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Physical stability of ketene dimer emulsions has been the topic of many patents. For example, Edwards, et al. (U.S. Pat. No. 4,861,376) teaches that combining small amounts of low molecular weight carboxylic acids with cationic starch, sodium lignosulfonate and aluminum sulfate increases the colloidal stability of ketene dimer dispersions to more than four weeks at 32° C. Schmid, et al. (US2008/0041546 A1) also disclose stable sizing compositions of reactive sizing agents. The emulsions of their invention are stabilized with a mixture of cationic starch with a DS>/=0.05, anionic dispersant and a linear nitrogen-containing polymer. Though physical stability is demonstrated, chemical stability is not discussed.
Dextra Type Rebar Cold-Swaged Coupling Sleeve-High-Grade Customized Decorative Metal Bag Lock Accessories (JH0003), see, for example, U.S. Pat. No. 4,861,376 to Edwards, et al. or U.S. Pat. No. 4,964,915 to Blixt, et al.High-End Customized Ladies Carrier Paper Bag Shopping Bag for Clothes/Apparel/Gift Box-Geeklink 1 Gang Scene Panel Smart Home Remote Control Wireless Light Switch Feedback Touch Controller Alert Alarming Apparatus.Wireless WiFi Smart Socket-Wood Planer Knives for Cutting Machine, that has been pH adjusted as disclosed in US2008/0041546 A1, are also physically unstable, solidifying on storage (see Example 5 of US2008/0041546 A1).
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Qt4-20 Concrete Interlocking Paving Block Machine / Electric Brick Making Machine.Best Selling American Style Residential Apartment Privacy Aluminum Wooden Door Handles and Locks) adjusting the pH of a vinylamine-containing polymer below about 3.3, 2) blending the pH adjusted vinylamine-Investment Casting Floor Drain SS316, 3)Air Pipe Fittings Compressed Air Quick Connect Pneumatic Coupling)Aluminium Foil or Hot Seal 8006/8011/8079/8021 for Food Industry with FDA, QS, SGS Certification.
In a preferred embodiment of the invention,Wire Mesh Gravity Feed Bottle Shelves Pusher.
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Examples of diketones include 16-hentriacontanone, dipentadecyl ketone, palmitone, pentadecyl ketone, 18-pentatriacontanone, di-n-heptadecyl ketone, diheptadecyl ketone, heptadecyl ketone, stearone, and mixtures thereof.
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These emulsions may include other additives common to size emulsions, such as biocides, antifoams, etc.
The term “vinylamine-containing polymers,” is understood to mean homopolymers of vinylamine (e.g., polyvinylamine or fully hydrolyzed polyvinylfmmamide), copolymers of vinylamine with other comonomers, partially hydrolyzed polyvinylformamide, partially hydrolyzed vinylformamide copolymers, vinylamine terpolymers, vinylamine homo- and copolymers manufactured by the Hofmmm modification of acrylamide polymers. Examples of such polymers can be found in U.S. Pat. No. 6,159,340 to Niessner, et al.
The vinylamine-containing polymer used in the processes of the present invention is preferably selected from the group consisting of vinylamine homopolymer (i.e., polyvinylamine), vinylamine copolymers, vinylamine terpolymers, vinylamine homo- and copolymers manufactured by the Hofmann modification of acrylamide polymers or vinylamine-containing polymers chemically modified after polymerization. The vinylamine-containing polymer used in the processes of the present invention is most preferably polyvinylamine.
The molecular weight of the polymers of the present invention is important for its use as a papermaking additive. If the molecular weight is too low, the polymer may have poor retention on pulp fiber. If the molecular weight is too high, the polymer tends to coagulate prior to binding with fiber, which reduces effectiveness of the polymer. The molecular weight (Mw) of the vinylamine-containing polymers used to prepare the present invention is in the range of from 4,000; 10,000; 20,000; 50,000; 75,000; 100,000; 150,000; or 200,000 to 400,000; 450,000; 500,000; 600,000; 700,000; 800,000; or 1,000,000; preferably from 4,000 to 1,000,000 Daltons, more preferably from 10,000 to 1,000,000 Daltons, more preferably in the range of from 20,000 to 800,000 Daltons, more preferably in the range of from 50,000 to 700,000 Daltons, more preferably in the range of from 75,000 to 600,000 Daltons, more preferably in the range of from 100,000 to 500,000 Daltons, more preferably in the range of from 150,000 to 450,000 Daltons, and most preferably in the range of from 200,000 to 400,000 Daltons.
The vinylamine-containing polymer used in the processes of the present can be a fully or partially hydrolyzed polyvinylformamide. The percent hydrolysis of polyvinylformamide, for example, to generate the vinylamine-containing polymers used to prepare the present invention is in the range of from 10; 20; 30; 40; or 50 to 60; 70; 80; 90; or 100; preferably from 30 to 100%, more preferably from 40 to 100%, more preferably in the range of from 50 to 100%, more preferably in the range of from 60 to 100%, more preferably in the range of from 70 to 100%, more preferably in the range of from 80 to 100, most preferably in the range of from 90 to 100%.
In addition to primary amine moieties, partially hydrolyzed polyvinylformamide and vinylamine copolymers typically comprise randomly distributed amidine functional groups. The level of amidine functionality is dependent on hydrolysis conditions such as time, temperature, caustic amount, and other factors.
Lightweight Solar Generator Lithium Battery Solar Charger Bank 400W-containing polymer, such as polyvinylamine, must first be adjusted to a stable pH below about 3.3. A pH below 3.0 is preferred, more preferably below 2.5 and a pH between 2.1 and 2.5 is most preferred. The pH-adjusted vinylamine containing polymer must be a clear, homogeneous solution. The pH adjustment can be made using mineral or organic acids. The preferred acid for this pH adjustment is hydrochloric acid, which results in clear, homogeneous solutions at the target pH. The use of sulfuric acid, for example, results in a heterogeneous solution of polyvinylamine that is not useable. Organic acids (e.g.,Stainless Steel BSPT NPT Female Threaded End 1/4 to 2 Inch Full Bore Swing Type Check Valve for Pipe System) can also be used. Other commercially available acids include methylsulfonic acid, hydrobromic acid,Wholesale High Pressure Steel Oxygen/Argon/Helium Gas Cylinder.
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Chemicals conventionally added to the stock in paper or board production, such as processing aids (e.g., retention aids, drainage aids, contaminant control additives, etc.) or other functional additives (e.g., wet or dry strength additives, dyes,3D Hologram PVC Security Card with Micro Print, etc.)Wireless Electronic Kitchen Food Barbecue Thermometer.
The following examples are given for the purpose of illustrating the present invention. All patis and percentages are by weight unless otherwise indicated.
In the following examples,Qt500 Large Cast Iron of Car Die, including stock preparation, refining and storage. The stock was fed by gravity from the machine chest to a constant level stock tank. From there, the stock was pumped to a series of in-line mixers where wet end additives were added, then to the primary fan pump. The stock was diluted with white water at the fan pump to about 0.2%Cheap Anti-Slip Horse Stall Rubber Mat Stable Rubber Cow Mat. Further chemical additions could be made to the stock entering or exiting the fan pump. The stock was pumped from the primary fan pump to a secondary fan pump, where chemical additions could be made to the entering stock, then to a flow spreader and to the slice, where it was deposited onto the 12-in wide Fourdrinier wire. Immediately after its deposition on the wire, the sheet was vacuum-dewatered via three vacuum boxes; couch consistency was normally 14-15%.
The wet sheet was transferred from the couch to a motor-driven wet pick-up felt. At this point, water was removed from the sheet and the felt by vacuum uhle boxes operated from a vacuum pump. The sheet was further dewatered in a single-felted press and left the press section at 38-40%Cheap Anti-Slip Horse Stall Rubber Mat Stable Rubber Cow Mat.
Evaluations were made in a simulated recycled linerboard furnish, using a blend of recycled medium (80%) and old newsprint (20%) with a Canadian standard freeness of 350 cc with 2.75% sodium lignosulfonate added to simulate anionic trash. The hardness and alkalinity were 126 ppm and 200 ppm, respectively. Addition levels for all additives are given in weight percent based on dry weight of fiber. 0.3%Laboratory High Altitude Low Pressure Life Testing Machine(Sta-Lok 300, Tate & Lyle)China Professional Mold Maker for Plastic Helmet. No other wet end additives were used. Stock temperature was maintained at 55 C. The headbox pH was controlled to 7.5 with caustic.
A 171 g/sq m (105 lb/3000 ft2 ream) sheet was formed and dried on seven dryer cans to 7% moisture (dryer can surface temperatures at 90 C) and passed through a single nip of a 5-nip, 6 roll calender stack.PVC Coated Vinyl Tarpaulin Waterproof Anti UV Fabric(50% RH, 25 C) for a minimum of 7 days.
AKD emulsion:Wireless Smart CCTV WiFi IP Camera for Home Security,Guangzhou Supplier Low Carbon Steel Binding Wire in Guangzhou(Hercules Incorporated, Wilmington Del.). The pH specification for this product is 2.1-4.2.
Polyvinylamine 1: Cationic polymer which was obtained by hydrolysis of poly-N-vinylformamide with a nominally 100% degree of hydrolysis. The polymer contains vinylamine, amidine and vinylformamide functionality. Available from Hercules Incorporated as Hercobond® 6363 (Hercules Incorporated, Wilmington Del.).
Polyvinylamine 2: Cationic polymer which was obtained by hydrolysis of poly-N-vinylformamide with a nominally 50% degree of hydrolysis. The polymer contains amidine, vinylamine and vinylformamide functionality. Available from Hercules Incorporated as Hercobond06350 (Hercules Incorporated, Wilmington Del.).
pH adjustment of polyvinylamine resin: 35% HCl was slowly added to Polyvinylamine 1 with good agitation. The pH was monitored as the HCl was added. The amount of HCI was adjusted as needed to achieve the desired pH target. The pH was rechecked after several hours to make sure the pH was stable. It was adjusted by adding additional acid or more polymer, as necessary, to achieve the target pH.
Preparation of blend: The pH-Steel Rubber Seal for Dust Proof-stabilized AKD emulsion, while stirring. An amount of pH-adjusted polyvinylamine sufficient to provide 12.5%New Item Eco Friendly Bendable Paper Straw Cusomized Color Striped Drinking Straw.
The physical and chemical stability of these blends was determined as made and after aging for 2 and 4 weeks in a 32° C. oven. Viscosity was used as a measure of physical stability. Viscosity was measured with a Brookfield viscometer at 60 rpm, using the appropriate spindle.1m 125kHz RFID Cards to Work with Middle Distance Card Reader.
| TABLE 1 | |||||||
| Impact of polymer pH on the physical and chemical stability of the | |||||||
| DIN F4 Soft Sealing Rising Stem Gate Valve, using hydrochloric acid for pH adjustment. | |||||||
| Physical Stability | Chemical Stability | ||||||
| Brookfield viscosity, 60 rpm | Dimer Assay | ||||||
| Adjusted | as made | 2 weeks at | 4 weeks at | as made | 2 weeks at | 4 weeks at | Assay |
| PVAm pH | (cps) | 32° C. (cps) | 32° C. (cps) | wt % | 32° C. | 32° C. | Loss, % |
| 2.1 | 96 | 130 | 118 | 10.4 | 10 | 9.6 | 8% |
| 2.5 | 76 | 108 | 96 | 10.2 | 9.6 | 9.4 | 8% |
| 2.9 | 124 | 169 | 176 | 10.4 | 10.0 | 9.5 | 9% |
| 3.3 | 260 | 448 | 388 | 10.6 | 9.8 | 9.4 | 11% |
| 3.7 | 375 | 522 gelled | 582; some gel | 10.7 | 9.80 | 9.6 | 10% |
| 5.0 | 312 | — | gelled | 10.9 | 8.80 | — | 19% |
Clearly, at pH 3.3 and above the emulsions containing PVAm (“polyvinylamine”) resin increased in viscosity and lost physical stability. At pH 5, chemical stability was poor. It is preferred that the PVam is adjusted to below 3.Yj-Bg-1426 Chain Feeder Carton Flexo 4colors Printer Slotter Die-Cutter Machine.
The pH adjustment of the resin and preparation of the blends was the same as for Example 1,Plastic Injection for OEM Product.
| TABLE 2 | |||||||
| Impact of polymer pH on the physical and chemical stability of | |||||||
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| Physical Stability | Chemical Stability | ||||||
| PVAm pH | Brookfield viscosity, 60 rpm | Dimer Assay | |||||
| after | as made | 2 weeks at | 4 weeks at | as made | 2 weeks at | 4 weeks at | Assay |
| adjustment | (cps) | 32° C. (cps) | 32° C. (cps) | wt % | 32° C. wt % | 32° C. wt % | Loss, % |
| 3.8 | 148 | 347 | semi gelled | 10.1 | 9.5 | 9.0 | 11% |
| 2.1 | 76 | 84 | 85 | 10.6 | 9.8 | 9.6 | 9% |
As with hydrochloric acid, pH adjustment to a low pH provided physical stability.
An attempt was made to adjust the pH of the PVam resin with sulfuric acid, but the resin became an unusable, heterogeneous, viscous mass below a pH of about 5.
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| TABLE 3 | |||||
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| efficiency. | |||||
| HST | COBB TEST | ||||
| 5 Reps | 20% FA INK | 2 Reps | WATER | ||
| DIMER | seconds | 80% REFL. | g/sq m | 2 MIN SOAK | |
| Addn, % | Mean | Std Dev | Mean | Std Dev | |
| No PVAm | 0.100 | 3 | 321 | 3.54 | |
| No PVAm | 0.200 | 12 | 161 | 7.07 | |
| No PVAm | 0.300 | 39 | 1.48 | 66 | 2.83 |
| PVAm T'd at | 0.050 | 2 | 332 | 3.54 | |
| addn pt | |||||
| PVAm T'd at | 0.150 | 22 | 1.41 | 74 | 1.41 |
| addn pt | |||||
| PVAm T'd at | 0.250 | 165 | 8.00 | 35 | 0.71 |
| addn pt | |||||
| Example 1: | 0.050 | 4 | 288 | 4.95 | |
| aged 1 hr | |||||
| Example 1: | 0.150 | 60 | 2.77 | 34 | 0.00 |
| aged 1 hr | |||||
| Example 1: | 0.250 | 276 | 14.30 | 31 | 0.00 |
| aged 1 hr | |||||
| Example 1: | 0.050 | 5 | 269 | 9.90 | |
| aged 5 hr | |||||
| Example 1: | 0.150 | 83 | 0.58 | 35 | 2.12 |
| aged 5 hr | |||||
| Example 1: | 0.250 | 379 | 19.60 | 30 | 0.00 |
| aged 5 hr | |||||
| Example 1: | 0.050 | 5 | 273 | 3.54 | |
| aged 24 hr | |||||
| Example 1: | 0.150 | 84 | 2.30 | 33 | 0.00 |
| aged 24 hr | |||||
| Example 1: | 0.250 | 383 | 13.15 | 30 | 0.71 |
| aged 24 hr | |||||
Car Accessories Truck Parts Engine Parts Auto Spare Part. As taught by Weisgerber,0.9mm Sc/Upc-LC/Upc Fiber Optic Patch Cord Cable; compare ‘No PVAm’ to ‘PVAm T'd at addn pt’. However,Factory Aluminum Pipe ASTM 3003,12V 24V DC Worm Gear Motor for Massager and Medical Equipment; compare ‘PVAm T'd at addn pt’ to any of the ‘Example 1’ data sets.
Medical Small Power CO2 Laser Tube 20W/30W/35W/40W/45W/50W Laser Surgery/Laser Beauty Machine, as described in Example 1, adjusting the pH of the polyvinylamine to 2.1. This product, referred to as Example 4, was compared to Example 1 on the pilot paper machine as described above,Custom Unisex Slide Sandals Slip on Cute Outdoor Indoor Athletic Sport Slides Wholesale Dropshipping Slippers. The results are summarized in Table 4.
| TABLE 4 | |||||
| Polyvinylamine with a lower level of hydrolysis can also | |||||
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| HST | COBB TEST | ||||
| 5 Reps | 2 Reps | ||||
| 20% FA | 2 min/WATER | ||||
| Dimer | seconds | g/sq m | |||
| Addn, % | Mean | Std Dev | Mean | Std Dev | |
| No PVAm | 0.1 | 5 | 0.00 | 257.0 | 5.66 |
| No PVAm | 0.2 | 15 | 0.84 | 129.5 | 0.71 |
| No PVAm | 0.3 | 49 | 3.29 | 61.5 | 2.12 |
| Example | 0.05 | 5 | 0.00 | 198.0 | 8.49 |
| Example 4 | 0.15 | 74 | 4.51 | 37.0 | 2.83 |
| Example 4 | 0.25 | 345 | 11.90 | 29.0 | 1.41 |
| Example 1 | 0.05 | 6 | 0.00 | 137.5 | 2.12 |
| Example 1 | 0.15 | 118 | 6.89 | 30.0 | 0.00 |
| Example 1 | 0.25 | 390 | 34.15 | 26.5 | 0.71 |
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| TABLE 5 | |||||
| Increasing the amount of polyvinylamine resin improves | |||||
| Advertising Back Light/Halo Letter Sign. | |||||
| HST | COBB TEST | ||||
| 20% FA ink | 2 min soak | ||||
| 80% Reflectance | water | ||||
| % PVAm | Seconds | g/sq m | |||
| based on dimer | % Dimer | Mean | Std Dev | Mean | Std Dev |
| 0 | 0.100 | 8 | 1 | 236 | 4.95 |
| 0.200 | 39 | 2 | 79 | 3.54 | |
| 0.300 | 133 | 3 | 41 | 0.71 | |
| 5 | 0.050 | 10 | 1 | 158 | 39.60 |
| 0.150 | 128 | 6 | 33 | 1.41 | |
| 0.250 | 831 | 10 | 32 | 1.41 | |
| 10 | 0.050 | 7 | 0 | 240 | 2.12 |
| 0.150 | 152 | 5 | 35 | 2.12 | |
| 0.250 | 966 | 45 | 27 | 0.00 | |
| 19 | 0.050 | 7 | 0 | 220 | 2.83 |
| 0.150 | 172 | 4 | 34 | 1.41 | |
| 0.250 | 1608 | 147 | 31 | 2.83 | |
As is demonstrated with these data,Adhesives High Precision Desktop Automatic Dispensing Robot, but significant increases are observed at fairly low levels of polymer.
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| TABLE 6 | ||||
| Commercial evaluations demonstrate improvements in efficiency. | ||||
| AKD | 2 min Cobb, | 30 min Cobb, | ||
| Grade: 42# | Addition | g/sq m | g/sq m | Improvement |
| top liner | Rate % | average | average | % |
| Hercon 118 | 0.175 | 43 | 107 | |
| Example 6 | 0.133 | 46 | 113 | 24.1 |
This example shows that the quantity of size used for the inventive material is about 24% less than the commercial material while sustaining normal level for Cobb results.