Oil-in-water emulsion and preparation method thereof

Abstract

The invention provides an alkyl ketene dimer emulsion and a preparation method thereof. More specifically, the present invention discloses a three-component emulsion which is readily prepared using a device having both low emulsifying ability and high shear rate ability to prepare an AKD emulsion having excellent quality, high efficiency, and short preparation time.

Description

Technical Field

[0001] The present invention provides an oil-in-water emulsion and a method for preparing the same. More specifically, the preparation of an alkyl ketene dimer emulsion is described. The ternary emulsion is easy to prepare using equipment with low emulsifying ability and high shear rate ability to prepare an AKD emulsion with excellent quality, high efficiency, and short preparation time. Background Art

[0002] Alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), and paraffin are used as sizing agents for providing water resistance in a papermaking system. These substances are hydrophobic and are produced in the form of liquid oil or solid wax. Generally, these additives need to be dispersed into an oil-in-water emulsion before being used in the papermaking system. In order to obtain good application performance, the emulsions of these hydrophobic materials must possess certain characteristics. The emulsions must remain sufficiently stable for a long time to ensure that they do not lose physical or chemical properties from the production point to the paper machine.

[0003] Due to these requirements, the preparation of sizing agent emulsions for hydrophobic paper has become the basis for improving product stability and / or sizing efficiency. Previous attempts have included producing stable high-solid-content ketene dimer dispersions by incorporating water-soluble carboxylic acids into a standard starch-based stabilizing system or using a cationic starch with a higher degree of substitution as an emulsifier. Other methods have been used: adding a cationic polymer post to the dispersion of a hydrophobic cellulose reactive sizing agent prepared with starch. Other attempts have been made to add a water-soluble polymer post to a starch-stabilized hydrophobic paper sizing agent dispersion in an attempt to improve stability and sizing performance. However, all of the above hydrophobic cellulose reactive sizing agent dispersions are stabilized by starch.

[0004] In addition to starch, other polymers have also been tried for stabilizing the aqueous dispersion of cellulose reactive sizing agents, such as anionic hydrophobically modified cellulose derivatives for improving the sizing effect in a papermaking furnish. Other methods use a cellulose reactive sizing agent with a coagulating dispersant containing an anionic component and a cationic component to stabilize the emulsion and improve sizing performance.

[0005] As the formulation is improved, the production method is equally important. In the production process of a hydrophobic dispersant or oil emulsion, generally four steps are adopted: an aqueous phase and an oil phase preparation step, a premixing step, a homogenization step, and a cooling step. The aqueous phase preparation involves cooking starch or dissolving a polymer in water. For a starch-stabilized hydrophobic dispersant, starch cooking takes time and may cause stability problems in the final emulsion. The premixing preparation step refers to forming a coarse emulsion of a hydrophobic material in the aqueous phase before homogenization.

[0006] The coarse emulsion is pumped through a high-pressure homogenizer, such as a Gaulin high-pressure homogenizer or a Hammelmann high-pressure pump. Large hydrophobic droplets enter the valve area at high pressure and low speed. When the droplets enter the adjustable tight clearance area between the valve and the seat, the speed increases rapidly and the pressure decreases accordingly. The intense energy release causes turbulence and local pressure differences, which will tear the particles. Then, a fine emulsion is formed by further reducing the droplets to less than 1 micron and having a narrow particle size distribution.

[0007] Overall, the limitations of the above methods are the need for complex, expensive, and bulky equipment capable of applying high homogenization shear and / or pressure, as well as strict procedures for emulsification ratio, temperature, etc. to produce a satisfactory stable emulsion with the desired specific size.

[0008] Other paper product sizing processes involve forming an aqueous sizing emulsion without high shear forces, the emulsion containing an alkenyl succinic anhydride component post-diluted with a cationic component. Current processes for emulsifying ASA consistently show that low-shear ASA emulsions have inferior sizing effects compared to high-shear ASA emulsions when post-diluted with cationic starch.

[0009] Other processes have used modified starches or polymers to enhance the sizing performance of low-shear emulsification systems.

[0010] Other known methods teach the use of an aqueous emulsion containing AKD and an emulsifier selected from polyoxyalkylene alkyl ethers or polyoxyalkylene alkyl aryl ethers or the corresponding mono-esters or di-esters.

[0011] So far, most emulsification processes require multiple pieces of equipment. Especially when emulsifying preparations containing AKD and / or paraffin, in addition to dedicated equipment, such emulsification also involves high capital investment and a large amount of space.

[0012] Subsequent research found that by mixing AKD with a preparation containing, for example, polydimethyldiallylammonium chloride (PolyDADMAC) and / or polyacrylamide and a dispersant (such as a condensate of naphthalene sulfonic acid and formaldehyde), an AKD emulsion suitable for papermaking can be produced. It was also found that this emulsification system can be extended to the emulsification of other hydrophobic chemicals (such as ASA or paraffin). These preparations are easily emulsified using a simple colloid mill or other high-speed shear emulsification equipment, which can prepare the sizing emulsion on-site.

[0013] To simplify the oil emulsification process and reduce chemical and equipment costs, researchers conducted studies, used combinations of various chemicals, and modified known equipment, such as using recycled turbine pumps and colloid mills with high-speed shearing capabilities. An example of the equipment used to prepare ASA emulsions is the Hercules Prequel Starch Alkaline Size Emulsifier (HASE). This equipment was originally designed to emulsify ASA with liquid starch in a continuous process and feed the emulsion directly into the paper machine. Although qualified ASA emulsions can be prepared using this equipment, there are some problems in producing AKD emulsions. Current formulations and equipment modifications have solved these problems.

[0014] Other objects, advantages, and features to be protected will be set forth in the following description, some of which will become apparent to those skilled in the art upon viewing the following content, or will be learned by practicing the present technology. The objects and advantages of the inventive concept disclosed and claimed in the present invention will be realized and attained by the compositions and methods (including their functional equivalents) particularly pointed out in the appended claims. Summary of the Invention

[0015] The present disclosure provides a composition for a papermaking process that imparts water resistance to the final product. The composition is in the form of an oil-in-water emulsion and comprises: a first component selected from poly(diallyldimethylammonium chloride) (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component selected from alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), paraffin wax, or any combination thereof; and a dispersant. The emulsion may optionally contain a fatty acid, such as stearic acid.

[0016] The present disclosure also provides a method for preparing an oil-in-water emulsion. The method includes providing a composition that comprises: a first component selected from poly(diallyldimethylammonium chloride) (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, or any combination thereof; a second component selected from alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and a dispersant. The composition is homogenized to produce an emulsion.

[0017] Finally, the present disclosure provides a method for forming a paper product, the method comprising adding an emulsion composition to a papermaking process, the emulsion composition comprising: a first component selected from polydiallyldimethylammonium chloride (polyDADMAC), polyacrylamide (PAM), polyamine, polyethyleneimine (PEI), polyvinyl alcohol or any combination thereof; a second component selected from alkyl ketene dimer, alkenyl succinic anhydride, paraffin or a combination thereof; and a dispersant. The emulsion composition can be added to the wet end of the papermaking process or applied to the surface of the plugging paper.

[0018] This summary is intended to introduce some concepts in a simplified form that are further described in the detailed description below. 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

[0019] Figure 1 Schematic diagram of the improved HASE emulsification system used in Example 2.

[0020] Figure 2 Schematic diagram of the improved HASE emulsification system used in Example 2.

[0021] Figure 3 The performance of the AKD when using P&W paper stock is shown.

[0022] Figure 4 The performance of AKD when using OCC paper stock is shown.

[0023] Figure 5 Schematic diagram of the colloid mill emulsification system used in the study. DETAILED DESCRIPTION

[0024] The following specific embodiments are merely exemplary and are not intended to limit the invention or the application and use of the invention. The word "exemplary" as used herein means "used as an example, instance or illustration". Therefore, any embodiment described herein as "exemplary" need not be interpreted as a preferred embodiment or superior to other embodiments. All embodiments described herein are exemplary embodiments, intended to enable those skilled in the art to implement or use the invention, rather than to limit the scope of the invention as defined by the claims. In addition, the present invention is not intended to be bound by any express or implied theory presented in the aforementioned technical field, background technology, content of the invention or the following specific embodiments.

[0025] The present invention provides an emulsion composition which can be added to the wet end of a papermaking process or applied to the surface of formed paper to provide resistance to aqueous liquids. The emulsion composition comprises: a first component selected from poly(diallyldimethylammonium chloride) (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, or any combination thereof; a second component selected from alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), paraffin wax, and combinations thereof; and a dispersant.

[0026] The emulsion composition is based on the coacervate concept, wherein two polymers with opposite charges (anionic and cationic) are mixed in a certain ratio to produce a stable colloidal coacervate which acts as an emulsifier or a dispersant and stabilizes the emulsified or dispersed sizing agent.

[0027] In some aspects, the anionic component is an anionic polyelectrolyte selected from polycarboxylates, polysulfates, and polysulfonates (such as lignosulfonates). The cationic component can be selected from cationic polyamines, polysulfonium, polyamidoamines, or combinations thereof.

[0028] In some aspects of the emulsion composition, the first component is selected from polymers which can be anionic, cationic, or non-anionic. The polyamine can be a primary, secondary, tertiary, or quaternary amine, or can comprise a mixture of amines of different strengths such as polyethyleneimine. Particularly useful polymers in these compositions include homopolymers and copolymers having a molecular weight (Mw) of about 10,000 or higher, the molecular weight (Mw) being determined by size exclusion chromatography.

[0029] In some aspects of the emulsion composition, quaternary polyamines are used, such as poly(diallyldialkylammonium chloride) wherein the alkyl moiety has 1 to about 6 carbon atoms; polyvinylamine; and derivatives thereof. Other cationic components can be quaternary polyamines such as poly(diallyldialkylammonium chloride) wherein the alkyl moiety has 1 to about 6 carbon atoms.

[0030] In the context of the present application, the term "polyacrylamide" refers to polyacrylamide in which both cationic and anionic units are present in an aqueous solution. Amphoteric polyacrylamide is obtained by copolymerizing acrylamide or methacrylamide with both anionic and cationic monomers. Amphoteric polyacrylamide can also be obtained by copolymerizing acrylamide with both anionic and cationic monomers.

[0031] In some aspects of the emulsion composition, the alkyl ketene dimer has the general formula (I)

[0032]

[0033] wherein R 1 and R2 represents a saturated or unsaturated hydrocarbon group having 8 to 36 carbon atoms and may be straight-chain or branched and having 6 alkyl chains and 12 to 20 carbon atoms, such as cetyl and octadecyl.

[0034] The alkenyl succinic anhydride (ASA) used in the present invention is well-known and consists of an unsaturated hydrocarbon chain containing a side-chain succinic anhydride group. The liquid ASA preferably used in the present invention is usually prepared by a two-step process using α-olefin as a raw material. First, the olefin is isomerized by randomly shifting the double bond from the α-position. In the second step, as shown in the following reaction scheme, the isomerized olefin is reacted with an excess of maleic anhydride to obtain the final ASA structure.

[0035]

[0036]

[0037] If the isomerization step is omitted, isomerized olefin, maleic anhydride or alkenyl succinic anhydride (ASA) is obtained. If the chain length of the starting α-olefin is in the range of C-14 to C-22 and may be linear or branched, ASA that is solid at room temperature can be produced. For the present composition, ASA is prepared by reacting maleic anhydride with an olefin containing 14 - 18 carbon atoms. Typical ASA can be purchased from Albemarle Corporation in Baton Rouge, Louisiana. Representative starting olefins for reacting with maleic anhydride to prepare the ASA for the present formulation include: octadecene, tetradecene, hexadecene, nonadecene, 2-n-hexyl-1-octene, 2-n-octyl-1-dodecene, 2-n-octyl-1-decene, 2-n-dodecyl-1-octene, 2-n-octyl-1-octene, 2-n-octyl-1-nonene, 2-n-hexyl-1-decene and 2-n-heptyl-1-octene.

[0038] Paraffin wax is usually obtained by separating and extracting hydrocarbons with good crystallinity from the oily distillate moiety in the vacuum distillation of crude oil. Paraffin wax is a colorless or white transparent solid wax containing linear hydrocarbons as the main component and having a melting point of about 40 °C to about 90 °C.

[0039] Other exemplary hydrophobic anhydrides that can be stabilized with the polymer having this formulation can be used as sizing agents.

[0040] In some aspects of the emulsion composition, the dispersant is an anionic surface-active polyelectrolyte, such as polycarboxylate (e.g., polyacrylate, carboxymethyl cellulose, hydrolyzed polyacrylamide), polysulfate (e.g., polyvinyl sulfate, polyethylene sulfate) or polysulfonate (e.g., polyvinyl sulfonate, lignosulfonate).

[0041] In some aspects of the emulsion composition, the anionic surfactant can be selected from alkyl, aryl or alkylaryl sulfates; alkyl, aryl or alkylaryl carboxylates; alkyl, aryl or alkylaryl sulfonates; or combinations thereof.

[0042] In some aspects, the alkyl moiety can have from 1 to about 18 carbon atoms, the aryl moiety can have from about 6 to about 12 carbon atoms, and the alkylaryl moiety can have from about 7 to about 30 carbon atoms. These moieties can be propyl, butyl, hexyl, decyl, dodecyl, phenyl or benzyl, as well as linear or branched alkylbenzene derivatives of carboxylates, sulfates and sulfonates.

[0043] In other aspects, the anionic component can be selected from polycarboxylates, polysulfates and polysulfonates. These can include lignosulfonate or lignin sulfonate, such as sodium, calcium, ammonium, iron or chromium salts.

[0044] In one aspect, the anionic component can be sodium lignosulfonate or a condensate of naphthalenesulfonic acid and formaldehyde, such as Tamol of BASF TM series products, such as Tamol TM NN9401.

[0045] In some aspects of the emulsion, based on the total weight of the composition, the composition contains the first component in an amount of about 0.1 wt% to about 30 wt%, or about 0.1 wt% to about 20 wt%, about 0.5 wt% to about 15 wt%.

[0046] In some aspects of the emulsion, based on the total weight of the composition, the second component is present in an amount of about 0.1 wt% to about 50 wt%, or about 1 wt% to about 60 wt%, or about 5 wt% to about 40 wt%.

[0047] In yet another aspect of the emulsion, based on the total weight of the composition, the dispersant is present in an amount of about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 1 wt%, or about 0.25 wt% to about 0.75 wt%.

[0048] In yet another aspect of the emulsion, the composition further comprises a fatty acid, such as stearic acid. Based on the total weight of the composition, the fatty acid can be present in the composition in an amount of about 0.1 to about 10 wt%, or about 1 to about 5 wt%.

[0049] In yet another aspect of the emulsion composition, the emulsion is added to the furnish before forming the paper product, or the emulsion composition can be applied to the outer surface of the formed paper. This renders the formed product more resistant to aqueous liquids compared to untreated paper, where the water resistance is studied using the TAPPI T 441 Cobb test.

[0050] In some aspects, a method for preparing an oil-in-water emulsion is provided. The method includes providing an emulsion composition comprising: a first component selected from poly(diallyldimethylammonium chloride) (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component selected from alkyl ketene dimers, alkenyl succinic anhydrides, paraffins, and combinations thereof; and a dispersant. The composition is homogenized to prepare the emulsion.

[0051] In some aspects of the method, the first component is selected from polyDADMAC or polyDADMAC derivatives, such as copolymers of acrylamide and diallyldimethylammonium chloride.

[0052] In some aspects of the method, the second component is an alkyl ketene dimer.

[0053] In some aspects of the method, the dispersant is selected from lignosulfonates, condensates of naphthalenesulfonic acid and formaldehyde, copolymers of acrylamide and sulfonic acid, and combinations thereof.

[0054] In some aspects of the method, based on the total weight of the composition, the emulsion composition contains the first component in an amount of about 0.1 wt% to about 30 wt%, or about 0.1 wt% to about 20 wt%, about 0.5 wt% to about 15 wt%.

[0055] In other aspects of the method, based on the total weight of the composition, the second component is present in an amount of about 0.1 wt% to about 50 wt%, or about 1 wt% to about 60 wt%, or about 5 wt% to about 40 wt%.

[0056] In yet another aspect of the method, based on the total weight of the composition, the dispersant is present in an amount of about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 1.0 wt%, or about 0.25 wt% to about 0.75 wt%.

[0057] In some aspects of the method, the emulsion composition further comprises a fatty acid, such as stearic acid. Based on the total weight of the composition, the fatty acid can be present in the composition in an amount of about 0.1 to about 10 wt%, or about 1 to about 5 wt%.

[0058] In some aspects of the method, the composition is homogenized using a rotor / stator generator, a high-pressure device, or a sonicator.

[0059] In some aspects of the method, the composition is homogenized using a rotor / stator engine (such as a colloid mill) with a linear shear force of at least 23 m / s.

[0060] In other aspects of the method, the composition is homogenized using a high-pressure device (such as a piston pump).

[0061] In some aspects of the method, the average particle size of the emulsion is less than 2 microns and can be less than 1 micron.

[0062] In yet another aspect, a method of forming a paper product is provided, the method comprising providing an emulsion composition comprising: a first component selected from polydiallyldimethylammonium chloride (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, and combinations thereof; a second component selected from alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), paraffin wax, and combinations thereof; and a dispersant.

[0063] The emulsion composition can be added to the furnish at any point in the papermaking process, such as in a blending chest or at other points in the wet end of the process. The emulsion composition can also be applied to the surface of the produced paper, such as at the forming section, drying section, or calender rolls. The emulsion can be applied by spraying, coating, film transfer, soaking, or other known means used in papermaking.

[0064] In some aspects of the method, the paper product can be, for example, paper products such as cardboard, carton board, and aseptic packaging, copy paper, and coated paper.

[0065] Examples

[0066] Example 1 – Laboratory Waring Blender Study

[0067] AKD emulsification studies were completed using the Waring blender method. This study examined the emulsifying ability of different ground starches containing the Prequel TM product (calcium salt of long-chain fatty acid). The following procedure was employed:

[0068] Aqueous phase preparation - Add the target water to a 2-liter glass beaker and mix well with a overhead stirrer with Tamol TM at a stirring speed maintained at about 500 to 800 rpm. Add the required grams of polymer to homogenize with Tamol TM for 5 minutes. Adjust the pH to 4.5. Place the 2-liter glass beaker containing the emulsion in a water bath and heat this phase (aqueous phase) to 70 °C.

[0069] Emulsification step - The aqueous phase (70 °C) and molten AKD (AKD placed in a preheated oven at 85 °C) were mixed in a Waring blender equipped with four blades and capable of generating high shear forces to break the oil into small droplets, thereby forming an emulsion. The blender was covered and set at the highest speed, and the contents were homogenized for 1 minute to produce an AKD oil-in-water emulsion. Based on % AKD, the emulsion was diluted to 10 - 15% and sieved through a 100-mesh paper cone paint strainer. The properties of the AKD emulsion were obtained and stability tests were conducted in an oven at 32 °C.

[0070] The combination of PolyDADMAC and Hercobond was studied TM 1620 (polymer of 2-methylenesuccinic acid, with 2-(dimethylamino)ethyl 2-methylacrylate, N,N-dimethyl-2-propenamide, 2-propenamide and sodium 2-methylpropene-1-sulfonate (1:1), sulfate) was studied. Overall, as shown in Tables 1 and 2, PolyDADMAC and Hercobond TM 1620 exhibited good ability to emulsify AKD wax. The AKD emulsion prepared with PolyDADMAC and Hercobond TM 1620 produced an emulsion with a smaller average particle size. The results also showed that different percentages of AKD polymer and Tamol TM (polymer of naphthalenesulfonic acid and formaldehyde, sodium salt) under stirring affected the average particle size of AKD in the final emulsion. It was also observed that better emulsification was achieved, i.e., a higher tearing strength was produced, and further, better emulsification stability could be provided either at a higher blender speed or a longer stirring time.

[0071] Table 1 - Waring blender - AKD emulsification, using PolyDADMAC

[0072]

[0073]

[0074] Table 2 - Waring blender - AKD emulsification, using Hercobond TM 1620

[0075] Test Water (g) 1620(g) 1865(g) 9401(g) Median 90％ 2μm 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

[0076] Laboratory Waring blender studies showed that the use of a composition containing polyDADMAC and Hercobond TM 1620 could fully emulsify AKD wax.

[0077] Example 2 - Emulsification Study of Regenerative Turbine Pumps

[0078] In this study, a Hercules Prequel Starch Alkaline Size Emulsifier (HASE) was used, which included a Burks TM regenerative turbine pump. This pump generates high shear forces that can emulsify AKD, ASA, and paraffin / polyDADMAC or Hercobond TM 1620. However, unlike ASA, AKD and paraffin are solids and need to be melted before being pumped into the turbine pump. The HASE was modified to include a blending tank for water phase preparation, an AKD melting tank, a screw pump, and a hot water tank (see Figure 1 ).

[0079] In addition to Figure 1 the configuration shown, the system was also modified, and two types of emulsification systems as shown in Figure 1 and 2 were used in this study. As described above, in the first type (see Figure 1 ), AKD was premixed with the water phase and then pumped through the starch pipeline to the HASE. In the second type (see Figure 2 ), molten AKD was added through the HASE gear pump, and the water phase was added through an additional screw pump through the starch pipeline. The main difference between these two types of systems is that in type 1 ( Figure 1 ), AKD is mixed with the water phase and then fed into the turbine pump; while in type 2 ( Figure 2 ), AKD and the water phase are added to the HASE at different points.

[0080] The study showed that emulsification can be achieved using either type 1 or type 2 of the HASE system. The produced emulsions were sampled, evaluated, and diluted for further oven stability testing. As shown in Tables 3 and 4 below, the average particle size of the emulsions produced by the first type of system was in the range of 900 - 1200 μm and the stability of the emulsions was poor.

[0081] However, when using the improved HASE system shown in Figure 2 , the flow rate of AKD increased, and the particle size distribution (PSD) of the emulsion was narrower than that of the emulsion obtained using the HASE system shown in Figure 1 . After adding 2% polyacrylamide (PAC), the emulsions prepared using polyDADMAC showed higher stability. The results also showed that stearic acid helped emulsify AKD and reduced the average particle size of the emulsion.

[0082] Table 3 - Performance and Stability Results of Medium - scale Test Type 1 - AKD Emulsion of HASE

[0083]

[0084] Table 4 - Performance and Stability Results of Medium - scale Test Type 1 - AKD Emulsion of HASE

[0085]

[0086] Table 5 - HASE Medium - scale Test Type 2 – Using Hercobond TM Performance and Stability Results of AKD Emulsion with 1620

[0087]

[0088] Table 6 - HASE Medium - scale Test Type 2 - Using Hercobond TM Performance and Stability Results of AKD Emulsion with 1620

[0089]

[0090] Table 7 - Performance and Stability Results of AKD Emulsion Using polyDADMAC

[0091]

[0092] Table 8 - Performance and Stability Results of AKD Emulsion Using polyDADMAC

[0093]

[0094] Adopt Figure 2 the process shown, and the sizing performance was compared with the typical starch product Hercules PTV TM M5083. Emulsions were prepared using Hercobond TM 1620 and stearic acid or polyDADMAC and stearic acid, and the Cobb values of both were better than those of PTV TM M5083.

[0095] In addition, we found that the particle size of the emulsion highly depends on the ratio of AKD to the polymer. Acceptable emulsions were prepared using HASE, polyDADMAC and Hercobond TM 1620, and the average particle size was smaller when using polyDADMAC. It was also found that PAC helps to improve the stability of the emulsion prepared with polyDADMAC. The results also showed that adding stearic acid to the formulation reduced the particle size distribution (PSD).

[0096] Although studies have shown that the PSD of the AKD / polyDADMAC and AKD / Hercobond TM 1620 emulsions produced is acceptable, the results show that the emulsion samples are unstable after 3 days of storage at room temperature and have an even shorter stability time at 32 °C. However, for on-site application, the emulsion quality is acceptable.

[0097] In addition, AKD emulsions were also prepared using a turbine pump. And ASA was tried. Tables 9, 10 and 11 show the emulsion results. The ASA was emulsified and had a good particle size distribution.

[0098] Table 9 - Performance and stability results of ASA emulsions using polyDADMAC

[0099]

[0100] Table 10 - Performance and stability results of ASA emulsions using Hercobond TM 1620

[0101]

[0102] Example 3 - Colloid mill test

[0103] The following study was carried out using a colloid mill GRS2000 / 05 from Shanghai SGN Machinery Equipment Co., Ltd. An emulsification system was designed using the above colloid mill as Figure 5 shown. The system was designed to have two main parts: a) a blending tank and b) a colloid mill. They were connected by a laboratory flexible impeller pump. This pump circulated the premixed liquid from the blending tank to the colloid mill.

[0104] In this study, water and Tamol TM were added to the blending tank and mixed for 10 minutes. At this time, the polymer liquid was added to the tank and the pH value was adjusted. The temperature of the mixture was raised to 60 °C. At this time, AKD was added to the blending tank and mixing continued for another 20 minutes. The system began to circulate. After 1 cycle, an emulsion sample was collected from the emulsion storage tank and measured. This process continued for several cycles. When the measured and found average particle size was about 1000 microns, another emulsion sample was collected and diluted for further stability testing. The emulsion was diluted 4 times and the temperature of the sampled emulsion was lowered to below 30 °C. Circulation continued until the average particle size of the emulsion was below 800 microns or the circulation time exceeded 80 minutes. The colloid mill was stopped and the emulsion was collected for other tests.

[0105] Studies have shown that when AKD and Hercobond TMIt is easy to emulsify when mixed with 1620 or polyDADMAC. After 1 to 6 cycles, the average particle size is between 0.70 - 0.90 mm. Tamol TM The ratio to AKD is fixed at 0.03:1. As shown in Tables 11, 12, 13 and 14, even when the ratio of AKD to Hercobond TM to 1620 increases to 13.3:1, the average particle size of the emulsion is still below 0.85 mm (850 μm). Except for Sample V, all emulsions remained stable after 28 days in the oven stability test with the oven temperature set at 32 °C.

[0106] Table 11 - Colloid Mill Study - AKD Emulsion Samples Using 15 kg Hercobond TM 1620

[0107]

[0108] Table 12 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample V

[0109]

[0110] Table 13 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample VI

[0111]

[0112]

[0113] Table 14 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample VI

[0114]

[0115] Example 4 - AKD Emulsion Samples Using 20 kg polyDADMAC

[0116] This study used the procedure described in Example 2. Two different ratios of AKD to polyDADMAC were evaluated in this study. The ratio of AKD to polyDADMAC of 5:1 ensured that the particle size of the emulsion was less than 0.9 mm (900 μm) within 25 minutes. The results are shown in Tables 15, 16 and 17.

[0117] Table 15 - Colloid Mill Study - AKD Using 20 kg polyDADMAC

[0118]

[0119] Table 16 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample I

[0120]

[0121]

[0122] Table 17 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample II

[0123]

[0124] Example 5 - Colloid Mill Study - AKD Emulsion Samples Using 20 kg of polyDADMAC and 2 kg of stearic acid

[0125] The procedure described in Example 2 was used in this study. In this study, 5% stearic acid solution was added to AKD according to Tables 18, 19, and 20. The results showed that the particle size distribution of the produced emulsion dropped to the required range within a shorter grinding time, indicating higher emulsification efficiency. The diluted emulsion samples remained stable at 32°C during the first week, but became unstable after 7 days. As shown in Tables 19 and 20, the samples diluted with 3% PAC showed better stability.

[0126] Table 18 - Colloid Mill Study - AKD Using 20 kg of polyDADMAC and 2 kg of stearic acid

[0127]

[0128] Table 19 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample III

[0129]

[0130] Table 20 - Colloid Mill Study - Diluted AKD Emulsion Samples from Sample IV

[0131]

[0132] Example 6 - Colloid Study - AKD Emulsion Samples Using 15 kg of polyDADMAC

[0133] The procedure described in Example 2 was used in this study. This study was completed using a ratio of 7.5:1 (AKD / polyDADMAC). The results are shown in Tables 21, 22, and 24. After circulating through the system for 45 minutes, the average particle size of the AKD emulsion was approximately 0.9 - 1.0 mm (900 - 1,000 μm).

[0134] Table 21 - Colloid Study - AKD Emulsion Samples Containing 15 kg of polyDADMAC

[0135]

[0136] Table 22 - Colloid Study - Diluted AKD Emulsion Samples from Sample X

[0137]

[0138] Table 23 - Colloid Study - Diluted AKD Emulsion Samples from Sample XI

[0139]

[0140] Example 7 - Colloid Mill Study - AKD Emulsion Samples Using 15 kg of polyDADMAC and 2.22 kg of stearic acid

[0141] The procedure described in Example 2 was used in this study. In this study, stearic acid was added to polyDADMAC to form an emulsion. When the colloid mill started to circulate the mixture, AKD wax particles were added to the system. The heat generated during the emulsification process melted the AKD and emulsified it sufficiently. The temperature of the aqueous phase was suitable for directly adding the AKD wax to the emulsification process, thus eliminating the heating step.

[0142] We found that by adding stearic acid to the formulation, the desired average particle size and particle size distribution were easily achieved. The stability study showed that the diluted emulsion samples were stable for 2 to 3 weeks at 32°C. It was also found that the diluted emulsion samples containing PAC had the desired stability. The results are shown in Tables 24, 25, and 26.

[0143] Table 24 - Colloid Mill Study - AKD Emulsion Samples Using 15 kg of polyDADMAC and 2.22 kg of stearic acid

[0144]

[0145] Table 25 - Colloid Mill Study - Diluted AKD Emulsion Samples from XII

[0146]

[0147] Table 26 - Colloid Mill Study - Diluted AKD Emulsion Samples from XIII

[0148]

[0149] Example 8 - Colloid Mill Study - Paraffin Emulsion Samples Using 15 kg of polyDADMAC and 2.22 kg of stearic acid

[0150] In addition to the emulsification of AKD wax, paraffin wax was emulsified with polyDADMAC and lignosulfonate by a colloid mill as described above. Table 27 shows the physical properties after the emulsion preparation and after 1 week of storage. After 2 cycles of the emulsification process, the emulsion showed a good particle size distribution.

[0151] Table 27 - Colloid Mill Study - Paraffin Wax Emulsion Prepared with polyDADMAC

[0152]

[0153] Example 9 - Sizing Study

[0154] After the stability test, multiple AKD emulsion samples stored at room temperature were selected and the sizing performance of the AKD emulsion samples was compared with PTV TM M5083 (starch) samples in the case of using P&W and OCC furnish respectively. Generally speaking, the sizing performance of the AKD emulsions prepared in the experiment was comparable to that of PTV TM M5083 (see Figure 3 and Figure 4 ). It was found that the performance of the AKD emulsion prepared with Hercobond TM 1620 and polyDADMAC in the OCC system was significantly better than that of PTV TM M5083.

[0155] In the P&W system, the sizing performance of PTV TM M5083 was better than that of the AKD emulsion prepared at a dosage of 7.5 kg / ton. When the dosage was increased, the sizing performance of the AKD emulsion prepared with Hercobond TM 1620 was comparable to that of PTV TM M5083 (a typical AKD emulsion using starch). However, the sizing performance of the AKD emulsion prepared with polyDADMAC was poor. Although not bound by theory, this may be due to the high feeding amount of polyDADMAC.

[0156] Example 10 - Colloid Mill Study - AKD Wax Emulsion Sample Using 15 kg PAK Resin

[0157] In addition, AKD wax emulsified with PolyDADMAC and amphoteric PAM, PAE (polyamide - epichlorohydrin), and Tamol were passed through a colloid mill as described above. Table 28 shows the physical properties after the emulsion preparation and after 2 and 4 weeks of storage. After 2 cycles of the emulsification process, the emulsion showed a good particle size distribution.

[0158] Table 28 - Colloid Mill Study - AKD Wax Emulsified with PAE Resin

[0159]

[0160] Although at least one exemplary embodiment has been presented in the foregoing detailed description of the subject matter of the present invention, it should be understood that a vast number of variations exist. It should also be understood that one or more exemplary embodiments are merely examples and are not intended to limit in any way the scope, applicability, or configuration of the subject matter of the present invention. On the contrary, the foregoing detailed description will provide those skilled in the art with a convenient roadmap for implementing the exemplary embodiments of the subject matter of the present invention. It should be understood that various changes may be made to the functions and arrangements of the elements described in the exemplary embodiments without departing from the scope of the subject matter of the present invention as set forth in the appended claims.

Claims

1. A composition for treating paper products, comprising: a) A first component selected from polydiallyldimethylammonium chloride (polyDADMAC), polyacrylamide (PAM), polyamines, polyethyleneimine (PEI), polyvinyl alcohol, or combinations thereof; b) A second component selected from alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), 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 polyDADMAC and / or a polyDADMAC derivative.

3. The composition according to claim 1 or 2, wherein the second component of the composition is alkyl ketene dimer.

4. The composition according to any one of claims 1 - 3, wherein the dispersant in the composition is selected from lignosulfonates, condensates of naphthalenesulfonic acid and formaldehyde, copolymers of acrylamide and sulfonic acid, and combinations thereof.

5. The composition according to any one of claims 1 - 4, wherein, based on the total weight of the composition, the first component is present in the composition in an amount of about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 20 wt%, or about 0.5 wt% to about 15 wt%.

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

7. The composition according to any one of claims 1 - 6, wherein, based on the total weight of the composition, the dispersant is present in the composition in an amount of about 0.1 wt% to about 10.0 wt%, or about 0.1 wt% to about 1 wt%, or about 0.25 wt% to about 0.75 wt%.

8. The composition according to any one of claims 1 - 7, further comprising a saturated or unsaturated fatty acid.

9. The composition according to claim 8, wherein, based on the total weight of the composition, the fatty acid is present in the composition in an amount of about 0.1 to about 10 wt%, or about 1 wt% to about 10 wt%.

10. The composition according to any one of claims 1 - 9, wherein the paper product treated with the composition has higher water resistance compared to an untreated paper product.

11. A method for preparing an oil-in-water emulsion, wherein the method comprises: Providing a composition comprising: a. A first component selected from polydiallyldimethylammonium chloride (polyDADMAC), polyacrylamide, polyamines, polyethyleneimine, polyvinyl alcohol, and combinations thereof; b. A second component selected from alkyl ketene dimer, alkenyl succinic anhydride, paraffin wax, and combinations thereof; and c. A dispersant; and Homogenizing the composition to produce an emulsion.

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

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

14. The method according to any one of claims 11-13, wherein the second component in the composition is alkyl ketene dimer.

15. The method according to any one of claims 11-14, wherein the dispersant in the composition is selected from lignosulfonates, condensates of naphthalenesulfonic acid and formaldehyde, copolymers of acrylamide and sulfonic acid, and combinations thereof.

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

17. The method according to any one of claims 11-16, wherein based on the total weight of the composition, the second component is present in the composition in an amount of about 1 wt% to about 60 wt%, or about 1 wt% to about 50 wt%, or about 5 wt% to about 40 wt%.

18. The method according to any one of claims 11-17, wherein based on the total weight of the composition, the dispersant is present in the composition in an amount of about 1.0 wt% to about 10 wt%, or about 0.1 wt% to about 1 wt%, or about 0.25 wt% to about 0.75 wt%.

19. The method according to any one of claims 11-18, wherein based on the total weight of the composition, the composition further comprises about 0.1 to about 10 wt%, or about 1 wt% to about 5 wt% of fatty acid.

20. A method for producing a paper product, comprising: - providing the emulsion composition according to claim 1; and - treating the paper with the emulsion composition to form a paper product.

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