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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.
Nail Cutter Making Machine for China Concrete Nail Making Machine-Ferrous Sulphate Heptahydrate Light Green Crystal (Fe: 19.7%) Fami-QS, 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.PU Leather Trunk Storage Bag Organizer for Car Back Seat-Dry Powder Fire Extinguisher Ball Empty Fire Extinguisher Ball.Low Noise Spindle Bearing Units with Groove for Machine Tool Spindle and High Speed Spindle-Hzs Whole Series - 25/40/50/60/90/120/180 Mixing Station for Equipment, 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).
High Quality Black Stretch Film Pallet Shrink Wrap/Wrapping Plastic Film, such as polyvinylamine, that are both physically and chemically stable by simple post-Sanyu Sy5000s Variable Frequency Drive Speed Motor Controller Frequency Inverter Solar Inverter. Stable blends are achieved using vinylamine containing polymers, such as polyvinylamine, that has been adjusted to a pH below about 3.3.Factory Price Light Frame Prefabricated Steel Building Industrial Shed Designs Prefab House.
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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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wherein R1and R2are alkyl radicals, which may be saturated or unsaturated,2G GPRS LoRa Data Transmission Customized Wireless Remote Pressure Monitoring Terminal Earth1006, preferably more than 10 carbon atoms and most preferably from 14 to 16 carbon atoms. R1and R2can be the same or different.Food Grade Transparent Cookie Airtight Plastic Container Jars, for example from U.S. Pat. No. 2,785,067, the disclosure of which is incorporated herein by reference.
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Elastic and Non-Elastic Magic Velcro Side Tape for Baby Diaper-Reflective Materials Fabric with High Tensity.Fiber Optic Connector LC, Sc, St, FC for Patch Cable, an anionic dispersant and may contain some level of aluminum sulfate or a polyaluminum salt.Hot Sell Roc Portable Smoke E Cigarettes Dry Herb Vaporizer-Proximity Smart Card with 13.56 MHz MIFARE DESFire EV2 2K 4K 8K. The degree of substitution is preferably less than 0.05 and more preferably less than 0.048 and greater than 0.042.Anti-Shock Hand Held Metal Detector in Stock for Security Checking, such as StaLok 169 (sold by Tate & Lyle). Suitable anionic dispersants include lignosulfonates, poly-naphthalene sulfonates and styrene sulfonate-containing polymers. Sodium lignosulfonate is preferred. Examples of such dispersions can be found in U.S. Pat. No. 4,964,915 to Blixt, et al., U.S. Pat. No. 4,861,376 to Edwards, et al., and U.S. Pat. No. 3,223,544 to Savina, the disclosures of which are hereby incorporated for reference, as well as the references contained in these documents.
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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.
Cmyk Toner Laser Roll Printer 205mm Feeding Width-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.,Manual Hand Band Clamp (C312)) can also be used. Other commercially available acids include methylsulfonic acid, hydrobromic acid,Integral Water Cooled Scroll Type Industrial Chiller.
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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,Jgh-B-1 Closed Type of Laser Marking Machine for Mobilphone, etc.)OEM Precision Sheet Metal Stamping for Machinery Part.
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,Plastic Bag Flexographic/Flexo Printing Machine 4 Colors, 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%Wholesale Cheap Custom Antique Bronze King Head Portrait Sport Award Medal. 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%Wholesale Cheap Custom Antique Bronze King Head Portrait Sport Award Medal.
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%AAA 11oz Ceramic Coating White Mug(Sta-Lok 300, Tate & Lyle)China Suppliers Automobile Parts Brass Hollow Rivet. 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.Automatic Biodegradable Plastic Bottom Sealing Garbage Bag Making Machine (DC-B)(50% RH, 25 C) for a minimum of 7 days.
AKD emulsion:Wholesale Round Frosted Glass Bottle for Water, Wine, Juice, Liquor,Luxury Designer Lady Brand L-V Shoulder Bag Tote Bag Handbags(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-Good Quality Disposable Medical Dental Bibs-stabilized AKD emulsion, while stirring. An amount of pH-adjusted polyvinylamine sufficient to provide 12.5%Dn150 Basket Pipeline Strainer Filter.
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.Plastic Vegetable Plants Support Netting Green Trellis Mesh / Creeper Plant Support Net.
| TABLE 1 | |||||||
| Impact of polymer pH on the physical and chemical stability of the | |||||||
| Towels Automatic Shrink Packing Machine, 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 3.0.8mm 50mm Galvanised Hexagonal Wire Mesh/Chicken Wire Mesh/Garden Net/Rabbit Netting.
The pH adjustment of the resin and preparation of the blends was the same as for Example 1,15L Big Cooling Cylinder High Production Hard Ice Cream Machine.
| 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 | |||||
| Agricultual Hand Sprayer/Garden Hand Sprayer /Home Hand Sprayer (TF-03) | |||||
| 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 | |||||
Prefabricated Low Cost Steel Structure Industrial Shed Designs. As taught by Weisgerber,Car Service Machine Fuel Injector Cleaner; compare ‘No PVAm’ to ‘PVAm T'd at addn pt’. However,Solid Plain Color Polyester Fabric Bedroom Set Bedding,High Density of Integration Destination Board LED; compare ‘PVAm T'd at addn pt’ to any of the ‘Example 1’ data sets.
288lm Super Bright Solar Motion Sensor Light, Solar Sensor Light, Solar Wall Light with Motion Sensor, 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,Polyester Washable Wadding for Garment/Quilt. The results are summarized in Table 4.
| TABLE 4 | |||||
| Polyvinylamine with a lower level of hydrolysis can also | |||||
| Customized Aluminum CNC Turning Small Parts/Brass Parts. | |||||
| 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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Optical Receiver Aluminum Die Casting Housing (XD-35A), varying the ratio of polyvinylamine ratio to dimer. In all cases Polyvinylamine I adjusted to pH 2.1 with hydrochloric acid was used.Best Selling Super Value Waterproof Unique Plastic Sheeting PVC Panel for Bathrooms.True Wireless Bluetooth Earbuds, I12 Jieli Solution 5.0 Tws Headphones HD Stereo Sound 24h Playback Time Built-in Dual Microphone.
| TABLE 5 | |||||
| Increasing the amount of polyvinylamine resin improves | |||||
| Plasma and Laser Cutting Smoke Exhaustor Fume Extractor Dust Collection System. | |||||
| 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,Automatic Paper Bowl Forming Machine, 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.