CA2227605A1 - Synthetic cationic polymers as promoters for asa sizing - Google Patents
Synthetic cationic polymers as promoters for asa sizing Download PDFInfo
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- CA2227605A1 CA2227605A1 CA002227605A CA2227605A CA2227605A1 CA 2227605 A1 CA2227605 A1 CA 2227605A1 CA 002227605 A CA002227605 A CA 002227605A CA 2227605 A CA2227605 A CA 2227605A CA 2227605 A1 CA2227605 A1 CA 2227605A1
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
Synthetic cationic polymers are used as promoters for alkenyl succinic anhydride sizing. The addition of certain synthetic cationic polymers that are reactive with alkenyl succinic anhydride are shown to improve the sizing efficieny of the hydrophobic, cellulose sizing material in papermaking. Synthetic cationic polymers were intended to replace starch as an effective promoter in papermaking.
Description
CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 SYNTHETIC CATIONIC POLYMERS
AS PROMOTERS FQR ASA SIZING
Technical Field This invention relates to emulsions using synthetic cationic polymers as promoters for alkenyl succinic anhydride sizing, and more specifically to an emulsion containing alkenyl succinic anhydride and a synthetic cationic polymer that enhances sizing efficiency and a method of using the same.
R~:kground of the Invention Sizing agents in the papermaking process are used to promote reduced water and ink absorption in the paper product as well as to resist P~queous acid and alkaline solutions.
AS used herein, the temm "papef is conle",plated to include any sheet-like masses and molded products made from fibrous cellulosic materials which may be derived from both natural and synthetic sources.
Paper is often sized with various materials to increase resistance to water as well as to other types of aqueous solutions. These materials are referred to as sizes or sizing and they may be introduced during the actual papemmaking process. Alternatively, the sizes or sizing may be applied to the surface of the finished web or sheet.
One example of a sizing agent is alkenyl succinic anhydride ("ASA"). ASA, usefulin the sizing of cellulose materials, has gained considerable commercial success in papermaking, particularly as an alternative to the conventional rosin-alum sizing system.
The use of ASA as a sizing agent is well known in the art, as described in Farley and Wasser, "Sizing with Alkenyl Succinic Anhydride" in The Sizing of Paper, W.F. Reynolds, Ed., TAPPI, 1989, Chapter 3. See also U.S. Patent No. 3,968,005, which is incorporated herein by reference.
ASAis water insoluble and hydrolytically unstable. Therefore, it must be emulsified at the paper mill prior to use. Specifically, the art requires that for retention the sizing agents be used in conjunction with a material that is cationic in nature, or is capable of producing one or more cations or other positively charged groups. Emulsification is normally achieved by passing the ASA and a protective colloid, starch and/or synthetic polymer, through a device such as a homogenizer, high shear turbine pump, etc.
Cationic starch plays several important roles in ASA sizing. First, it aids in the generation of small particle size ASA emulsions. Small particle size, in the micron range, is required for good sizing efficiency. Second, it imparts good physical stability to the W O 97/05330 PCT~US96/12231 emulsion. ASA emulsions must be stable in order to prevent deposits and press picking once they have been added to the paper fumish. Third, it retains the emulsion on the fiber surfaces and promotes sizing efficiency. Sizing levels for a given amount ofASA are found to increase several-fold as the amount of cationic starch in the pulp fumish increases.
Normally, cationic starch is used at a ratio of 2 to 4 times that of the ASA to give optimum sizing efficiency.
Certain problems arise with the use of cationic starch, however. For example, the starch must be cooked at the mill, thus requiring large scale cooking equipment and storage tanks. More importantly, starch is susce,clillc to biological dey~dalion, resulting in slime growth and the creation of deposits on paper mill equipment, causing runnability pl.~ble",s in the fomm of press picking, felt filling and poor cylinder vat consislency control.
It may be desirable, in some cases, to make the ASA sizing system function independently of cationic starch. The variation in batch-to-batch starch viscosity and solids, and the need to cool the starch before emulsification can lead to unwanted variation in ASA
emulsion particle size. Some paper mills do not like to use starch because of the difficult cooking and handling requirements. Others, where fine paper grades are made and where much of the ASA sizes are currently being used, require cationic starch for dry strength, but the mills would prefer to use lower cost cationic com starches. Generally, more expensive cationic potato starch gives better results for ASA sizing.
Synthetic polymers as altematives to cationic starch for ASA emulsification, andspecitically to overcoming the problems associated with cationic starch, have been studied.
The synthetic cationic polymers of the art as altemative to starch are not reactive with ASA.
For example, U.S. Patent No. 4,657,946 teaches an improved emulsification of ASA sizing agent by using cationically charged water soluble vinyl addition polymers. The '946 patent teaches a paper sizing method and emulsion using cationically charged, water soluble, vinyl addition polymers and condensation polymers that provide improved emulsification of alkenyl succinic anhydride sizing agents. U.S. Patent No. 5,224,993 teaches a saponified sizing agent for paper derived from the dehydration condensation of an alkenyl succinic anhydfide and an organic carboxylic acid with a polyalkylene polyamine and the saponification of the remaining carboxyl groups with alkali following the dehydration condensation. U.S. Patent No. 4,629,655 teaches a size composition as a solid product produced by mixing a cation!c polymer suitable for functioning as a size retention aid and a size suitable for sizing a substrate. The process for sizing a substrate in the '655 patent comprises dispersing the solid in an aqueous mixture, applying the resultant mixture to a substrate, and causing the size to be fixed to the substrate thereby. However, the synthetic CA 0222760~ 1998-01-23 ~ 7 ~
1 7 ~~
cationic polymers of the art have only been marginally successful as a suitable replacement for starch. None of these synthetic cationic polymers contain functional groups that are reactive with ASA. The synthetic cationic polymers of the art which serve as additives and co-emulsifying agents for ASA sizing do not enhance sizing (or do not serve as good 5 promoters).
Various patents disclosing polymers that are reactive with ASA do not teach the use for promoting the efficiency of sizing agent. For example, these patents include U.S. Patent No. 5,232,553, which teaches a papermaking process using polyvinylaminals in which the paper product obtained from the pulp slurry contains fine particles of material. The '553 10 patent relates to the use of poly(vinylamine) and aldehyde for increasing the retention of the fines in the paper product.
In developing an altemative to starch in the ASA emulsions, it is generaily found that producing a synthetic cationic polymer having high viscosity to generate small particles size emulsions and acting as a retention aid is not particularly difficult. The difficulty lies in 15 developing a synthetic cationic polymer that promotes the sizing efficiency of ASA by providing ASA reactive groups that can anchor the ASA to the fiber surface.
Various other patents make use of similar synthetic cationic polymers but do notteach an increase in sizing efficiency in papermaking. An anhydrous dispersion of a polyelectrolyte in a liquid reactive size is claimed in EP-A-0 200 504. U.S. Patent No.
4,217,214 teaches the use of high molecular weight polyvinylamine hydrochloride for the flocculation of suspended solids in water purification or waste water clarification systems.
U.S. Patent Nos. 4,957,977 and 5,281,307 teach a paper strength increasing agent using a vinylamine copolymer. U.K. Patent Application GB 2,268,758A teaches a paper wet strength improvement by wet- or dry-end addition of an amine-functional poly(vinyl alcohol) and a cellulose reactive size which is a 4 or 5 membered cyclic ester or anhydride having one or more alkyl or alkenyl substituents of 4 or more carbon atoms and having a total of at least 8 carbon atoms in the substituents. In fact, patents that are directed to synthetic cationic polymers in the art do not specifically relate to increasing the efficiency of paper sizing.
While the synthetic agents of the art have met with some success, there has beena need in the paper industry to produce a more effective cationic agent that is useful as a promoter for sizing to avoid the problems generally associated with cationic starch. Such a cationic agent would be reactive with ASA and would significantly enhance sizing efficiency.
AMEt~iDED SHE~
CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 ~ummary of the Invention According to the present invention, there is provided methods in papemmaking forimproving the sizing efficiency of a hydrophobic, cellulose sizing material which co~ uri~es adding thereto a synthetic cationic polymer that is reactive with said sizing material. Groups that are reactive with ASA include primary amine and hydroxyl. The pr~t~rr~d sizing material is alkenyl succinic anhydride. The preferred synthetic cationic polymer comprises a copolymer of primary amine. Also provided is a synthetic cationic polymer which co, l - IS
one or more non-sizing reactive monomers, particularly, non-ASA reactive monomers, like acrylic acid. For the purpose of this invention, the term non-sizing reactive monomer (or non-ASA reactive monomer) refers to a monomer that does not result in a significant reaction with a sizing material. The synthetic cationic polymer may be a copolymer of vinyl alcohol and vinylamine. The synthetic cationic polymer may also be a copolymer of acrylamide and vinylamine.
There is also provided a method in papemmaking for improving the sizing efficiency of a hydrophobic, cellulose sizing material which comprises adding to a cellulose sizing agent an effective amount of a synthetic cationic polymer containing hydroxyl and/or primary amine groups. Preferably the polymer comprises about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
There is provided a method in papemmaking for improving the sizing efficiency of an alkenyl succinic anhydride comprising adding thereto a synthetic cationic polymer of about 20 to about 90 mole % acrylamide and about 80 to about 10 mole % vinylamine.
This invention discloses an alkaline sizing emulsion for improving the sizing efficiency in papermaking COI I ~pris;l ,9 a hydrophobic cellulose sizing material and a copolymer of cationic vinylamine that is reactive with said sizing material. Preferably, the sizing material is alkenyl succinic anhydride. It is preferable to have as a copolymer co"~p,isi"g a synthetic polymer of about 20 to about 90 mole % acrylamide and about 80 to about 10 mole % vinylamine. It is also preferable to have as a copolymer comprising a synthetic polymer of about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
There is also provided an alkaline sizing emulsion comprising an alkenyl succinic anhydride sizing material and an effective amount of a synthetic cationic polymer reactive with the sizing material wherein the polymer contains hydroxyl and/or primary amine groups.
As provided herein, the term "effective amount" is defined as the quantity of material needed to increase the sizing efficiency of a sizing agent.
CA 0222760~ 1998-01-23 Det~iled Description of the Preferred Embodiments Various synthetic cationic polymers were evaluated as replacements for cationic starch that is nommally used in the ASA paper sizing process. Cationic starch has been shown to be a good sizing promoter for ASA.
To del"on~lldLe the effect of various synthetic cationic polymers on ASA sizing promotion performance based on an increase in sizing efficiency using cationic starch were evaluated in comparison with a variety of different synthetic cationic polymers. It should be noted that starch is distinct from the synthetic cationic polymers because starch is a natural substance rather than synthetic.
Paper handsheets containing the size and promoter were prepared and used for sizing evaluation. For the purpose of this invention a handsheet is col"p~ised of pulp fillers, sizing agent (ASA) and promoter (a cationic starch or a synthetic cationic polymer).
Emulsification of ASA usin~ cationic polyacrylamide:
For each handsheet evaluation an ASA emulsion is prepared in deioni~ed water.
The emulsification procedure proceeds as follows: 24.0 9 of deionized water was weighed into a small (about 35 mL capacity) stainless steel blender jar. About 1 9 of ASA (~:~;9l ,ed by difference) is added and the blender is run at high speed for five minutes. Based on the c. ~ ted ASA conce~L~lion the sample was immediately diluted to 0.25% with cold pH
3 deionized water to rllilli~ e hydrolysis. The sample was kept on ice until used for the handsheet evaluation. Particle size was estimated to be in the 1.5 to 2 micron range.
A variety of synthetic cationic polymers containing copolymers of amide and amine groups as well as alcohol and amine groups are within the scope of the invention. Each of the polymers and copolymers was selected for evaluation because each containsfunctional groups (i.e. primary amine or hydroxyl) that can react with ASA.
Cationic polyvinylalcohol may contain 6 mole % vinylamine groups (PVOH/PVA) and have a molecular weight in the range of from 80 to 140 k daltons. The copolymer was prepared by hydrolysis of a copolymer of vinylacetate and N-vinyl fommamide.
Polyvinylamine (PVA) and polyvinylamine.HCI (PVA/HCI) are co"l~"~plaled as useful in this invention. The PVA is of a low molecular weight and is supplied as a 12.8% solution.
The PVA.HCI may be a medium molecular weight powder.
Polyallylamine.HCI (PAA) and copolymer of allylamine and diallylamine.HCI
(PAA/PDAA) are also contemplated as being useful in this invention. The PAA has an average molecular weight of about 100 k daltons and is supplied as a 40% aqueoussolution. The PAA/PDAA has a weight average molecular weight of 50 k daltons.
CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 The Hofmann degradation of polyacrylamide using sodium hypochlorite introduces primary amine and carboxyl groups. Samples were prepared colllail ,i"g about 40 mole %
primary amine using polyacrylamide samples of four different molecular weights ranging from 14 to 200 k daltons using the procedure from Tanaka (see, H. Tanaka, J. Polymer Science: Polymer Letters Edition 16, 87-89 (1978)).
Table I presents the Hofmann degradation products of polyacrylamide. In analyzing the amine and carboxyl contents of the Hofmann degradation products, it is shown that the variation in molecular weights does not significantly change the concenLrdlion of amine content, carboxyl content or isoelectric pH.
Table I
Molecular mole % mole %
FY~mple weight amine c~rboxyl Isoelectric pH
(k daltons) 4 14 47 14 8.5 In addition to ASA-reactive synthetic cationic polymers, various non ASA- reactive synthetic cationic polymers were conside,~d as plumoLe,~, for example, acrylamide/methacryloxyethyltnmethyl ammonium chloride (acrylamide/Q6) copolymer, polyethylenimine (polymer with average molecular weight of 50 to 60 k daltons, containing mostly secondary amine groups), Mannich quatemary of polyacrylamide, and terpolymers of acrylamide, acryloxyethyltrimethylammonium chloride (Q9) and alkyl methacrylate.
The ASA primarily used is ACCOSIZE~ 18 (available from Cytec Industries Inc.).
Promotion of ASA .~i7ing:
The sizing level achievable with ASA significantly increases (is promoted) as the amount of cationic starch in the system increases. The magnitude of the increase and that sizing continues to increase even with relatively large amount of cationic starch, up to 3:1 ratio of starch to ASA. Because of this effect, a high ratio of cationic starch to ASA is used in current commercial practice. It does not matter whether the cationic starch is part of the ASA emulsion or whether it is added separately to the furnish. As shown in this invention, the sizing level of an ASA sizing agent may also be significantly increased by increasing the concentration of synthetic cationic polymers that are reactive with ASA.
CA 0222760~ 1998-01-23 W O 97/05330 PCTrUS96/12231 H~ndsheet ev~ tion of polymers as ASA promoters The handsheet experiments are done usir~g the following procedure. The fumish is a 50t50 mixture of bleached hardwood and softwood kraft pulps beaten to a Canadian Standard Freeness of ~00 to which 15% by weight of pr~c;~.ilal~d calcium carbonate is added and the pH adjusted to 7.5. While stirring, a batch of 0.6% cons;slency stock containing 109 of fiber is treated with the promoter, followed by a given dosage of ASA
emulsion, then with 1.0 Ib/ton of anionic polyacrylamide retention aid. Fifteen seconds of contact time is allowed between each addition. Three-2.8 9 handsheets (50 Ib/Tappi ream) are fommed, pressed with 1-1/2 weights, and dried one minute on the rotary drum drier at 1 0 240~F.
Basis weight and sizing are measured on the sheets after conditioning for at least 24 hours at 23 ~C and 50% R.H. The handsheets are tested for ink penetration using a sizing test of the type described in Tappi Standard T-530 pm-83. It measures the elapsed time after contacting one side of the paper with ink for the reflectance of the opposite side to fall to 80% of its initial value. The ink is the same as described in T-530 pm-83, but contains no formic acid and is buffered to pH 7. The tests are nomlalized to 50 Ib/Tappi ream basis weight assuming sizing is prupo,lional to the cube of the basis weight.
While it is apparent that the invention herein disclosed is well cr'c~ ed to describe the invention stated above, it should well be appreciated that numerous modifications and embodiments may be devised by those skilled in the art, and it is intended that the appended claims cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
EXAMPLES 5 TO 14 (Comparative) Example 5 of Table ll shows the results of an evaluation of the ink penetration of an ASA emulsion made with a 90/10 mole ratio AMD/Q6 copolymer. This same emulsion was then post-diluted with either additional AMD/Q6 copolymer (a synthetic cationic polymer) or with cationic starch. The ASA dosage was 0.15% on fiber in all the examples.
Post-dilution with additional AMD/Q6 copolymer (Examples 6 to 9) shows that the sizing efficiency does not increase appreciably, since the copolymer is not reactive with ASA.
Examples 10 to 14 show that the AMD/Q6 copolymer post-diluted with cationic starch provided marked increase in sizing efficiency. As used herein, ink penetration is provided for in seconds. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive).
CA 0222760~ 1998-01-23 Table ll Post Dilution with Post Dilution with Ex~rnple C~tionic Polymer C~tionic St~rch Ink Penetration (Ratio to ASA) (Ratio to ASA) (sec) 5 (initial emulsion) 0.13 - 70 6 0.5 - 138 7 1.0 - 117 8 2.0 - 64 9 3.0 - 86 - 0.5 187 11 - 1.0 254 12 - 2.0 329 13 - 3.0 349 14 - 4.0 396 EXAMPLES 15 TO 23 (Comparative) Table lll p,~se~ results of an evaluation that is similar to that presented in Table Il. The 90/10 mole ratio AMD/Q6 copolymer of these examples is made by inverse 20 emulsion techniques. Example 15 shows the sizing obtained with ASA emulsion made using the AMD/Q6 copolymer. The ASA dosage is 0.15% on fiber in all the exa",pl~s. This same emulsion is then post diluted with either additional AMD/Q6 copolymer (Exanlp cs 16 to 18) or with cationic starch (Examples 19 to 23). These examples (Exdlllp Es 15 to 18) show that the addition of inverse emulsion AMD/Q6 copolymer does not increase sizing 25 efficiency since the copolymer is not reactive with ASA. Examples 19 to 23 show that the inverse AMD/Q6 copolymer diluted with cationic starch provided marked increase in sizing efficiency. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive).
Table lll Post Dilution with Post Dilution with F~rnple C~tionic Polymer Cationic St~rch Ink Penel,~lion (Ratio to ASA) (Ratio to ASA) (sec) 15(initial emulsion) 0.13 - 62 16 0.5 - 78 17 1.0 ~ 35 18 2.0 - 11 19 - 0.5 130 - 1.0 189 21 - 2.0 257 22 - 3.0 290 23 - 4.0 340 CA 0222760~ 1998-01-23 EXAMPLES 24 TO 32 (Comparative) Table IV shows the results of an evaluation that is similar to those presented in Tables ll and lll. In this case, the synthetic cationic copolymeris 99/1 mole ratio AMD/Q9.
An ASA emulsion is prepared using water only, Example 24. The ASA dosage was 0.125%
5 on fiber in all of the examples. This same emulsion is then post diluted with either AMD/Q9 copolymer (Examples 25 to 27) or with cationic starch (Examples 28 to 32). These examples demonstrate that the addition of AMD/Q9 copolymer does not increase sizing efficiency since the copolymer is not reactive with ASA. Post dilution with cationic starch provides a marked increase in sizing efliciency. It is shown that the effect of the increase 10 in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q9 copolymer (which is not ASA-reactive).
Table IV
Post Dilution with Post Dilution with FY~rnple Cationic Polymer Cationic Starch Ink Penetration (Ratio to ASA) (Ratio to ASA) (sec) 24 (initial emulsion) - - 6 0.5 - 8 26 1.0 - 4 27 2.0 - 5 29 - 0.6 77 - 1.2 89 31 - 2.4 157 32 - 4.8 179 EXAMPLES 33 TO 41 (Comparative) Table V shows that the results of an evaluation of sizing as a function of promoter dosage for various promoters. Each of the examples in Table V is conducted using 0.2%
on fiber of ASA. Examples 33 to 35 use a 18/20/2 mole percent terpolymer of acrylamide/Q9/n-dodecylmethacrylate terpolymer. This is a non-ASA reactive polymer.
Examples 36 to 38 use cationic potato starch as the promoter. Examples 39 to 41 use PVOH/PVA as the promoter. Ink penetration is provided for in seconds. These examples show that the promotion effect of PVOH/PVA, an ASA-reactive polymer, increases the sizing efficiency by increase in dosage.
CA 0222760~ 1998-0l-23 W O 97/OS330 PCTrUS96/12231 Table V
Dosage of E~rnple C~tionic Polymer Ink Penetration (% on fiber) (sec) 33 0.05 2 34 0.10 2 0.20 2 36 0.05 10 37 0.10 5 38 0.20 58 39 0.05 44 0.10 48 41 0.20 195 EXAMPLES 42 TO 49 (Comparative) Table Vl presents the results of an evaluation of the sizing as a function of promoter dosage for various promoters. Each of the exdr~'-s in Table Vl are conducted using 0.15% on fiber. Examples 4Z to 45 use cationic potato starch as the promoter. Examples 46 to 49 use PVOH/PVA as the promoter. Other parameters of this analysis are similar to those of Table V (Examples 33 to 41). Table Vl demon~lldtes that PVOH/PVA is a more effective promoter than cationic potato starch (over the range of 0.075 to 0.45 Ib/ton).
These examples show that the promoter efficiency is a function of promoter concentration.
Here, the PVOH/PVA is a much more effective promoter than cationic potato starch when the cationic polymer (either the synthetic cationic polymer or the starch) concentration is less than about 0.45% on fiber.
Table Vl Dosage of FY~rnple ~tionic Polymer Ink Penetration (% on Fiber) (sec) 42 0.075 160 43 0.15 157 44 0.30 194 0.45 222 46 0.075 251 47 0.15 269 48 0.30 315 49 0.45 214 CA 0222760~ 1998-01-23 W O 97/05330 PCTrUS96/12231 EXAMPLES 50 TO 55 (Comparative) Table Vll presents the results of an evaluation of sizing as a function of p~u~ult:r dosage for various promoters, as in Table V (Examples 3~ to 41). The emulsions of Table Vll are prepared in the presence of either the PVOH/PVA or the cationic potato starch at 5 0.5/1 ratio to ASA. After emulsification, additional PVOH/PVA or cationic potato starch is added to the furnish to give dosages of 0.075, 0.15 or 0.3% on fiber. Examples 50 to 52 use cationic potato starch as the promoter. Examples 53 to 55 use PVOHtPVA, an ASA-reactive polymer, as the promoter. These examples clell~onsll~le that the pru""~ter efficiency is a function of the sizing concentration and the reactivity of the promoter with the sizing material.
Table Vll Dosage of FY~rnple ~ tionic Polymer Ink Penetration (% on Fiber) (sec) 0.075 140 51 0.15 232 52 0.30 171 53 0.075 208 54 0.15 254 0.30 314 EXAMPLES 56 TO 70 (Comparative) Table Vlll shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table Vl (Examples 42 to 49). Examples 56 to 59 use polyethylenimine as the promoter. Example 60 to 63 use a Hofmann degradation product as the promoter (Table 1, Example 1). Exdmp'~s 64 to 66 use cationic potato starch as the promoter. Ex~lllp'~s 67 to 70 use PVOH/PVA as the promoter. These examples show that ASA-reactive synthetic cationic polymers (both PVOH/PVA and the Hofmann degradation product) provide promoting effect to ASA sizing. The polyethylenimine, which is not ASA-reactive, does not.
-CA 0222760~ 1998-01-23 Table Vl l l Dosage of Ex~mple C~tionic Polymer Ink Penetration (% on fiber) (sec) 56 0.075 2 57 0.15 4 58 0.30 2 59 0.45 2 0.075 28 61 0.15 92 62 0.30 242 63 0.45 184 64 0.075 111 0.15 144 66 0.45 282 67 0.075 225 68 0.15 285 69 0.30 434 0.45 350 EXAMPLES 71 TO 82 (Comparative) Table IX shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table Vl (ExdlllF'Es 42 to 49). The dosage of ASA is 0.2% on dry fiber. Examples 71 to 73 use a Mannich quatemary of polyacrylamide as the promoter. Examples 74 to 76 use cationic potato starch as the promoter. Examples 77 to 79 use PVOH/PVA as the promoter. Exdlllp'Es 80 to 82 use a Hofmann degradation product as the promoter (Table 1, Example 1). This experiment shows that the two ASA-reactive synthetic cationic polymers (PVOH/PVA and the Hofmann degradation product) provide promoting effect to sizing. The Mannich quatemary of polyacrylamide, which is not ASA-reactive, does not.
, CA 0222760~ 1998-01-23 WO 97/05330 PCT~US96/12231 Table IX
Dosage of FY~mple C~tionic Polymer Ink Penetration (% on fiber) (sec) 7t 0.075 2 72 0.15 2 73 0.3~ 2 74 0.15 7 0.30 24 76 0.45 101 77 0.0375 40 78 0.075 45 79 0.15 129 0.075 73 81 0.15 72 82 0.30 177 EXAMPLES 83 TO 106 (Comparative) Table X shows the results of an evaluation of sizing as a function of promoter dosage for various promoters as in Table Vl (Examples 42 to 49). 0.15% ASA on fiber is used. Examples 83 to 85 use PAA/PDAA of 50 k daltons molecular weight as the promoter. Examples 86 to 88 use PAA of 100 k daltons molecular weight as the promoter.
Examples 89 to 91 use a Hofmann degradation product of 14 k daltons molecular weight (Table 1 Example 4) as the promoter. Examples 92 to 94 use a Hofmann degradationproduct of 47 k daltons molecular weight (Table 1 Example 3) as the promoter. EXdmp'~s 95 to 97 use a Hofmann degradation product of 77 k daltons molecular weight (Table 1 Example 2) as the promoter. Examples 98 to 100 use a Hofmann degradation product of 200 k daltons molecular weight (Table 1 Example 1) as the promoter. Examples 101 to 103 use cationic potato starch as the promoter. Examples 104 to 106 use PVOH/PVA as the pru",~ter. These examples show that the promoting effect of the Hofmann degradation products increases with increasing molecular weight. Also these examples show that the promoting effect of the Hofmann degradation products increases with increasing amount of the p~u",oler with the sizing material.
CA 0222760~ 1998-01-23 WO 97/05330 PCT~US96112231 Table X
Dosage of FY~n1PIe C~tionic Polymer Ink Penetr~tion (% on fiber) (sec) 83 0.075 11 84 0.15 40 0.30 29 86 0.075 2 87 0.15 88 0.30 3 89 0.075 2 0.15 91 0.30 7 92 0.075 2 93 0.15 2 94 0.30 2 0.075 15 96 0.15 20 97 0.30 111 98 0.075 71 99 0.1~ 194 100 0.30 236 101 0.15 236 102 0.30 312 103 0.45 373 104 0.075 308 105 0.15 491 106 0.30 389 EXAMPLES 107 TO 130 (Comparative) Table Xl shows the comparative results of an evaluation of the ink penetration as a function of promoter dosage for various promoters, as in Table X (Examples 83 to 106).
Examples 107 to 109 use a Hofmann degradation product of 14 k daltons molecular weight (Table 1, Example 4) and Examples 110 to 112 use a Hofmann degradation product of 47 k daltons molecular weight (Table 1, Example 3) as the promoter. Examples 113 to 115 use a Hofmann degradation product of 77 k daltons (Table 1, Example 2) as the promoter.
Examples 116 to 118 use a Hofmann degradation product of 200 k daltons molecular -W O 97/05330 PCTrUS96/12231 weight (Table 1, Example 1) as the promoter. Examples 119 to 121 use PVA as the promoter. Examples 122 to 124 use PVA.HCI as the promoter. Examples 125 to 127 use PVOH/PVA as the promoter. Eka"~p'es 128 to 130 use cationic potato starch as thepromoter. These examples show that both PVA and PVA.HCI are effective promoters for 5 ASA. Both are ASA-reactive. It again shows that PVOH/PVA is an effective promoter, and that the effectiveness of the Hofmann degradation products increase with increasing molecular weight.
Table Xl Dosage of Fx~rnple C:~tionic Polymer Ink Penetr~tion (% on fiber) (sec) 107 0.30 4 108 0.45 5 109 0.60 60 110 0.30 111 0.45 112 0.60 113 0.15 6 114 0.30 24 115 0.45 127 116 0.075 194 117 0.15 153 118 0.225 240 119 0.15 258 120 0.30 449 121 0.45 260 122 0.15 129 123 0.30 477 124 0.45 406 125 0.0375 178 126 0.075 280 127 0.15 337 128 0.15 108 129 0.30 334 130 0.45 326 CA 0222760~ 1998-01-23 EXAMPLES 131 TO 154 (Comparative) Table Xll presents a further co",pa,~live evaluation of PVOH/PVA polymer as a sizing promoter for ASA. The performance of PVOH/PVA polymer as sizing promoter is compared to the use of cationic starch as the promoter. The synthetic polymer is evaluated 5 under varying mole percent of PVA in the PVAtPVOH polymer as well as under varying molecular weight and dosage of the PVAtPVOH polymer. Each evaluation is conducted using 0.15 mole % on fiber of ASA. It is shown that at higher PVA mole % content (i.e.
at 6 or 18 mole %) the PVOHtPVA promoter is more efficient than cationic starch. At levels of 3 mole % of PVA or less the copolymer is not effective as a promoter. It is also 10 shown that better efficiency is obtained with higher molecular weight samples.
Table Xll Cationic Molecular Ink FY~rnr'~ PVA ~h W~i~ht ~Q~g~ PenetrAtinr~
mole % (% on fiber) (k daltons) (% on fiber) (sec) 131 <1 -- 50-120 0.15 132 <1 -- 50-120 0.30 133 <1 -- 50-120 0.45 134 3 -- 50-120 0.15 135 3 50-120 0.30 136 3 -- 50-120 0.45 137 6 -- 36 0.0375 5.5 138 6 -- 36 0.075 21 139 6 -- 36 0.15 48 140 6 -- 95 0.0375 141 6 -- 95 0.075 23 142 6 -- 95 0.15 98 143 6 -- 80-140 0.0375 47 144 6 -- 80-140 0.075 119 145 6 -- 80-140 0.15 378 146 18 -- 75 0.0375 30 147 18 -- 75 0.075 259 148 18 -- 75 0.15 204 149 -- 0.15 -- -- 34 150 -- 0.15 -- -- 13.6 151 -- 0.30 -- -- 239 152 -- 0.30 -- -- 271 153 -- 0.45 -- -- 275 154 -- 0.45 -- -- 540 CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 EXAMPLES 1~5 TO 159 (Comparative) The paper that is used for the exampies in Table Xlll is made on a pilot paper machine. The ASA is emulsified either with a copolymer of acrylamide/methyl chloride quaternary salt of dimethylaminoethyl methacrylate (AMD/Q6) or with cationic potato starch.
5 The emulsion is added to the pulp at the down leg of the stuff box. ASA dosage is kept constant at 0.175%. The fumish is 70130 bleached hardwoodlsoftwood with 25% (on dry fiber) added precipitated CaCO3. In Example 155, the AMD/Q6 copolymer is provided in a final ratio to ASA of 0.13/1. In Example 156, the total AMD/Q6 copolyrner is provided as in Example 155, but with additional polymer addition bringing the final ratio of AMD/Q6 to ASA as 1.0/1. In Example 157, the ASA emulsion is made using a 90/10 AMD/Q6 inverse emulsion copolymer, with a final polymer/ASA ratio of 0.13/1. The result of these three examples show the average sizing for Examples 155, 156 and 157 as 20, 41 and 5 secon~s, respectively. This demon~lldles that the sizing was low, relative to the standard emulsions. Increasing the level of copolymer from 0.13:1 to 1:1 resulted only in a small 15 increase in sizing. It is shown that synthetic cationic polymers do not give sizing (or increase sizing efficiency) if the polymer is not reactive with the sizing material. In comparison, Examples 158 and 159 are ASA emulsions made using cationic starch in a ratio to ASA of 2.1/1. The much higher sizing values show the promoting effect of the ASA
reactive cationic starch.
Table Xlll Ratio of Ratio of FY~m~le CAtionic StArch CAtionic Polymer Ink PenetrAtion (sec~
155 - 0.13 20 156 - 1.0 41 157 - 0.13 5 1~8 2.1 - 225 159 2.1 - 219
AS PROMOTERS FQR ASA SIZING
Technical Field This invention relates to emulsions using synthetic cationic polymers as promoters for alkenyl succinic anhydride sizing, and more specifically to an emulsion containing alkenyl succinic anhydride and a synthetic cationic polymer that enhances sizing efficiency and a method of using the same.
R~:kground of the Invention Sizing agents in the papermaking process are used to promote reduced water and ink absorption in the paper product as well as to resist P~queous acid and alkaline solutions.
AS used herein, the temm "papef is conle",plated to include any sheet-like masses and molded products made from fibrous cellulosic materials which may be derived from both natural and synthetic sources.
Paper is often sized with various materials to increase resistance to water as well as to other types of aqueous solutions. These materials are referred to as sizes or sizing and they may be introduced during the actual papemmaking process. Alternatively, the sizes or sizing may be applied to the surface of the finished web or sheet.
One example of a sizing agent is alkenyl succinic anhydride ("ASA"). ASA, usefulin the sizing of cellulose materials, has gained considerable commercial success in papermaking, particularly as an alternative to the conventional rosin-alum sizing system.
The use of ASA as a sizing agent is well known in the art, as described in Farley and Wasser, "Sizing with Alkenyl Succinic Anhydride" in The Sizing of Paper, W.F. Reynolds, Ed., TAPPI, 1989, Chapter 3. See also U.S. Patent No. 3,968,005, which is incorporated herein by reference.
ASAis water insoluble and hydrolytically unstable. Therefore, it must be emulsified at the paper mill prior to use. Specifically, the art requires that for retention the sizing agents be used in conjunction with a material that is cationic in nature, or is capable of producing one or more cations or other positively charged groups. Emulsification is normally achieved by passing the ASA and a protective colloid, starch and/or synthetic polymer, through a device such as a homogenizer, high shear turbine pump, etc.
Cationic starch plays several important roles in ASA sizing. First, it aids in the generation of small particle size ASA emulsions. Small particle size, in the micron range, is required for good sizing efficiency. Second, it imparts good physical stability to the W O 97/05330 PCT~US96/12231 emulsion. ASA emulsions must be stable in order to prevent deposits and press picking once they have been added to the paper fumish. Third, it retains the emulsion on the fiber surfaces and promotes sizing efficiency. Sizing levels for a given amount ofASA are found to increase several-fold as the amount of cationic starch in the pulp fumish increases.
Normally, cationic starch is used at a ratio of 2 to 4 times that of the ASA to give optimum sizing efficiency.
Certain problems arise with the use of cationic starch, however. For example, the starch must be cooked at the mill, thus requiring large scale cooking equipment and storage tanks. More importantly, starch is susce,clillc to biological dey~dalion, resulting in slime growth and the creation of deposits on paper mill equipment, causing runnability pl.~ble",s in the fomm of press picking, felt filling and poor cylinder vat consislency control.
It may be desirable, in some cases, to make the ASA sizing system function independently of cationic starch. The variation in batch-to-batch starch viscosity and solids, and the need to cool the starch before emulsification can lead to unwanted variation in ASA
emulsion particle size. Some paper mills do not like to use starch because of the difficult cooking and handling requirements. Others, where fine paper grades are made and where much of the ASA sizes are currently being used, require cationic starch for dry strength, but the mills would prefer to use lower cost cationic com starches. Generally, more expensive cationic potato starch gives better results for ASA sizing.
Synthetic polymers as altematives to cationic starch for ASA emulsification, andspecitically to overcoming the problems associated with cationic starch, have been studied.
The synthetic cationic polymers of the art as altemative to starch are not reactive with ASA.
For example, U.S. Patent No. 4,657,946 teaches an improved emulsification of ASA sizing agent by using cationically charged water soluble vinyl addition polymers. The '946 patent teaches a paper sizing method and emulsion using cationically charged, water soluble, vinyl addition polymers and condensation polymers that provide improved emulsification of alkenyl succinic anhydride sizing agents. U.S. Patent No. 5,224,993 teaches a saponified sizing agent for paper derived from the dehydration condensation of an alkenyl succinic anhydfide and an organic carboxylic acid with a polyalkylene polyamine and the saponification of the remaining carboxyl groups with alkali following the dehydration condensation. U.S. Patent No. 4,629,655 teaches a size composition as a solid product produced by mixing a cation!c polymer suitable for functioning as a size retention aid and a size suitable for sizing a substrate. The process for sizing a substrate in the '655 patent comprises dispersing the solid in an aqueous mixture, applying the resultant mixture to a substrate, and causing the size to be fixed to the substrate thereby. However, the synthetic CA 0222760~ 1998-01-23 ~ 7 ~
1 7 ~~
cationic polymers of the art have only been marginally successful as a suitable replacement for starch. None of these synthetic cationic polymers contain functional groups that are reactive with ASA. The synthetic cationic polymers of the art which serve as additives and co-emulsifying agents for ASA sizing do not enhance sizing (or do not serve as good 5 promoters).
Various patents disclosing polymers that are reactive with ASA do not teach the use for promoting the efficiency of sizing agent. For example, these patents include U.S. Patent No. 5,232,553, which teaches a papermaking process using polyvinylaminals in which the paper product obtained from the pulp slurry contains fine particles of material. The '553 10 patent relates to the use of poly(vinylamine) and aldehyde for increasing the retention of the fines in the paper product.
In developing an altemative to starch in the ASA emulsions, it is generaily found that producing a synthetic cationic polymer having high viscosity to generate small particles size emulsions and acting as a retention aid is not particularly difficult. The difficulty lies in 15 developing a synthetic cationic polymer that promotes the sizing efficiency of ASA by providing ASA reactive groups that can anchor the ASA to the fiber surface.
Various other patents make use of similar synthetic cationic polymers but do notteach an increase in sizing efficiency in papermaking. An anhydrous dispersion of a polyelectrolyte in a liquid reactive size is claimed in EP-A-0 200 504. U.S. Patent No.
4,217,214 teaches the use of high molecular weight polyvinylamine hydrochloride for the flocculation of suspended solids in water purification or waste water clarification systems.
U.S. Patent Nos. 4,957,977 and 5,281,307 teach a paper strength increasing agent using a vinylamine copolymer. U.K. Patent Application GB 2,268,758A teaches a paper wet strength improvement by wet- or dry-end addition of an amine-functional poly(vinyl alcohol) and a cellulose reactive size which is a 4 or 5 membered cyclic ester or anhydride having one or more alkyl or alkenyl substituents of 4 or more carbon atoms and having a total of at least 8 carbon atoms in the substituents. In fact, patents that are directed to synthetic cationic polymers in the art do not specifically relate to increasing the efficiency of paper sizing.
While the synthetic agents of the art have met with some success, there has beena need in the paper industry to produce a more effective cationic agent that is useful as a promoter for sizing to avoid the problems generally associated with cationic starch. Such a cationic agent would be reactive with ASA and would significantly enhance sizing efficiency.
AMEt~iDED SHE~
CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 ~ummary of the Invention According to the present invention, there is provided methods in papemmaking forimproving the sizing efficiency of a hydrophobic, cellulose sizing material which co~ uri~es adding thereto a synthetic cationic polymer that is reactive with said sizing material. Groups that are reactive with ASA include primary amine and hydroxyl. The pr~t~rr~d sizing material is alkenyl succinic anhydride. The preferred synthetic cationic polymer comprises a copolymer of primary amine. Also provided is a synthetic cationic polymer which co, l - IS
one or more non-sizing reactive monomers, particularly, non-ASA reactive monomers, like acrylic acid. For the purpose of this invention, the term non-sizing reactive monomer (or non-ASA reactive monomer) refers to a monomer that does not result in a significant reaction with a sizing material. The synthetic cationic polymer may be a copolymer of vinyl alcohol and vinylamine. The synthetic cationic polymer may also be a copolymer of acrylamide and vinylamine.
There is also provided a method in papemmaking for improving the sizing efficiency of a hydrophobic, cellulose sizing material which comprises adding to a cellulose sizing agent an effective amount of a synthetic cationic polymer containing hydroxyl and/or primary amine groups. Preferably the polymer comprises about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
There is provided a method in papemmaking for improving the sizing efficiency of an alkenyl succinic anhydride comprising adding thereto a synthetic cationic polymer of about 20 to about 90 mole % acrylamide and about 80 to about 10 mole % vinylamine.
This invention discloses an alkaline sizing emulsion for improving the sizing efficiency in papermaking COI I ~pris;l ,9 a hydrophobic cellulose sizing material and a copolymer of cationic vinylamine that is reactive with said sizing material. Preferably, the sizing material is alkenyl succinic anhydride. It is preferable to have as a copolymer co"~p,isi"g a synthetic polymer of about 20 to about 90 mole % acrylamide and about 80 to about 10 mole % vinylamine. It is also preferable to have as a copolymer comprising a synthetic polymer of about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
There is also provided an alkaline sizing emulsion comprising an alkenyl succinic anhydride sizing material and an effective amount of a synthetic cationic polymer reactive with the sizing material wherein the polymer contains hydroxyl and/or primary amine groups.
As provided herein, the term "effective amount" is defined as the quantity of material needed to increase the sizing efficiency of a sizing agent.
CA 0222760~ 1998-01-23 Det~iled Description of the Preferred Embodiments Various synthetic cationic polymers were evaluated as replacements for cationic starch that is nommally used in the ASA paper sizing process. Cationic starch has been shown to be a good sizing promoter for ASA.
To del"on~lldLe the effect of various synthetic cationic polymers on ASA sizing promotion performance based on an increase in sizing efficiency using cationic starch were evaluated in comparison with a variety of different synthetic cationic polymers. It should be noted that starch is distinct from the synthetic cationic polymers because starch is a natural substance rather than synthetic.
Paper handsheets containing the size and promoter were prepared and used for sizing evaluation. For the purpose of this invention a handsheet is col"p~ised of pulp fillers, sizing agent (ASA) and promoter (a cationic starch or a synthetic cationic polymer).
Emulsification of ASA usin~ cationic polyacrylamide:
For each handsheet evaluation an ASA emulsion is prepared in deioni~ed water.
The emulsification procedure proceeds as follows: 24.0 9 of deionized water was weighed into a small (about 35 mL capacity) stainless steel blender jar. About 1 9 of ASA (~:~;9l ,ed by difference) is added and the blender is run at high speed for five minutes. Based on the c. ~ ted ASA conce~L~lion the sample was immediately diluted to 0.25% with cold pH
3 deionized water to rllilli~ e hydrolysis. The sample was kept on ice until used for the handsheet evaluation. Particle size was estimated to be in the 1.5 to 2 micron range.
A variety of synthetic cationic polymers containing copolymers of amide and amine groups as well as alcohol and amine groups are within the scope of the invention. Each of the polymers and copolymers was selected for evaluation because each containsfunctional groups (i.e. primary amine or hydroxyl) that can react with ASA.
Cationic polyvinylalcohol may contain 6 mole % vinylamine groups (PVOH/PVA) and have a molecular weight in the range of from 80 to 140 k daltons. The copolymer was prepared by hydrolysis of a copolymer of vinylacetate and N-vinyl fommamide.
Polyvinylamine (PVA) and polyvinylamine.HCI (PVA/HCI) are co"l~"~plaled as useful in this invention. The PVA is of a low molecular weight and is supplied as a 12.8% solution.
The PVA.HCI may be a medium molecular weight powder.
Polyallylamine.HCI (PAA) and copolymer of allylamine and diallylamine.HCI
(PAA/PDAA) are also contemplated as being useful in this invention. The PAA has an average molecular weight of about 100 k daltons and is supplied as a 40% aqueoussolution. The PAA/PDAA has a weight average molecular weight of 50 k daltons.
CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 The Hofmann degradation of polyacrylamide using sodium hypochlorite introduces primary amine and carboxyl groups. Samples were prepared colllail ,i"g about 40 mole %
primary amine using polyacrylamide samples of four different molecular weights ranging from 14 to 200 k daltons using the procedure from Tanaka (see, H. Tanaka, J. Polymer Science: Polymer Letters Edition 16, 87-89 (1978)).
Table I presents the Hofmann degradation products of polyacrylamide. In analyzing the amine and carboxyl contents of the Hofmann degradation products, it is shown that the variation in molecular weights does not significantly change the concenLrdlion of amine content, carboxyl content or isoelectric pH.
Table I
Molecular mole % mole %
FY~mple weight amine c~rboxyl Isoelectric pH
(k daltons) 4 14 47 14 8.5 In addition to ASA-reactive synthetic cationic polymers, various non ASA- reactive synthetic cationic polymers were conside,~d as plumoLe,~, for example, acrylamide/methacryloxyethyltnmethyl ammonium chloride (acrylamide/Q6) copolymer, polyethylenimine (polymer with average molecular weight of 50 to 60 k daltons, containing mostly secondary amine groups), Mannich quatemary of polyacrylamide, and terpolymers of acrylamide, acryloxyethyltrimethylammonium chloride (Q9) and alkyl methacrylate.
The ASA primarily used is ACCOSIZE~ 18 (available from Cytec Industries Inc.).
Promotion of ASA .~i7ing:
The sizing level achievable with ASA significantly increases (is promoted) as the amount of cationic starch in the system increases. The magnitude of the increase and that sizing continues to increase even with relatively large amount of cationic starch, up to 3:1 ratio of starch to ASA. Because of this effect, a high ratio of cationic starch to ASA is used in current commercial practice. It does not matter whether the cationic starch is part of the ASA emulsion or whether it is added separately to the furnish. As shown in this invention, the sizing level of an ASA sizing agent may also be significantly increased by increasing the concentration of synthetic cationic polymers that are reactive with ASA.
CA 0222760~ 1998-01-23 W O 97/05330 PCTrUS96/12231 H~ndsheet ev~ tion of polymers as ASA promoters The handsheet experiments are done usir~g the following procedure. The fumish is a 50t50 mixture of bleached hardwood and softwood kraft pulps beaten to a Canadian Standard Freeness of ~00 to which 15% by weight of pr~c;~.ilal~d calcium carbonate is added and the pH adjusted to 7.5. While stirring, a batch of 0.6% cons;slency stock containing 109 of fiber is treated with the promoter, followed by a given dosage of ASA
emulsion, then with 1.0 Ib/ton of anionic polyacrylamide retention aid. Fifteen seconds of contact time is allowed between each addition. Three-2.8 9 handsheets (50 Ib/Tappi ream) are fommed, pressed with 1-1/2 weights, and dried one minute on the rotary drum drier at 1 0 240~F.
Basis weight and sizing are measured on the sheets after conditioning for at least 24 hours at 23 ~C and 50% R.H. The handsheets are tested for ink penetration using a sizing test of the type described in Tappi Standard T-530 pm-83. It measures the elapsed time after contacting one side of the paper with ink for the reflectance of the opposite side to fall to 80% of its initial value. The ink is the same as described in T-530 pm-83, but contains no formic acid and is buffered to pH 7. The tests are nomlalized to 50 Ib/Tappi ream basis weight assuming sizing is prupo,lional to the cube of the basis weight.
While it is apparent that the invention herein disclosed is well cr'c~ ed to describe the invention stated above, it should well be appreciated that numerous modifications and embodiments may be devised by those skilled in the art, and it is intended that the appended claims cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
EXAMPLES 5 TO 14 (Comparative) Example 5 of Table ll shows the results of an evaluation of the ink penetration of an ASA emulsion made with a 90/10 mole ratio AMD/Q6 copolymer. This same emulsion was then post-diluted with either additional AMD/Q6 copolymer (a synthetic cationic polymer) or with cationic starch. The ASA dosage was 0.15% on fiber in all the examples.
Post-dilution with additional AMD/Q6 copolymer (Examples 6 to 9) shows that the sizing efficiency does not increase appreciably, since the copolymer is not reactive with ASA.
Examples 10 to 14 show that the AMD/Q6 copolymer post-diluted with cationic starch provided marked increase in sizing efficiency. As used herein, ink penetration is provided for in seconds. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive).
CA 0222760~ 1998-01-23 Table ll Post Dilution with Post Dilution with Ex~rnple C~tionic Polymer C~tionic St~rch Ink Penetration (Ratio to ASA) (Ratio to ASA) (sec) 5 (initial emulsion) 0.13 - 70 6 0.5 - 138 7 1.0 - 117 8 2.0 - 64 9 3.0 - 86 - 0.5 187 11 - 1.0 254 12 - 2.0 329 13 - 3.0 349 14 - 4.0 396 EXAMPLES 15 TO 23 (Comparative) Table lll p,~se~ results of an evaluation that is similar to that presented in Table Il. The 90/10 mole ratio AMD/Q6 copolymer of these examples is made by inverse 20 emulsion techniques. Example 15 shows the sizing obtained with ASA emulsion made using the AMD/Q6 copolymer. The ASA dosage is 0.15% on fiber in all the exa",pl~s. This same emulsion is then post diluted with either additional AMD/Q6 copolymer (Exanlp cs 16 to 18) or with cationic starch (Examples 19 to 23). These examples (Exdlllp Es 15 to 18) show that the addition of inverse emulsion AMD/Q6 copolymer does not increase sizing 25 efficiency since the copolymer is not reactive with ASA. Examples 19 to 23 show that the inverse AMD/Q6 copolymer diluted with cationic starch provided marked increase in sizing efficiency. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive).
Table lll Post Dilution with Post Dilution with F~rnple C~tionic Polymer Cationic St~rch Ink Penel,~lion (Ratio to ASA) (Ratio to ASA) (sec) 15(initial emulsion) 0.13 - 62 16 0.5 - 78 17 1.0 ~ 35 18 2.0 - 11 19 - 0.5 130 - 1.0 189 21 - 2.0 257 22 - 3.0 290 23 - 4.0 340 CA 0222760~ 1998-01-23 EXAMPLES 24 TO 32 (Comparative) Table IV shows the results of an evaluation that is similar to those presented in Tables ll and lll. In this case, the synthetic cationic copolymeris 99/1 mole ratio AMD/Q9.
An ASA emulsion is prepared using water only, Example 24. The ASA dosage was 0.125%
5 on fiber in all of the examples. This same emulsion is then post diluted with either AMD/Q9 copolymer (Examples 25 to 27) or with cationic starch (Examples 28 to 32). These examples demonstrate that the addition of AMD/Q9 copolymer does not increase sizing efficiency since the copolymer is not reactive with ASA. Post dilution with cationic starch provides a marked increase in sizing efliciency. It is shown that the effect of the increase 10 in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q9 copolymer (which is not ASA-reactive).
Table IV
Post Dilution with Post Dilution with FY~rnple Cationic Polymer Cationic Starch Ink Penetration (Ratio to ASA) (Ratio to ASA) (sec) 24 (initial emulsion) - - 6 0.5 - 8 26 1.0 - 4 27 2.0 - 5 29 - 0.6 77 - 1.2 89 31 - 2.4 157 32 - 4.8 179 EXAMPLES 33 TO 41 (Comparative) Table V shows that the results of an evaluation of sizing as a function of promoter dosage for various promoters. Each of the examples in Table V is conducted using 0.2%
on fiber of ASA. Examples 33 to 35 use a 18/20/2 mole percent terpolymer of acrylamide/Q9/n-dodecylmethacrylate terpolymer. This is a non-ASA reactive polymer.
Examples 36 to 38 use cationic potato starch as the promoter. Examples 39 to 41 use PVOH/PVA as the promoter. Ink penetration is provided for in seconds. These examples show that the promotion effect of PVOH/PVA, an ASA-reactive polymer, increases the sizing efficiency by increase in dosage.
CA 0222760~ 1998-0l-23 W O 97/OS330 PCTrUS96/12231 Table V
Dosage of E~rnple C~tionic Polymer Ink Penetration (% on fiber) (sec) 33 0.05 2 34 0.10 2 0.20 2 36 0.05 10 37 0.10 5 38 0.20 58 39 0.05 44 0.10 48 41 0.20 195 EXAMPLES 42 TO 49 (Comparative) Table Vl presents the results of an evaluation of the sizing as a function of promoter dosage for various promoters. Each of the exdr~'-s in Table Vl are conducted using 0.15% on fiber. Examples 4Z to 45 use cationic potato starch as the promoter. Examples 46 to 49 use PVOH/PVA as the promoter. Other parameters of this analysis are similar to those of Table V (Examples 33 to 41). Table Vl demon~lldtes that PVOH/PVA is a more effective promoter than cationic potato starch (over the range of 0.075 to 0.45 Ib/ton).
These examples show that the promoter efficiency is a function of promoter concentration.
Here, the PVOH/PVA is a much more effective promoter than cationic potato starch when the cationic polymer (either the synthetic cationic polymer or the starch) concentration is less than about 0.45% on fiber.
Table Vl Dosage of FY~rnple ~tionic Polymer Ink Penetration (% on Fiber) (sec) 42 0.075 160 43 0.15 157 44 0.30 194 0.45 222 46 0.075 251 47 0.15 269 48 0.30 315 49 0.45 214 CA 0222760~ 1998-01-23 W O 97/05330 PCTrUS96/12231 EXAMPLES 50 TO 55 (Comparative) Table Vll presents the results of an evaluation of sizing as a function of p~u~ult:r dosage for various promoters, as in Table V (Examples 3~ to 41). The emulsions of Table Vll are prepared in the presence of either the PVOH/PVA or the cationic potato starch at 5 0.5/1 ratio to ASA. After emulsification, additional PVOH/PVA or cationic potato starch is added to the furnish to give dosages of 0.075, 0.15 or 0.3% on fiber. Examples 50 to 52 use cationic potato starch as the promoter. Examples 53 to 55 use PVOHtPVA, an ASA-reactive polymer, as the promoter. These examples clell~onsll~le that the pru""~ter efficiency is a function of the sizing concentration and the reactivity of the promoter with the sizing material.
Table Vll Dosage of FY~rnple ~ tionic Polymer Ink Penetration (% on Fiber) (sec) 0.075 140 51 0.15 232 52 0.30 171 53 0.075 208 54 0.15 254 0.30 314 EXAMPLES 56 TO 70 (Comparative) Table Vlll shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table Vl (Examples 42 to 49). Examples 56 to 59 use polyethylenimine as the promoter. Example 60 to 63 use a Hofmann degradation product as the promoter (Table 1, Example 1). Exdmp'~s 64 to 66 use cationic potato starch as the promoter. Ex~lllp'~s 67 to 70 use PVOH/PVA as the promoter. These examples show that ASA-reactive synthetic cationic polymers (both PVOH/PVA and the Hofmann degradation product) provide promoting effect to ASA sizing. The polyethylenimine, which is not ASA-reactive, does not.
-CA 0222760~ 1998-01-23 Table Vl l l Dosage of Ex~mple C~tionic Polymer Ink Penetration (% on fiber) (sec) 56 0.075 2 57 0.15 4 58 0.30 2 59 0.45 2 0.075 28 61 0.15 92 62 0.30 242 63 0.45 184 64 0.075 111 0.15 144 66 0.45 282 67 0.075 225 68 0.15 285 69 0.30 434 0.45 350 EXAMPLES 71 TO 82 (Comparative) Table IX shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table Vl (ExdlllF'Es 42 to 49). The dosage of ASA is 0.2% on dry fiber. Examples 71 to 73 use a Mannich quatemary of polyacrylamide as the promoter. Examples 74 to 76 use cationic potato starch as the promoter. Examples 77 to 79 use PVOH/PVA as the promoter. Exdlllp'Es 80 to 82 use a Hofmann degradation product as the promoter (Table 1, Example 1). This experiment shows that the two ASA-reactive synthetic cationic polymers (PVOH/PVA and the Hofmann degradation product) provide promoting effect to sizing. The Mannich quatemary of polyacrylamide, which is not ASA-reactive, does not.
, CA 0222760~ 1998-01-23 WO 97/05330 PCT~US96/12231 Table IX
Dosage of FY~mple C~tionic Polymer Ink Penetration (% on fiber) (sec) 7t 0.075 2 72 0.15 2 73 0.3~ 2 74 0.15 7 0.30 24 76 0.45 101 77 0.0375 40 78 0.075 45 79 0.15 129 0.075 73 81 0.15 72 82 0.30 177 EXAMPLES 83 TO 106 (Comparative) Table X shows the results of an evaluation of sizing as a function of promoter dosage for various promoters as in Table Vl (Examples 42 to 49). 0.15% ASA on fiber is used. Examples 83 to 85 use PAA/PDAA of 50 k daltons molecular weight as the promoter. Examples 86 to 88 use PAA of 100 k daltons molecular weight as the promoter.
Examples 89 to 91 use a Hofmann degradation product of 14 k daltons molecular weight (Table 1 Example 4) as the promoter. Examples 92 to 94 use a Hofmann degradationproduct of 47 k daltons molecular weight (Table 1 Example 3) as the promoter. EXdmp'~s 95 to 97 use a Hofmann degradation product of 77 k daltons molecular weight (Table 1 Example 2) as the promoter. Examples 98 to 100 use a Hofmann degradation product of 200 k daltons molecular weight (Table 1 Example 1) as the promoter. Examples 101 to 103 use cationic potato starch as the promoter. Examples 104 to 106 use PVOH/PVA as the pru",~ter. These examples show that the promoting effect of the Hofmann degradation products increases with increasing molecular weight. Also these examples show that the promoting effect of the Hofmann degradation products increases with increasing amount of the p~u",oler with the sizing material.
CA 0222760~ 1998-01-23 WO 97/05330 PCT~US96112231 Table X
Dosage of FY~n1PIe C~tionic Polymer Ink Penetr~tion (% on fiber) (sec) 83 0.075 11 84 0.15 40 0.30 29 86 0.075 2 87 0.15 88 0.30 3 89 0.075 2 0.15 91 0.30 7 92 0.075 2 93 0.15 2 94 0.30 2 0.075 15 96 0.15 20 97 0.30 111 98 0.075 71 99 0.1~ 194 100 0.30 236 101 0.15 236 102 0.30 312 103 0.45 373 104 0.075 308 105 0.15 491 106 0.30 389 EXAMPLES 107 TO 130 (Comparative) Table Xl shows the comparative results of an evaluation of the ink penetration as a function of promoter dosage for various promoters, as in Table X (Examples 83 to 106).
Examples 107 to 109 use a Hofmann degradation product of 14 k daltons molecular weight (Table 1, Example 4) and Examples 110 to 112 use a Hofmann degradation product of 47 k daltons molecular weight (Table 1, Example 3) as the promoter. Examples 113 to 115 use a Hofmann degradation product of 77 k daltons (Table 1, Example 2) as the promoter.
Examples 116 to 118 use a Hofmann degradation product of 200 k daltons molecular -W O 97/05330 PCTrUS96/12231 weight (Table 1, Example 1) as the promoter. Examples 119 to 121 use PVA as the promoter. Examples 122 to 124 use PVA.HCI as the promoter. Examples 125 to 127 use PVOH/PVA as the promoter. Eka"~p'es 128 to 130 use cationic potato starch as thepromoter. These examples show that both PVA and PVA.HCI are effective promoters for 5 ASA. Both are ASA-reactive. It again shows that PVOH/PVA is an effective promoter, and that the effectiveness of the Hofmann degradation products increase with increasing molecular weight.
Table Xl Dosage of Fx~rnple C:~tionic Polymer Ink Penetr~tion (% on fiber) (sec) 107 0.30 4 108 0.45 5 109 0.60 60 110 0.30 111 0.45 112 0.60 113 0.15 6 114 0.30 24 115 0.45 127 116 0.075 194 117 0.15 153 118 0.225 240 119 0.15 258 120 0.30 449 121 0.45 260 122 0.15 129 123 0.30 477 124 0.45 406 125 0.0375 178 126 0.075 280 127 0.15 337 128 0.15 108 129 0.30 334 130 0.45 326 CA 0222760~ 1998-01-23 EXAMPLES 131 TO 154 (Comparative) Table Xll presents a further co",pa,~live evaluation of PVOH/PVA polymer as a sizing promoter for ASA. The performance of PVOH/PVA polymer as sizing promoter is compared to the use of cationic starch as the promoter. The synthetic polymer is evaluated 5 under varying mole percent of PVA in the PVAtPVOH polymer as well as under varying molecular weight and dosage of the PVAtPVOH polymer. Each evaluation is conducted using 0.15 mole % on fiber of ASA. It is shown that at higher PVA mole % content (i.e.
at 6 or 18 mole %) the PVOHtPVA promoter is more efficient than cationic starch. At levels of 3 mole % of PVA or less the copolymer is not effective as a promoter. It is also 10 shown that better efficiency is obtained with higher molecular weight samples.
Table Xll Cationic Molecular Ink FY~rnr'~ PVA ~h W~i~ht ~Q~g~ PenetrAtinr~
mole % (% on fiber) (k daltons) (% on fiber) (sec) 131 <1 -- 50-120 0.15 132 <1 -- 50-120 0.30 133 <1 -- 50-120 0.45 134 3 -- 50-120 0.15 135 3 50-120 0.30 136 3 -- 50-120 0.45 137 6 -- 36 0.0375 5.5 138 6 -- 36 0.075 21 139 6 -- 36 0.15 48 140 6 -- 95 0.0375 141 6 -- 95 0.075 23 142 6 -- 95 0.15 98 143 6 -- 80-140 0.0375 47 144 6 -- 80-140 0.075 119 145 6 -- 80-140 0.15 378 146 18 -- 75 0.0375 30 147 18 -- 75 0.075 259 148 18 -- 75 0.15 204 149 -- 0.15 -- -- 34 150 -- 0.15 -- -- 13.6 151 -- 0.30 -- -- 239 152 -- 0.30 -- -- 271 153 -- 0.45 -- -- 275 154 -- 0.45 -- -- 540 CA 0222760~ 1998-01-23 W O 97/05330 PCT~US96/12231 EXAMPLES 1~5 TO 159 (Comparative) The paper that is used for the exampies in Table Xlll is made on a pilot paper machine. The ASA is emulsified either with a copolymer of acrylamide/methyl chloride quaternary salt of dimethylaminoethyl methacrylate (AMD/Q6) or with cationic potato starch.
5 The emulsion is added to the pulp at the down leg of the stuff box. ASA dosage is kept constant at 0.175%. The fumish is 70130 bleached hardwoodlsoftwood with 25% (on dry fiber) added precipitated CaCO3. In Example 155, the AMD/Q6 copolymer is provided in a final ratio to ASA of 0.13/1. In Example 156, the total AMD/Q6 copolyrner is provided as in Example 155, but with additional polymer addition bringing the final ratio of AMD/Q6 to ASA as 1.0/1. In Example 157, the ASA emulsion is made using a 90/10 AMD/Q6 inverse emulsion copolymer, with a final polymer/ASA ratio of 0.13/1. The result of these three examples show the average sizing for Examples 155, 156 and 157 as 20, 41 and 5 secon~s, respectively. This demon~lldles that the sizing was low, relative to the standard emulsions. Increasing the level of copolymer from 0.13:1 to 1:1 resulted only in a small 15 increase in sizing. It is shown that synthetic cationic polymers do not give sizing (or increase sizing efficiency) if the polymer is not reactive with the sizing material. In comparison, Examples 158 and 159 are ASA emulsions made using cationic starch in a ratio to ASA of 2.1/1. The much higher sizing values show the promoting effect of the ASA
reactive cationic starch.
Table Xlll Ratio of Ratio of FY~m~le CAtionic StArch CAtionic Polymer Ink PenetrAtion (sec~
155 - 0.13 20 156 - 1.0 41 157 - 0.13 5 1~8 2.1 - 225 159 2.1 - 219
Claims (10)
1. In a papermaking process which comprises providing a paper furnish or paper web comprised of fiber and adding thereto alkenyl succinic anhydride, the improvement which comprises increasing the sizing efficiency of said alkenyl succinic anhydride by adding to said paper furnish or paper web an amount of greater than 0.0375%, based on said fiber, of a synthetic polymer comprised of hydroxyl groups and/or primary amine groups that is reactive with alkenyl succinic anhydride to provide in paper formed from said paper furnish or paper web an increased sizing level that is greater than the sizing level obtained if 0.0375%, based on said fiber, of said polymer were used.
2. A process as claimed in Claim 1, wherein said (c) is polyvinylamine.
3. A process as claimed in Claim 1, wherein said (c) is comprised of hydroxyl groups.
4. A process as claimed in Claim 1, wherein said (c) has a molecular weight of at least 47,000 and is comprised of (i) carboxyl groups and (ii) primary amine groups.
5. A process as claimed in Claim 4, wherein said (c) is a Hofmann degradation product of polyacrylamide.
6. In a sizing composition comprised of alkenyl succinic anhydride that is added to a paper furnish or paper web comprised of fiber, the improvement which comprises increasing the sizing efficiency of said alkenyl succinic anhydride by adding to said sizing composition an amount of greater than 0.0375%, based on said fiber, of a synthetic polymer comprised of hydroxyl groups and/or primary amine groups that is reactive with alkenyl succinic anhydride to provide in paper formed from said paper furnish or paper web an increased sizing level that is greater than the sizing level obtained if 0.0375%, based on said fiber, of said polymer were used.
7. A composition as claimed in Claim 6, wherein said (c) is polyvinylamine.
8. A composition as claimed in Claim 6, wherein said (c) is comprised of hydroxyl groups.
9. A composition as claimed in Claim 6, wherein said (c) has a molecular weight of at least 47,000 and is comprised of (i) carboxyl groups and (ii) primary amine groups.
10. A composition as claimed in Claim 9, wherein said (c) is a Hofmann degradation product of polyacrylamide.
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| US50828695A | 1995-07-27 | 1995-07-27 | |
| US08/508,286 | 1995-07-27 |
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| CA2227605A1 true CA2227605A1 (en) | 1997-02-13 |
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| CA002227605A Abandoned CA2227605A1 (en) | 1995-07-27 | 1996-07-25 | Synthetic cationic polymers as promoters for asa sizing |
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| EP (1) | EP0840822A1 (en) |
| KR (1) | KR19990035963A (en) |
| CN (1) | CN1192256A (en) |
| AR (1) | AR003054A1 (en) |
| AU (1) | AU6597996A (en) |
| BR (1) | BR9610142A (en) |
| CA (1) | CA2227605A1 (en) |
| CO (1) | CO4560502A1 (en) |
| MX (1) | MX9800482A (en) |
| NO (1) | NO980330D0 (en) |
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| ZA (1) | ZA966342B (en) |
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| DE19801064A1 (en) * | 1998-01-14 | 1999-07-15 | Bayerische Motoren Werke Ag | Motor vehicle operation security system |
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| US7795210B2 (en) * | 2001-10-10 | 2010-09-14 | Novo Nordisk A/S | Protein remodeling methods and proteins/peptides produced by the methods |
| US7696163B2 (en) | 2001-10-10 | 2010-04-13 | Novo Nordisk A/S | Erythropoietin: remodeling and glycoconjugation of erythropoietin |
| US7473680B2 (en) | 2001-11-28 | 2009-01-06 | Neose Technologies, Inc. | Remodeling and glycoconjugation of peptides |
| TW200504265A (en) * | 2002-12-17 | 2005-02-01 | Bayer Chemicals Corp | Alkenylsuccinic anhydride surface-applied system and uses thereof |
| US7943789B2 (en) | 2002-12-17 | 2011-05-17 | Kemira Oyj | Alkenylsuccinic anhydride composition and method of using the same |
| CA2519092C (en) | 2003-03-14 | 2014-08-05 | Neose Technologies, Inc. | Branched water-soluble polymers and their conjugates |
| EP1613261A4 (en) | 2003-04-09 | 2011-01-26 | Novo Nordisk As | Intracellular formation of peptide conjugates |
| US20070026485A1 (en) | 2003-04-09 | 2007-02-01 | Neose Technologies, Inc. | Glycopegylation methods and proteins/peptides produced by the methods |
| WO2005012484A2 (en) | 2003-07-25 | 2005-02-10 | Neose Technologies, Inc. | Antibody-toxin conjugates |
| US20080305992A1 (en) | 2003-11-24 | 2008-12-11 | Neose Technologies, Inc. | Glycopegylated erythropoietin |
| ES2445948T3 (en) | 2003-11-24 | 2014-03-06 | Ratiopharm Gmbh | Glycopegylated Erythropoietin |
| ES2560657T3 (en) | 2004-01-08 | 2016-02-22 | Ratiopharm Gmbh | O-linked glycosylation of G-CSF peptides |
| WO2006010143A2 (en) | 2004-07-13 | 2006-01-26 | Neose Technologies, Inc. | Branched peg remodeling and glycosylation of glucagon-like peptide-1 [glp-1] |
| EP1799249A2 (en) | 2004-09-10 | 2007-06-27 | Neose Technologies, Inc. | Glycopegylated interferon alpha |
| DK2586456T3 (en) | 2004-10-29 | 2016-03-21 | Ratiopharm Gmbh | Conversion and glycopegylation of fibroblast growth factor (FGF) |
| JP4951527B2 (en) | 2005-01-10 | 2012-06-13 | バイオジェネリックス アーゲー | GlycoPEGylated granulocyte colony stimulating factor |
| CN101228315A (en) * | 2005-03-03 | 2008-07-23 | 凯米拉公司 | Reduced shear cellulose reactive sizing agent for wet end applications |
| US20070154992A1 (en) | 2005-04-08 | 2007-07-05 | Neose Technologies, Inc. | Compositions and methods for the preparation of protease resistant human growth hormone glycosylation mutants |
| US20070105755A1 (en) | 2005-10-26 | 2007-05-10 | Neose Technologies, Inc. | One pot desialylation and glycopegylation of therapeutic peptides |
| US20090048440A1 (en) | 2005-11-03 | 2009-02-19 | Neose Technologies, Inc. | Nucleotide Sugar Purification Using Membranes |
| WO2008011633A2 (en) | 2006-07-21 | 2008-01-24 | Neose Technologies, Inc. | Glycosylation of peptides via o-linked glycosylation sequences |
| US8969532B2 (en) | 2006-10-03 | 2015-03-03 | Novo Nordisk A/S | Methods for the purification of polypeptide conjugates comprising polyalkylene oxide using hydrophobic interaction chromatography |
| CA2682897C (en) | 2007-04-03 | 2016-11-22 | Biogenerix Ag | Methods of treatment using glycopegylated g-csf |
| US20080277084A1 (en) * | 2007-05-09 | 2008-11-13 | Buckman Laboratories International, Inc. | ASA Sizing Emulsions For Paper and Paperboard |
| MX2009013259A (en) | 2007-06-12 | 2010-01-25 | Novo Nordisk As | Improved process for the production of nucleotide sugars. |
| US8088250B2 (en) | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
| PL2257311T3 (en) | 2008-02-27 | 2014-09-30 | Novo Nordisk As | Conjugated factor viii molecules |
| CN101693927B (en) * | 2009-10-21 | 2013-03-20 | 陕西科技大学 | Long-chain alkyl alcohol modified ASA waterproof fatliquoring agent and process for preparing same |
| US8852400B2 (en) * | 2010-11-02 | 2014-10-07 | Ecolab Usa Inc. | Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer |
| WO2014132175A1 (en) | 2013-03-01 | 2014-09-04 | Basf Se | Aqueous emulsion of a sizing agent |
| US9567708B2 (en) | 2014-01-16 | 2017-02-14 | Ecolab Usa Inc. | Wet end chemicals for dry end strength in paper |
| US9702086B2 (en) | 2014-10-06 | 2017-07-11 | Ecolab Usa Inc. | Method of increasing paper strength using an amine containing polymer composition |
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| CN106917324B (en) | 2015-12-25 | 2019-11-08 | 艺康美国股份有限公司 | A kind of paper-making sizing method and its paper of preparation |
| US10006171B2 (en) * | 2016-04-25 | 2018-06-26 | Ecolab Usa Inc. | Methods and compositions for enhancing sizing in papermaking process |
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| CN110577672A (en) * | 2018-06-07 | 2019-12-17 | 国家纳米科学中心 | Controllable hydrophilic and hydrophobic nano cellulose film, and preparation method and application thereof |
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| GB8511379D0 (en) * | 1985-05-03 | 1985-06-12 | Allied Colloids Ltd | Compositions for sizing paper |
| US4657946A (en) * | 1984-06-25 | 1987-04-14 | Nalco Chemical Company | Paper sizing method and emulsion |
| CA2100117C (en) * | 1992-07-15 | 1997-10-07 | Lloyd M. Robeson | Paper wet-strength improvement with cellulose reactive size and amine functional poly(vinyl alcohol) |
| US5281307A (en) * | 1993-01-13 | 1994-01-25 | Air Products And Chemicals, Inc. | Crosslinked vinyl alcohol/vinylamine copolymers for dry end paper addition |
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| WO1997005330A1 (en) | 1997-02-13 |
| NO980330L (en) | 1998-01-26 |
| BR9610142A (en) | 1999-02-02 |
| CN1192256A (en) | 1998-09-02 |
| AR003054A1 (en) | 1998-05-27 |
| AU6597996A (en) | 1997-02-26 |
| KR19990035963A (en) | 1999-05-25 |
| EP0840822A1 (en) | 1998-05-13 |
| NO980330D0 (en) | 1998-01-26 |
| MX9800482A (en) | 1998-04-30 |
| CO4560502A1 (en) | 1998-02-10 |
| ZA966342B (en) | 1997-02-11 |
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