EP1171492B1 - Bifunctional polymers - Google Patents
Bifunctional polymers Download PDFInfo
- Publication number
- EP1171492B1 EP1171492B1 EP99967997A EP99967997A EP1171492B1 EP 1171492 B1 EP1171492 B1 EP 1171492B1 EP 99967997 A EP99967997 A EP 99967997A EP 99967997 A EP99967997 A EP 99967997A EP 1171492 B1 EP1171492 B1 EP 1171492B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituent
- paper
- substituents
- starch
- phosphonated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
-
- 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
- D21H21/18—Reinforcing agents
Definitions
- One embodiment of the present invention is the use in paper making of a polymer composition having a polymeric core, one or more phosphonated substituents effective for bonding with an inorganic material, and one or more sulphonated substituents effective for bonding with a polysaccharide material.
- the polymeric core comprises one or more polymer units selected from polymerizable monomeric units, such as by condensation or free radical methods, preferably from allylic units, epoxidic units, and vinylic units.
- the polymeric core can be composed of varying proportions or sequences of substituted or unsubstituted monomeric (or polymeric units of allylic units, epoxidic units and vinylic units. Not all allylic unit, epoxidic units, or vinylic units need be the same as the other respective allylic units, epoxidic units, or vinylic units, but they can be. Such difference can result from hydrolysis reactions, among others, and whether intended or not.
- Such allylic, epoxidic and vinylic units can have one or more of the phosphonated or sulphonated substituents attached before or after polymerization.
- Such units of the core can be repeating in a predictable sequence or repeat randomly.
- A if not hydrogen, is an (C 1 -C 6 ) alkylene, e.g., methylene, ethylene, propylene, butylene, pentylene or hexylene.
- alkylenes can have a (C 1 -C 3 ) alkyl substituent, e.g., methyl, ethyl or propyl.
- the halogen which can be a substituent on an alkyl or alkylene chain herein is selected from bromine, chlorine and fluorine atoms.
- the (C 1 -C 3 ) alkyls are methyl, ethyl and n-propyl.
- the preferred epoxide monomeric unit can be represented by the formula -CHR-O-CH 2 , wherein R is hydrogen or lower alkyl or alkylene, e.g. alkylene having one to six carbon atoms.
- such preferred alkylenes can have one or more (C 1 -C 3 ) alkyl substituent(s), e.g.. methyl, ethyl, or propyl.
- the halogen which can be a substituent on an alkyl chain herein is selected from bromine, chlorine, and fluorine atoms. Such halogens can be substituents on the alkylene chain also.
- the nitrogen, N can also be a quaternary nitrogen, including, but not limited to, combinations of the groups above.
- alkylenes can have a (C 1 -C 3 ) alkyl substituent, e.g., methyl, ethyl, or propyl.
- the halogen which can be a substituent on an alkyl chain herein is selected from bromine, chlorine, and fluorine atoms. Such halogens can be substituents on the alkylene chain also.
- E is hydrogen, hydroxyl, or ether; preferably hydrogen.
- the nitrogen, N can also be a quaternary nitrogen, including, but not limited to, combinations of the groups above.
- D sodium
- - SO 3 - D can be represented as - SO 3 - Na + .
- - SO 3 - D can be represented as - SO 3 CH 3 .
- Non-limiting examples of the substituent groups are:
- the molecular weight of the composition having the above core and substituents ranges from about 100,000 to about 20,000,000.
- the more preferred molecular weight ranges from about 500,000 to about 5,000,000.
- the more preferred molecular weight is about 500,000 to about 5,000,000.
- the selection and amount of the optional cationic or neutrally charged amide substituent for reducing the electrostatic charge density and for hydrogen bonding will vary according to the selection of the phosphonated and sulphonated substituents.
- an embodiment of the present invention is a method for improving the strength in paper comprising the addition of certain polymers compositions of the above polymer to a paper furnish optionally containing fillers.
- the preferred polymers are copolymers comprising acrylamide monomers and phosphonated monomers or sulphonated monomers or are terpolymers comprising acrylamide monomers, phosphonated monomers and sulphonated monomers.
- the addition of the polymer composition can be prior to the headbox of a paper machine in either the thick or thin stock. Split or multiple addition points and other strategies can be used. The amount added will vary according to the nature of the papermaking furnish and the intended use of the paper produced, but should be typically in the range of from about one pound to about five pounds of polymer composition per ton of furnish.
- the polymer in admixture with starch provides a synergistic increase in the strength of the paper produced.
- the synergistic effect is signified by the fact that no amount of either additional polymer or starch, when used alone, can provide an equivalent result to the combination of polymer and starch.
- the starch useable are those typically useable for papermaking.
- Such starch can be synthetic, such as ethylated or oxidized forms; or organic, such as potato based, preferably cationic potato starch, or corn based, such as cationic waxy maize.
- one embodiment of the present invention is a process for the production of paper comprising the admixing of starch and a polymer composition comprising one or more polymers of the group consisting of acrylamide polymers, acrylamide polymers co-polymerized with a monomer containing a pendent sulfonic acid group or a phosphonic acid a group, and terpolymers of acrylamide co-polymerized with both a monomer containing a pendant sulfonic acid group and a monomer containing pendant phosphonic acid group.
- Such admixing occurs prior to or during the preparation of the furnish before providing the furnish to the paper machine.
- an embodiment of the present invention is a process comprising effectively admixing the starch and polymer composition to produce a paper sheet having an unexpected synergistic increase in strength over the strength when either starch or polymer composition is used alone.
- Such "Synergistic Increase” is measured by comparing the strength attained by the combination of starch and polymer composition over the absence of both starch and polymer composition in comparison to the additive sums of the separate increases in strength of each of the starch and polymer composition alone over the absence of both starch and polymer compositions in the formed paper. Stated in the form of an equation:
- the amount of starch useable will vary in accordance with the particular furnish and paper being produced. Such amounts can typically range from about five to about fifty pounds per ton of paper. Similarly, the amount of the polymer composition can typically range from about one to about ten pounds per ton of paper.
- Handsheets were made using a 75% hardwood / 25% softwood blend of bleached northern Kraft pulps, co-refined at 1.6% consistency to an endpoint of 400 Canadian Standard Freeness. The refined pulp was diluted to 0.3125% consistency for papermaking. Hercon 75 cationic alkyl ketene dimer emulsion was added to the furnish at the rate of 0.25%. The terpolymer of the PAM, AMPS and vinylphosphonic acid (VPA) was added to the furnish at the rate of 0.25% when specified. Albacar® HO precipitated calcium carbonate was added to the furnish batch for each set of handsheets in amounts adjusted to achieve filler levels of approximately 14, 21, and 28%.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
Description
-(PO3)-2 (Na+1)2 when sodium is the moiety; or
-(PO3)-2 (Ca+2)1 when calcium is the moiety.
"D" may also represent a pairing of hydrogen and salt moiety. e.g. -(PO3) H+1 Na+1.
- PO3H2 - PO3(CH3)2 - PO3(H)(CH3)
- CH2PO3H2 - CH2PO3(CH3)2 -CH2PO3(H)(CH3)
- C(=O) NH CH2 PO3H2
-C(=O) NH CH2 SO3 H -C(=O) NH C(CH3)2CH2 SO3 H
-CH2C(=O)NH C(CH3)2CH2SO3 H - CH2C(=O)N(CH3)C(CH3)2CH2SO3H
-C(=O)NH2 - CH2C(=O)NH2
-C(=O)NH CH3 - C (=O)N+(CH3)3
Polymer Composition | Molecular Weight |
99% AMPS 1% VPA | 75,000 |
125,000 | |
500,000 | |
89% PAM 10% AMPS 1% VPA | 500,000 |
2,000,000 | |
5,000,000 | |
85% PAM 10% AMPS 5% VPA | 75,000 |
500,000 | |
2,000,000 | |
5,000,000 | |
AMPS = 2-acrylamido - 2-methylpropanesulfonic acid monomers | |
VPA = vinylphosphonic acid monomers | |
PAM = polyacrylamide monomers |
Sample No. | Molecular Weight | AMPS | PAM | VPA | Glass Transition Temperature |
1 | 2,100,000 | --- | 100 | --- | 120.9 |
2 | 1,800,000 | 10 | 90 | --- | 110.93 |
3 | 1,000,000 | --- | 90 | 10 | 78.78 |
4 | 500,000 | 10 | 85 | 5 | 83.63 |
5 | 1,000,000... | 10 | 89 | 1 | 96.87 °C |
Molecular weights determined by intrinsic viscosity method. | |||||
AMPS - weight percent 2-acrylamido - 2 - methylpropane sulfonic acid. | |||||
PAM - weight percent polyacrylamide. | |||||
VPA - weight percent vinylphosphonic acid. |
Claims (20)
- A method for the manufacture of paper comprising adding to a paper furnish a polymer composition comprising a polymeric core; one or more phosphonated substituents and one or more sulphonated substituents; and optionally, one or more cationic or neutrally charged amide substituents.
- A method according to Claim 1 wherein the polymeric core comprises one or more polymer units selected from alkylic units and vinylic units.
- A method according to Claim 1 or Claim 2 wherein the phosphonated substituent(s) are of the formula-A-P (=O)(-OD1)(-OD2), wherein "P" is phosphorus; "O" is oxygen; and "A" is selected from a carbon-to-phosphorus link or from an unsubstituted or substituted (C1-C6) alkylene, wherein the substituent is independently selected from (C1-C3) alkyls and halogens, or from a carbonyl (-CO), carbonylaminos, alkylenecarbonylaminos, carbonylaminoalkylenes, or alkylenecarbonylaminoalkylenes; and "D" is a hydrogen proton or a salt moiety selected from aluminum, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zinc ions.
- The composition of any of the preceding Claims wherein the sulphonated substituent(s) are of the formula -A-S (=O)2(-OD1), wherein "S" is sulphur, "O" is oxygen; and "A" is selected from a carbon-to-sulphur link or from an unsubstituted or substituted (C1-C6) alkylene, wherein the substituent is independently selected from (C1-C3) alkyls and halogens, or from a carbonyl (-CO-), carbonylaminos, alkyllenecarbonylaminos, carbonylaminoalkelenes, or alkylenecarbonylaminoalalkylenes; and "D" is a hydrogen proton or a salt moiety selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanius and zinc ions.
- A method according to any of the preceding Claims wherein the cationic or neutrally charged amide substituent is of the formula -A1-C(=O)-N(B)R1R2, wherein "C" is carbon; "O" is oxygen; "N" is nitrogen; "A1" is an unsubstituted or substituted (C1-C6) Ikylene, wherein the substituents are independently selected from (C1-C3) alkyls and halogens; and "B" is hydrogen, hydroxyl, or ether; and "R1" and "R2" are each independently hydrogen, halogen or a (C1-C3) alkyl.
- A method according to any of the preceding Claims wherein the phosphonated substituent is selected from the group consisting of-PO3H2, -PO3(CH3)2, -PO3(H)(CH3), -CH2PO3H2, -CH2PO3(CH3) 2, -CH2PO3(H)(CH3), -C(=O)NHCH2PO3H2; the sulphonated substituent selected from the group consisting of -C(=O)NHC(CH3)2CH2SO3H, -C(=O)NHCH2SO3H, -CH2C(=O)NHC(CH3)2, -CH2SO3H, and -CH2C(=O)N(CH3)C(CH3)2CH2SO3H; and the amide substituent selected from the group consisting of -C(=O)NH2, CH2C(=O)NH2-C(=O)NHCH3, and -C(=O)N+(CH3)3.
- A method according to Claim 6 in which the phosphonated substituent is -PO3H2; the sulphonated substituent is -C(=O)NHC(CH3)2CH2SO3H; and the amide substituent is C(=O)NH2.
- A method according to any of the preceding Claims wherein the ratio of phosphonated substituents to sulphonated substituents is 10/90 to 1/99.
- A method according to any of the preceding Claims wherein the ratio of the amide substituent to the phosphonated substituents is 10/1 or higher.
- A method according to any of the preceding Claims wherein the average molecular weight of the composition ranges from 100,000 to 20,000,000.
- A method according to any of the preceding Claims wherein there is less than 15 wt % cross-linking.
- The composition of any of the preceding Claims wherein the cross-linking is less than 1 wt %.
- A method according to any of the preceding Claims in which the furnish also contains one or more fillers.
- The method of any preceding Claims further comprising the addition of starch to the paper furnish.
- The method of Claim 14 wherein the starch is ethylated or oxidised starch or potato based or corn starch.
- The method of Claim 14 or Claim 15 wherein the amount of starch ranges from five to fifty pounds per ton of paper.
- The method of any Claims 14 to 16 wherein the amount of the polymer composition ranges from one to ten pounds per ton of paper.
- A paper composition comprising paper containing fillers and a composition comprising a polymeric core; one or more phosphonated, one ore more sulphonated substituents; and optionally, one or more cationic or neutrally charged amide substituents.
- A paper composition according to Claim 18 also containing starch.
- The paper composition of Claim 19 wherein the starch is ethylated or oxidised starch or potato used cornstarch.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US286742 | 1999-04-06 | ||
US286745 | 1999-04-06 | ||
US09/286,742 US6090242A (en) | 1999-04-06 | 1999-04-06 | Method of improvement strength of papers |
US09/286,745 US6287423B1 (en) | 1999-04-06 | 1999-04-06 | Paper composition for improved sheet properties |
PCT/IB1999/002101 WO2000059965A1 (en) | 1999-04-06 | 1999-12-22 | Bifunctional polymers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1171492A1 EP1171492A1 (en) | 2002-01-16 |
EP1171492B1 true EP1171492B1 (en) | 2003-09-03 |
Family
ID=26964044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99967997A Expired - Lifetime EP1171492B1 (en) | 1999-04-06 | 1999-12-22 | Bifunctional polymers |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1171492B1 (en) |
JP (1) | JP2002541276A (en) |
CN (1) | CN1149238C (en) |
AT (1) | ATE248867T1 (en) |
AU (1) | AU2455300A (en) |
BR (1) | BR9917249A (en) |
CA (1) | CA2366474A1 (en) |
DE (1) | DE69911073T2 (en) |
HK (1) | HK1045534B (en) |
NO (1) | NO20014814L (en) |
PT (1) | PT1171492E (en) |
WO (1) | WO2000059965A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10334133A1 (en) | 2003-07-25 | 2005-02-24 | Basf Ag | Aqueous composition and its use for papermaking |
US9752283B2 (en) | 2007-09-12 | 2017-09-05 | Ecolab Usa Inc. | Anionic preflocculation of fillers used in papermaking |
US8747617B2 (en) | 2007-09-12 | 2014-06-10 | Nalco Company | Controllable filler prefloculation using a dual polymer system |
US8778140B2 (en) | 2007-09-12 | 2014-07-15 | Nalco Company | Preflocculation of fillers used in papermaking |
US8088250B2 (en) | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
FR3001236B1 (en) | 2013-01-22 | 2015-06-26 | Emin Leydier | AQUEOUS COMPOSITION FOR THE PRODUCTION OF FIBROUS SHEET CARRIERS WITH IMPROVED MECHANICAL STRENGTH PROPERTIES, PROCESS, USE, FIBROUS CARRIERS AND MANUFACTURED ARTICLES THEREOF |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3926718A (en) * | 1974-04-30 | 1975-12-16 | Calgon Corp | Process of improving water drainage from paper webs by addition of a water soluble block polymer to a cellulosic pulp slurry |
EP0113438B1 (en) * | 1982-12-09 | 1989-03-08 | CASSELLA Aktiengesellschaft | Water soluble polymers, their preparation and their use |
DE3248019A1 (en) * | 1982-12-24 | 1984-06-28 | Cassella Ag, 6000 Frankfurt | WATER-SOLUBLE COPOLYMERS, THEIR PRODUCTION AND THEIR USE |
US5336316A (en) * | 1993-05-06 | 1994-08-09 | Bj Services Company | Cementing composition and method using phosphonated polymers to improve cement slurry properties |
DE4330699A1 (en) * | 1993-09-10 | 1995-03-16 | Hoechst Ag | Vinylsulfonic acid polymers |
DE4343993A1 (en) * | 1993-12-22 | 1995-06-29 | Stockhausen Chem Fab Gmbh | Graft copolymers of unsaturated monomers and polyhydroxy compounds, process for their preparation and their use |
JPH08134792A (en) * | 1994-11-11 | 1996-05-28 | Nippon P M C Kk | Additive for papermaking and papermaking method |
DE19508936A1 (en) * | 1995-03-13 | 1996-09-19 | Basf Ag | Complexing agent for the paper industry |
AU3913197A (en) * | 1996-08-15 | 1998-03-06 | Hercules Incorporated | Amphoteric polyacrylamides as dry strength additives for paper |
-
1999
- 1999-12-22 BR BR9917249-6A patent/BR9917249A/en not_active Application Discontinuation
- 1999-12-22 EP EP99967997A patent/EP1171492B1/en not_active Expired - Lifetime
- 1999-12-22 CA CA002366474A patent/CA2366474A1/en not_active Abandoned
- 1999-12-22 WO PCT/IB1999/002101 patent/WO2000059965A1/en active IP Right Grant
- 1999-12-22 DE DE69911073T patent/DE69911073T2/en not_active Expired - Fee Related
- 1999-12-22 AU AU24553/00A patent/AU2455300A/en not_active Abandoned
- 1999-12-22 PT PT99967997T patent/PT1171492E/en unknown
- 1999-12-22 JP JP2000609471A patent/JP2002541276A/en not_active Withdrawn
- 1999-12-22 CN CNB998165980A patent/CN1149238C/en not_active Expired - Fee Related
- 1999-12-22 AT AT99967997T patent/ATE248867T1/en not_active IP Right Cessation
-
2001
- 2001-10-03 NO NO20014814A patent/NO20014814L/en not_active Application Discontinuation
-
2002
- 2002-09-26 HK HK02107083.1A patent/HK1045534B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE248867T1 (en) | 2003-09-15 |
DE69911073D1 (en) | 2003-10-09 |
WO2000059965A1 (en) | 2000-10-12 |
DE69911073T2 (en) | 2004-04-01 |
CN1348473A (en) | 2002-05-08 |
NO20014814D0 (en) | 2001-10-03 |
NO20014814L (en) | 2001-10-03 |
JP2002541276A (en) | 2002-12-03 |
HK1045534B (en) | 2005-02-18 |
AU2455300A (en) | 2000-10-23 |
EP1171492A1 (en) | 2002-01-16 |
CN1149238C (en) | 2004-05-12 |
HK1045534A1 (en) | 2002-11-29 |
BR9917249A (en) | 2002-01-08 |
PT1171492E (en) | 2004-01-30 |
CA2366474A1 (en) | 2000-10-12 |
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