Agglomerated rubber particles and method of preparing

Abstract

A synthetic latex composition, comprising rubber particles, natural surfactants, a novel acid stable surfactant and water for use in agglomeration processes. The invention is also directed to a reproducible method for preparing agglomerated latex particles to control and achieve particle size targets within a specified range and distribution, by utilizing the inventive latex composition and process conditions, but without the use of elevated temperature, pressurization or mechanical agitation of prior art processes.

Claims

1. A method for agglomerating rubber particles, comprising: a. providing a latex emulsion formulated with a natural surfactant; b. adding an additional surfactant additive that is acid stable to the latex emulsion to form a mixture, wherein the acid stable surfactant comprises either sodium dodecyl benzene sulfonate or a naphthalene sulfonic acid condensate polymer, with formaldehyde functionality, ammonium salt; c. reducing the pH of the mixture to a range of about 5.0 to 3.5 by addition of an acid, wherein the acid comprises phosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, or acetic acid; d. allowing the pH-reduced mixture to sit at room temperature with no agitation for a set period of time so that agglomerated rubber particles are formed; and e. stabilizing the agglomerated rubber particles with a base.

2. The method as set forth in claim 1, wherein the acid is phosphoric acid or acetic acid.

3. The method as set forth in claim 1 wherein the natural surfactant is potassium oleate, potassium rosinate or potassium dimerate.

4. The method as set forth in claim 1 wherein the acid stable surfactant is sodium dodecylbenzene sulfonate.

5. The method as set forth in claim 1 wherein the acid stable surfactant is a naphthalene sulfonic acid condensate polymer, with formaldehyde functionality, ammonium salt.

6. A method for agglomerating rubber particles, comprising: a. providing a latex emulsion formulated with a natural surfactant, wherein the latex emulsion comprises a polymeric compound that is a homopolymer or copolymer of a 1,3-diene rubber, ethylene-propylene-diene terpolymer, acrylate-diene interpolymer rubber, polyisoprene rubber, or mixtures thereof; b. adding an additional surfactant that is acid stable to the latex emulsion to form a mixture, wherein the additional surfactant comprises either sodium dodecyl benzene sulfonate or a naphthalene sulfonic acid condensate polymer, with formaldehyde functionality, ammonium salt; c. reducing the pH of the mixture to a range of about 5.0 to 3.5, by adding an acid, wherein the acid comprises phosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, or acetic acid; d. allowing the pH-reduced mixture to sit at room temperature with no application of pressure or agitation for a set period of time for agglomeration of rubber particles; and e. stabilizing the agglomerated rubber particles with a base.

7. The method as set forth in claim 6, wherein the polymeric compound is butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, styrene, -methylstyrene, vinyltoluene, or vinylpyridine.

8. A method for agglomerating rubber particles, comprising: a. providing a butadiene latex emulsion formulated with a natural surfactant, wherein the natural surfactant is potassium oleate, potassium rosinate or potassium dimerate; b. adding an acid stable surfactant that is a naphthalene sulfonic acid condensate polymer, with formaldehyde functionality, ammonium salt to the latex emulsion to form a mixture; c. reducing the pH of the mixture to about 4.5 to 3.0 by adding phosphoric acid or acetic acid; d. allowing the pH-reduced mixture to sit at room temperature with no application of pressure or agitation for a set period of time for agglomeration of rubber particles; and e. stabilizing the agglomerated butadiene particles with a base.

9. An agglomerated rubber particle product made by the method of claim 8.

10. An agglomerated rubber particle product made by the method of claim 6.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates an embodiment of the inventive process components, steps and pH conditions throughout.

DETAILED DESCRIPTION OF THE INVENTION

(2) The present invention is directed to a composition useful in agglomeration processes for converting small rubber particles to large rubber particles, wherein the particle size achieved during agglomeration is controlled within a specified range and distribution. The present invention is also directed to an agglomeration method useful for tailoring rubber particle sizes to specific applications. The present invention is also directed to resin products prepared utilizing the latex composition of the invention and the large rubber particles produced thereby.

(3) As used in the invention, soap shall mean and include natural and synthetic surfactants of the novel surfactant system. Soap and surfactant are used interchangeably herein and include both the natural surfactants used to formulate the latex emulsion and the novel pH-stable surfactant additive.

(4) The term rubbers shall mean and include natural or synthetic polymeric compounds, which may be dispersed in water to form an emulsion.

(5) Latex or latex emulsion means and includes a dispersion of natural or synthetic polymeric compounds in water. In the present invention, latex is synonymous with rubber.

(6) Agglomeration, as used in the present invention, means the control of particle size growth and distribution in a process wherein larger rubber particles are formed from the smaller particles of a latex.

(7) Coagulation, as used in the present invention, means uncontrolled particle growth in a process wherein larger rubber particles are formed from the smaller particles of a latex.

(8) Particle size means and includes the average particle size (in nanometers) for the rubber particles of the initial latex or achieved through use of the agglomeration process.

(9) Distribution or particle size distribution means and includes the sizes of particles that present and in what proportions (relative particle amount as a percentage, where the total amount of particles is 100%), in the sample particle group to be measured.

(10) Various small rubber particle latex may be utilized in the inventive method. These rubbers include polymeric compounds such as 1,3-diene rubbers, ethylene-propylene-diene terpolymers, acrylate-diene interpolymer rubbers, polyisoprene rubbers, and mixtures thereof. Particularly preferred rubbers are those of 1,3-diene rubbers, such as butadiene, isoprene, chloroprene and the like. The rubber may be diene homopolymers or copolymers of dienes with one or more copolymerizable monoethylenically unsaturated monomers. Other useful polymers include: acrylonitrile, methacrylonitrile, styrene, -methylstyrene, vinyltoluene, and vinylpyridine. Other useful polymers will be evident to one skilled in the art. Specific polymers utilized depend on the final end product and desired properties thereof.

(11) Generally, the inventive composition comprises:

(12) a latex formulated with a natural surfactant; and

(13) a novel surfactant additive that is pH (acid) stable.

(14) Useful natural surfactants include potassium oleate, potassium dimerate and potassium rosinate. The pH (acid) stable surfactant additive includes sodium dodecylbenzene sulfonate and a novel naphthalene sulfonic acid condensate polymer with formaldehyde functionality, ammonium salt.

(15) The inventive composition comprises synthetic latex present in amounts ranging from 15 to 60% total solids (TS), preferably 35 to 45% total solids. Typical latex emulsions are formulated with a natural surfactant present in amounts ranging from 0.1 to 5 parts per hundred weight of polymer. The pH (acid) stable surfactant additive is present in the inventive composition in amounts ranging from 0.1 to 50% by weight, based upon the weight of the synthetic latex. Total solids (TS) of the pH (acid) stable surfactant additive and grams and parts utilized are set forth in the examples.

(16) The pH of the inventive latex emulsion composition prior to use in the inventive agglomeration method ranges from about 8 to about 14.

(17) Emulsion polymerization of ethylenic monomers result in a latex having an average particle size of 50 to 150 nanometers. Utilizing the inventive method and inventive composition as described herein, the resultant latex was agglomerated to produce a new latex with a larger particle size between 200 and 450 nanometers with a monomodal distribution.

(18) The inventive method comprises the steps of:

(19) a. providing a synthetic latex emulsion formulated with a natural surfactant;

(20) b. adding a novel pH (acid) stable surfactant additive to form a mixture;

(21) c. reducing the pH of the mixture by addition of certain organic or inorganic acids to destabilize the natural surfactant and allow the particles to agglomerate;

(22) d. allowing the pH-reduced mixture to sit without agitation for a period of time ranging from 0 to 12 hours during which agglomeration occurs;

(23) e. adding a base to re-generate the natural surfactant.

(24) The inventive method proceeds without application of heat or pressure or use of agitation techniques of traditional agglomeration processes.

(25) Acids useful in the inventive method include: Phosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid or acetic acid. Acids added to the mixture are available commercially in concentrations of 38% to 100% by weight. Acids utilized in the inventive mixture in concentrations ranging from 0.1M to 10M, preferably ranging from about 1M to 2M.

(26) During the agglomeration process, pH is reduced to a range of from about 5 to about 3.5, preferably from 3.25-3.75. The pH during the agglomeration process is lower than that utilized in known processes.

(27) Advantageously, the inventive method may be utilized at ambient temperatures and without the need for agitation equipment or pressurizing the mixture as in prior art methods. The time period for optimal agglomeration ranges from about 0 to 48 hours, preferably from about 2 to 8 hours. The time of agglomeration is a critical factor, as times outside the recited ranges do not provide for consistently reproducible results or optimal average particle size. It was determined that monomodal particle size distributions were achieved if agglomeration times of less than 8 hours were maintained. At extended agglomeration times, polymodal particle size distributions occurred, which are less desirable.

(28) After agglomeration has been achieved, the mixture is treated with base and the natural surfactant is regenerated. A schematic reflecting the inventive method is set forth in FIG. 1.

(29) The invention is illustrated by the examples. The examples are not intended to limit the scope of the invention.

EXAMPLES

Test Methodology

(30) Particle size was determined by the Dynamic Light Scattering (DLS) technique. A NICOMP 380 DLS was utilized and reported average and distribution using the Intensity-weighted average method.

(31) Raw Materials Utilized

(32) The following materials were utilized in the examples:

(33) Butadiene Latex (BL), a synthetic latex utilized in the inventive method disclosed herein. BL's traditionally are formulated with a variety of surfactants including natural surfactants to stabilize the emulsion prior to agglomeration.

(34) Potassium Oleatea surfactant derived from oleic acid and potassium hydroxide

(35) Rosinatea surfactant derived from rosin acids and sodium hydroxide or potassium hydroxide. Potassium rosinate is used in the examples.

(36) Dimer acida surfactant derived from covalently bonded C.sub.10-C.sub.22 carboxylic acids which are neutralized with ammonium hydroxide, sodium hydroxide or potassium hydroxide. Potassium dimerate is used in the examples.

(37) Naphthalene sulfonic acid condensate polymer, with formaldehyde functionality, ammonium salt (W-307 in examples)a new emulsifier available from GEO Specialty Chemicals as Lomar PWA liquid.

(38) Sodium Dodecylbenzene sulfonate (W-59 in examples)

(39) Acetic Acidorganic acid

(40) Phosphoric Acidinorganic acid

Example 1Comparison of pH Stable Surfactant Additives

(41) Variables that were modified in testing included surfactant parts, latex dilution, pH target and type of surfactant. BL used in Examples 1-3 was formulated with potassium oleate, a natural soap, unless otherwise specified. In this example, BL was further treated with acid stable surfactant additives (W-59 and W-307). W-59 was used in 9 of the 12 tests and W-307 (a new, naphthalene sulfonic acid condensate with formaldehyde functionality, ammonium salt) was used as an additional surfactant in the other 3 tests. Acetic acid was used as the acidifier to pH-reduce the emulsion to allow agglomeration to occur.

(42) W-59 is desirable to use as it is stable at low pH and has a transparent color. After 120 hours, one W-307 sample was re-stabilized with 10% KOH to arrest particle size growth. Another W-307 sample had its pH reduced further to see if additional growth would occur.

(43) Results are shown in the Tables below. TABLE 1 shows results of experiments utilizing the W-59 soap additive, while TABLE 2 shows results of the experiments with the W-307 soap additive, both using 1 M acetic acid. The W-307 group achieved higher particle (PS) size results.

(44) TABLE-US-00001 TABLE 1 BL w/W-59 and 1.0M Acetic Acid TS (total solids) 20% 20% 20% 20% 20% 20% 20% 20% 20% W-59 Soap TS (total solids) BL 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% 40% 40% 40% BL (gm) 230.4 230.4 230.4 230.4 230.4 230.4 250.0 250.0 250.0 W-59 Soap (parts) 0.25 0.75 1.25 0.25 0.75 1.25 0.25 0.75 1.25 W-59 Soap (gm) 1.25 3.75 6.25 1.25 3.75 6.25 1.25 3.75 6.25 1.0M Acetic Acid (gm) 15 15 16 9 8 9 15 15 15 pH (initial) 8.55 8.55 8.62 8.54 8.55 8.63 8.49 8.56 8.61 pH (final) 5.00 5.00 5.00 6.00 6.00 6.00 5.00 5.00 5.00 Comments PS (nm) (average) (start) 119 119 119 119 119 119 119 119 119 1 hr. 24 hr. 48 hr. 72 hr. 170 129 118 128 114 114 148 123 117 96 hr. 167

(45) TABLE-US-00002 TABLE 2 BL w/W-307 and 1.0M Acetic Acid TS (total solids) 51.8% 51.8% 51.8% W-307 Soap TS (total solids) BL 43.4% 43.4% 43.4% BL (gm) 230.4 230.4 230.4 W-307 Soap (parts) 1.30 2.60 3.90 W-307 Soap (gm) 2.50 5.00 7.50 1.0M Acetic Acid (gm) 15 15 15 pH (initial) 8.38 8.32 8.28 pH (final) 5.00 5.00 5.00 Comments 10% KOH added pH taken to 4.75 to pH = 9.5 after 120 hours after 120 hours, PS growth arrested PS (nm) average (start) 119 119 119 1 hr. 24 hr. 48 hr. 72 hr. 223 244 235 96 hr. 213 245 120 hr. 221 144 hr. 222 250

Example 2Soap Reduction

(46) From Example 1, it was determined that lower amounts (parts) of soap correlated to higher average particle size with improved control of the rate and distribution of particle size.

(47) A second round of experiments was run using less soap additive in efforts to determine the lowest effective level for the novel surfactant additive.

(48) Acetic acid was still used as the acidifier, and variables, such as pH target, soap parts, acid concentration (1 M vs 2 M) and type of soap were evaluated. The goals were two-fold. The first goal was to achieve average particle sizes of 350, 300, 350 and 400 nm. The second goal was to prevent unacceptable levels of coagulated rubber during the agglomeration process. The first round of testing (Example 1) only achieved a maximum 250 nm average particle size. This round of tests was altered to achieve higher particle size targets. The experiments and results are shown below in TABLE 3. Some of the experiments with W-59 were repeated to measure reproducibility, and the results are shown in TABLE 4.

(49) TABLE-US-00003 TABLE 3 BL w/W-59 and Acetic Acid #1 2M BL w/W-307 and Acetic 1M 1M 1M acetic Acid (1M) TS (Total solids) Soap 20% 20% 20% 20% 47.6% 47.6% TS (Total solids) BL 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% BL (gm) 230.4 230.4 230.4 230.4 230.4 230.4 W-59 Soap (parts) 0.01 0.10 0.10 0.10 0.01 0.10 W-59 Soap (gm) 0.05 0.50 0.50 0.50 0.02 0.21 Acetic acid (gm) 15 15 18 9 pH (initial) 8.39 8.40 8.35 8.39 8.39 8.39 pH (final) 5.00 5.00 4.80 4.80 5.00 5.00 Comments Some Some Some Excessive Some Some coag. on coag. on coag. on coag. on coag. on coag. on stirrer stirrer stirrer stirrer stirrer stirrer PS (nm) (average) (start) 119 119 119 119 119 119 1 hr. 24 hr. 212 184 204 231 211 185 48 hr. 235 207 231 242 72 hr.

(50) TABLE-US-00004 TABLE 4 BL w/W-59 and Acetic BL w/W-59 and Acetic Acid #2 Acid #3 1M 1M 2M 1M 1M 2M TS (Total solids) Soap 20% 20% 20% 20% 20% 20% TS (Total solids) BL 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% BL (gm) 230.4 230.4 230.4 230.4 230.4 230.4 W-59 (parts) 0.01 0.10 0.10 0.01 0.10 0.10 W-59 (gm) 0.05 0.50 0.50 0.05 0.50 0.50 Acetic acid (gm) 15 18 9 15 18 9 pH (initial) 8.39 8.35 8.39 8.39 8.35 8.39 pH (final) 5.00 4.80 4.80 5.00 4.80 4.80 Comments Some Some Excessive Some Some Excessive coag on coag on coag on coag on coag on coag on stirrer stirrer stirrer stirrer stirrer stirrer PS (nm) (average) start 119 119 119 119 119 119 1 hr. 24 hr. 184 230 219 211 209 240 48 hr. 72 hr.

(51) The results from this round of experiments reflected that there is a lower limit of soap additive beyond which particle size growth will not occur. As is reflected in the above Tables 3 and 4, the soap parts were lowered too far, which caused some coagulum to form on the stirrer thus affecting particle size growth. It was also noted that excess coagulum was produced if 2M acid concentration was used. Use of 1M acid solutions resulted in a more controlled process. The example is functional and defines undesired reaction at higher acid concentrations.

Example 3pH Reduction Through Phosphoric Acid

(52) It was found that the inventive formulation can be pH-reduced using phosphoric acid (H.sub.3PO.sub.4). The addition of H.sub.3PO.sub.4 allows the pH to be reduced to a lower level than traditional processes as compared to that achieved with acetic acid. The pKa of acetic acid is 4.75 compared to 2.15 for phosphoric acid. By dropping the BL latex to a lower pH, the average particle size (PS) achieved was larger because more surfactant molecules were destabilized. This destabilization allowed direct agglomeration of rubber particles and, therefore, a larger particle size was achieved.

(53) The following experiment was set up to explore how various pH levels, soap concentrations, amount of acid, and types of surfactant affect the average particle (PS) achieved for the latex. The PS growth results are shown after 24 hours, after which most of the PS growth had already occurred. W-59 was used in 8 of the 12 trials due to its cleanliness, clarity, and high stability, while W-307 was used in the other 4 trials. The experiments and results are shown below in Tables 5 and 6.

(54) TABLE-US-00005 TABLE 5 BL w/W-307 and Phosphoric Acid 1M 1M 1M 2M TS (Total solids) Soap 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 43.4% 43.4% 43.4% 43.4% BL (gm) 230.4 230.4 230.4 230.4 W-307 Soap (parts) 0.20 0.34 0.50 0.50 W-307 Soap (gm) 0.42 0.74 1.05 1.05 Phosphoric acid used (gm) 12 12 12 12 pH (initial) 8.30 8.28 8.32 8.32 pH (final) 3.00 3.00 3.00 3.00 Comments Too much Clean Clean Clean coag. PS (nm) (average) (start) 119 119 119 119 1 hr. 24 hr. 345 284 251 281

(55) TABLE-US-00006 TABLE 6 BL w/W-59 and Phosphoric Acid 1M TS (Total solids) Soap 20% 20% 20% 20% 20% 20% 20% 20% TS (Total solids) BL 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% 43.4% BL (gm) 230.4 230.4 230.4 230.4 230.4 230.4 230.4 230.4 W-59 Soap (parts) 0.10 0.10 0.50 0.50 0.25 0.25 0.30 0.40 W-59 Soap (gm) 0.50 0.50 2.50 2.50 1.25 1.25 1.50 2.00 Phosphoric acid used (gm) 9 11 10 12 12 12 120 pH (initial) 8.18 8.18 8.39 8.39 8.39 8.35 8.33 8.36 pH (final) 3.50 4.50 3.50 4.50 3.00 3.50 3.00 3.00 Comments Too much 0.1 parts Medium 10% coag to was not coag KOH drop pH sufficient added to 3.5, to drop to pH = dropped pH 9.5 to 5.5 PS (nm)(average) (start) 119 119 119 119 119 119 119 119 1 hr. 24 hr. 224 175 140 267 230 228 191

(56) From the results above, it can be seen that use of W-307 rather than W-59 resulted in larger particle size as in Example 1. By using the BL formulated with W-307 and pH reduced by H.sub.3PO.sub.4, several higher average PS targets (250 nm to 300 nm) were achieved. The W-59 samples achieved the 200 nm average particle size target only. The W-59 sample that achieved up to 250 nm average PS had too much coagulum and was, therefore, unacceptable from an efficiency standpoint.

Example 4Potassium Dimerate Formulated BL

(57) Two alternative surfactants to potassium oleate were proposed to determine their effect on particle size after agglomeration. All previous BL compositions were made with potassium oleate as the primary stabilizing surfactant, but potassium dimerate and potassium rosinate are two natural surfactant alternatives. Both acetic acid and phosphoric acid were tested at various dispersant (surfactant) levels to determine the effect on particle size growth. The results are shown in Tables 7 and 8 below for potassium dimerate formulated BL.

(58) TABLE-US-00007 TABLE 7 Potassium Dimerate - BL BL w/W-307 and 1M Acetic Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 37.8% 37.8% 37.8% 37.8% BL (gm) 264.6 264.6 264.6 264.6 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Acetic (gm) 10 10 10 10 pH (initial) 8.80 8.80 8.80 8.80 pH (final) 5.00 5.00 5.00 5.00 Comments Low coag. Low coag. Low Low coag. coag. PS (nm) (average) (start) 99 99 99 99 1 hr. 181 172 185 196 3 hr. NA NA NA NA 24 hr. 197 185 198 225 48 hr. 197 188 198 231

(59) TABLE-US-00008 TABLE 8 Potassium Dimerate - BL Potassium Dimerate BL BL w/W-307 and 1M Phosphoric Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 37.8% 37.8% 37.8% 37.8% BL (gm) 264.6 264.6 264.6 264.6 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Phosphoric Acid (gm) 12 12 12 12 pH (initial) 8.80 8.80 8.80 8.80 pH (final) 3.50 3.50 3.50 3.50 Comments High High Med/Low Low coag. coag. coag. coag. PS (nm) (average) (start) 99 99 99 99 1 hr. 277 216 3 hr. 339 317 24 hr. 361 367 48 hr. 389 378

(60) As seen from the data and observations, the BL agglomerated with acetic acid was low in coagulum, but did not produce high particle size (>350 nm). The phosphoric acid agglomerations had high coagulum with no W-307 addition, but at 1.0 parts of W-307 the material had low coagulum and reached a particle size of 367 nm after 24 hours of agglomeration. This demonstrates that potassium dimerate is a viable alternative surfactant to achieve large particle size in agglomerated latex.

Example 5Rosinate Acid Formulated BL

(61) As mentioned in Example 4, potassium rosinate may also be used in place of potassium oleate as the surfactant. For BL, potassium rosinate is a natural, pH-sensitive, soap used in other products. Two runs of BL were made using potassium rosinate as the surfactant. The first run achieved low particle size, so another run was made. The effect of acid type was evaluated and the results are shown below in Tables 9, 10, 11 and 12. Both acetic acid and phosphoric acid were tested against various ph-stable surfactant levels added to the latex. The average particle size was measured at 1, 24 and 48 hour intervals. The particle size target was 350 nm.

(62) TABLE-US-00009 TABLE 9 Potassium Rosinate BL BL w/W-307 and 1M Acetic Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 41.2% 41.2% 41.2% 41.2% BL (gm) 242.7 242.7 242.7 242.7 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Acetic Acid (gm) 6.0 17 17 17 pH (initial) 8.50 8.50 8.50 8.50 pH (final) 5.00 5.00 5.00 5.00 Comments High coag. Med/Low Low Low coag. coag. coag. PS (nm) (average) (start) 102 102 102 102 1 hr. 289 215 213 24 hr. 333 245 253 48 hr. 339 256 249

(63) TABLE-US-00010 TABLE 10 Potassium Rosinate BL BL w/W-307 and 1M Phosphoric Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 41.2% 41.2% 41.2% 41.2% BL (gm) 242.7 242.7 242.7 242.7 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Phosphoric Acid (gm) 15 15 15 15 pH (initial) 8.50 8.50 8.50 8.50 pH (final) 3.50 3.50 3.50 3.50 Comments High coag. High Low Low coag. coag. coag. PS (nm) (average) (start) 102 102 102 102 1 hr. 220 172 24 hr. 243 192 48 hr. 242 201

(64) TABLE-US-00011 TABLE 11 Potassium Rosinate BL BL w/W-307 and 1M Acetic Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 38.8% 38.8% 38.8% 38.8% BL (gm) 257.7 257.7 257.7 257.7 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Acetic Acid (gm) 7 7 8 9 pH (initial) 8.10 8.10 8.10 8.10 pH (final) 5.00 5.00 5.00 5.00 Comments Med/Low Low coag. Low/No Low/No coag. coag. coag. PS (nm) (average) (start) 124 124 124 124 1 hr. 219 167 140 145 24 hr. 240 182 155 146 48 hr. 153

(65) TABLE-US-00012 TABLE 12 Potassium Rosinate BL BLE w/W-307 and 1M Phosphoric Acid TS (Total solids) W307 47.6% 47.6% 47.6% 47.6% TS (Total solids) BL 38.8% 38.8% 38.8% 38.8% BL (gm) 257.7 257.7 257.7 257.7 W-307 Soap (parts) 0.0 0.1 0.50 1.00 W-307 Soap (gm) 0.0 0.21 1.05 2.10 1M Phosphoric Acid (gm) 6 6 6 6 pH (initial) 8.10 8.10 8.10 8.10 pH (final) 3.50 3.50 3.50 3.50 Comments High coag. High Low Low coag. coag. coag. PS (nm) (average) (start) 124 124 124 124 1 hr. 147 140 24 hr. 154 140 48 hr.

(66) While in accordance with the Patent Statutes, the best mode and preferred embodiments have been set forth, the scope of the invention is not limited thereto, but rather, by the scope of the attached claims.