AKD EMULSION AND METHOD OF MAKING

Abstract

Provided is an alkyl ketone dimer emulsion and the preparation thereof. More particularly, described is a 3-component emulsion, which is easy to prepare using low emulsification ability—high shear speed capability equipment to prepare the AKD emulsion with excellent quality, high efficiency, and less preparation time.

Description

This application claims the benefit of US Provisional application number 63/381,937, filed 2 Nov. 2022, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

Oil-in-water emulsions and a method of making the emulsions are provided. In particular, the preparation of alkyl ketone dimer emulsions is described. This 3-component emulsion is easy to prepare using low emulsification ability - high shear speed capability equipment to prepare the AKD emulsion with excellent quality, high efficiency, and less preparation time.

BACKGROUND

Alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA) and a paraffin wax are applied in papermaking system as the sizing agent that provides water resistance. These substances are hydrophobic and are produced as liquid oil or solid wax. Normally, the additives need to be dispersed as an oil-in-water emulsion before being used in a paper making system. To get good application performance, the emulsion of these hydrophobic materials must have certain characteristics. The emulsions must be stable for a time sufficient to get them from the point of manufacture to the paper machine without loss of properties, physical or chemical.

Because of these requirements, the preparation of emulsions of hydrophobic paper sizing agents has been the basis for improving stability and/or sizing efficiency of the product. Prior attempts have included producing stable high solids dispersions of ketene dimer by incorporating water soluble carboxylic acids in a standard starch-based stabilization system or by using cationic starches with a higher degree of substitution as an emulsifier. Other process have used post-addition of cationic polymers to the dispersions of hydrophobic cellulose reactive sizing agents which are prepared with starch. Other attempts were made using post-addition of water-soluble polymers to starch stabilized dispersions of hydrophobic paper sizing agents in an attempt to improve stability and size performance. :However, all of the dispersions of hydrophobic cellulose reactive sizing described above were stabilized by starch.

In addition to starches, other polymers have been used in an effort to stabilize aqueous dispersions of cellulose reactive sizing agents, such as an anionic, hydrophobically modified cellulose derivative used to provide improved sizing efficacy in paper making furnishes. Other process have used cellulose reactive sizing agents with a coacervate dispersion agent comprising an anionic component and a cationic component to stabilize the emulsion and improve sizing performance.

With the formulation improvement, the ways of production are equally important. In hydrophobic dispersants or oil emulsions production processes, there are generally four steps that are employed. A water and oil phase preparation step, a premix step, a homogenization step, and a cooling step. The water phase preparation involves cooking a starch or dissolving polymer into water. For the starch stabilized hydrophobic dispersants, starch cooking takes times and could lead to stabilization problems of final emulsions. The premix preparation step refers to the formation of a coarse emulsion of hydrophobic materials in water phase prior to homogenization.

The coarse emulsion is pumped though a high-pressure homogenizer, for example, a Gaulin high-pressure homogenizer or a Ilia.mmel mann high-pressure pump. The big hydrophobic droplets enter the valve area at high pressure and low velocity. As the droplets enters the adjustable, close clearance area between the valve and seat, there is a rapid increase in velocity with a corresponding decrease in pressure. The intense energy release cause turbulence and localized pressure differences, which will tear apart the particles. Then the fine emulsion is formed by further reducing the droplets to less than 1 micron with a narrow particle size distribution.

In general, the limitation of the above approach is the need for complex, expensive and heavy equipment capable of exerting high homogenizing shear and/or pressures, together with rigid procedures regarding emulsifying proportions, temperatures, etc. for producing a satisfactory stable emulsion of the desired particular size.

Other processes for sizing paper products have included forming, in the absence of high shearing forces, an aqueous sizing emulsion comprising an alkenyl succinic anhydride component which is post-diluted with a cationic component. Current processes for emulsifying ASA consistently demonstrate that the low shear ASA emulsions when post-diluted with cationic starch are less effective sizing agents than high shear ASA emulsions.

Other processes have used modified starches or polymers to enhance sizing performance of low shear emulsification systems.

Other known processes teach using an aqueous emulsion containing AKD and an emulsifier selected from polyoxyalkylene alkyl or polyoxyalkylenealkylaryl ethers or corresponding mono- or diesters.

Until now, most emulsification processes require several pieces of equipment, especially when it comes to the emulsification of a formulation containing AKD and/or paraffinic wax, which in addition to the specialized equipment, involves high financial investment and a large amount of space.

It was found in the following studies that an acceptable AKD emulsion for use in papermaking can be produced by combining the AKD with a formulation containing, for example, a PolyDADMAC and/or a polyacrylamide together with a dispersant, such as a condensed polymer of naphthalene-sulfonic acid with formaldehyde. it was also found that the emulsification system could be expanded to the emulsification of other hydrophobic chemicals, such as, ASA or paraffinic wax. These formulations are easy to emulsify using a simple colloidal mill, other high speed shearing emulsification equipment, which allows for the ability to make the sizing emulsions on-site.

To simplify the oil emulsion process and lower the chemical and equipment costs, studies were done, using various combinations of chemicals, and modifying known equipment, e.g., using regeneration turbine pumps and a colloid mill which has high speed shearing capabilities. One example of a piece of equipment used in preparing emulsions of ASA's is the Hercules Prequel Starch Alkaline Size Emulsifier (HASE). The equipment was originally designed to emulsify ASA with liquid starch in a continuous process, feeding the emulsion directly to the paper machine. Although, an acceptable ASA emulsion can be prepared using this equipment, there were issues with producing AKD emulsions. The present formulation and modification of equipment solve these issues.

Additional objects, advantages, and features of what is claimed will be set forth in the description that follows and in part will become apparent to those skilled in the art, upon examination of the following or may be learned by the practice of the technology. The objects and advantages of the presently disclosed and claimed inventive concepts will be realized and attained by means of the compositions and methods particularly pointed out in the appended claims, including the functional equivalents thereof.

BRIEF SUMMARY

This disclosure provides for a composition used in papermaking processes to provide water resistance of the final product. The composition is in the form of an oil-in-water emulsion that includes a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component chosen from an alkyl ketene dimer (RD), alkenyl succinic anhydride (ASA), a paraffin wax, or any combination thereof; and a dispersant. The emulsion can optionally contain fatty acids, such as stearic acid.

This disclosure also provides for a method of preparing an oil-in- - water emulsion. The method includes providing a composition comprising a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide wAm), a polyamine, a polyethyleneimine (PEI), a polyvinyl alcohol, or any combination thereof; a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and a dispersant. The composition is homogenized, thus producing the emulsion.

Finally, this disclosure provides for a method of forming a paper product that includes adding to a papermaking process an emulsion composition comprising a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), a polyvinyl alcohol, or any combination thereof; a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, or combinations thereof; and a dispersant. The emulsion composition can be added to the wet-end of a papermaking process or applied to the surface of the formed paper.

This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1, is a schematic of the modified HA SE emulsification system used in Example 2.

FIG. 2, is a schematic of the modified HASE emulsification system used in Example 2.

FIG. 3, shows AKD performance with P&SV furnish

FIG. 4, shows AKD performance with OCC furnish.

FIG. 5, is a schematic of the colloidal mill emulsification system used in the studies.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. As used herein, the word “exemplary” means “serving as an example, instance, or illustration.” Thus, any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments. All of the embodiments described herein are exemplary embodiments provided to enable persons skilled in the art to make or use the invention and not to limit the scope of the invention which is defined by the claims. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary, or the following detailed description.

Provided is an emulsion composition that can be added to the wet end of a papermaking process or applied to the surface of the formed paper to provide resistance to aqueous liquids. The emulsion composition contains a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, or any combination thereof; a second component chosen from an alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, and combinations thereof; and a dispersant.

The emulsion composition is based upon a coacervate concept, wherein two oppositely charged polymers (anionic and cationic) are mixed in such a proportion to produce a stabilized colloidal coacervate which functions as an emulsifier or dispersant and stabilizes the emulsified or dispersed sizing agents.

In some aspects, the anionic component is an anionic polyelectrolyte selected from the group consisting of a polycarboxylate, polysulfate and polysulfonate, such as a lignosulfonate. The cationic component can be chosen from a cationic polyamine, a polysulfonium, a polyamidoainine, or combinations thereof.

In some aspects of the emulsion composition, a first component is chosen from a polymer which could be anionic, cationic, or non-anionic. The polyamines may be primary amines, secondary amines, tertiary amines, or quaternary amines or may contain a mixture of different strength amine groups such as polyethyleneimine. The polymers which are particularly useful in these compositions include homopolymers and copolymers having a molecular weight (Mw) of about 10,000 or higher, as determined by size exclusion chromatography.

In some aspects of the emulsion composition, a quaternaty polyamine, such as poly (diallyldialkylammonium chloride) is used wherein the alkyl moiety has I to about 6 carbons; a polyvinylamine; and their derivatives. Other cationic components can be a quaternary polyamine such as a poly(diallyldialkylammonium chloride), wherein the alkyl moiety has I to about 6 carbons.

In the context of the present application the term “a polyacrylamide” denotes a polyacrylamide where both cationic and anionic units are present in an aqueous solution. Amphoteric polyacrylamide is obtained by copolymerization of acrylamide or methactylamide together with both anionic and cationic monomers. The amphoteric polyacrylamide can be obtained by copolymerization of acrylamide together with both anionic and cationic monomers. In some aspects of the emulsion composition, alley ketene dimers having general formula (I)

wherein R¹ and R² represent saturated or unsaturated hydrocarbon groups, the hydrocarbon groups having from 8 to 36 carbon atoms and can be straight or branched and having 6 chain alkyl groups and 12 to 20 carbon atoms, such as hexadecyl and octadecyl groups.

The alkenyl succinic anhydrides (ASA) used in this invention are well known and are composed of unsaturated hydrocarbon chains containing pendant succinic anhydride groups.

ASA, which are preferred in this invention, are usually made in a two-step process starting with an alpha olefin. The olefin is first isomerized by randomly moving the double bond from the alpha position, in the second step the isomerized olefin is reacted with an excess of maleic anhydride to give the final ASA structure as indicated in the following reaction scheme.

Isomerized Olefin, Maleic Anhydride, or Alkenyl Succinic Anhydride (ASA) results if the isomerization step is omitted. ASA's that are solid at room temperature may be produced if the chain length of the starting alpha olefin is in the C-14 to C-22 range and may be linear or branched. For the purpose of current compositions, the ASA's were prepared by reaction of maleic anhydride: with olefins containing 14-18 carbon atoms, Typical ASA's are commercially available fr©m Albemarle Corporation, Baton Rouge, La. Representative starting olefins for reaction with maleic anhydride to prepare ASAs for use in the present formulation include: octadecene, tetradecene, hexadecene, eicodecene, 2-nhexyl-1-octene, 2-n-octyl-1-dodecene, 2-n-octyl-l-decene, 2-n-dodecyl-l-octene, 2-n-octyl-1-octene, 2-n-octyl-1- nonene, 2-n-hexyl-1-decent: and 2-n-heptyl-1-octene.

The paraffin wax is generally Obtained through separation and extraction of a hydrocarbon of good crystallizability from the oily distillate moiety in reduced-pressure distillation of crude oil. It is a colorless or white transparent solid wax containing a linear hydrocarbon as the main ingredient and has a melting point of about 40° C. to about 90° C. Other exemplary hydrophobic acid anhydrides that may be stabilized with the polymers of this formulation are useful as sizing agents.

In some aspects of the emulsion composition, the dispersant is an anionic surface-active polyelectrolyte, such as polycarboxylates (e.g., polyaciylates, carboxymethyl cellulose, hydrolyzed polyacrylamides), polysulfates (e.g., polyvinyl sulfate, polyethylene sulfate) or polysulfonates (e.g., polyvinyl sulfonate, lignin sulfonates).

In some aspects of the emulsion composition, the anionic surfactants can be chosen from alkyl, aryl or alkyl aryl sulfates, alkyl, aryl or alkyl aryl carboxylates, alkyl, aryl or alkyl aryl sulfonates, or combinations thereof

In some aspects, the alkyl moieties can have from 1 to about 18 carbons, the aryl moieties can have from about 6 to about 12 carbons, and the alkyl aryl moieties can have from about 7 to about 30 carbons. The moieties can be propyl, butyl, hexyl, decyl, dodecyl, phenyl, or benzyl groups, and linear or branched alkyl benzene derivatives of the carboxylates, sulfates, and sulfonates.

In other aspects, the anionic component can be chosen from polycarboxylates, polysulfates and polysulfonates. These can include a ligno- or lignin sulfonate, such as the sodium salt, calcium salt, ammonium salt, iron salt or chromium salt.

In one aspect, the anionic component can be sodium lignosulfonate or a naphthalene-sulfonic acid with formaldehyde condensed polymer, for example BASF's Tamol™ line of products, such as Tamor™ NN9401.

In some aspects of the emulsion, the composition comprises the first component in an amount of from about 0.1 wt. % to about 30 wt. %, or from about 0.1 wt. % to about 20 wt. %, from about 0.5 wt. % to about 15 wt. % based on the total weight of the composition

In some aspects of the emulsion, the second component in an amount of from about 0.1 wt. % to about 50 wt. %, or from about 1 wt. % to about 60 wt. %, or from about 5 wt. % to about 40 wt. % based on the total weight of the composition.

In yet other aspects of the emulsion, the dispersant is present in an amount of from about 0.1 wt. % to about 10 wt. % or from about 0.1 wt. % to about 1 wt. %, or from about 0.25 wt. % to about 0.75 wt. % based on the total weight of the composition.

In yet other aspects of the emulsion, the composition further contains fatty acid, such as stearic acid. The fatty acid can be present in the composition in an amount of from about 0.1 to about 10 wt. %, or from 1 wt. % to about 5 wt. % based on the total weight of the composition.

In still other aspects of the emulsion composition, the emulsion is added to a papermaking furnish prior to forming a paper product or the emulsion composition can be applied to the outer surface of the formed paper. This results in higher water resistance to aqueous liquids of the formed product when compared with an untreated paper, in which water resistance studies were conducted using the TAPPI T 441 Cobb Test.

In some aspects, there is provided a method of preparing an oil-in-water emulsion. The method includes providing an emulsion composition that includes a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), a polyvinyl alcohol, and combinations thereof; a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and a dispersant. The composition is homogenized thereby producing the emulsion.

In some aspects of the method, the first component is chosen from a polyDADMAC or a polyDADMAC derivative, such as a copolymer of acrylamide and diallyl dimethyl ammonium chloride.

In some aspects of the method, the second component is an alkyl ketene dimer.

In some aspects of the method, the dispersant is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, a copolymer of acrylamide and sulfonic acid, and combinations thereof

In some aspects of the method, the emulsion composition contains the first component in an amount of from about 0.1 wt. % to about 30 wt. %, or from about 0.1 wt. % to about 20 wt. %, from about 0.5 wt. % to about 15 wt. % based on the total weight of the composition.

In other aspects of the method, the second component is present in an amount of from about 0.1 wt. % to about 50 wt. %, or from about 1 wt. % to about 60 wt. %, or from about 5 wt. % to about 40 wt. % based on the total weight of the composition.

In yet other aspects of the method, the dispersant is present in an amount of from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 1.0 wt. %, or from about 0.25 wt. % to about 0.75 wt. % based on the total weight of the composition.

In some aspects of the method, the emulsion composition further includes fatty acids, for example, stearic acid. The fatty acid can be present in the composition in an amount of from about 0.1 to about 10 wt. %, or from about 1 wt. % to about 5 wt. %. based on the total weight of the composition.

In some aspects of the method, the composition is homogenized using a rotor%stator generator, a high-pressure device, or a sonic disruptor.

In some aspects of the method, the composition is homogenized using a rotorlstator generator having a linear shear force of at least 23 mls, such as a colloidal mill,

In other aspects of the method, the composition is homogenized using a high-pressure device, such as piston pump.

In some aspects of the method, the emulsion has a mean particle size of less than 2 micron and can be less than 1 micron.

In yet other aspects, provided is a method of forming a paper product that includes providing an emulsion composition containing a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide wAm), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component chosen from an alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, and combinations thereof; and a dispersant.

The emulsion composition can be added to the furnish at any point of the papermaking process, for example, at the blend chest or other points in the wet-end of the process. The emulsion composition can also be applied to the surface of the paper produced, for example, at the forming section, dryer section or calendar rolls. The emulsion can be applied by spraying, coating, film transferring, soaking, or other known means used in pa.permaking.

In some aspects of the method, the paper product can be, for example, paperboard, cardboard, and aseptic packaging, copy paper and coated paper among other paper products.

EXAMPLES

Example 1—Lab Waring Blender Study

An AKD emulsification study was accomplished using Waring blender method. The study looked at the emulsification ability of different mill starch with Prequel™ products (calcium salts of long chain fatty acids). The following steps were followed:

Aqueous phase preparation—Charge the target water and mix well with Tamol™ with overhead stirrer in a 2-liter(?) glass beaker while maintaining a stirring speed of about 500 to 800 rpm. and charge required gram of polymer to homogenize with Tamol™ for 5 min. Adjust pH to 4.5. The 2-liter glass beaker with emulsion was placed int© a water bath and heated this phase (aqueous phase) to 70° C.

Emulsification step—The aqueous phase (at 70° C.) and melted AKD (the AKD was kept in a pre-heated oven at 85° C.) were combined in a Waring blender equipped four- blades and capable of generating high shear force capable of breaking the oil into small droplets forming an emulsion. The blender was capped and set on the highest speed setting and the contents homogenized for 1 minute producing an AKD oil-in-water emulsion, Based on the % AKD, the emulsion was diluted to 10-15% and screened with 100 mesh paper cone paint strainers. The AKD emulsion properties were obtained and a 32° C. oven stability test was conducted.

A combination of PolyDADMAC and Hercobond™ 1620 (butanedioic acid, 2-methylene-, polymer with 2-(dimethylaminoethyl 2-methyl-2-propenoate, N,N-ditnethyl-2-propenamide, propenamide and sodium 2-methyl-2-propene-l-sulfonate (1:1), sulfate) were studied. In general, PolyDADMAC and Hercobond™ 1620 showed good emulsification ability compared with AKD wax as shown in Tables 1 and 2, The AKI) emulsion prepared with PolyDADMAC and Hercobond™ 1620 resulted in an emulsion having a smaller average particle size. The results also showed that different percentages of AKI) polymer and Tamol™ (naphthalenesulfonic acid, polymer with formaldehyde, sodium salt) with stirring impacted the average particle size of AKD in the final emulsion. It was also observed that better emulsification was accomplished i.e., gave the higher tear force which in turn gave the better emulsification ability, either at higher speeds of the blender or longer stirring times.

TABLE 1
Waring Blender -AKD emulsification with PolyDADMAC
Run	Water	PolyDADMAC	1865	9401
Order	(g)	(g)	(g)	(g)	Media	90%	2 um	Mean	SD
1	68.802	9.217	21.505	0.476	0.8150	1.2288	99.55	0.8573	0.2879
2	73.306	9.820	16.367	0.507	0.8859	1.4238	98.15	0.9545	0.3721
3	78.620	6.897	13.793	0.690	1.1423	2.1681	87.09	1.3005	NA
4	64.819	14.472	20.260	0.449	0.5990	0.8072	100	0.6082	0.1479
5	68.802	15.361	15.361	0.476	0.7197	0.9983	100	0.7398	0.2013
6	74.950	19.231	12.821	0.064	1.1586	3.4128	74.08	1.6990	1.6143
7	61.622	16.216	21.622	0.541	0.5911	0.7829	100	0.5986	0.1394
8	68.199	9.479	22.117	0.205	0.8003	1.2272	99.42	0.8473	0.2967
9	68.199	15.798	15.798	0.205	0.6435	0.8692	100	0.6565	0.1658
10	72.800	10.118	16.863	0.219	0.9054	1.4688	97.76	0.9778	0.3889
11	77.867	7.353	14.706	0.074	1.1116	2.0409	89.32	1.2413	0.6151
12	68.504	12.461	18.692	0.343	0.7087	0.9855	100	0.7255	0.1999

TABLE 2
Waring Blender -AKD emulsification with Hercobond ™ 1620
	Water	1620	1865	9401
Run	(g)	(g)	(g)	(g)	Median	90%	2 um	Mean	SD
1	68.220	13.650	17.804	0.326	0.7335	1.0662	100	0.7592	0.2331
2	61.271	16.575	22.099	0.055	0.6784	0.9491	100	0.6925	0.1939
3	68.543	16.085	15.175	0.197	0.8269	1.2796	100	0.8744	0.3140
4	67.614	9.091	22.727	0.568	0.7730	1.1426	99.847	0.8052	0.2644
5	62.632	15.789	21.053	0.526	0.6228	0.8437	100	0.6330	0.1578
6	70.000	17.647	11.765	0.588	0.7134	1.0184	100	0.7370	0.2205
7	64.620	15.165	20.029	0.1860	0.7760	1.1272	99.839	0.8096	0.2492

The Lab Waring blender study showed AKD wax can be adequately emulsified using a composition comprising polyDADMAC and Hercobond™ 1620.

Example 2—Regenerative Turbine Pump Emulsification Study

In this study, a Hercules Prequel Starch Alkaline Size Emulsifier (HASE) was used, which includes a Burks™ regenerative turbine pump. The pump generates high shear force which can emulsify the AKD, ASA and paraffinic wax 1polyDADMAC or Hercobond™ 1620. However, unlike ASA, AKD and paraffinic wax is solid and required melting before being pumped into the turbine pump. The HASE was modified by including a blending tank for water phase preparation, a AKD melting tank, a screw pump, and a hot water tank (see FIG. 1).

In addition to the configuration shown in FIG. 1, the system was modified and both versions of this emulsification system as shown in FIG. 1 and 2 were used in the study. The first version (see FIG. 1) as described above, premixed AKD with the water phase and was then pumped to the HASE through the starch line. In the second version (see FIG. 2), a melted AKD was added through HASE's gear pump, and the water phase by an additional screw pump through the starch line. The main difference between the two versions of the systems is in version 1 (FIG. 1) the AKD is mixed with the water phase before feeding into turbine pump and in version 2 (FIG. 2) the AKD and water phase are added to the HASE at different points.

The study indicated that emulsification can be accomplished through the use of either version 1 or 2 of the BASE system. The produced emulsions were sampled, evaluated, and diluted for further oven stability testing. As shown in Table 3 and 4 below, the mean particle size of the emulsion produced by the first version system was at range of 900-1200 μm and the stability of the emulsion was poor.

However, when using the modified HASE system shown in FIG. 2, the flow rate of AKD increased and the particle size distribution (PSD) of the emulsion was narrower than the resulting emulsion using the HASE system shown in FIG. 1. The emulsion prepared using polyDADMAC showed more stability after adding 2% polyacrylamide (PAC). Results also show stearic acid helped AKD emulsification and decreased the average particle size of the emulsion.

TABLE 3
HASE middle scale trial version 1 - AKD emulsion
properties and stability results
45 kg AKD, 45 kg Hercobond ™ 1620, 60 kg water,
0.45 kg Tamol ™
					Starting Vis:
			TS %:		60.0 cps
			17.8%		Final Visc.
	Original	AKD %:	1 Week	1 Week	After 1 week;
	emulsion	14.96%	23° C.	32° C.	82.8 cps
Median	1.3247	1.106	1.0100	0.9999
90%	2.2786	2.0282	1.7490	1.9607
2 um	83.669	89.561	94.185	90.632
Mean	1.4672	1.0402	1.1164	1.1429
SD	0.6507	0.6236	0.5053	0.6666

TABLE 4
HASE middle scale trial version 1 - AKD emulsion
properties and stability results
30 kg AKD, 25 kg PolyDADMAC, 0.3 kg Tamol ™,
45 kg water
					Starting Visc:
			TS %:		36.9 cps
		1:1 dilution	18.93%	1 Week	Final Visc.
	Original	Assay:	1 Week	32° C.	After 1 week
	emulsion	11.854%	23° C.	(Gel)	698.9 cps
Median	0.9585	0.9073	0.9630	5.8679
90%	1.4460	1.5141	1.7917	13.0072
2 um	98.511	96.827	93.139	27.903
Mean	1.0155	0.9943	1.1034	6.3428
SD	0.3329	0.4328	0.5703	5.1579

TABLE 5
HASE middle scale trial version 2-AKD emulsion with Hercobond ™ 1620
properties and stability results
PolyDADMAC	1:1 dilution
AKD	AKD 14.5%, 1620 15.3%, Stearic
48 kg/h	acid 0.73%, Tamol ™ 0.28%
	Original					32 C.
	emulsion	0 day	3 days	15 days	30 days	12 days
Median	0.8871	0.8871	0.9899	0.9761	0.9139	1.0414
90%	1.2147	1.2147	1.6921	1.656	1.471	1.8562
2 um	100	100	94.917	95.49	97.713	92.526
Mean	0.9052	0.9052	1.0929	1.0725	0.9868	1.1654
SD	0.2316	0.2316	0.4906	0.4731	0.3861	0.5655
Viscosity				56.3		121.4

TABLE 6
HASE middle scale trial version 2-AKD
emulsion with Hercobond ™ 1620
properties and stability results
	1:1 dilution
AKD	AKD 16.21%, 1620 13.8%-15%, Stearic
64 kg/h	acid 0.81%, Tamol ™ 0.15%
	Original					32 C.
	emulsion	0 day	3 days	15 days	30 days	12 days
Median	0.8464	0.8464	0.8894	0.9702	0.9125	1.0058
90%	1.1419	1.1419	1.5282	1.6513	1.4794	1.8213
2 um	100	100	96.572	95.449	97.439	92.868
Mean	0.8619	0.8619	0.9843	1.0697	0.9911	1.1406
SD	0.2156	0.2156	0.458	0.4763	0.4022	0.5854
Vis-				57.1		280.9
cosity

TABLE 7
AKD emulsion with polyDADMAC properties and stability results
PolyDADMAC	1:1 Dilution
AKD flow		TS %	AKD (16.4%), PolyDADMAC (13.6%),	PAC
48 kg/h		(22.91)	Stearic acid (0.76%), Tamol ™ (0.28%)	(2%)
	Original					32 C.				32 C.
	emulsion	0 day	3 days	15 days	30 days	12 days	0 day	15 days	30 days	12 days
Median	0.8318	0.8318	0.9502	1.1385	1.1775	Gel	0.8007	0.9653	0.9121	1.1107
90%	1.145	1.145	1.5781	2.4373	3.2434	Unstable	1.0962	1.624	1.5009	2.2189
2 um	100	100	96.668	83.167	75.038	Unstable	100	95.875	97.183	86.626
Mean	0.8519	0.8519	1.0338	1.3716	1.6371	Unstable	0.8171	1.0593	0.9952	1.3175
SD	0.2283	0.2283	0.4293	0.8626	1.3981	Unstable	0.2071	0.461	0.4141	0.7827
Viscosity		111		175.4		Unstable	36.7	64.8		66.9

TABLE 8
AKD emulsion with polyDADMAC properties and stability results
PolyDADMAC	1:1 dilution
AKD flow	TS	AKD (19.5%), PolyDADMAC (10.3%),	PAC
64 kg/h	(25.78%)	Stearic acid (0.90%), Tamol ™ (0.20%)	(2%)
	Original					32 C.				32 C.
	Emulsion	0 day	3 days	15 days	30 days	12 days	0 day	15 days	30 days	12 days
Median	0.776	0.776	0.8972	1.27	1.433	2.2855	0.7239	0.9789	0.9726	1.1925
90%	1.024	1.0242	1.9961	3.0268	4.4441	6.4611	0.9963	1.6931	1.6785	2.715
2 um	100.00	100.000	90.046	74.424	63.217	44.917	100	94.827	95.13	79.459
Mean	0.784	0.7839	1.1011	1.6062	2.1198	3.0663	0.7332	1.0852	1.0773	1.4949
SD	0.184	0.1839	0.7568	1.1565	2.0079	2.8211	0.2043	0.4952	0.4829	1.0521
Viscosity		201.3		378.9		12.7	41.9	60.5		24.3

A size performance comparison with Hercules PTV™ M5083, a typical starch product, was conducted using the process shown in FIG. 2. Emulsions were prepared using Hercobond™ 1620 and stearic acid or PolyDADMAC and stearic acid in which both gave the better Cobb value than PTV™ M5083.

In addition, it was found that the particle size of the emulsion was highly dependent on the ratio of AKD and polymer. Using the HASE the polyDADMAC and Hercobond™ 1620 produced acceptable emulsions with the polyDADMAC giving a lower average particle size. It was also found that the PAC help the stability of emulsion prepared with polyDADMAC. Results also indicated that adding stearic acid to the formulation resulted in lower PSD.

While the study indicated that an acceptable PSI) of the produced AKD/polyDADMAC and AKE)/Hercobond™ 1620 emulsions, results indicated that the emulsion samples were unstable after 3 days storage at room temperature and an even shorter stability time at 32° C. But for on-site application, the emulsion quality was acceptable.

Besides, AKD emulsion was prepared through the turbine pump. The ASA was also tried. The table 9, 10 and 11 shows the emulsion results. The ASA was emulsified with good particle size distribution.

TABLE 9
ASA emulsion with polyDADMAC properties and stability results
PolyDADMAC	ASA:polyDADMAC:Tamol ™
ASA flow 64 kg/h	1:1:0.03
	Original	30	60
	Emulsion	min	min
Median	0.563	0.58	0.573
90%	0.778	0.812	0.79
2 um	100	100	100
Mean	0.576	0.594	0.585
SD	0.154	0.162	0.155

TABLE 10
ASA emulsion with Hercobond ™ 1620
properties and stability results
	Hercobond ™ 1620	ASA:1620:Tamol ™ =
	ASA flow 64 kg/h		1:1:0
	Original	30	60
	Emulsion	min	min
	Median	0.53	0.540	0.536
	90%	0.644	0.643	0.660
	2 um	100	100.000	100.000
	Mean	0.54	0.543	0.550
	SD	0.107	0.110	0.108

Example 3—Colloidal mill trial

The following study was done using a colloidal mill CRS 2000/05 from Shanghai SGN Machinery and Equipment Co., Ltd. An emulsification system was designed using the colloidal mill noted above and as shown in FIG. 5, The system was designed to have two main parts, a) a blending tank and b) a colloid mill. They were connected by a lab flexible impeller pump. The pump circulated a premix liquid from blending tank to colloidal mill.

In this study, water and Tamorim were added into the blending tank and mixed for 10 minutes at which time polymer liquid was added into the tank and pH was adjusted. The temperature of the mixture was raised to 60° C. at which time AKD was added to the blending tank and mixing continued for an additional 20 minutes, the system was started to cycle. After 1 cycle, a sample of the emulsion from the emulsion storage tank was acquired and measured. The process was continued for several cycles and once the mean particle size was measured and found to be about 1000 microns, another emulsion sample was acquired and diluted for fUrther stability testing. The emulsion was diluted by a factor of 4 and the temperature of the sampled emulsion dropped below 30° C. Circulation was continued until the mean particle size of the emulsion was below 800 micron or circulation time was more than 80 minutes. The colloidal mill was stopped, and the emulsion was collected for additional testing.

The study indicated AKD was easily emulsified when combined with Hercobonem 162.0 or polyDADMAC. The average particle size was between 0.70-0.90 mm after 1 to 6 times cycles. The Tamor to AKD ratio was fixed to 0.03:1. As shown in Table 11, 12, 13 and 14, the average particle size of the emulsion reached below 0.85 mm (850 pm) even when the ratio of AKD to Hercobond™ 1620 was increased to 13.3:1, With the exception of Sample V, the emulsions were stable after 28 days in an oven stability test where the oven temperature was set at 32° C.

TABLE 11
Colloidal mill study - AKD emulsion samples with
15 kg Hercobond ™ 1620
AKD - 40 kg, Hercobond ™ 1620 - 15 kg, Stearic acid -
2 kg, Tamol ™ - 1.2 kg, water - 41.8 kg
	Sample	1 cycle	6 cycles	7 cylces
	no.	V	VI	VII
	Median	1.0206	0.8006	0.7823
	90%	1.6132	1.1064	1.0717
	2 um	96.627	99.254	100.0000
	Mean	1.0953	0.8226	0.8001
	SD	0.4087	0.2146	0.2020

TABLE 12
Colloidal mill study - the diluted
AKD emulsion sample from sample V
V
4 times		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32 ° C.	32° C.	32° C.	RT
Median	1.0204	1.0544	1.0896	1.0785	1.1227	0.9916
90%	1.6403	1.8242	2.1299	2.7665	3.1432	1.6138
2 um	96.096	93.064	88.076	81.397	78.597	96.231
Mean	1.102	1.1719	1.2685	1.51	1.7047	1.0773
SD	0.4286	0.5424	0.7318	1.5485	2.0506	0.4369
pH	4.64-3.7		3.67		3.63
Viscosity	7.6	6.7	16.1	35.8	33.5	7.7
TS %	11.40		11.56/9.28		11.26/9.45

TABLE 13
Colloidal mill study - the diluted
AKD emulsion sample from sample VI
VI
4 times		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.8121	0.8351	0.8544	0.8415	0.8076	0.7965
90%	1.1246	1.1957	1.3044	1.3301	1.2957	1.1256
2 um	100	99.82	98.792	98.563	98.681	99.904
Mean	0.8357	0.8686	0.9115	0.9031	0.8667	0.8235
SD	0.221	0.2519	0.3325	0.3563	0.3574	0.2355
pH	4.46-3.80		3.93		4.06
Viscosity	8.8	7.9	14.5	14.9	13.3	6.6
TS %	11.44		11.47/		11.4/
			10.41		10.39

TABLE 14
Colloidal mill study - the diluted
AKD emulsion sample from sample VI
VII
4 times		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.7876	0.7879	0.8037	0.7796	0.8328	0.7668
90%	1.0804	1.0965	1.1959	1.2389	1.3586	1.0743
2 um	100	100	99.555	98.857	97.857	100
Mean	0.8073	0.8108	0.8441	0.8341	0.9113	0.7888
SD	0.2053	0.216	0.2794	0.3373	0.4069	0.2165
pH	4.45-3.70		3.89		3.77
Vis-	8.1	6.8	12.8		14.5	10.7
cosity
TS %	11.61		11.57/		11.42/
			10.59		10.41

Example 4—AKD emulsion samples with 20 polyDADMAC

The procedure described in Example 2 was used in this study. In this study two different ratios of AKD to polyDADMAC were evaluated. A ratio was 5:1 AK.D to polyDADMAC enabled the emulsion to reach a particle size below 0.9 mm (900 μm) within 25 minutes. Results can be seen in Table 15, 16 and 17.

TABLE 15
Colloidal mill study - AKD with 20 kg polyDADMAC
AKD - 40 kg, PolyDADMAC - 20.2 kg, Tamol ™ -
1.2 kg, water - 38.8 kg
	Sample	1 cycle	3 cycles
	no.	I	II
	Median	0.8352	0.7750
	90%	1.2041	1.0573
	2 um	99.797	100
	Mean	0.8703	0.7931
	SD	0.2561	0.1976

TABLE 16
Colloidal mill study - the diluted AKD emulsion sample from sample I
I	Dilution and PAC 3%
4 times		7 days	14 days	21 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.7727	0.766	0.983	2.332	0.764	0.759	0.782	0.7925	0.784	0.7801	0.756
90%	1.0541	1.074	4.237	10.442	1.087	1.031	1.0767	1.0883	1.114	1.1102	1.042
2 um	100	100	78.743	48.33	100	100	100	100	99.89	99.894	100
Mean	0.7905	0.789	1.984	4.239	0.790	0.777	0.803	0.8144	0.812	0.8082	0.777
SD	0.1976	0.217	2.105	4.450	0.226	0.1937	0.206	0.2065	0.235	0.2347	0.207
pH	3.86		3.35			3.97		3.86		3.93
Viscosity	14.5	14.2	142.2	760.8	13.8	10.8	10.2	10.4	10.3	10.5	11
TS %	12.83%		13.42/13.07%			14.32%		14.46/13.42%		14.98/13.95%

TABLE 17
Colloidal mill study - the diluted AKD emulsion sample from sample II
II	Dilution and PAC 3%
4 times		7 days	14 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.7941	4.2596	Gel	0.7829	0.7700	0.7854	0.8087	0.7694	0.7773	0.7789
90%	1.1208	10.9244	Unstable	1.0767	1.0679	1.1136	1.1346	1.1018	1.1076	1.1018
2 um	99.903	37.383	Unstable	100	100	99.878	99.875	99.883	99.885	99.905
Mean	0.8221	4.9629	Unstable	0.8041	0.7923	0.8153	0.8389	0.7986	0.8059	0.806
SD	0.232	4.4613	Unstable	0.2058	0.2086	0.2326	0.2334	0.236	0.2351	0.2292
pH	3.1		Unstable		4.01		3.84		3.84
Viscosity	13.4	114.8	Unstable	14.9	10.5	9.3	9.5	9.4	9.9	10.1
TS %	13.33%		Unstable		13.90%		13.86/10.83		14.81/12.93

Example 5—Colloidal mill study—AKD emulsion samples with 20 kg poivDADMAC and 2 kg stearic acid

The procedure described in Example 2 was used in this study. in this study a 5% stearic acid solution was added to AKD according to Tables 18, 19 and 20. Results show that the particle size distribution of the produced emulsion was decreased to the desired range in a shorter milling time indicating more efficient emulsification. The diluted emulsion samples were stable over the first week at 32° C. but became unstable after 7 days, As can be seen in Tables 19 and 20, the samples diluted with 3% PAC showed better stability.

TABLE 18
Colloidal mill study - AKD with 20 kg
polyDADMAC and 2 kg stearic acid
AKD - 40 kg, PolyDADMAC - 20 kg, Stearic acid -
2 kg, Tamol ™ - 1.2 kg, water - 36.8 kg
	Sample	1 cycle	3 cycles
	no.	III	IV
	Median	0.7577	0.7059
	90%	1.0452	0.9547
	2 um	100	100
	Mean	0.7726	0.7137
	SD	0.2024	0.1755

TABLE 19
Colloidal mill study - the diluted AKD emulsion sample from sample III
III	Dilution and PAC 3%
4 times		7 days	14 days	21 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.765	0.742	0.9606	Gel	0.75	0.748	0.758	0.7549	0.743	0.7675	0.748
90%	1.058	1.033	3.983	Unstable	1.03	1.020	1.041	1.0336	1.035	1.0797	1.045
2 um	100	100	80.80	Unstable	100	100	100	100	100	100	100
Mean	0.785	0.764	1.777	Unstable	0.768	0.767	0.779	0.7746	0.766	0.7944	0.771
SD	0.207	0.208	2.361	Unstable	0.201	0.196	0.199	0.197	0.208	0.216	0.211
pH	3.52		3.21	Unstable		3.79		3.8		3.84
Viscosity	14.1	13.6	315.4	Unstable	14.4	11.7	10	11	10.2	10.1	10.5
TS %	12.72		12.76/11.79	Unstable		13.76		13.67/12.45		13.9/12.7

TABLE 20
Colloidal mill study - the diluted AKD emulsion sample from sample IV
IV	Dilution and PAC 3%
4 times		7 days	14 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.7212	0.7175	Gel	0.7406	0.7159	0.7169	0.7259	0.7179	0.7251	0.7312
90%	0.9706	0.9877	Unstable	0.969	0.9639	0.9733	0.989	0.9843	0.9877	1.0221
2 um	100	100	Unstable	100	100	100	100	100	100	100
Mean	0.7355	0.7369	Unstable	0.7273	0.7299	0.7335	0.7444	0.7364	0.7434	0.7549
SD	0.1768	0.194	Unstable	0.1838	0.1752	0.1828	0.1896	0.191	0.1912	0.2101
pH	3.63		Unstable		3.85		3.8		3.78
Viscosity	14.2	14.3	Unstable		9.8	9.9	10.7	9.6	10.1	10.7
TS %	12.58		Unstable	28 days	13.53		13.62/12.13		13.73/13.03
				32° C.

Example 6—Colloidal study—AKD emulsion samples with 15 kg polyDADMAC,

The procedure described in Example 2 was used in this study. This study was done using a 7,5:1 ratio (AKD/polyDADMAC). Results can be seen in Tables 21, 22 and 24. The mean particle size of AKD emulsion was about 0.9-1.0 mm (900-1,000 μm) after 45 minutes of circulation through the system.

TABLE 21
Colloidal study -AKD with 15 kg polyDADMAC
AKD - 45 kg, PolyDADMAC - 15 kg, Tamol ™ -
1.35 kg, water - 38.65 kg
	Sample	1 cycle	4 cycles
	no.	X	XI
	Median	0.9798	0.9148
	90%	1.4951	1.3159
	2 um	97.83	99.345
	Mean	1.044	0.9579
	SD	0.3838	0.2864

TABLE 22
Colloidal study - the diluted AKD emulsion sample from sample X
X	Dilution and PAC 3%
4 times		7 days	14 days	21 days	28 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.948	0.889	0.966	0.949	0.918	0.897	0.944	0.891	0.9243	0.900	0.947	0.821
90%	1.387	1.351	1.596	1.683	1.612	1.401	1.455	1.345	1.4109	1.404	1.463	1.229
2 um	99.04	98.89	96.237	94.76	95.77	98.43	97.89	98.94	98.466	98.34	97.95	99.46
Mean	0.995	0.944	1.056	1.063	1.017	10.958	1.013	0.944	0.9834	0.964	1.013	0.866
SD	0.305	0.325	0.446	0.523	0.487	0.354	0.369	0.320	0.3425	0.354	0.363	0.286
pH	4.1		3.38		3.35		4.04		3.82		3.98
Viscosity	11.1	10.2	23.5	23.6	27.5	11.3	8.3	7.8	7.6	7.6	7.4	10.5
TS %	12.65		12.87/11.75		12.72/12.15		13.57		14.42/10.57		13.92/11.14

TABLE 23
Colloidal study - the diluted AKD emulsion sample from sample XI
XI	Dilution and PAC 3%
4 times		7 days	14 days	21 days	28 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.908	0.835	0.916	0.893	0.913	0.871	0.861	0.836	0.876	0.853	0.859	0.864
90%	1.29	1.218	1.468	1.548	1.565	1.303	1.241	1.215	1.276	1.240	1.274	1.273
2 um	99.53	99.66	97.59	96.06	96.18	99.10	99.66	99.67	99.478	99.60	99.40	99.47
Mean	0.946	0.873	0.990	0.999	1.010	0.921	0.899	0.874	0.918	0.892	0.904	0.907
SD	0.270	0.268	0.395	0.492	0.470	0.310	0.264	0.265	0.280	0.27	0.290	0.285
pH	3.96		3.34		3.39		4.01		3.9		3,84
Viscosity	11.1	10.8	16.4	27	29.8	11.7	8.4	7.9	8.1	8.1	8.3	12.3
TS %	12.91		10.00/11.61		11.04/10.89		13.89		14.61/11.40		14.16/11.75

Example 7—Colloidal mill study—AKD emulsion samples with 15 kg polyDADMAC and 2.22 kg stearic acid

The procedure described in Example 2 was used in this study. in this study, stearic acid was added to the polyDADMAC in forming the emulsions, The AKD wax granules were added to the system when the colloid mill began circulation of the mixture. With the heat generated by the emulsification process, the AKD was melted and well emulsified. The temperature of the water phase was such that the AKD wax was added directly to emulsification process, thus eliminating a heating step.

It was found with the addition of stearic acid to the formulation, the desired mean particle size and particle size distribution was easily achieved. The stability study showed the samples of the diluted emulsion were stable for 2 to 3 weeks at 32° C. The diluted emulsion samples that included PAC were also found to have the desired stability. Results can be seen in Tables 24, 25 and 26.

TABLE 24
Colloidal mill study - AKD with 15 kg
polyDADMAC and 2.22 kg stearic acid
AKD - 45 kg, PolyDADMAC - 15 kg, Stearic acid -
2.25 kg, Tamol ™ 1.35 kg, water - 36.4 kg
		15 min recycling and	30 min sampling
	Sample	sampling 6.1 l/min	6.1 l/min
	no	XII	XIII
	Median	0.8252	0.8067
	90%	1.2037	1.1406
	2 um	99.566	99.852
	Mean	0.866	0.8383
	SD	0.2682	0.2401

TABLE 25
Colloidal mill study - the diluted AKD emulsion sample from XII
XII	Dilution and PAC 3%
4 times		7 days	14 days	21 days	28 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.823	0.755	0.795	0.869	0.839	0.845	0.771	0.766	0.794	0.803	0.791	0.754
90%	1.141	1.059	1.163	2.503	3.664	1.043	1.067	1.079	1.134	1.179	1.152	1.065
2 um	99.90	100	99.65	87.1	83.10	99.79	100	100	99.85	99.61	99.66	100
Mean	0.851	0.778	0.833	1.738	1.657	0.867	0.793	0.791	0.826	0.843	0.829	0.778
SD	0.230	0.214	0.268	1.703	2.502	0.222	0.207	0.219	0.243	0.269	0.265	0.218
pH	3.77		3.38		3.39		3.95		3.68		3.63
Visc.	11.1	11.2	18.8	82	78.9	12.3	10.4	8.9	12.1	14.1	14.8	10.2
TS %	13.55		13.34/12.07		13.57/13.01		14.32		14.21/13.71		14.46/13.69
Assay %	10.07		9.29		9.07		9.53		9.08		9.30

TABLE 26
Colloidal mill study - the diluted AKD emulsion sample from XIII
XIII	Dilution and PAC (3%)
4 times		7 days	14 days	21 days	28 days	28 days		7 days	14 days	21 days	28 days	28 days
dilution	0 day	32° C.	32° C.	32° C.	32° C.	RT	0 day	32° C.	32° C.	32° C.	32° C.	RT
Median	0.7959	0.77	0.801	0.8959	gel	0.793	0.767	0.762	0.788	0.7758	0.781	0.785
90%	1.0913	1.06	1.195	6.332	Unstable	1.092	1.038	1.059	1.122	1.121	1.130	1.020
2 um	100	100	99.38	75.44	Unstable	100	100	100	99.86	99.84	99.83	100
Mean	0.8176	0.79	0.846	2.226	Unstable	0.829	0.785	0.785	0.819	0.808	0.814	0.785
SD	0.2067	0.21	0.287	3.190	Unstable	0.218	0.192	0.208	0.237	0.246	0.249	0.209
pH	3.8		3.37		Unstable		3.93		3.66		3.68
Viscosity	12.1	11.6	22.3	625.9	Unstable	12.8	8.5	9.3	12.6	18.5	18.7	11.5
TS %	13.74		13.66/13.27		Unstable		14.58		14.67/13.12		14.64/13.67
Assay %	10.16		9.54		Unstable		9.74		9.47		9.32

Example 8—Colloidal mill study—paraffinic wax emulsion samples with 15 kg polyDADMAC and 2.22 kg stearin; acid

In addition to the emulsification of AKD wax, paraffinic wax was emulsified with potyDADMAC and lignin sulfonate through the colloid mill described above. Table 27 shows the physical properties of the emulsions after preparation and after storage for 1 week. The emulsion showed good particle size distribution after going through 2 cycles of the emulsification process.

TABLE 27
Colloidal mill study - paraffinic wax
emulsion prepared with polyDADMAC
	20% PolyDADMAC, 40% Wax		Dilution,
	F66H, 1.2% Lignin Sulfonate		PAC1460 (1%)
	1	2		23° C.
	cycle	cycles		1 week
	Median	0.8545	0.7939	0.7951	0.8554
	90%	1.4567	1.2294	1.229	1.3361
	2 um	98.245	99.275	99.409	98.797
	Mean	0.9032	0.8439	0.8422	0.915
	SD	0.3267	0.308	0.3048	0.337
	pH	6.88	6.9		6.98
	Viscosity	95.6	120.2		36.4

Example 9—Sizing Study

After the stability test, a number of AKD emulsion samples stored at room temperature were selected and a sizing performance comparison was accomplished comparing the AKD emulsion samples with PTV™ M5083 (starch) samples with 1?'&W and OCC furnish, respectively. In general, the AKD emulsion prepared in the trial showed a comparable size performance with PTV™ M5083 (see FIG. 3 and FIG. 4). It was seen in the OCC system the AKD emulsion prepared in combination with Hercobond™ 1620 and polyDADMAC showed significantly better performance than the PTV™ M5083.

In P&W system, PTV™ M5083 showed better sizing performance than when the AKD emulsion was prepared at 7.5 kg/ton. When the dosage increased, the AKD prepared with Hercobond™ 1620, showed a comparable size performance with PTV″' M5083 (typical AKI) emulsion with starch). However, the AKD emulsion prepared with polyDADMAC, showed poorer size performance. Although not to be bound by theory, this is likely caused by the high charge of polyDADMAC.

Example 10—Colloidal mill study—AKD wax emulsion samples with 15 kg PAK resin In addition, PolyDADMAC and amphoteric PAM emulsifying AKD wax, PAE

(polyamide-epichlorohydrin) and Tamol through the colloid mill described above. Table 27 shows the physical properties of the emulsions after preparation and after storage for 2, 4 weeks. The emulsion showed good particle size distribution after going through 2 cycles of the emulsification process.

TABLE 28
Colloidal mill study - AKD wax emulsified with PAE resin
16.5% PAE, 40% AKD wax, 1.2% Tamol
	1	2	32° C.	23° C.
	cycle	cycles	2 weeks	1 week
Median	0.8245	0.6134	0.7396	0.7418
90%	1.4367	0.9006	1.13	1.12
2 um	98.245	100	99.284	99.685
Mean	0.8832	0.6187	0.7919	0.7817
SD	0.3276	0.2234	0.3918	0.37
pH	3.65	3.70		3.82
Viscosity	10.3	9.30		10.5

While at least one exemplary embodiment has been presented in the foregoing detailed description of the inventive subject matter, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the inventive subject matter in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the inventive subject matter. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the inventive subject matter as set forth in the appended claims.

Claims

1. A composition for treating a paper product comprising:

a) a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide (PAM), a polyamine, a polyethyleneimine (PEI), polyvinyl alcohol, or combinations thereof;

b) a second component chosen from an alkyl ketene dime (AKD), alkenyl succinic anhydride (ASA), a paraffin wax, or combinations thereof,. and

c) a dispersant;

wherein the composition is in the form of an emulsion.

2. The composition according to claim 1, wherein the first component of the composition is a polyDADMAC and/or polyDADMAC derivative.

3. The composition according to claim 1, wherein the second component of the composition is an alkyl ketene dimer.

4. The composition according to claim 1, wherein the dispersant in the composition is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, copolymer of acrylamide, sulfonic acid, and combinations thereof.

5. The composition according to claim 1, wherein the first component in the composition is present in an amount of from about 0.1 wt. % to about 30 wt. %, about 0.1 wt. % to about 20 wt. %, about 0.5 wt. % to about 15 wt. %, based on the total weight of the composition.

6. The composition according to claim 1, wherein the second component in the composition is present in an amount of from about 0.1 wt. % to about 60 wt. %, or about 1 wt. % to about 50 wt. %, or about 5 wt. % to about 40 wt. %, based on the total weight of the composition.

7. The composition according claim 1, wherein the dispersant in the composition is present in amount of from about 0.1 wt. % to about 10.0 wt. %, or about 0.1 wt. % to about 1 wt. %, or about 025 wt. % to about 0.75 wt. %, based on the total weight of the composition.

8. The composition according to claim 1, further comprising a saturated or unsaturated fatty acid.

9. The composition according to claim 8, wherein the fatty acid in the composition is present an amount of from about 0.1 to about 10 wt. %, or about I wt. % to about 10 wt. %, based on the total weight of the composition.

10. The composition according to claim 1, wherein a paper product treated with the composition has higher water resistance compared with an untreated paper product.

11. A method of preparing an oil in water emulsion, wherein the method comprises:

providing a composition comprising a. a first component chosen from a polydiallyldimethylammonium chloride (polyDADMAC), a polyacrylamide, a polyamine, a polyethyleneimine, a. polyvinyl alcohol, and combinations thereof; b. a second component chosen from an alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and c. a dispersant; and

homogenizing the composition to produce the emulsion.

12. The method according to claim 11, wherein the first component in the composition is chosen from a polyDADMAC and/or a polyDADMAC derivative.

13. The method according to claim 12, wherein the polyDADMAC derivative is a copolymer of acrylamide and diallyl dimethyl ammonium chloride.

14. The method according to claim 11, —herein the second component in the composition is an alkyl ketene dimer.

15. The method according to claim 11, wherein the dispersant in the composition is chosen from a lignin sulfonate, a condensed polymer of naphthalene-sulfonic acid with formaldehyde, a copolymer of acrylamide and sulfonic acid, and combinations thereof

16. The method according to claim 11, wherein the first component in the composition is present in an amount of from about 0.1 wt. % to about 30 wt. %, or about 0.5 wt. % to about 15 wt. % based on the total weight of the composition.

17. The method according to claim 11, wherein the second component in the composition is present in an amount of from about 1 wt. % to about 60 wt. %, or about 1 wt. % to about 50 wt. %, or about 5 wt. % to about 40 wt. % based on the total weight of the composition.

18. The method according to claim 11, wherein the dispersant in the composition is present in amount of from about 1.0 wt. % to about 10 wt. %, or about 0.1 wt../i) to about 1 wt. %, or about 0.25 wt. % to about 0.75 wt. %, based on the total weight of the composition.

19. The method according to claim 11, wherein the composition further comprises a fatty acid in an amount of from about 0.1 to about 10 wt. %, or about 1 wt. % to about 5 wt. %, based on the total weight of the composition.

20. A method of producing a paper product comprising;

providing an emulsion composition according to claim 1; and

treating paper with the emulsion composition to form the paper product.