Abstract:
Provided are surfactant compositions that are useful as alternatives to alkylphenol ethoxylates (APEs) type surfactants in emulsion polymerization. The surfactant compositions comprise: an alkyl alkoxylate sulfate of formula (I): R—O—(C 3 H 6 O) x (C 2 H 4 O) y —S0 3 M, wherein R, x, y, and M are as defined herein.

Description:
FIELD 
     This invention relates to a surfactant composition that is useful as an alternative to alkylphenol ethoxylates (APEs) as an emulsifier for emulsion polymerization. The surfactant composition contains an alkyl alkoxylate sulfate of the chemical structure described below. 
     BACKGROUND 
     Surfactants are broadly used as wetting agents in waterborne formulations. For instance, alkylphenol ethoxylates (APEs) are widely recognized as good surfactants in a large variety of applications. APE surfactants, however, suffer from a poor public perception of their environmental compatibility. In addition, they are subject to increasing environmental regulation aimed at reducing their consumption in many applications, including in emulsion polymerization (EP). Therefore, the use of APE type surfactants is declining and suppliers are seeking to provide other surfactants to replace them. 
     Emulsion polymerization (EP) is a polymerization process in which poorly water soluble monomers are emulsified in water with the aid of emulsifiers and then polymerized with initiators. Surfactants play a key role in emulsion polymerization and in particular, APE based surfactants are generally considered the standard. However, in view of the issues with APE surfactants as discussed above, there is a need for new non-APE materials that exhibit properties suitable for emulsion polymerization. Such properties may include reduced foaming, emulsion formulation stability, and mechanical stability. 
     The problem addressed by this invention is the provision of new surfactants that are commercially viable alternatives for APE materials in emulsion polymerization. 
     STATEMENT OF INVENTION 
     We have now found that surfactant compositions as described herein exhibit a number of useful properties that are comparable to, and in some instances better than, properties observed with APE surfactants. Such properties include, for example, one or more of good surface tension reduction, low and moderate foam with foam collapse, rapid wetting, and formulation stability. Moreover, surfactant compositions of the invention, which are derived from seed oils, are biodegradable. Advantageously, therefore, the surfactant compositions of the invention are viable alternatives to APE surfactants for emulsion polymerization. 
     In one aspect, there is provided a surfactant composition comprising an alkyl alkoxylate sulfate of formula I:
 
R—O—(C 3 H 6 O) x (C 2 H 4 O) y —SO 3 M  (I)
 
wherein x is a real number within a range of from 0.5 to less than 4; y is a real number within a range of from 2 to 15; M is a cation; and R is a mixture of seed-oil based linear alkyl moieties with an alkyl moiety distribution as follows, wherein each wt % is based upon weight of all alkyl moieties present in the distribution and all wt % for each distribution total 100 wt %:
 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Carbon Atoms in Alkyl Moiety 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
                   
                 C 6   
                  0 wt %-40 wt % 
               
               
                   
                   
                 C 8   
                 20 wt %-40 wt % 
               
               
                   
                   
                 C 10   
                 20 wt %-45 wt % 
               
               
                   
                   
                 C 12   
                 10 wt %-45 wt % 
               
               
                   
                   
                 C 14   
                  0 wt %-40 wt % 
               
               
                   
                   
                 C 16 -C 18   
                  0 wt %-15 wt % 
               
               
                   
                   
               
             
          
         
       
     
     In another aspect, there is provided a surfactant composition comprising an alkyl alkoxylate sulfate of formula I, as described above, together with a nonionic alkyl alkoxylate of formula II:
 
R—O(C 3 H 6 O) x (C 2 H 4 O) y —H  (II)
 
wherein x is a real number within a range of from 0.5 to less than 4; y is a real number within a range of from 2 to 15; and R is a mixture of seed-oil based linear alkyl moieties with an alkyl moiety distribution as follows wherein each wt % is based upon weight of all alkyl moieties present in the distribution and all wt % for each distribution total 100 wt %:
 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Carbon Atoms in Alkyl Moiety 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
                   
                 C 6   
                  0 wt %-40 wt % 
               
               
                   
                   
                 C 8   
                 20 wt %-40 wt % 
               
               
                   
                   
                 C 10   
                 20 wt %-45 wt % 
               
               
                   
                   
                 C 12   
                 10 wt %-45 wt % 
               
               
                   
                   
                 C 14   
                  0 wt %-40 wt % 
               
               
                   
                   
                 C 16 -C 18   
                  0 wt %-15 wt % 
               
               
                   
                   
               
             
          
         
       
     
     In a further aspect, there is provided a method of using a surfactant composition as described herein as an emulsifier in an emulsion formulation. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
         FIG. 1  is plot showing foaming properties for an inventive emulsion according to one embodiment of the invention (example 3-5) and a comparative emulsion (example 3-6). 
         FIG. 2  is plot showing foaming properties for an inventive emulsion according to one embodiment of the invention (example 3-7) and comparative emulsions (example 3-8). 
         FIG. 3  is plot showing foaming properties for an inventive emulsion according to one embodiment of the invention (example 3-9) and a comparative emulsion (example 3-10). 
     
    
    
     DETAILED DESCRIPTION 
     Unless otherwise indicated, numeric ranges, for instance as in “from 2 to 10,” are inclusive of the numbers defining the range (e.g., 2 and 10). 
     Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. 
     As noted above, the invention provides a surfactant composition comprising an alkyl alkoxylate sulfate of formula I. The surfactant composition exhibits several useful properties, including one or more of good surface tension reduction, low foam and quick foam collapse, rapid wetting, and calcium ion stability. The advantageous properties render the surfactant composition suitable as an emulsifier for emulsion polymerization. 
     The alkyl alkoxylate sulfate is of the following formula I:
 
R—O—(C 3 H 6 O) x (C 2 H 4 O) y —SO 3 M  (I)
 
In Formula I, each C 3 H 6 O moiety may also be called a propyleneoxy (—CH 2 —CH(CH 3 )—O—) or PO moiety and each C 2 H 4 O moiety may also be called a ethyleneoxy or EO moiety. In addition, x is a real number within a range of from 0.5 to 3, y is a real number within a range of from 2 to 15, and M is a cation. Finally, R represents a mixture of seed-oil based linear alkyl moieties with an alkyl moiety distribution in accord with the ranges shown in Table I below.
 
                                       TABLE 1                   Percentages of alkyl moieties                    Alkyl Moiety                   Carbon Chain   Weight               Length   Percent                           C 6      0-40               C 8     20-40               C 10     20-45               C 12     10-45               C 14      0-40               C 16      0-15                        
wherein each wt % is based upon weight of all alkyl moieties present in the distribution and all wt % for each distribution total 100 wt %.
 
     As shown in Table 1, R can be a mixture of just three alkyl moieties, C 8 , C 10  and C 12 . Any one or more of C 6 , C 14  and C 16  alkyl moieties may, but need not be, present in surfactant compositions of the present invention. When present, the amounts of C 6 , C 14  and C 16  alkyl moieties may satisfy any of their respective ranges as shown in Table 1 as long as all weight percentages total 100 wt %. 
     Formula I above includes variables “x” and “y” that, taken together, establish a degree of alkoxylation in an oligomer distribution. Individually, “x” and “y” represent average degrees of, respectively, propoxylation and ethoxylation. The degree of propoxylation or “x” preferably falls within a range of from 0.5 to less than 4, more preferably within a range of from 0.5 to 3, still more preferably within a range of from 2 to 3, and even more preferably within a range of from 2.5 to 3. In some embodiments, x is 3. The degree of ethoxylation or “y” preferably falls within a range of from 2 to 10, more preferably within a range of from 2 to 8, still more preferably within a range of from 2 to 3, and even more preferably within a range of from 2.5 to 3. In some embodiments, y is 3. 
     The moiety M in formula I is a cation. Preferably, M is an alkali metal or ammonium, more preferably it is sodium, potassium, or ammonium, and even more preferably M is sodium or ammonium. 
     A preferred subset of surfactant compositions of the present invention as represented by Formula I include x being within a range of from 2.5 to 3, y is within a range of from 2 to 10 and R has an alkyl moiety distribution as shown in Table 2 below. 
                                       TABLE 2                   Percentages of alkyl moieties                    Alkyl Moiety                   Carbon Chain   Weight               Length   Percent                           C 6      0-36               C 8     22-40               C 10     27-44               C 12     14-35               C 14      5-13               C 16     0-5                        
In other words, the surfactant compositions as shown in Table 2 includes a mixture of at least four alkyl moieties, C 8 , C 10 , C 12  and C 14 . Either or both of C 6 , and C 16  alkyl moieties may, but need not be, present in surfactant compositions of this preferred subset of the invention. When present, the amounts of C 6  and C 16  alkyl moieties may satisfy any of their respective ranges as shown in Table 1 as long as all weight percentages total 100 wt %.
 
     In some embodiments, in addition to the alkyl alkoxylate sulfate of formula I, the surfactant composition of the invention also comprises a nonionic alkyl alkoxylate of formula II:
 
R—O—(C 3 H 6 O) x (C 2 H 4 O) y —H  (II)
 
In Formula II, x is a real number within a range of from 0.5 to 3, y is a real number within a range of from 2 to 15, and R represents a mixture of seed-oil based linear alkyl moieties with an alkyl moiety distribution in accord with ranges shown in Table 3 below.
 
                                       TABLE 3                   Percentages of alkyl moieties                    Alkyl Moiety                   Carbon Chain   Weight               Length   Percent                           C 6      0-40               C 8     20-40               C 10     20-45               C 12     10-45               C 14      0-40               C 16      0-15                        
wherein each wt % is based upon weight of all alkyl moieties present in the distribution and all wt % for each distribution total 100 wt %.
 
     As shown in Table 3, R can be a mixture of just three alkyl moieties, C 8 , C 10  and C 12 . Any one or more of C 6 , C 14  and C 16  alkyl moieties may, but need not be, present in surfactant compositions of the present invention. When present, the amounts of C 6 , C 14  and C 16  alkyl moieties may satisfy any of their respective ranges as shown in Table 1 as long as all weight percentages total 100 wt %. 
     In formula II above “x” preferably falls within a range of from 0.5 to less than 4, more preferably within a range of from 0.5 to 3, still more preferably within a range of from 2 to 3, and even more preferably within a range of from 2.5 to 3. In some embodiments, x is 3. In formula 2, “y” preferably falls within a range of from 2 to 10, more preferably within a range of from 2 to 8, still more preferably within a range of from 2 to 3, and even more preferably within a range of from 2.5 to 3. In some embodiments, y is 3. 
     Preferred nonionic alkyl alkoxylates of formula I include compounds in which x is from 2.5 to 3, y is from 2 to 10 and R has an alkyl moiety distribution as shown in Table 4 below. 
                                       TABLE 4                   Percentages of alkyl moieties                    Alkyl Moiety                   Carbon Chain   Weight               Length   Percent                           C 6      0-36               C 8     22-40               C 10     27-44               C 12     14-35               C 14      5-13               C 16     0-5                        
The surfactant compositions as shown in Table 4 includes a mixture of at least four alkyl moieties, C 8 , C 10 , C 12  and C 14 . Either or both of C 6 , and C 16  alkyl moieties may, but need not be, present in surfactant compositions of this preferred subset of the invention. When present, the amounts of C 6  and C 16  alkyl moieties may satisfy any of their respective ranges as shown in Table 4 as long as all weight percentages total 100 wt %.
 
     When the nonionic alkyl alkoxylate of formula II is present in the surfactant composition of the invention, the groups R, x, and y in formula I and formula II may be the same or different. In some embodiments, the groups R, x, and y in formula I and formula II are the same. 
     In some embodiments, the surfactant composition of the invention comprises an alkyl alkoxylate sulfate of formula I and a nonionic alkyl alkoxylate of formula II, wherein the weight ratio of the alkyl alkoxylate sulfate of formula I to the nonionic alkyl alkoxylate of formula II is from 99:1 to 10:90. In some embodiments, the weight ratio is from 95:5 to 50:50, alternatively from 90:10 to 70:30. 
     In some embodiments, the surfactant composition of the invention further comprises water. 
     In some embodiments, the surfactant composition of the invention comprises an alkyl alkoxylate sulfate of formula I, a nonionic alkyl alkoxylate of formula II, and water. In some embodiments, the amount of the alkyl alkoxylate sulfate of formula I is from 20 to 75% by weight, preferably from 30 to 60% by weight; the amount of the alkoxylate of formula II is from 0.1 to 30% by weight, preferably from 0.1 to 10% by weight; and the amount of water is from 25 to 75% by weight, preferably from 40 to 70% by weight, based on the total weight of the alkyl alkoxylate sulfate of formula I, the nonionic alkyl alkoxylate of formula II, and the water. 
     The surfactant composition of the invention may comprise additional additives, such as other surfactants/emulsifiers, and other additives commonly use in emulsion polymerization. In some embodiments, the surfactant composition of the invention further comprises a nonionic surfactant of the formula III: R 1 O-(AO) z —H (III), wherein R′ is linear or branched C 6 -C 24  alkyl, AO at each occurrence is ethyleneoxy, propyleneoxy, butyleneoxy (—CH 2 —CH(CH 2 CH 3 )—O—), or random or block mixtures thereof, and z is from 1 to 50. 
     The surfactant compositions of the invention exhibit good surface tension reduction, low and moderate foam with foam collapse, rapid wetting, and they provide formulation stability properties, including good Ca 2+  stability. Ca 2+  stability may be understood as the tolerance of an emulsion to electrolytes. In downstream application, numerous additives may be mixed with an emulsion, thus, a good Ca 2+  stability indicates a good formulation stability. As a result of these properties, the surfactant compositions are suitable for use as emulsifiers in emulsion polymerization and indeed may be used as replacements for traditional APE based emulsifiers. 
     The emulsions in which the surfactant compositions of the invention may be used as emulsifiers are typically aqueous emulsions or dispersions of polymers and/or copolymers which are normally obtainable by emulsion polymerization. There are no particular restrictions as to the nature of the polymers and copolymers in these formulations. Polymers or copolymers based on the following monomer units are preferred: acrylic acid, acrylates, butadiene, methacrylic acid, methacrylates, styrene, and vinyl acetate. Thus for instance in some embodiments an emulsion formulation according to the invention comprises a surfactant composition as described above (including all described embodiments thereof), water, and a monomer. 
     A person of ordinary skill in the art can readily determine the effective amount of the surfactant composition of the invention that should be used in an emulsion polymerization formulation, via a combination of general knowledge of the applicable field as well as routine experimentation where needed. For instance, in some embodiments, a quantity of from 0.01 to 10 phm (per hundred monomer) by active weight of the surfactant composition, alternatively from 0.1 to 5 phm by active weight of the surfactant composition, or alternatively from 0.2 to 3 phm by active weight of the surfactant composition, based on the total weight of monomers used in the emulsion polymerization, may be suitable. 
     Alkyl alkoxylates sulfate of formula I may be prepared by the sulfation of nonionic alkyl alkoxylates of formula II. For instance, the Chemithon sulfation process via sulfur trioxide is a sulfation process well known to those skilled in the art. Typically, pre-heated nonionic alkyl alkoxylate (40° C.) may be first contacted with an air-diluted sulfur trioxide in a continuous thin-film reactor, resulting is a quick and exothermic reaction. The crude sulfuric ester acid may be collected at about 55° C. A prompt neutralization by NaOH or NH 4 OH to transform sulfuric ester acid to sulfate salt is advantageous to avoid dark color formation and to reduce formation of impurities. Precise control of the molar ratio of SO 3  to nonionic alkyl alkoxylate is preferred in order to produce high quality alkyl alkoxylate sulfate. 
     Nonionic alkyl alkoxylates of formula II as described above may be purchased from commercial vendors or they may be prepared by those skilled in the art using literature techniques (see for instance U.S. Pat. No. 7,906,474, which is incorporated herein by reference). In a typical procedure, the alkoxylate may be prepared in a sequential manner that includes propoxylation (adding PO or propyleneoxy) moieties of an alcohol or mixture of alcohols to form a PO block followed by ethoxylation (adding EO or ethyleneoxy) moieties to form an EO block attached to the PO block, but spaced apart from R which represents alkyl moieties from the alcohol or mixture of alcohols. One may either begin with a mixture of alcohols that provides a distribution of alkyl moieties and then sequentially propoxylate and ethoxylate the mixture or separately propoxylate and ethoxylate select alcohols and then combine such alkoxylates (propoxylated and ethoxylated alcohols) in proportions sufficient to provide a distribution as shown in Table 3 above. 
     Some embodiments of the invention will now be described in detail in the following Examples. 
     EXAMPLES 
     Materials Used in the Examples Include the Following 
     “Alkyl Alkoxylate Sulfate” means R—O—(C 3 H 6 O) x (C 2 H 4 O) y —SO 3 M, where x is 3, y is 3, M is NH 4  or Na, and R is derived from a C 6-16  alcohol blend. 
     “Nonionic alkyl alkoxylate 1” means R—O—(C 3 H 6 O) x (C 2 H 4 O) y —H, where x is 3, y is 3, and R is derived from a C 6-16  alcohol blend. 
     “Nonionic alkyl alkoxylate 2” means R 2 —O—(C 3 H 6 O) x (C 2 H 4 ) y —H, where x is 5.5, y is 9, and R 2  is 2-ethyl hexanol (non-inventive material). 
     “Alkyl Alkoxylate Sulfate Blend” means a blend of the above Alkyl Alkoxylate Sulfate and nonionic alkyl alkoxylate 1. 
     “APE Sulfate” means nonylphenol-(EO)4 Sulfate (an APE material) available from Rhodia as RHODAPEX® CO-436 (comparative material). 
     “APE-free sulfate” means a C12-14 alcohol(EO)4 sulfate available from Cognis as DISPONIL® FES-32 (comparative material). 
     Nonylphenol Ethoxylate: An APE material available from The Dow Chemical Company. 
     Example 1 
     Lab-Scale Samples of Alkyl Alkoxylate Sulfate are Prepared Based on Chemithon Sulfation Process 
     
       
                 
         
             
             
         
      
     
     Pre-heated non-ionic alkyl alkoxylate 1 (40° C.) is firstly contacted with an air-diluted liquid sulfur trioxide in a continuous thin-film reactor, which is a quick and exothermic reaction. Molar ratio of SO 3  to nonionic surfactant is maintained in the range of 0.85-1.0 by adjustment of nonionic surfactant flow rate in the range of 3-5 kg/h. According to the application needs, we intentionally set this molar ratio range to keep a certain ratio of nonionic surfactants in the final products. Crude sulfuric ester acid (intermediate product) is collected at about 55° C. 
     A prompt neutralization of crude sulfuric ester acid by NaOH or NH4OH avoids formation of dark color and maintains a good impurity profile. Precise control of the molar ratio of SO 3  to non-ionic alkyl alkoxylate 1 produces high quality alkyl alkoxylate sulfate, in particularly with reduced formation of 1,4-dioxane. 
     Formation of the desired Alkyl Alkoxylate Sulfate is confirmed by NMR. The  13 C NMR spectrum shows the disappearance of —CH 2 OH carbon at the chemical shift at δ=61.5 ppm and the presence of —CH 2 OSO 3   −  carbon at δ=70.0 ppm, which indicates the conversion of nonionic alkyl alkoxylate to alkyl alkoxylate sulfate. 
     Example 2 
     Property Testing 
     Various properties of inventive and comparative compositions are tested. Tests are conducted as follows. 
     Surface Tension and CMC measurement. Aqueous solution of a surfactant at 4000 ppm is prepared as mother solution and a series of solutions at lower concentrations down to 1 ppm are prepared by diluting the mother solution. The surface tension of each solution is measured following the procedure of GB/T-5549-2010. Surface tension values are plotted against concentration and CMC is determined from the break point of the plot. 
     Ross-Miles Foam Height test. 300 mL of aqueous solution of surfactant at 0.2% wt. is prepared; then, the measurements are carried out following standard method GB/T-7462-94; 
     Draves wetting measurement. 1 L of aqueous solution of a surfactant at 0.1% wt. is prepared; cotton cloth is cut at the same size. With reference to standard method GB/T-11983-2008, wetting time to the cotton cloth is recorded in the surfactant solution. 
     Surfactant Ca 2+  stability test: measured using standard test GB/T-7381-2010. 
     Alkaline Resistance test. measured using standard test GB/T-5556-2003; 
     Viscosity measurement. at room temperature (20° C.), spindle #62 and at 60 rpm; using standard test GB/T-5561-1994. 
     Testing results are shown in Table 5. 
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Surfactant properties of inventive and comparative compositions 
               
             
          
           
               
                   
                 Inventive 
                 Inventive example 2-2 
                   
                   
               
               
                   
                 example 2-1 
                 Alkyl Alkoxylate 
                   
                   
               
               
                   
                 Alkyl 
                 Sulfate + Nonionic 
                 Comparative 
                 Comparative 
               
               
                   
                 Alkoxylate 
                 alkyl alkoxylate 1 
                 example 2-3 
                 example 2-4 
               
               
                   
                 Sulfate 
                 (component b) 
                 APE Sulfate 
                 APE-free sulfate 
               
               
                   
                 (component a) 
                 (90:10 by wt) 
                 (comparative) 
                 (comparative) 
               
               
                   
               
             
          
           
               
                 Active content (wt. %) 
                 60 
                 60 
                 58-60 
                 30-32 
               
               
                 Appearance (20° C.) 
                 clear, pale 
                 clear, pale yellow 
                 clear, pale 
                 clear, pale 
               
               
                   
                 yellow 
                   
                 yellow 
                 yellow 
               
               
                 Surface Tension at 
                 38 
                 33 
                 34 
                 42 
               
               
                 CMC (mN/m, 20° C.) 
                   
                   
                   
                   
               
               
                 CMC (ppm) 
                 500 
                 125 
                 300 
                 200 
               
               
                 Foam Height (Ross 
                 108/95 
                 107/89 
                 106/102 
                 113/112 
               
               
                 Miles, 0/5 min at 0.2% wt.) 
                   
                   
                   
                   
               
               
                 Draves wetting (s, 
                 59.8 +/− 7.8 
                 14.7 +/− 0.7 
                 5.9 +/− 0.4 
                 263.0 +/− 32.9 
               
               
                 0.1% wt.) 
                   
                   
                   
                   
               
               
                 Ca 2+  stability (CaCl 2 , 
                 15-20% wt. 
                 15-20% wt 
                 &lt;2.5% wt. 
                 ≈15% wt. 
               
               
                 1% wt.) 
                   
                   
                   
                   
               
               
                 Anti-alkaline (NaOH, 
                 10-15% wt 
                 10-15% wt 
                 &lt;2.5% wt. 
                 10-15% wt. 
               
               
                 1% wt.) 
                   
                   
                   
                   
               
               
                 Viscosity (cP, at 20° C. 
                 367 
                 259 
                 120.5 
                 63.5 
               
               
                 &amp; 60 rpm, #62 probe) 
               
               
                   
               
             
          
         
       
     
     As is apparent from Table 5, in comparison with APE sulfate or APE-free sulfate, the inventive compositions showed various useful properties. For instance, the Alkyl Alkoxylate Sulfate of the invention and its blend with nonionic alkyl alkoxylate 1 show comparable properties, including: surface tension at 33 mN/m, is lower than APE sulfate and APE-free sulfate (low surface tension is expected to enhance surfactant wetting ability); CMC is similar as APE-free sulfate, and lower than APE sulfate; foam property improves with regards to both APE-sulfate and APE-free sulfate; wetting property is much better than the APE-free sulfate; and Ca 2+  stability and alkaline resistance are similar as APE-free sulfate, and superior than APE sulfate. 
     Example 3 
     Emulsion Polymerization 
     Basic Formula of Styrene-Butyl Acrylate Emulsion: 
     Monomers include: butyl acrylate, styrene, acrylamide and acrylic acid; 
     Initiator is ammonium persulfate; 
     Glass transition temperature (Tg): 23° C.; 
     Anionic surfactants: 0.51 phm (per hundred monomer); non-ionic surfactants: 0.54 phm. 
     Basic Formulation of Pure Acrylate Emulsion: 
     Monomers include: acrylic acid, butyl acrylate, methacrylic acid; 
     Glass transition temperature (Tg): 10° C.; 
     Anionic surfactants: 1.0 phm. 
     Basic Polymerization Procedure of Styrene-Butyl Acrylate Emulsion: 
     Pre-emulsify the Alkyl Alkoxylate Sulfate composition with sodium bicarbonate, water and above mentioned monomers. Add the second part of surfactant composition and water into the reactor; start heating to the temperature in the range of 80-90° C.; then, add the first part of ammonium persulfate. Start dropwise addition of pre-emulsion with the second part of ammonium persulfate during 3 h. After addition, keep at the same temperature for 1 h; an emulsion polymerization is performed. After cooling down to room temperature and pH adjustment by aqueous ammonia adjusted to neutral at 40° C., the polymer emulsion is obtained. 
     Preparation of Other Emulsions: 
     For the other emulsions preparation, the procedure described above is followed. Emulsifier composition is changed. See the below Table 6 for the emulsifier details of other emulsions. 
                                       TABLE 6                   Details of emulsion preparation                Emulsion               Example   type   Surfactant composition   +Non-ionic               Inventive   St-Acrylate   Alkyl Alkoxylate Sulfate   —       example 3-5       Blend (inventive example                   2-2)           Comparative   St-Acrylate   APE-sulfate   —       example 3-6       (comparative example 2-3)           Inventive   St-Acrylate   Alkyl Alkoxylate Sulfate   Nonionic alkyl       example 3-7       Blend (inventive example   alkoxylate 2               2-2)           Comparative   St-Acrylate   APE-sulfate   Nonylphenol       example 3-8       (comparative example 2-3)   Ethoxylate       Inventive   Pure-   Alkyl Alkoxylate Sulfate   —       example 3-9   Acrylate   Blend (inventive example                   2-2)           Comparative   Pure-   APE-free sulfate   —       example   Acrylate   (comparative example 2-4)           3-10                    
Foaming Property
 
     Low foaming performance is desired in emulsions, which can reduce the use of defoamer in the downstream emulsion applications and also increase the production efficiency. In highly viscous emulsions, low foaming is particularly desired to reduce product defects in both coating and adhesive applications. 
     Test procedure. The emulsion is diluted to 1% by weight of its solid content. Then, 250 mL of diluted emulsion are poured into a test tube. Air-bubble (air-flow at 1.8 L/s) the aqueous emulsion solution for 1 min; stop air-bubbling and record the foam heights in the next 5 min.—The study is carried out in duplicate, and the results are reproducible at ±5% and the average reported. Comparisons of inventive compositions to commercial APE sulfate and APE-free sulfate are made. Foam test results are shown in  FIGS. 1-3 . 
       FIG. 1  compares inventive example 3-5 (see Table 6) and comparative example 3-6. As is apparent, the inventive emulsion exhibited impressive low foam and quick foam collapse relative to the comparative emulsion. 
       FIG. 2  compares foam properties for inventive example 3-7 versus comparative example 3-8. Again, the inventive emulsion showed better low foam and quicker foam collapse property than the comparative material. 
       FIG. 3  compares inventive example 3-9 to comparative example 3-10. The inventive emulsion showed quicker foam collapse than the comparative material. 
     Ca 2+  Stability 
     Test method: Add CaCl 2  aqueous solution (concentration at 5 or 10% wt.) into 20 ml of emulsion; store the CaCl 2  containing emulsion for 48 h at room temperature; any agglomeration or non-homogeneity present in the emulsion signifies poor Ca 2+  stability, consequently, failure in the Ca 2+  stability test. Test results are shown in Table 7. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Test Results of Ca2+ stability 
               
             
          
           
               
                   
                 Example 
                 Emulsion type 
                 Surfactant Composition 
                 Ca 2+  stability 
               
               
                   
               
               
                 Comparison A 
                 Inventive 
                 St-Acrylate 
                 Alkyl Alkoxylate Sulfate 
                 &lt;10 mL of CaCl 2  aq. (10% wt.) 
               
               
                   
                 example 3-5 
                   
                 Blend 
                   
               
               
                   
                   
                   
                 (inventive example 2-2) 
                   
               
               
                   
                 Comparative 
                 St-Acrylate 
                 APE-sulfate 
                  &lt;4 mL of CaCl 2  aq. (5% wt.) 
               
               
                   
                 example 3-6 
                   
                 (comparative example 2-3) 
                   
               
               
                 Comparison B 
                 Inventive 
                 St-Acrylate 
                 Alkyl Alkoxylate Sulfate 
                 &gt;20 mL of CaCl 2  aq. (10% wt.) 
               
               
                   
                 example 3-7 
                   
                 Blend 
                   
               
               
                   
                   
                   
                 (inventive example 2-2) + 
                   
               
               
                   
                   
                   
                 Nonionic alkyl alkoxylate 2 
                   
               
               
                   
                 Comparative 
                 St-Acrylate 
                 APE-sulfate (comparative 
                  &lt;4 mL of CaCl 2  aq. (5% wt.) 
               
               
                   
                 example 3-8 
                   
                 example 2-3) + NonylPhenol 
                   
               
               
                   
                   
                   
                 Ethoxylate 
                   
               
               
                 Comparison C 
                 Inventive 
                 Pure-Acrylate 
                 Alkyl Alkoxylate Sulfate 
                 &lt;10 mL of CaCl 2  aq. (10% wt.) 
               
               
                   
                 example 3-9 
                   
                 Blend 
                   
               
               
                   
                   
                   
                 (inventive example 2-2) 
                   
               
               
                   
                 Comparative 
                 Pure-Acrylate 
                 APE-free sulfate 
                 &lt;10 mL of CaCl 2  aq. (5% wt.) 
               
               
                   
                 example 3-10 
                   
                 (comparative example 2-4) 
               
               
                   
               
             
          
         
       
     
     In Table 7, the comparison A shows that in St-Acrylate emulsion, when no nonionic surfactant is added as emulsifier, the emulsion with Alkyl Alkoxylate Sulfate Blend as emulsifier demonstrates better Ca 2+  stability than the one with APE sulfate. 
     The comparison B compares combinations of classic APE sulfate+nonylphenol ethoxylate with Alkyl Alkoxylate Sulfate composition plus alkyl alkoxylate in St-Acrylate emulsion. The emulsion with Alkyl Alkoxylate Sulfate as emulsifier has a better Ca 2+  stability than the classic APE sulfate and nonylphenol ethoxylate in the surfactant composition. Alkyl Alkoxylate Sulfate Blend offers not only an eco-friendly profile but also better performance on Ca 2+  stability. 
     In the comparison C, APE-free Sulfate and Alkyl Alkoxylate Sulfate Blend in Pure-Acrylate emulsion are compared. Again, inventive Alkyl Alkoxylate Sulfate Blend exhibits superior Ca 2+  stability. 
     Polymerization Stability 
     Polymerization stability in emulsion polymerization: collect reaction aggregates by washing, drying at ambient conditions and weigh to determine the amount of aggregates. A percentage by weight of aggregates to the total weight of the monomer indicates the polymerization stability. Small values indicate better polymerization stability. 
     Particle size and its distribution in polymer emulsion: using Zeta Potential particle analyzer (Malvern Nano ZS), an average particle diameter in the emulsion is measured. 
     Mechanic stability test: the emulsions (400 g) are rotated for 30 min with 2500 rpm. The generated aggregates are filtered through a 200-mesh filter. The filter residue is rinsed, dried and weighed for comparison. Less aggregate indicates good mechanical stability. 
     Results. Among those tests, the emulsion with inventive Surfactant Blend achieves similar performance as those with APE or APE-free sulfate emulsifiers.