 g), SBisK (14.00 g), Oligomer 7 (26.12 g), bis (4-hydroxylphenyl) -1,4-diisopropylbenzene (17.32 g) and anhydrous potassium carbonate (8.98 g).

Table 4. Ex situ data summary for block polymers 31-37 Table 5. Ex situ data summary for block polymers 31-37 Example 38 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-di? Uorobenzonitrile (6.10 g), SBisK (13.35 g), Oligomer 7 (22.21 g), 2 , 2'-biphenol (15.83 g) and anhydrous potassium carbonate (15.27 g).

Example 39 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile (5.88 g), SBisK (14.03 g), Oligomer 7 (22.21 g), 2, 2 '-biphenol (15.83 g) and anhydrous potassium carbonate (15.27 g). MEA 27 contains this block copolymer.

Example 40 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile (5.31 g), SBisK (13.88 g), Oligomer 7 (20.90 g), 2, 2 '-biphenol (14.90 g) and anhydrous potassium carbonate (14.37 g).

Example 41 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile (3.88 g), SBisK (14.57 g), Oligomer 7 (29.39 g), 2, 2 '-biphenol (13.96 g) and anhydrous potassium carbonate (13.48 g).

Example 42 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile • (3.66 g), SBisK (15.93 g), Oligomer 7 (29.39 g), 2, 2'-biphenol (13.96 g) and anhydrous potassium carbonate (13.47 g).

Example 43 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile (3.18 g), SBisK (14.97 g), Oligomer 7 (27.43 g), 2.2 '-biphenol (13.03 g) and anhydrous potassium carbonate (12.58 g).

Example 44 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-difluorobenzonitrile (1.92 g), SBisK (13.83 g), Oligomer 7 (31.35 g), 2, 2 '-biphenol (11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 45 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-benzodifluoronitrile (1.71 g), SBisK (14.47 g), Oligomer 7 (31.35 g), 2, 2 '-biphenol (11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 46 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-benzodifluoronitrile (1.47 g), SBisK (15.20 g), Oligomer 7 (31.35 g), 2, 2 '-biphenol (11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 47 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-benzodifluoronitrile (3.62 g), SBisK (13.39 g), Oligomer 7 (16.98 g), bis (4) -hydroxylphenyl) -1,4-diisopropylbenzene (22.52 g) and anhydrous potassium carbonate (11.68 'g).

Example 48 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: 2,6-benzodifluoronitrile (2.17 g), SBisK (14.49 g), Oligomer 7 (23.51 g), bis (4) -hydroxylphenyl) 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Table 6. Ex situ data summary for block polymers 26-48 Table 7. Summary of in situ data for block polymers 38-44, 47 and 48 Example 49 F-terminal Oligomer 8: DP = 6 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (3.97 g), SBisK (14.82 g), Oligomer 8 (22.78 g) ), bis (4-hydroxylphenyl) 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 50 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (3.97 g), SBisK (14.82 g), Oligomer 8 (22.78 g), bis (4-hydroxylphenyl) 1 , 4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g).

Example 51 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (3.02 g), SBisK (12.90 g), Oligomer 8 (18.98 g), bis (4-hydroxylphenyl) 1,4-diisopropylbenzene (17.32 g) and anhydrous potassium carbonate (8.98 g).

Example 52 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.70 g), SBisK (13.51 g), Oligomer 8 (18.98 g), bis (4-hydroxylphenyl) 1,4-diisopropylbenzene (17.32 g) and anhydrous potassium carbonate (8.98 g).

Example 53 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (1.28 g), SBisK (13.34 g), Oligomer 8 (25.63 g), bis (4-hydroxylphenyl) -1, -diisopropylbenzene (15.59 g) and anhydrous potassium carbonate (8.08 g).

Example 54 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (0.95 g), SBisK (13.97 g), Oligomer 8 (25.63 g), bis (4-hydroxylphenyl) 1,4-diisopropylbenzene (15.59 g) and anhydrous potassium carbonate (8.08 g).

Example 55 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (0.61 g), SBisK (14.63 g), Oligomer 8 (25.63 g), bis (4-hydroxylphenyl) 1 , 4-diisopropylbenzene (15.59 g) and anhydrous potassium carbonate (8.08 g).

Example 56 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (5.34 g), SBisK (12.16 g), Oligomer 8 (22.78 g), 2,2'-biphenol ( 11.17 g) and anhydrous potassium carbonate (10.78 g).

Example 57 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (3.97 g), SBisK (14.82 g), Oligomer 8 (22.78 g), bis (4-hydroxylphenyl) 1,4-diisopropylbenzene (20.78 g) and anhydrous potassium carbonate (10.78 g). 8. Ex situ data summary for block polymers 37-42 Example 59 OH-terminal oligomer 9: DP = 4 This oligomer 9 is synthesized in a similar manner as described in the synthesis of oligomer 17, using the following compositions: BisK (43.90 g), 9,9-bis (4-hydroxy1-phenyl) fluorene (94.00 g), and anhydrous potassium carbonate (48.20 g), 540 ml of DMSO and 270 ml of toluene.

Example 60 This block polymer was synthesized in a similar manner as described in the synthesis of Example 13, using the following compositions: BisK (9.37 g), SBisK (15.64 g), Oligomer 9 (19.72 g), BisZ (19.32 g) and anhydrous potassium carbonate (14.37 g).

Example 61 This block polymer is synthesized in a similar manner to that described in the synthesis of Example 13, using the following compositions: BisK (5.04 g), SBisK (15.59 g), Oligomer 9 (29.58 g), BisZ (12.88 g) and anhydrous potassium carbonate (10.78 g).

Example 62 This block polymer is synthesized in a manner similar to that described in the synthesis of Example 13, using the following compositions: BisK (2.54 g), SBisK (16.22 g), Oligomer 9 (36.97 g), BisZ (9.39 g) and anhydrous potassium carbonate (8.98 g).

Table 9. Ex situ data summary for block polymers 43-45 Table 10. Summary of in situ data for polymers of block 2, 43-47.

MEA analysis conditions: 3 mg / cm2 Pt-Ru at the anode, 2 mg / cm2 Pt at the cathode, cellular temperature 60 ° C, stoichiometric airflow 2.5, methanol fuel 1M.

Example 63 Oligomer 10: DP = 4 This oligomer is synthesized in a similar manner to that described for oligomer 10, using the following compositions: 4,4'-difluorobenzofone (BisK 34.91 g, 0.16 mol), 9, 9 '-bis (4-hydroxyphenyl) fluorene (42.05 g, 0.12 mol) and anhydrous potassium carbonate (25.87 g, 0.187 g) mol), 220 ml of DMSO and 110 ml of toluene. This block polymer is synthesized in a similar manner to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK 7.75 g, 0.0355 mol), 3,3'-disulfonated-4,4 '-difluorobenzophone ((SBisK 15.00 g, 0.0355 mol), Oligomer 1 (20.90 g), BisZ (21.47 g, 0.08 mol) and anhydrous potassium carbonate (14.37 g, 0.10 mol), 250 ml of DMSO and 125 ml of toluene. it has an inherent viscosity of 0.49 dl / g in DMAc (0.25 g / dl) .The dilation suspended for one day in 8M methanol at 80 ° C was 52%, the crossing in 8M methanol was 0.016 mg.mil / cc. min.cm2 (not blocked, the conductivity was 0.013 S / cm (not blocked) and 0.034 S / cm (blocked).

Example 64 This block polymer is synthesized in a similar manner to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK 5.72 g, 0.026 mol), 3,3'-disulfonafo-4, 4 ' -difluorobenzofone (SBisK, 17.04 g, 0.040 mol), Oligomer 10 (19.59 g), BisZ (20.12 g, 0.075 mol) and anhydrous potassium carbonate (13.47 g, 0.097 mol), 250 ml of DMSO and 125 ml of toluene. This polymer has an inherent viscosity of 0.72 dl / g in DMAc (0.25 g / dl). Example 65 This block polymer is synthesized in a similar manner to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK 4.68 g, 0.021 mol), 3,3 '-disulfonated-4,4' -difluorobenzofone (SBISK 19.06 g, 0.045 mol), Oligomer 10 (19.59 g), 9, 9-bis (4-hydroxyphenyl) fluoroate (26.28 g, 0.075 mol) and 125 ml of toluene.

Example 66 This block polymer is synthesized in a similar manner to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 4.68 g, 0.021 mol), 3,3'-disulfonated-4, 4 -difluorobenzofone (SBisK, 19.06 g, 0.040 mol), Oligomer 10 (19.59 g), bisphenol (13.96 g, 0.075 mol) and anhydrous potassium carbonate (13.47 g, 0.075 mol), 250 ml of DMSO and 125 ml of toluene.

Example 67 This example illustrates the block copolymer system using the block BisK-0 in the non-ionic region and SBisK-Z in the ionic region, the non-ionic region consists of 11%. The size of block BisK-0 is 6. Oligomer 11: DP = 6 Example 66 This block polymer is synthesized in a similar manner to that described in oligomer 10, using the following compositions: 4,4'-difluorobenzofone (BisK, 65.46 g, 0.30 mol), 4,4 '-didihydroxyphenylether (0.50.55 g, 0.25 mol) and anhydrous potassium carbonate (44.92 g, 0.325 mol), 540 ml of DMSO and 270 ml of toluene.

Example 67 This block polymer is synthesized in a similar manner to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 6.51 g, 0.030 mol), 4,4-difluorobenzofone (BisK, 6.51 g , 0.030 mol), 3,3'-disulfonated-4,4-difluorobenzophone (SBisK, 17.40 g, 0.041 mol), oligomer 11 (22.40 g), BisZ (21.47 g, 0.08 mol) and anhydrous potassium carbonate (14.37 g) , 0.10 mol), 250 ml of DMSO and 125 ml of toluene.

Example 68 This block polymer is synthesized in a manner similar to that described in Example 1, using the following compositions: 4,4'-difluorobenzophone (BisK, 4.68 g, 0.021 mol), 3,3 '-disulfonated-4, 4 -difluorobenzofone (SBisK, 19.06 g, 0.040 mol), Oligomer 2 (19.59 g), 1,5-dihydroxynaphthalene (12.01 g, 0.075 mol) and anhydrous potassium carbonate (13.47 g, 0.075 mol), 250 ml of DMSO and 125 ml of toluene. Examples 69-75 illustrate a block copolymer system using the same BisK-Z in the nonionic region, but sBisK are several phenolaryl block groups having different chain mobility and chemical affinity in the ion region. The size of the non-ionic block is 8 and the concentration of the block is 11%.

Example 69 illustrates the ion region consisting of the unit sBisK-Z Oligomer 12: DP = 8 This oligomer 12 is synthesized in a similar manner as described in oligomer 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 65.46 g, 0.3 mol), BisZ (70.44 g, 0.262 mol) and anhydrous potassium carbonate (17.97 g, 0.13 mol), 540 ml of anhydrous DMSO (270 ml) of toluene. This block polymer was synthesized in the manner as described in Example 1, using the following compositions: 4,4'-difluorobenzophone (BisK, 4.57 g, 0.021 mol), 3,3 '-disulfonated-4,4'-difluorobenzophone (SBisZ 17.41 g, 0.041 mol), Oligomer 12 (29.72 g) BisZ (18.78 g, 0.07 mol) and anhydrous potassium carbonate (12.57 g, 0.091 mol), 270 ml of anhydrous DMSO and 135 ml of toluene. This polymer has an inherent viscosity 0.62 dl / g in DMAc (0.25 g / dl).

Example 70 illustrates the ion region consisting of the sBisK-FL unit. This block polymer is synthesized in a manner similar to that described in Example 1, using the following compositions: 4,4 '-difluorobenzofone (BisK, 3.91 g, 0.0179 mol ), 3,3 '-disulfonated-4,4-difluorobenzofone (SBisK, 14.92 g, 0.06 mol), Oligomer 12 (25.27 g), 9, 9-bis (4-hydroxyphenyl) fluorene (21.02 g, 0.07 mol) and anhydrous potassium carbonate (10.78 g, 0.078 mol), 250 ml of DMSO and 125 ml of toluene. This polymer has an inherent viscosity of 0.84 dl / g in DMAc (0.25 g / dl).

Example 71 illustrates the ion region consisting of the sBisK unit: This block polymer is synthesized in a manner similar to that described in Example 1, using the following compositions: 4,4 '-difluorobenzophone (BisK, 3.91 g, 0.0179 mol) , 3,3 '-disulfonated-4,4-difluorobenzophone ((SBisK, 14.92 g, 0.035 mol), Oligomer 12 (25.47 g), 4,4'- (hexafluoroisopropylidene) -diphenol (20.17 g, 0.06 mol) and carbonate of anhydrous potassium (10.78 g, 0.078 mol), 250 ml of DMSO and 125 ml of toluene. This polymer has an inherent viscosity of 0.47 dl / g in DMAc (0.25 g / dl).

Example 72 illustrates the ion region consisting of the sBisK-B unit: This block polymer is synthesized in a manner similar to that described in Example 1, using the following compositions: 4,4 '-difluorobenzofone (BisK, 4.57 g, 0.021 mol), 3,3'-disulfonated-4,4 '-difluorobenzophone (SBISK, 17.41 g, 0. 041 mol), Oligomer 12 (29.72 g), 4, '-dihydroxybiphenyl (13.03 g, 0.07 mol) and anhydrous potassium carbonate (12.57 g, 0. 091 mol), 250 ml of DMSO and 125 ml of toluene. This polymer has an inherent viscosity of 1.01 dl / g in DMAc (0.25 g / dl).

Example 73 illustrates the ionic region consisting of the SBisK-O unit: This block polymer is synthesized in a manner similar to that described in Example 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 4.57 g, 0.021 mol), 3,3'-disulfonated-4,4-difluorobenzophone ((SBisK, 17.41 g, 0.041 mol), Oligomer 12 (29.72 g), 4,4 '-dihydroxyphenyl ether (14.15 g, 0.07 mol) and carbonate of Anhydrous potassium (12.57 g, 0.091 mole), 250 ml of DMSO and 125 ml of toluene This polymer has an inherent viscosity of 0.94 dl / g in DMAc (0.25 g / dl).

Example 74 This block polymer was synthesized in a similar manner as described in the synthesis of Example 1, using the following conditions: 4,4'-difluorobenzofone 1,298 g, 0.0059 mol), 3,3'-disulfonated-4, ' -difluorobenzofone (SBisK, 23,736 g, 0.056 mol), Oligomer 12 (29.72 g), 4,4'-dihydroxyphenyl (13.03 g, 0.07 mol) and anhydrous potassium carbonate (12.57 g, 0.091 mol), 250 ml of DMSO and 125 ml of toluene. This polymer has an inherent viscosity of 1.35 dl / g in DMAc (0.25 g / dl).

Example 75 This block polymer was synthesized in a similar manner as described in the synthesis of Example 1, using the following conditions: 4,4 '-difluorobenzophone (BisK, 3.91 g, 0.018 mol), 3,3'-disulfonated- 4, 4 '-difluorobenzophone (SBisK, 14.92 g, 0.035 mol), Oligomer 12 (25.47 g), 1,5-dihydroxynephthalene (9.61 g, 0.060 mol) and anhydrous potassium carbonate (10.71 g, 0.078 mol), 206 ml of DMSO and 103 ml of toluene. This polymer has an inherent viscosity of 1.10 dl / g in (0.25 g / dl).

Table II summarizes the impact of chain length and flexible in the ion region on the final membrane properties of examples 10-16.

Example 76 illustrates the block copolymer system using the BisK-Z block in the non-ionic and multicomponent region (more than 2 units) in the ionic region, as compared to the random copolymer of the multicomponent system.

Example 76 This block polymer was synthesized in a similar manner as described in the synthesis of Example 1, using the following conditions: 4, '-difluorobenzophone (BisK, 3.91 g, 0.0179 mol), 3-disulfonated-4, 4' - difluorobenzofone ((SBisK, 14.92 g, 0.035 mol), Oligomer 12 (25.27 g), BisZ (8.05 g, 0.035 mol), 9, 9-bis (4-hydroxyphenyl) fluorene (10.51 g, 0.035 mol) and potassium carbonate anhydrous (10.78 g, 0.078 mol), 250 ml of DMSO and 125 ml of toluene.This polymer has an inherent viscosity of 1.02 dl / g in (0.25 g / dl) Its one day swelling in 8 M to 80 ° methanol C was 63%, crossover in methanol was 0.036 mg min.cm2 (not boiled) and 0.038 mg il / cc.min.cm2 (boiled), the conductivity was 0.026 S / cm (without boiling) and 0.047 S / cm (boiled).

Example 77 Oligomer 13 (FL4): DP = 4 In a 500 ml three-neck round flask, equipped with agitator, thermometer probe connected with a nitrogen inlet and Dean-Stark trap / condenser are added 4,4 '-difluorobenzofone (BisK, 34.91 g, 0.16 moles), 9.9-bis- (4-hydroxyphenyl) fluorene ( 42.05 g, 0.12 moles) and anhydrous potassium carbonate (25.87 g, 0.187 moles), 220 ml of DMSO and 110 ml of toluene. The reaction mixture was stirred slowly under a slow stream of nitrogen. After heating to ~ 85 ° C for 1 hour and to ~ 120 ° C for 1 hour, the reaction temperature was raised to ~ 170 ° C for 2 hours. After cooling to ~70 ° C with continuous stirring, the solution was poured into 1 liter of cooled methanol with vigorous stirring. The precipitates were filtered and washed with deionized water four times and dried at 80 ° C overnight and then dried at 80 ° C under vacuum for 2 days. The block copolymer was synthesized in a similar manner as described in the synthesis of oligomer 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 4.68 g), 3,3'-disulfonated-4,4 '-difluorobenzophone ((SBisK, 19.06 g), Oligomer 13 (19.59 g), 9, 9-bis (4-hydroxyphenyl) fluorene (26.28 g) and anhydrous potassium carbonate (13.48 g), 240 ml of DMSO and 120 ml of toluene. This polymer has an inherent viscosity of 1.00 dl / g in (0.25 g / dl).

Example 78 This block polymer was synthesized in a similar manner as described in the Oligomer 10 synthesis, using the following compositions: 4,4'-difluorobenzophone (BisK, 4.68 g), 3, 3 '-disulfonated-4, 4' -difluorobenzofone (SBisK, 19. 06 g), Oligomer 10 (19.59 g), 4,4 '-biphenol (13.97 g) and anhydrous potassium carbonate (13.48 g), 240 ml of DMSO and 120 ml of toluene. This polymer has an inherent viscosity of 1.89 dl / g in DMAc (0.25 g / dl).

Example 79 This block polymer was synthesized in a similar manner as described in the Oligomer 10 synthesis, using the following compositions: 4,4'-difluorobenzofone 4.68 g), 3,3'-disulfonated-4,4 '-difluorobenzophone (SBisK, 19.06 g), Oligomer 10 (19.59 g), 2,7-dihydroxynaphthalene (12.01 g), and anhydrous potassium carbonate (13.48 g), 240 ml and 120 ml of toluene. This polymer has an inherent viscosity of 1.00 dl / g in DMAc (0.25 g / dl).

Example 80 Oligomer 14 (A8): DP = 8 This oligomer was synthesized in a similar manner as described in the synthesis of oligomer 1 using the following compositions: 4,4'-difluorobenzofone (BisK, 87.28 g), 4,4'- (1,4-phenyleneisopropyl) bisphenol (79.90 g) and anhydrous potassium carbonate (62.88 g), 560 ml of DMSO and 280 ml of Toluene. A block copolymer was synthesized in a similar manner as described in the synthesis of oligomer 1, using the following compositions: 4,4'-difluorobenzofone (BisK, 1.94 g), 3,3'-disulfonated-4,4 '-difluorobenzophone (SBisK, 7.50 g), Oligomer 14 (11.66 g), 9, 9-bis (4-hydroxyphenyl) fluorene (10.51 g) and anhydrous potassium carbonate (5.39 g), 120 ml of DMSO and 60 ml of toluene. This polymer has an inherent viscosity of 0.84 dl / g in (0.25 g / dl).

Example 81 This block polymer was synthesized in a similar manner as described in the synthesis of Example 1, using the following compositions: 4,4'-difluorobenzophone (BisK, 1.94 g), 3,3'-disulfonated-4, 4 '-difluorobenzofone (SBisK, 7.50 g), Oligomer 14 (11.66 g), 4,4' -biphenol (5.58 g), and anhydrous potassium carbonate (5.39 g), 120 ml of DMSO and 60 ml of Toluene. This polymer has an inherent viscosity of 1.12 dl / g in DMAc (0.25 g / dl).

Example 82 This block polymer was synthesized in a similar manner as described in the synthesis of the example, using the following compositions: 4,4 '-difluorobenzophone (BisK, 1.94 g), 3,3'-disulfonated-4,4' - difluorobenzophone (SBisK, 7.50 g), Oligomer 14 (11.66 g), (4-hydroxyphenyl) cyclohexane (8.05 g), and anhydrous potassium carbonate (5.39 g), 120 ml of DMSO and 60 ml of Toluene. This polymer has an inherent viscosity of 0.64 dl / g in DMAc (0.25 g / dl).

Example 83 This block polymer was synthesized in a similar manner as described in the synthesis of Example 1, using the following compositions: 4,4'-difluorobenzofone (Bisk, 0. 64 g), 3,3 '-disulfonated-4,4' -difluorobenzophone (SBisK, 11.88 g), Oligomer 14 (13.60 g), 9, 9-bis (4-hydroxyphenyl) fluorene (12.26 g), and carbonate of anhydrous potassium (6.29 g), 150 ml of DMSO and 75 ml of Toluene. This polymer has an inherent viscosity of 0.68 dl / g in "DMAc (0.25 g / dl).

Example 84 - This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4, '-difluorobenzophone (Bisk 1.94 g), 3'3'-disulfonated-4, 4' - difluorobenzofone (SBisK, 7.50 g), Oligomer 14 (11.66 g), 4,4'- (1,4-phenylenedisopropylidene) -bisphenol (6.85 g), and anhydrous potassium carbonate (5.39 g), 120 ml of DMSO and 60 ml of Toluene. This polymer has an inherent viscosity of 0.84 dl / g in (0.25 g / dl).

Example 85 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4 '-difluorobenzophone (BisK, 2.42 g), 3,3'-disulfonated-4, 4' -difluorobenzofone (SBisK, 9.37 g), Oligomer 14 (14.57 g), 2,7-dihydroxynaphthalene (6.00 g), and anhydrous potassium carbonate (6.74 g), 120 ml of DMSO and 60 ml of Toluene. This polymer has an inherent viscosity of 0.97 in DMAc (0.25 g / dl).

Example 86 Oligomer 15 (AF8): DP = 8 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions:, 4'-difluorobenzophone (BisK, 87.28 g), 4.4 '- (hexafluoroisopropylidene) diphenol (117.69 g) and anhydrous potassium carbonate (62.88 g), 560 ml of DMSO and 280 ml of Toluene.

Example 87 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4'-difluorobenzophone (BisK, 3.88 g), 3,3'-disulfonated-4, 4 ' -difluorobenzofone (SBisK, 15.00 g), Oligomer 15 (29.12 g), (4-hydroxyphenyl) cyclohexane (16.10 g) and anhydrous potassium carbonate (10.78 g), 240 ml of DMSO and 120 ml of Toluene. This polymer has an inherent viscosity of 0.72 dl / g in DMAc (0.25 g / dl).

Example 88 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4 '-difluorobenzophone (BisK, 3.55 g), 3,3'-disulfonated-4, 4' -difluorobenzofone (SBisK, 13.75 g), Oligomer 15 (26.70 g), 9, 9-bis (4-hydroxyphenyl) fluorene (19.27 g), and anhydrous potassium carbonate (9.88 g), 240 ml of DMSO and 120 ml of Toluene This polymer has an inherent viscosity of 0.50 dl / g in DMAc (0.25 g / dl).

Example 89 This block polymer was synthesized in a similar manner as described in the synthesis of Oligomer 1, using the following compositions: 4,4 '-difluorobenzophone (BisK, 4.20 g), 3,3'-disulfonated-4, 4 '-difluorobenzofone (SBisK, 16.25 g), Oligomer 15 (31.55 g), 4,4' -biphenol (12.10 g), and anhydrous potassium carbonate (11.68 g), 240 ml of DMSO and 120 ml of Toluene. This polymer has an inherent viscosity of 1.29 dl / g in DMAc (0.25 g / dl).

Example 90 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4'-difluorobenzophone (BisK, 3.55 g), 3,3 '-disulfonated-4, 4' -difluorobenzofone (SBisK, 13.75 g), Oligomer 15 (26.70 g), 4,4'- (hexafluoroisopropylidene) diphenol (18. 49 g) and anhydrous potassium carbonate (9.88 g), 240 ml of DMSO and 120 ml of Toluene . This polymer has an inherent viscosity of 0.54 dl / g in DMAc (0.25 g / dl).

Example 91 This block polymer was synthesized in a similar manner as described in the Oligomer 1 synthesis, using the following compositions: 4,4'-difluorobenzophone (BisK, 4.20 g), 3,3'-disulfonated-4, 4 ' -difluorobenzofone (SBisK, 16.25 g), Oligomer 15 (31.55 g), 2,7-dihydroxynaphthalene (10.41 g) and anhydrous potassium carbonate (11.68 g), 240 ml of DMSO and 120 ml of Toluene. This polymer has an inherent viscosity of 1.08 dl / g in DMAc (0.25 g / dl).

Synthesis of regular block copolymers When the preparation of the fluorine-terminated oligomer is complete, the solution was cooled to 120 ° C and introduced directly into a reaction flask containing the phenoxy-terminated oligomer under a nitrogen atmosphere. To obtain the equivalent molar ratio of phenoxy end groups and fluorine end groups, the reaction flask of the phenoxy-terminated oligomer was washed three times with 20 ml of DMSO and the solution was washed three times with 20 ml of DMSO and the solution was combined and also poured into the reaction flask. Then the temperature was again raised to 175-180 ° C and maintained at this temperature for 6 hours. The reaction mixture was filtered and a solid was precipitated from acetone or methanol to obtain the crude product, then washed by hot water four times. Conductivity: 0.064 S / cm, swelling per area in 8 M methanol: 88%, methanol cross: 8.3 x 10"7 cm2 / s.

Example 92 Synthesis of Partial Block Polymer with Unsulfonated Hydrophobic Segment Preparation of the fluorinated end group oligomer 16 (segment size: n = 4). In a 500 ml round three neck flask, equipped with agitator, thermometer, nitrogen inlet and Dean-Stark trap / condenser are added Bis Z (80,508), Bis K (87.28 g) and anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene ( approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The oligomer precipitates from methanol to obtain the crude product, then washed with hot water four times. It is dried in an oven at 80 ° C for one day and vacuum oven at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (4.8878 g), S-Bis K (9.2884 g), oligomer 16 (11.2112 g), anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.015 S / cm, swelling per area in 8 M methanol: 51%, methanol cross: 3.5 x 10 ~ 7 cm2 / s.

Example 93 Synthesis of Partial Block Polymer with Unsulfonated Hydrophobic Segment Preparation of Fluoride End Group Oligomer 17 (BisZ / BisK) (segment size n = 4) In a 500 ml three neck round flask, equipped with stirrer Mechanical, thermometer, nitrogen inlet and Dean-Stark trap / condenser are added Bis Z (80,508), Bis K (87.28 g) and anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The oligomer is precipitated from methanol to obtain the crude product, then washed with hot water four times. It is dried in an oven at 80 ° C for one day and vacuum oven at 75 ° C for 2 days. Polymerization In a 500 ml three-necked round bottom flask, equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (5.2368 g), S-Bis K (8.4444 g), oligomer 17 (12.0112g, n = 4, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration) ). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.014 S / cm (0.038 S / cm, boiled), swelling by area in 8 M methanol: 60%, 8 M methanol cross: 0.019 mg / min-ml.ml.

Example 94 In a 500 ml three-necked round flask, equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z is added. (13.418), Bis K (4.28878 g), S-Bis K (9.2884 g), oligomer 17 (11.2112 g, n = 4, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours'. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.0146 S / cm (0.0378 S / cm, boiled), swelling by area in 8 M methanol: 51%, 8 M methanol cross: 0.022 mg / min-ml.ml.

Example 95 Synthesis of Partial Block Polymer with Unsulfonated Hydrophobic Segment Preparation of fluorine end group oligomer 18 (segment size n = 6). In a 500 ml round three-necked flask, equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser are added Bis Z (89.4533 g), 4, 4 '-difluorobenzofone (Bis K, 87.28 g), anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The reaction mixture is precipitated from methanol to obtain the crude product, then washed with hot water four times. It is dried in an oven at 80 ° C for one day and vacuum oven at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (4.8878 g), 3, 3 ' -4,4-difluorobenzofone (S-Bis K, 8.444 g), oligomer (9,953 g, n = 6, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product.

Example 96 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4, 4 'biphenol (8.3794 g), Bis K (1.2444 g), (S-Bis K, 1.2444 g), S-Bis K (12.9794 g), oligomer 18 (18.00 g, n = 4, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration) ). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.0427 S / cm (0.078 S / cm, boiled), swelling by area in 8 M methanol: 61%, 8 M methanol cross: 0.052 mg / min-ml .ml.

Example 98 In a 500 ml three-necked round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4, 4 'biphenol (8.3794 g), Bis K (1.1032 g) , (S-Bis K, 13.6625 g), oligomer 18 (15.1777 g, n = 4, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approx. 20% concentration of solids). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.067 S / cm (0.096 S / cm, boiled), swelling by area in 8 M methanol: 72%, 8 M methanol cross: 0.06 mg / min-ml .ml. Example 99 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4, 4 'biphenol (8.3794 g), Bis K (0.3078 g), S-Bis K (15.0287 g), oligomer 18 (16.0714 g, n = 4, fluorine end of BisZ / BisK composition), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.072 S / cm (0.0922 S / cm, boiled), swelling by area in 8 M methanol: 98%, 8 M methanol cross: 0.067 mg / min-ml.ml.

Example 100 In a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4, 4 '- (hexafluoro-isopropylidene) -diphenol (6 F, 16.8065 g), Bis K (4.8878 g), S-Bis K (9.2884 g), oligomer 18 (11.2112 g, n = 4, fluorine end of composition BisZ / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.007 S / cm (0.0122 S / cm, boiled), swelling by area in 8 M methanol: 24%, 8 M methanol cross: 0.016 mg / min-ml.ml.

Example 101 Synthesis of Partial Block Polymer with Unsulfonated Hydrophobic Segment Preparation of fluorine end group oligomer 19 (segment size n = 4). In a 500 ml three-necked round flask equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser are added 4,4'- (hexafluoro-isopropylidene) -diphenol (6 F, 100,839 g), Bis K (87.28 g), anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The reaction mixture is precipitated from methanol to obtain the crude product, then washed with hot water four times. It is dried in an oven at 80 ° C for one day and vacuum oven at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (4.8878 g), S-Bis K (9.2884 g), Oligomer 19 (12.7333 g, n = 4, fluorine end of composition 6F / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration) ). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.0114 S / cm (0.0321 S / cm, boiled), swelling by area in 8 M methanol: 38%, 8 M methanol cross: 0.013 mg / min-ml.ml.

Example 102 In a 500 ml three-necked round bottom flask equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, 4, 4 '- (1,4-phenyl-diisopropylidene) bisphenol ( 17.30 g), Bis K (4.8878 g), S-Bis K (9.2884 g), Oligomer 19 (12.733 g, n = 4, fluorine end of composition 6F / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.0102 S / cm (0.0215 S / cm, boiled), swelling by area in 8 M methanol: 37%.

Example 103 Synthesis of Partial Block Polymer with Unsulfonated Hydrophobic Segment Preparation of Fluoride End Group Oligomer 20 (6F / BisK) (segment size n = 8) In a 500 ml three neck round flask, equipped with stirrer Mechanical, thermometer, nitrogen inlet and Dean-Stark trap / condenser were added 4,4'- (hexafluoroisopropylidene) -diphenol (6 F, 117.6455 g), Bis K (87.28 g), anhydrous potassium carbonate (54 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 4 hours, then the temperature was increased to 175 ° C for 4 hours. The reaction mixture is precipitated from methanol to obtain the crude product, then washed with hot water four times. It is dried in an oven at 80 ° C for one day and vacuum oven at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask, equipped with mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (3.2729 g), S-Bis K (12.4151 g), Oligomer 20 (24.2454 g, n = 4, fluorine end of composition 6F / BisK), anhydrous potassium carbonate (9.0 g) were dissolved in a mixture of DMSO and toluene (approximately 20% solids concentration) ). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture precipitates from methanol to obtain the crude product. Conductivity: 0.011 S / cm (0.0211 S / cm, boiled), swelling by area in 8 M methanol: 37%, 8 M methanol cross: 0.023 mg / min-ml.ml.

EXAMPLE 104 The following examples demonstrate the effect of various block sizes and degree of sulfonation Preparation of Oligomer 21 (block size n = 4) In a 2-liter, three neck round bottom flask, equipped with mechanical stirrer, thermocouple, blanket heating, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (80,508), Bis K (87.28 g), anhydrous potassium carbonate (71.86 g) were dissolved in a mixture of DMSO and toluene, 720 ml and 360 ml respectively (concentration of approximately 20% solids). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C, then increasing the temperature to 175 ° C for 4 hours. The reaction mixture was precipitated to 2 liters of methanol to obtain the crude product; then wash with warm deionized water four times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask, equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (4.8878 g) ), sodium salt of S-Bis K (9.2902 g), Oligomer 21 (n = 4) (11.2112 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.67 dl / g. A sample was prepared for GPC analysis by dissolving 50 mg of polymer in 20 ml of DMAc containing 0.1 M LiBr. The sample was found to have a peak molecular weight of approximately 46,350 based on polystyrene standards.

Example 105 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (6.0441) g), sodium salt of S-Bis K (7.0521 g), Oligomer 21 (n = 4) (17.2480 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.49 dl / g.

EXAMPLE 106 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (3.8621) g), sodium salt of S-Bis K (11.2750 g), Oligomer 21 (n = 4) (17.2481 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.643 dl / g.

EXAMPLE 107 Preparation of Oligomer 22 (block size n = 8) In a 2-liter, three-necked round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser , Bis Z (70.4445), Bis K (65.4600 g), anhydrous potassium carbonate (47.1920 g) were dissolved in a mixture of DMSO and toluene, 540 ml and 270 ml respectively (concentration of approximately 20% solids). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C, then increasing the temperature to 175 ° C for 4 hours. The reaction mixture was precipitated to 2 liters of methanol to obtain the crude product; then wash with warm deionized water four times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days.

Polymerization In a 500 ml three-necked round bottom flask, equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (3.2729 g ), sodium salt of S-Bis K (12.4151 g), Oligomer 22 (n = 8) (21.2299 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.90 dl / g.

Example 108 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating mantle, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (4.8223) g), sodium salt of S-Bis K (9.4160 g), Oligomer 22 (n = 8) (21.2296 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.935 dl / g. A sample was prepared for GPC analysis by dissolving 50 mg of polymer in 20 ml of DMAc containing 0.1 M LiBr. The sample was found to have a peak molecular weight of about 106,040 based on polystyrene standards.

Example 109 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.418), Bis K (1.8984) g), sodium salt of S-Bis K (15.0757 g), Oligomer 22 (n = 8) (21.2296 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.992 dl / g.

EXAMPLE 110 Preparation of Oligomer 23 (block size n = 2) In a 2-liter, three-necked round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser , Bis Z (53.6721), Bis K (87.2800 g), anhydrous potassium carbonate (71.8692 g) were dissolved in a mixture of DMSO and toluene, 750 ml and 360 ml respectively (concentration of approximately 20% solids). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C, then increasing the temperature to 175 ° C for 4 hours. The reaction mixture was precipitated to 2 liters of methanol to obtain the crude product; then wash with warm deionized water four times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days.

Example 111 In a 500 ml three neck round bottom flask, equipped with mechanical stirrer, thermocouple, heating mantle, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (20.1270), Bis K (8.5424) g), sodium salt of S-Bis K (11.5917 g), Oligomer 23 (n = 2) (6.2215 g), anhydrous potassium carbonate (17.9 g) were dissolved in a mixture of dimethyl sulfoxide (DMSO) (180 ml) and toluene (90 ml) (approximately 20% solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.466 dl / g.

Example 112 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (20.1270 g), Bis K (9.9827) g), sodium salt of S-Bis K (8.8046 g), Oligomer 23 (n = 2) (6.2214 g), anhydrous potassium carbonate (27.0629 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (concentration of approximately 20% solids). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C, then the temperature was increased to 173-175 ° C for 4 - 4.5 hours. The reaction mixture was precipitated to 2 liters of methanol. The polymer was then washed with deionized water four times. Then the product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days.

Example 113 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating mantle, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (20.1270 g), Bis K (7.2661) g), sodium salt of S-Bis K (14.0620 g), Oligomer 23 (n = 2) (6.2217 g), anhydrous potassium carbonate (13.4759 g) were dissolved in a mixture of dimethyl sulfoxide (DMSO) (180 ml) and toluene (90 ml) (concentration of approximately 20% solids). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C, then the temperature was increased to 173-175 ° C for 4 - 4.5 hours. The reaction mixture was precipitated to 2 liters of methanol. The polymer was then washed with deionized water four times.

EXAMPLE 114 Preparation of Oligomer 24 (block size n = 12) In a 1 liter three neck round bottom flask, equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser , Bis Z (73.7990 g), Bis K (65.4600 g), anhydrous potassium carbonate (53.9019 g) were dissolved in a mixture of DMSO and toluene, 540 ml and 270 ml respectively (concentration of approximately 20% solids). The mixture was heated to reflux of toluene with stirring, maintaining the temperature at 140 ° C, then the temperature was increased to 175 ° C for 4 hours. The reaction mixture was precipitated to 2 liters of methanol to obtain the crude product; then washed with warm deionized water four times. Then the product was baked in the oven at 80 ° C for one day and dried under vacuum at 75 ° C for 2 days. In a 500 ml three neck round bottom flask, equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (20.1270), sodium salt of S- Bis K (28.1240 g), Oligomer 24 (n = 2) (31.2316 g), anhydrous potassium carbonate (13.5589 g) were dissolved in a mixture of dimethyl sulfoxide (DMSO) (300 ml) and toluene (100 ml) (ca. % solids concentration). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C for 6 hours, then the temperature was increased to 173-175 ° C for 4-4.5 hours. The reaction mixture was precipitated in 2 liters of methanol. Then the polymer was washed with deionized water 4 times. The dry sample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determine the inherent viscosity. It was found that the inherent viscosity of the polymer of the sodium salt was 0.490 dl / g.

Example 115 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser. Bis Z (16.1017 g), Bis K (6.3366 g), sodium salt of S-Bis K (11.6552 g), Oligomer 24 (n = 8) (12.7379 g), anhydrous potassium carbonate (10.7841 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (200 ml) and toluene (100 ml) (concentration of about 20% solids). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C, then the temperature was increased to 173-175 ° C for 4 - 4.5 hours. The reaction mixture was precipitated to 2 liters of methanol. The polymer was then washed with deionized water four times. It was found that the polymer has an inherent viscosity of 0.66 dl / g in proton form.

Example 116 In a 500 ml three neck round bottom flask equipped with mechanical stirrer, thermocouple, heating blanket, controller, nitrogen inlet and Dean-Stark trap / condenser, Bis Z (13.4180 g), sodium salt of S-Bis K (17.5670 g), Oligomer 24 (n = 8) (31.8444 g), anhydrous potassium carbonate (8.9837 g) were dissolved in a mixture of dimethylsulfoxide (DMSO) (250 ml) and toluene (125 ml) ( concentration of approximately 20% solids). The mixture was heated to toluene flow with stirring, maintaining the temperature at 140 ° C, then the temperature was increased to 173-175 ° C for 4 - 4.5 hours. The reaction mixture was precipitated to 2 liters of methanol. The polymer was then washed with deionized water four times. It was found that the polymer has an inherent viscosity of 0.83 dl / g in proton form.

Claims (11)

1. CLAIMS 1. An ion conductive copolymer, characterized in that it comprises a hydrophobic oligomer and an ion-conducting monomer randomly distributed within the polymer backbone.
2. 2. The ion-conducting copolymer according to claim 1, characterized in that the copolymer comprises at least two different hydrophobic oligomers.
3. 3. An ion conducting copolymer having the formula: wherein Ari, Ar2, Ar4, AR5, Ar7, Ar8, Ar9 and Ario are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, substituted aryl nitrile and Ar7 and / or Ar8 further comprise an ion conducting group, Xx and X are independently -C (O) - or S (0) 2, X2, X3, X5 and Xs are independently -O- or -S-; X7 is a bond, -C (O) - or -S (0) 2-. Ar3 and Ar6 are the same or different from each other and are: 25 wherein the ion conductive group comprises -S03H, -COOH, HPO3H or -S02NH-S02-RF wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the copolymer; Ri and R2 are independently -O-, or -S- where a, b and c are independently between 0.01 and 0.98 and a + b + c = l, where it is between 1 and 12, n is between 1 and 12, and where Y is a bond, -C (0) -, or -S (02) and R i may be present or absent when Y is a bond.
4. 4. An ion conductive copolymer having the formula: wherein Ar2, Ar2, Ar4, AR5, Ar7, Ar8, Ar9 and Ari0 are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, substituted aryl nitrile and Ar7 and / or Ar8 further comprises an ion conducting group, Xx and X are independently -C (O) - or S (0) 2, X2, X3, X5 and Xe are independently -O- or -S-; X7 is a bond, -C (O) - or -S (0) 2-. Ar3 and Ar6 are the same or different from each other and are: 25 wherein the ion conductive group comprises -S03H, -COOH, HPO3H or -S02NH-S02-RF wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the copolymer; Ri and R2 are independently -O-, or -S- where a, b and c are independently between 0.01 and 0.98 and a + b + c = l, where m is between 1 and 12, n is between 1 and 12 , and where Y is a link, -C (0) -, or -S (02) and Rrxo can be present or absent when Y is a link.
5. 5. An ion conductive copolymer, characterized in that it has the formula (Á? 3 -X Ari- iAraXa) m-A ^ -), / (- Ar6-? -?? -Ar ^ 5 At6-)? . { -A? ^ X7. Ari J - ArjrY-ÁriirKa wherein Arx, Ar2, Ar4, Ar5, Ar7, Ar8, Ar9 and Ario are independently phenyl, substituted phenyl naphthyl, terphenyl, aryl nitrile, substituted aryl nitrile and Ar7 and / or Ar8 further comprise an ion conductive group, Xx and X are independently -C (0) - 6 -S (0) 2 l X2, X3, X5 and Xs are independently -O-, or -S-; X7 is a bond, -C (O) - or S (0) 2-. The monomers Ar3 are the same or different between i and are wherein the monomers Ar6 are the same or different from each other and are wherein the ion conductive group comprises -S03H, -COOH, -HP03H or -S02NH- SO2-RF, wherein RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and the ion-conducting group is pendent to the fundamental chain of the copolymer; Ri and R2 are independently -0- or -S-, where a, b and c are independently between 0.01 and 0.98 and a + b + c = l, where m is between 1 and 10, n between 1 and 10, and where Y is a bond, -C (0) -, or -S (02) -, and Ari0 can be present or absent when Y is a link.
6. 6. An ion conductive copolymer, characterized in that it has the formula: where Ar is: where a is between 0.05 and 0.2, b is between 0.01 and 0.2 and c is between 0.5 and 0.95.
7. 7. An ion conductive copolymer, characterized in that it has the formula: a = 0.13, b = 0.036, c = 0.834
8. 8. An ion-conducting copolymer, characterized in that it has the formula Ar =? V a = 0.13, b = 0.036, c = 0.834
9. 9. A proton exchange membrane (PEM) characterized in that it comprises the ion conducting copolymer according to claims 1-8. A catalyst coated membrane (CCM), characterized in that it comprises the PEM according to claim 9, wherein all or part of at least one opposite surface of the PEM comprises a catalyst layer. 12. A fuel cell, characterized in that it comprises the MEA according to claim 11. 13. The fuel cell according to claim 12, characterized in that it comprises a hydrogen fuel cell. 14. The fuel cell according to claim 12, characterized in that it comprises a methanol fuel cell. 15. An electronic device, characterized in that it comprises the fuel cell according to claims 12 and 13. 16. A power source, characterized in that it comprises the fuel fuel cell according to claims 12 and 13. 17. A electric motor, characterized in that it comprises the fuel cell according to claims 12 and 13. 18. A vehicle, characterized in that it comprises the motor according to claim 16.