Patent Application
20080047678
A low molecular weight 90/10 mole % acrylamide/[2-(methyl-acryloyloxy ) ethyl]trimethylammonium chloride copolymer (AMD/Q6) was prepared by a free radical co-polymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 45.62 parts of 52.96% acrylamide solution, 10.45 parts of 75% Q6 solution, 2.4 parts of 2% sodium hypophosphite solution, and 53.93 parts of deionized water. The pH of the monomer solution was adjusted from 4.14 to 3.78 with a 20% solution of malic acid. The monomer solution was sparged with nitrogen for an hour before addition. The reactor vessel solution was prepared by addition of 278.46 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.63 to 3.76 with 0.57 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour.
The initiator solution was prepared by addition of 0.38 parts of ammonium persulfate into 7.87 parts of deionized water. This solution was sparged with nitrogen for half an hour just prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel 5 was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction.
The pH of the final product was equal to 3.1, bulk viscosity was equal to 90 cP (measured using Brookfield viscometer model DV-III, # 3 spindle, 12 rpm, at 25° C.) and viscosity of a 2% polymer solution was equal to 12 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.). Molecular weight of this polymer (Mw) is equal to 227,000 daltons.
A low molecular weight 90/10/5 mole % acrylamide/[2-(methylacryloyloxy)ethyl]trimethylammonium chloride/2-hydroxyethy methacrylate (AMD/Q6/HEMA) terpolymer was prepared by a free radical co-polymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 41.64 parts of 52.96% acrylamide solution, 10.11 parts of 75% Q6 solution, 2.44 parts of 97% HEMA solution, 2.4 parts of 2% sodium hypophosphite solution, and 55.86 parts of deionized water. The pH of this solution was equal to 3.82. The monomer solution was sparged with nitrogen for an hour before addition. The reactor vessel solution was prepared by mixing 278.27 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.47 to 3.63 with 0.76 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour just prior to use. The initiator solution was prepared by addition of 0.38 parts of ammonium persulfate into 7.87 parts of deionized water. This solution was sparged with nitrogen for half an hour prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction.
The pH of final product was equal to 3.1, bulk viscosity was equal to 70 cP (measured using Brookfield viscometer model DV-III, # 3 spindle, 12 rpm, at 25° C.) and viscosity of a 2% polymer solution was equal to 11 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.). Molecular weight of this polymer (Mw) is equal to 257,000 daltons.
Example 3
Evaluation of polymers from Example 1 and 2 was done by preparation of ASA emulsions with these polymers, characterization of the emulsion particle size distribution (Table 1), addition of these emulsions to the paper slurry, forming paper handsheets and measuring handsheets sizing (Table 2).
Emulsification of ASA Using Polymers
Alkenyl succinic anhydride (ASA) emulsions were prepared with polymers from example 1 and 2 at a 1/0.1 ASA/polymer ratio. Concentration of ASA during the emulsification was equal to 3.85 wt. %. ASA emulsions were prepared by following procedure:
Handsheets were prepared using a furnish of a 50/50 mixture of bleached hardwood and softwood kraft pulp refined to a Canadian Standard Freeness of 500 to which 15% by weight of precipitated calcium carbonate was added, and pH was adjusted to 7.8.
While mixing, a batch of 0.71% solids containing 10 g of cellulose fibers and calcium carbonate was treated with an ASA emulsion. After 60-sec contact time, an anionic retention aid was added and mixing continued for 15 sec. Three 2.8-g sheets of paper were formed using Standard (8″×8″) Nobel & Woods handsheet mold, to target basis weight of 50 Ib/Tappi Ream ,pressed between felts in the nip of a pneumatic roll press at about 15 psi and dried on the rotary dryer at 240° F. The dose of 3 lb/T of ASA and 1 lb/T of an anionic retention aid were applied.
Evaluation of Paper Sizing
The sizing of handsheets was tested using Bayer Ink Penetration test (BIP).
The BIP size testing method provides a fully automated application of ink to the under surface of the paper together with automatic measurement of the optical end point. This method uses the same principle as the TAPPI T 530 test but uses an instrument of our design, which provides an automated design and different geometry for light sources and detector. In particular, all steps of the BIP test were performed automatically with this apparatus. On the push of a start button, ink was pumped into a well until the ink contacted the under surface of the paper, determined electronically, and the timing of the ink penetration was obtained from a reflectance measurement and was displayed digitally. Neutral ink buffered to pH 7. 0 was used in all BIP testing and was prepared by dissolving 12. 5 g of naphthol green B dye in 500 mL of deionized water, and a pH 7 buffer solution was then added to bring the total volume to1000 mL at 23° C.
Handsheets were evaluated by the BIP test after a conditioning period of at least one day at 72 F and 50% relative humidity. Three handsheet specimens were tested, with two repetitions on each felt side, for a total of six tests.
To begin a BIP test, each paper specimen was inserted into the apparatus. A fiber optic source cable provided uniform illumination of the topside of the specimen.
A detector fiber optic cable viewed the same area of illumination. The initial reflectance of the specimen was determined automatically and stored for reference. The test ink was automatically metered by a metering pump from a reservoir into the bottom of a cone-shaped ink well until the ink contacted the underside of the paper specimen under test, at which time a timer was started electronically. The change in reflectance was periodically monitored automatically and the timer was stopped when a pre-specified percentage decrease in reflectance was reached. This decrease was about 20%, i. e., the specimen retained about 80% of its initial reflectance. The elapsed time of the test was displayed and recorded to the nearest second. Then a drain pump was started automatically and run for a period of time long enough to empty the ink in the well into a waste reservoir. The average test time for the three specimens on the felt side were calculated.
In Table 1 it is shown that ASA emulsion prepared with a polymer from Example 2 has smaller median particle size and narrower particle size distribution. In Table 2 it is shown that ASA emulsion prepared with polymer from Example 2 provides higher sizing than ASA emulsion prepared with a polymer from Example 1.
A low molecular weight 90/10/5/4 mole % acrylamide/[2-(methylacryloyloxy)ethyl]trimethylammonium chloride/2-hydroxyethy methacrylate/acrylic acid (AMD/Q6/HEMA/AA) tetrapolymer was prepared by a free radical co-polymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 99.13 parts of 52.96% acrylamide solution, 25.28 parts of 75% Q6 solution, 6.11 parts of 97% HEMA solution, 2.66 parts of 99% acrylic acid solution, 5.0 parts of 4% sodium hypophosphite solution, and 10.32 parts of deionized water. The pH of this solution was equal to 2.12. The monomer solution was sparged with nitrogen for an hour before addition. The reactor vessel solution was prepared by mixing 242.7 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.69 to 4.53 with 0.28 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour prior to use. The initiator solution was prepared by addition of 0.96 parts of ammonium persulfate into 7.28 parts of deionized water. This solution was sparged with nitrogen for half an hour prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction.
The pH of final product was equal to 2.03, bulk viscosity was equal to 2310 cP (measured using Brookfield viscometer model DV-III, # 3 spindle, 12 rpm, at 25° C.) and viscosity of a 2% polymer solution was equal to 7.0 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.). Molecular weight of this polymer (Mw) is equal to 212,000 daltons.
ASA emulsions were prepared with polymers from Examples 1, 2 and 4 at a 1/0.2 ASA/polymer ratio. Concentration of ASA during the emulsification was equal to 3.85 wt. %. ASA emulsions were prepared by the procedure described in Example 3 except that 0.8% polymer solution was used for emulsification. Handsheets were made and tested as it was described in Example 3.
In Table 3 it is shown that ASA emulsions prepared with a polymer from Example 2 and 4 have smaller median particle size and narrower particle size distribution than ASA emulsion prepared with a polymer from Example 1. Table 4 shows that ASA emulsified with polymers from Example 2 and 4 provides higher sizing than ASA emulsified with a polymer from Example 1.
ASA emulsion is prepared with a polymer from Example 4 at an ASA/polymer ratio of 1/0.2 and 1/1. These emulsions were compared to ASA emulsions prepared with conventional cationic starch at ASA/starch ratios of 1/0.2 and 1/1.
Emulsions were prepared as described in Example 3, except that a 0.8 wt. % polymer or starch solution was used to make an emulsion at 1/0.2 ASA/emulsifier ratio, and a 4 wt % solution of polymer or starch was used to make an emulsion at 1/1 ASA/emulsifier ratio. Stability of emulsions was checked after 2 hrs.
Handsheets were made and tested as it was described in Example 3.
At a 1/0.2 ASA/polymer ratio, ASA emulsion prepared with polymer from Example 4 has small median particle, narrow particle size distribution and is stable for at least two hours. This emulsion provides sizing of paper.
At the ratio of 1/0.2 ASA/starch, ASA emulsion has large median particle size, bimodal distribution and separates within 30 min. This emulsion doesn't provide sizing.
At the ratio of 1/1 of ASA/polymer and ASA/starch, ASA emulsions prepared with polymer and with starch have small median particle size and narrow particle size distribution, however ASA/starch emulsion is not useable after 2 hour, while ASA/polymer emulsion is not changed for at least two hours.
At 1/1 ratio, ASA emulsion prepared with starch outperforms emulsion prepared with polymer.
A high molecular weight 90/10 mole % acrylamide/ [2-(methylacryloyloxy)ethyl]trimethylammonium chloride copolymer (AMD/Q6) was prepared by a free radical co-polymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 45.62 parts of 52.96% acrylamide solution, 10.45 parts of 75% Q6 solution, and 56.30 parts of deionized water. The pH of the monomer solution was adjusted from 4.1 to 3.7 with 0.08 parts of 20% solution of malic acid. The monomer solution was sparged with nitrogen for an hour prior to addition. The reactor vessel solution was prepared by mixing 278.41 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.8 to 3.8 with 0.62 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour prior to addition.
The initiator solution was prepared by addition of 0.22 parts of ammonium persulfate into 8.03 parts of deionized water. This solution was sparged with nitrogen for half an hour prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction.
The pH of final product was equal to 3.05, bulk viscosity was equal to 2389 cP (measured using Brookfield viscometer model DV-III, # 3 spindle, 12 rpm, at 25° C.) and viscosity of a 2% polymer solution was equal to 62 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.). Molecular weight of this polymer (Mw) is equal to 1,000,000 daltons.
A high molecular weight 90/10/5 mole % acrylamide/ [2-(methylacryloyloxy) ethyl]trimethylammonium chloride/2-hydroxyethy methacrylate (AMD/Q6/HEMA) terpolymer was prepared by a free radical copolymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 41.64 parts of 52.96% acrylamide solution, 10.11 parts of 75% Q6 solution, 2.44 parts of 97% HEMA solution, and 58.26 parts of deionized water. The pH of this solution was equal to 3.62. The monomer solution was sparged with nitrogen for an hour before addition. The reactor vessel solution was prepared by mixing 278.30 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.87 to 3.81 with 0.73 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour prior to use.
The initiator solution was prepared by addition of 0.26 parts of ammonium persulfate into 7.99 parts of deionized water. This solution was sparged with nitrogen for half an hour prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction.
The pH of final product was equal to 3.16, bulk viscosity was equal to 1400 cP (measured using Brookfield viscometer model DV-III, # 3 lo spindle, 12 rpm, at 25° C.) and viscosity of a 2% polymer solution was equal to 50 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.). Molecular weight of this polymer (Mw) is equal. to 1,050,000 daltons.
ASA emulsions were prepared with polymers from Examples 7 and 8 at a 1/0.1 ASA/polymer ratio. Concentration of ASA during the emulsification was equal to 3.85 wt. %. ASA emulsions were prepared, and handsheets were made and tested as it was described in Example 3.
In Table 7 it is shown that an ASA emulsion prepared with the polymer from Example 8 has smaller median particle size than an emulsion prepared with the polymer from
Example 7. As it is shown in Table 8, sizing obtained with ASA emulsified Example 8 is significantly higher than sizing obtained with ASA emulsified with Example 7.
A high molecular weight 90/10/5 mole % acrylamide/[2-(methylacryloyloxy)ethyl]trimethylammonium chloride/2,3-dihydroxypropyl methacrylate (AMD/Q6/DHPMA) terpolymer was prepared by a free radical co-polymerization. The polymerization process was carried out by simultaneous, continuous addition of ammonium persulfate and monomer solutions to a reaction vessel that contained deionized water and chelating agent buffered with malic acid. The monomer solution was prepared by mixing 40.93 parts of 52.96% acrylamide solution, 9.93 parts of 75% Q6 solution, 2.87 parts of 100% DHPMA, and 58.66 parts of deionized water. The pH of this solution was adjusted from 4.9 to 4.05 with 0.6 parts of 20 % malic acid solution. The monomer solution was sparged with nitrogen for an hour before addition. The reactor vessel solution was prepared by mixing 278.65 parts of deionized water and 0.27 parts of 40% pentasodium diethylenepentaacetate. The pH of the reactor vessel solution was adjusted from 10.15 to 3.80 with 0.38 parts of 20% malic acid solution. The latter solution was sparged with nitrogen for an hour prior to addition.
The initiator solution was prepared by addition of 0.26 parts of ammonium persulfate into 7.99 parts of deionized water. This solution was sparged with nitrogen for half an hour prior to use. The addition of monomer solution and ammonium persulfate solution to the reactor vessel was carried out over 2.25 hr and 2.5 hr, respectively. The polymerization reaction was performed at 65° C. The reaction solution was maintained under the nitrogen purge throughout the course of reaction. The pH of final product was equal to 3.16, bulk viscosity was equal to 920 cP (measured using Brookfield viscometer model DV-III, # 3 spindle, 12 rpm, at 25° C.), and viscosity of a 2% polymer solution was equal to 39 cP (measured using Brookfield viscometer model DV-III, # 2 spindle, 30 rpm, at 25° C.).
ASA emulsions were prepared with polymers from Examples 7, 8 and 10 at a 1/0.1 ASA/polymer ratio. Concentration of ASA during the emulsification was equal to 7.4 wt. %. ASA emulsions were prepared as it was described in Example 3, except that 7.4 grams of ASA was added to 92.6 g of a 0.8 wt % polymer solution. Handsheets were made and tested as it was described in Example 3.
In Table 9 it is shown that ASA emulsions prepared with polymers from Example 8 and 10 have smaller median particle size than the emulsion prepared with the polymer from Example 7. As it is shown in Table 10, sizing obtained with ASA emulsified with polymers from Examples 8 and 10 is significantly higher than sizing obtained with ASA emulsified with the polymer from Example 7.
Although the present invention has been described in detail with reference to certain preferred versions thereof, other variations are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the versions contained therein.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US05/13334 | 4/19/2005 | WO | 00 | 6/17/2007 |
| Number | Date | Country | |
|---|---|---|---|
| 60580556 | Jun 2004 | US |
