Mixed ionic electronic conductors for improved charge transport in electrotherapeutic devices

Abstract

This invention addresses the need for efficient dry skin electrodes. Robust, flexible Mixed Ionic Electronic Conductor (MIEC) electrodes were prepared by an aqueous solution route resulting in electrically conductive networks of carbon nanotubes (CNTs) and ionically conductive elastic matrix. The flexible electrode was characterized in terms of conductivity, ionic charge transfer resistance, and water uptake. The flexible electrode maintained low resistance even after multiple cycles of 50% extension and contraction.

Claims

1. An electrode, comprising: coalesced elastomer particles, carbon nanotubes (CNTs), and a glycosaminoglycan; wherein the coalesced elastomer particles comprise exteriors; wherein the CNTs and the glycosaminoglycan are dispersed in a matrix of the coalesced elastomer particles; and wherein the CNTs and the glycosaminoglycan are disposed on the exteriors of the coalesced elastomer particles; wherein the electrode has a thickness and two major surfaces; and wherein at least 30 wt % of the CNTs are disposed on a major surface or within 10% of the thickness near the major surface.

2. The electrode of claim 1, comprising 0.4 to 4 wt % glycosaminoglycan.

3. The electrode of claim 1, comprising 10 to 60 wt % water.

4. The electrode of claim 1, comprising a mass ratio of the glycosaminoglycan to the CNT in a range of 0.5 to 5.

5. An apparatus for treating a patient comprising an array of the electrodes of claim 1.

6. An electrode, comprising: coalesced polymeric particles, electrical conductor, and ionic conductor; wherein the electrical conductor and the ionic conductor are dispersed in a matrix of the coalesced polymeric particles; wherein the coalesced polymeric particles comprise exteriors; wherein the electrical conductor and the ionic conductor are disposed on the exteriors of the coalesced polymeric particles; wherein the electrode comprises a top and bottom surface and the bottom surface is adapted to contact skin of a patient, wherein the electrode has a graded structure with an increasing ratio of the ionic conductor to the electrical conductor from the top to the bottom of the electrode.

7. The electrode of claim 6, wherein the polymeric particles are elastomeric; and wherein the electrode is made in a process wherein the electrical and ionic conductors are added to a dispersed phase of the coalesced polymeric particles.

8. The electrode of claim 6, wherein the graded structure is prepared by layer-by-layer fabrication of the electrode, with increasing levels of ionic conductor in successive layers; having at least 3 layers.

9. The electrode of claim 6, wherein the electrical conductor comprises particles having a height and a smallest width and wherein the particles have a number average aspect ratio of height to the smallest width dimension of at least 10.

10. The electrode of claim 6, wherein the electrical conductor comprises carbon nanotubes, graphene, graphite structures, and metal nanowires, and combinations thereof.

11. The electrode of claim 6, wherein the ionic conductor comprises hyaluronic acid, fluorosulfonic acids, sulfated polysaccharides and other mucoadhesive type compounds, or other phosphonic polyvinylsulfonic acids, and combinations thereof.

12. The electrode of claim 6, wherein the electrical conductor comprises carbon nanotubes (CNTs); wherein the electrode has a thickness and wherein at least 30 wt % of the CNTs are disposed on the bottom surface or within the 10% of the thickness near the bottom surface.

13. An electrode, comprising: coalesced polymeric particles comprising ionically conductive moieties that are bonded to the coalesced polymeric particles, and electrical conductor; wherein the coalesced polymeric particles comprise exteriors; wherein the electrical conductor and ionically conductive moieties are disposed on the exteriors of the coalesced polymeric particles; wherein the electrode has a thickness and two major surfaces; and wherein at least 30 wt % of the CNTs are disposed on a major surface or within 10% of the thickness near the major surface.

14. The electrode of claim 13, wherein the ionically conductive moieties are covalently bonded to the coalesced polymeric particles.

15. The electrode of claim 13, wherein the coalesced polymeric particles comprise styrene-butadiene elastomer, nitrile elastomers, polyurethane elastomers, silicone elastomers, poly aryl ether elastomers, polyphasphazene elastomers, acrylate elastomers, poly vinyl ether elastomers, perfluorinated polymeric elastomers, and combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic showing of the formation of MIEC.

(2) FIG. 2 shows bulk conductivity vs. CNT solid loading.

(3) FIG. 3 shows water uptake at different HA mass ratios.

(4) FIG. 4 shows water uptake at different HA sodium doping levels.

(5) FIG. 5 is a plot of ionic transfer number vs. material modification.

(6) FIG. 6 schematically illustrates an apparatus for iontophoresis.

(7) FIG. 7 illustrates surface resistance as a function of CNT loading for CNTs dispersed in an acrylate copolymer.

(8) FIG. 8 illustrates sheet resistance as a function of CNT loading for a CNT-polyurethane composite.

(9) FIG. 9 illustrates surface resistance as a function of CNT loading for CNTs dispersed in PVDF.

(10) FIG. 10 illustrates the test set-up to for examining the performance with skin simulant.

(11) FIG. 11 illustrates impedance of CNT composites with three different polymeric materials.

(12) FIG. 12 shows impedance of MIEC with different amounts of HA.

(13) FIG. 13 shows impedance of a gradient electrode as compared with an ungraded electrode.

DETAILED DESCRIPTION OF THE INVENTION

(14) The mixed-ionic-electronic conductors (MIECs) are an interconnected network of electrical and ionic conductors in an elastomeric matrix that provide: (1) high surface area for efficient capacitive charge-discharge; (2) high ionic conductivity for low interfacial resistance; (3) low ohmic resistance; and (4) excellent flexibility and toughness.

(15) Electrical and ionic conductors are embedded in a matrix in such a way that the electrical and ionic elements achieve percolation, i.e., a continuous interconnected network, at lower loading than would be achieved by simple random mixing. This allows superior electrical performance to be achieved while retaining good mechanical properties.

(16) The morphology may be controlled by using a polymer latex, in which polymer particles are dispersed in an aqueous phase, to template the organization of the electrical and ionic conductors, as shown in FIG. 1. Examples of suitable dispersions include elastomeric polymers such as nitrile butadiene rubber, natural rubber, silicone, Kraton-type, silicone acrylic, or polyurethane. Other suitable polymer lattices include polyvinylidene fluoride or polyvinylidene chloride. In such a dispersion, at least 90 mass % of the polymer particles are preferably in the range of 50 nm to 10 μm in diameter. The dispersion is cast and the volatiles (e.g., water) allowed to evaporate. During evaporation, the polymer particles coalesce to form a continuous fill. This process is the common one for creating nitrile gloves.

(17) The electrical and ionic conductors are added to the latex so that they are dispersed in the aqueous phase. Methods known in the art for balancing the pH and selecting any necessary dispersing agents can be used. Suitable electrical conductors are those that have high aspect ratio and are readily dispersed into aqueous solutions and include carbon nanotubes, graphene and graphite structures, and metal nanowires. Suitable ionic conductors include sodium hyaluronate, also called hyaluronic acid, fluorosulfonic acids like Nafion™, sulfated polysaccharides and other mucoadhesive type compounds, or other phosphonic polyvinylsulfonic acids. Likewise, anisotropic ionic conductive particles like graphene oxide and modified graphene oxide may be used. In some embodiments, HA is preferred due to its tendency to hydrate with the skin, improving the skin contact.

(18) By adding an electrical and ionic conductors to the dispersed phase of the latex, the conductors tend to coat the surface of the polymer particles, but not penetrate. As the latex is dried, the conductors tend to be confined at the interfaces, creating an interconnecting network, where the major phase is elastomeric and a connected thin, layer phase is the electronic/ionic conductors.

(19) The morphology of this network can be modified by changing the particle size of the polymer in the latex. Larger particle sizes require less conductor to reach an interconnected phase. The film formation temperature is also a tunable parameter that can used to modify the kinetics to achieve various kinetically trapped states. Other methods to achieve better than random mixing include self-assembling or self-stratifying coatings.

(20) In preferred embodiments, carbon nanotubes are the electrical conductors and hyaluronic acid (HA), or other glycosaminoglycan, along with moisture and ions, is the ionic conductor. Preferably, the MIECs have high conductivity of at least 1000 mS/cm, preferably at least 2000 mS/cm, or in the range of 2000 mS/cm to about 4000 mS/cm is desirable. In some preferred embodiments, the MIECs have high moisture retention such that the composite may absorb at least 20% water, up to 50% by mass water (corresponding to 100% of the weight of the dry composite), in some embodiments 20% to 50%, or 35% to 50% water.

(21) In some embodiments, the ionic element is organized into a gradient structure, getting progressively richer as the material gets closer to the skin. The electrode performance is improved by introducing a smooth transition from electronic conduction interface (from the current collector/Electrode interface) to ionic conduction interface (from the skin-to-electrode-interface). A gradient can be prepared by layer-by-layer fabrication of the electrode, with increasing levels of ionic conductor in successive layers.

(22) The invention could also involve combining two functionalities into one polymer, for example, an elastomer with ionic conductivity. This can be achieved, for example, with grafting of ionic segments from the polymer backbone. The ionic segments can be anionic, cationic or amphoteric. One method of grafting ionic segment is via co-polymerizing ion-containing monomers with non-ion-containing monomers. Another way of grafting ionic segment is via post functionalizing the elastomeric polymer.

(23) Examples of anionic segments include, but not limited to, sulfonic, carboxylic, phosphonic and combinations thereof. Examples of cationic segments includes alkyl ammonium derivatives such as the N,N-dimethyl amino ethyl functionality. Examples of amphoteric segments includes the combination of anionic and cationic segments.

(24) Examples of grafting anionic segments include, but are not limited to, co-polymerizing anion containing monomer such as styrene sulfonic acid with non-ion containing monomers such as styrene and butadiene to produce anion containing styrene-butadiene elastomer, namely sulfonated styrene-butadiene elastomer.

(25) Examples of grafting cationic segments include, but are not limited to, co-polymerizing cation containing monomer such as N,N-dimethyl aminoethyl methacrylate with non-ion containing monomers such as styrene and butadiene to produce cation containing styrene-butadiene elastomer, namely aminated styrene-butadiene elastomer.

(26) Examples of grafting amphoteric segments include, but are not limited to, co-polymerizing anion and cation containing monomer such as styrene sulfonic acid and N,N-dimethyl aminoethyl methacrylate with non-ion containing monomers such as styrene and butadiene to produce amphoteric ion containing styrene-butadiene elastomer, namely sulfonated and aminated styrene-butadiene elastomer.

(27) Examples of post functionalizing the elastomeric polymer include, but are not limited to, treating styrene butadiene elastomer with fuming sulfuric acid to produce anion-containing styrene-butadiene elastomer, namely sulfonated styrene-butadiene elastomer.

(28) Ion-containing monomers can be introduced into nitrile elastomers, polyurethane elastomers, silicone elastomers, poly aryl ether elastomers, polyphasphazene elastomers, acrylate elastomers, poly vinyl ether elastomers, perfluorinated polymeric elastomers, and the like.

(29) The invention includes methods of making electrodes according to the descriptions provided herein.

(30) The present invention is useful for making elastomers, preferably as cuffs or individually deposited electrodes. It is also useful for making electrodes with adhesive properties. The polymer matrix may include an adhesive-type polymer for skin adhesion.

(31) Treatment Methods

(32) The inventive electrode composition can be used in neuromuscular electrical stimulation (NMES) and iontophoretic drug delivery. In iontophoresis, an HA dressing matrix is powered by an assembly as illustrated in FIG. 6.

(33) Method of Making/Examples

(34) CNTs are commercially available and a dispersion can be formed by mixing with an aqueous solution of HA, and optionally with ultrasound. The CNT/HA dispersion is combined with an elastomer dispersion. In the examples, the dispersion was a commercial nitrile-butadiene dispersion commonly used for manufacturing nitrile gloves. The resulting dispersions can be tape cast into a robust, flexible, freestanding composite film, which can then be peeled off and cut into desired size and shape for an electrode.

(35) The process used to create these composites allows a very low loading of CNTs to be used and still reach saturation conductivities. The process starts with an elastomeric dispersion. For the examples in this disclosure, Zeon LX550L nitrile butadiene rubber was used. This material is a latex of acrylonitrile butadiene copolymer (NBR latex). In such a dispersion, the polymer particles are primarily 50 nm to 10 μm in diameter. The dispersion is cast and the volatiles (e.g. water) allowed to evaporate. During evaporation, the polymer particle coalesce to form a continuous film. This process is the common one for creating nitrile gloves.

(36) By adding a CNT/HA dispersion to this latex, the CNT and HA tend to coat the surface of the polymer particles, but not penetrate into the particles. The CNT/HA dispersion is prepared by mixing purified CNTs (0.1 to 1 wt %) and HA (0.1 to 5 wt %) in water with the assistance of sonication. Hyaluronic acid sodium salt was from Streptococcus Equi. and carbon nanotubes are purified single wall carbon nanotubes obtained from OCSiAl (<1% metallic impurities).

(37) As the latex is dried, the CNT/HA tends to be confined at the interfaces, creating an interconnecting network, where the major phase is elastomeric and a connected thin, layer phase is CNT/HA, or the electronic/ionic conductors.

(38) The morphology of this network can be modified by changing the particle size of the polymer in the latex. Larger particle sizes require less CNT/HA to reach an interconnected phase. The film formation temperature is also a tunable parameter that can used to modify the kinetics to achieve various kinetically trapped states.

(39) The final films are 85-90% polymer, 0.2 to 2 wt % CNT, and 0.2 to 4 wt % HA.

(40) As a comparative example, CNTs were randomly mixed in a silicone elastomer using typical compounding methods. The resulting composite had a conductivity that was 20 times less than the corresponding sample made according to the method of this Example.

(41) FIG. 2 shows the bulk conductivity of a flexible electrode as a function of the CNT loading. Bulk conductivity begins to increase near 0.2 wt % CNTs, associated with achieving a percolating network of CNTs. The percolating network allows a conductive pathway for electron carriers. As the loading of the CNTs increases, the conductivity of the electrode approaches a plateau. A conductivity of about 3000 mS/cm was obtained for an electrode composed of 1% CNTs and 1.2% HA in elastomer. The elastomer-CNT-HA electrode exhibits robustness to repeated stretching cycles. The film resistance shows negligible change after repeated stretching to 50% strain. The ionic conductivity and low interfacial resistance are provided by the HA and any moisture in the electrode.

(42) As a comparative example, CNTs were randomly mixed in a silicone elastomer using typical compounding methods. The resulting composite had a conductivity that was 20 times less than the corresponding sample made according to the method of Example 1.

(43) FIG. 3 shows the water uptake of flexible electrode as a function of time in water. The results indicate the affinity for water increases with increased HA content. The electrical resistance of the film was stable for a mass ratio of HA/CNT of about 2; above that value there was a loss of electrical conductivity, which may be due to expanded CNT-CNT junctions.

(44) The electrochemical performance of the elastomer-CNT-HA flexible electrodes was characterized by electrochemical impedance spectroscopy (EIS). The samples were assembled into a fixture using two identical ionic block electrodes (working and reference). The impedance is measured in a frequency domain (from 1 MHz to 1 Hz) by applying a small electrical perturbation namely voltage (10 mV) and recording the real and imaginary parts of the complex resistance. The obtained Nyquist plots the frequency dependence of the complex resistance for an electrode made of 0.11 wt % CNTs and 0.15 wt % HA in elastomer with different ionic (Na.sup.+) content are shown in FIG. 4. From the plots, it can be seen that the bulk resistance remains constant with increasing Na.sup.+ loading. The Randles cell model embedded in FIG. 4 was used to fit the obtained EIS data. The Randles model includes a bulk resistance, a double layer capacitance and an ionic interfacial charge transfer. By introducing Na.sup.+ into the elastomer-CNT-HA composite, the flexible electrode converts to a more ionic conductive material, resulting in an increase of ionic charge interfacial transfer resistance.

(45) The total conductivity of the composite material is the sum of partial conductivity of charge carrier expressed as
σ=FΣc.sub.i|z.sub.i|u.sub.i
Where F, c, z, and u are Faraday constant, concentration, charge number and mobility, respectively. The ratio of partial conductivity of a charge carrier to the total conductivity is defined as transference number of this charge carrier as

(46) $t_i=\frac{{\sigma }_i}{{\sigma }_{\mathrm{tot}}}$
According to the electrochemical impedance spectroscopy (EIS) measurement shown in FIG. 4, one can calculate the ionic transference number as a function of doping amount (sodium ion) in composite material. As shown Table 1, the ionic transference number increased by increasing the doping level.

(47) TABLE-US-00001 TABLE 1 Doping level (as NaCl %) t.sub.Na+ 0 0.07 0.01 0.13 0.1 0.17 1 0.19
The incorporation of 0.1 wt % to 1 wt % sodium made no significant difference on the ionic transference number. At 1 wt % NaCl, the ionic conductivity is approaching 20% of total conductivity which is higher than the pure metallic material.

(48) As shown in FIG. 5, the extent of the ionic conductivity, ionic transference number, in overall electrical performance of the film can easily be tuned by simply varying the Na.sup.+ content in HA component of the composite material. Increasing ionic transference number above 20% can be achieved by increasing the mass ratio of HA/CNT above about 3.

(49) Tensile testing was carried out by creating tensile test samples and testing on Instron. These materials had constant loading of HA but increasing CNT. As shown in Table 2, the modulus and strength increased by the addition of CNTs. The addition of 0.2 wt % to 0.5 wt % made no difference on the elongation. At 1 wt % CNT, the elongation was slightly decreased but still high.

(50) TABLE-US-00002 TABLE 2 0% 0.2% 0.5% 1% CNTs CNTs CNTs CNTs Modulus at 300% (MPa) 0.401 0.697 1.052 1.528 Modulus at 500% (MPa) 0.406 0.704 1.029 1.520 Tensile Stress at 0.654 0.821 1.164 1.722 Max Load (MPa) Maximum Extension 1805 1806 1806 1491 Stress at Max Extension 0.633 0.814 1.019 1.269
Self-Adhesive Conductive Electrode

(51) A self-adhesive acrylate copolymer water based emulsified is identified by trade name Pro-Aides, and Ghost Bond™. In a suitably sized vessel equipped with a suitable overhead mechanical stirrer (IKA overhead Model RW-20 manufactured by IKA-WERK, Germany), the water and acrylate copolymer emulsion are added at room temperature and mixed. Stirring is slowly increased until a vortex forms in the aqueous solution. The CNTs dispersed in HA aqueous solution, is slowly added to the vortex and allowed to mix until a uniform in composition is formed. The surface resistance obtained using 4-point measurement as a function of CNTs amount is shown in the FIG. 7.

(52) Other polymeric matrix capable for producing high performance medical grade conductive electrode

(53) Polyurethane (PU)

(54) A CNT aqueous dispersion prepared using ultrasonic treatment was mixed with as received Polyurethane emulsion in mass ratio indicated in the table below. A speed mixer such as FlackTek DAC 150 was used to homogenized CNTs into the polyurethane matrix. The surface resistance as a function of polymer content is shown in FIG. 8. From the figure it can be concluded that up to 50 wt % based on dry mass, the conductivity is similar to the conductivity of pure CNTs layer. In addition, the threshold amount of polyurethane at which the resistance increases drastically is about 50 wt %.

(55) Fluoro-Polymers Such as PVDF and Teflon

(56) A CNT aqueous dispersion prepared using ultrasonic treatment was mixed with an as-received fluoropolymer emulsion (such as PVDF) at different mass ratios. A speed mixer such as FlackTek DAC 150 was used to homogenized CNTs into a fluoropolymer matrix. The surface resistance as a function of PVDF is shown in the FIG. 9. Up to 30 wt % PVDF the conductivity of CNTs-PVDf composite material remains almost constant and a drastic increase of surface resistance occurs when the amount of PVDF in the matrix is higher than about 90 wt %.

(57) The performance of different electrodes was tested with a skin simulant, using the set-up shown in FIG. 10. SynDaver synthetic human tissue model was used for evaluation of the electrodes. Stainless steel discs were used as a current collectors. The electrode of interest (MIEC coating) was applied to the stainless steel disk and then contacted with the synthetic skin. Impedance Spectroscopy testing was performed with two electrodes; impedance was measured in the frequency domain from 1 MHz to 1 Hz by applying a small perturbation voltage.

(58) The impedance of CNT electrodes prepared using different polymer materials such as Polyurethane (PU), PVDF and Teflon are shown in FIG. 11. As shown in the figure, by incorporation of polymeric material with different toughness and moisture affinity one can tailor the electrical performance and the interfacial charge transfer.

(59) In preferred embodiments, the t.sub.i of the electrode is at least 0.10, preferably at least 0.13, in some embodiments in the range of 0.10 to about 0.20 or 0.15 to about 0.20. The electrode is doped with at least 0.01, or at least 0.10 or up to about 1 wt % sodium; or is doped with at least 0.01, or at least 0.10 or up to about 1 wt % sodium chloride.

(60) Tensile testing was carried out by creating tensile test samples and testing on Instron. These materials had constant loading of HA but increasing CNT. As shown in Table 3, the modulus and strength increased with the addition of CNTs. The addition of 0.2 wt % to 0.5 wt % made no difference on the elongation. At 1 wt % CNT, the elongation was slightly decreased but still high.

(61) TABLE-US-00003 TABLE 3 0% 0.2% 0.5% 1% CNTs CNTs CNTs CNTs Modulus at 300% (MPa) 0.401 0.697 1.052 1.528 Modulus at 500% (MPa) 0.406 0.704 1.029 1.520 Tensile Stress at 0.654 0.821 1.164 1.722 Max Load (MPa) Maximum Extension 1805 1806 1806 1491 Stress at Max Extension 0.633 0.814 1.019 1.269
Some preferred embodiments of the invention can be further characterized by the above data; for example, a modulus at 300% of least 1 or 0.7 to about 1.5 MPa; or a tensile stress at maximum load of at least 0.8, or at least 1.1, or 0.8 to about 1.7 MPa; or a maximum extension of at least 1800 or about 1800; or a stress at maximum extension of at least 0.8 or at least 1.0, or 0.8 to about 1.3 MPa; or any combination of these characteristics (which may be further combined with any of the other characteristics described herein.
Electrode Gradient Design

(62) In some embodiments, the ionic element is organized into a gradient structure, getting progressively richer as the material gets closer to the skin. The electrode performance is improved by introducing a smooth transition from electronic conduction interface (from the current collector/Electrode interface) to ionic conduction interface (from the skin-to-electrode-interface). A gradient can be prepared by layer-by-layer fabrication of the electrode, with increasing levels of ionic conductor in successive layers.

(63) The electrode performance is improved by introducing a smooth transition from electronic conduction interface (current collector/Electrode interface) to ionic conduction interface (skin-to-electrode-interface). FIG. 12 shows the Nyquist plot for two different MIEC compositions, with different ratios of HA/CNT. CNT loading was kept constant at 0.4 wt % of the electrode and the amount of HA was increased by decreasing the amount of solids from NBR. The interfacial resistance depends on HA loading. When it is too high, the interfacial and bulk conductivity decreases due to change in CNTs-CNTs connection. The use of a gradient allows better independent tuning of parameters.

(64) The composition of an electrode with a gradient configuration is summarized in the following table 4.

(65) TABLE-US-00004 TABLE 4 GRADIENT 1 Component wt % Ratio of HA/CNT Layer Contacting Stainless Steel CNT 0.6 2.59 HA 1.6 Solids of Zeon NBR 98 Layer in Middle CNT 0.85 3.70 HA 3.14 Solids of Zeon NBR 96.01 Layer Contacting Skin CNT 0.27 3.76 HA 1.02 Solids of Zeon NBR 98.71
Its impedance, measured in a frequency domain (from 1 MHz to 1 Hz) with a small electrical perturbation namely voltage (10 mV), is compared with an electrode made of 0.4 wt % CNTs and 1.5 wt % HA in elastomer as shown in FIG. 13 (“non-gradient”). As shown in FIG. 13, the incorporation of gradient structure with 0.2 wt % to 0.8 wt % CNTs significantly improves the interfacial charge transfer as indicated by the small semi-circle in the Nyquist plot at medium and low frequency domain.

(66) The data can be fit to a Randles cell model as discussed above, where the interfacial component of interest is described by a parallel circuit with capacitive (C2) and resistive (R2) elements. The gradient electrode is better described by two such parallel circuits but for comparison, the system was modeled as a resistor (R1) in series with one interfacial component. The results are shown in Table 5. As shown in Table 5, increasing the amount of HA to CNT in the non-gradient MIEC reduces the capacitance and increases the interfacial resistance. The gradient provides a system where these two can be decoupled, both C2 and R2 are lower for Gradient 1 than for MIEC 1.4X.

(67) TABLE-US-00005 TABLE 5 CNTs R1 C2 R2 Sample: xHA (%) (Ohm): (nC): (Ohm): MIEC 1.4X 1.4 0.45 1655 3.427 192.5 MIEC 2.6X 2.6 0.44 1697 2.850 286.3 MIEC 5.0X 5.0 0.43 1671 2.482 219.1 Gradient 1 2.59, 3.70, 0.62, 0.85, 1627 2.740 175.1 3.76 0.27 Gradient 2 1.40, 2.58, 0.62, 0.86, 1791 2.904 198.6 4.78 0.28
Contemplated Example for Making Anionic Styrene Butadiene Elastomer:

(68) In an emulsion reactor charge 51 mL of water, 3.5 grams of SDS and 0.2 grams of ascorbic acid. Maintain the temperature of the kettle around 4° C. Add 10 g of styrene 5 grams of SSA and 0.1 gram dodecyl mercaptan. Add of 10 mL of water containing 0.2 grams of potassium persulfate and 20 g of butadiene using a mass flow controller to the emulsion kettle at the same time for about 30 to One hour to produce sulfonated styrene butadiene elastomer product.

(69) Ingredients

(70) Range Wt (%)

(71) Styrene 5-10

(72) Butadiene 20-40

(73) Styrene Sulfonic acid sodium salt (SSA) 1-5

(74) Sodium dodecyl sulfate (SDS) 2-8

(75) Dodecyl mercaptan 0.01-0.1

(76) Potassium persulfate 0.01-0.2

(77) Ascorbic acid 0.01-0.2

(78) Water—Adjusted to 100 wt %

(79) Contemplated Example for making cationic styrene butadiene elastomer: In an emulsion reactor charge 51 mL of water, 3.5 grams of CTAB and 0.2 grams of ascorbic acid. Maintain the temperature of the kettle around 4° C. Add 10 g of styrene 5 grams of NN-DMEMA and 0.1 gram dodecyl mercaptan. Add of 10 mL of water containing 0.2 grams of potassium persulfate and 20 g of butadiene using a mass flow controller to the emulsion kettle at the same time for about 30 to One hour to produce aminated styrene butadiene elastomer product.

(80) Ingredients

(81) Range Wt (%)

(82) Styrene 5-10

(83) Butadiene 20-40

(84) N,N′-dimethyl aminoethyl methacrylate (NN-DMEMA) 1-5

(85) Cetyl trimethyl ammonium bromide (CTAB) 2-8

(86) Dodecyl mercaptan 0.01-0.1

(87) Potassium persulfate 0.01-0.2

(88) Ascorbic acid 0.01-0.2

(89) Water—Adjusted to 100 wt %