NZ622454B2 - Vinylamine containing copolymer microparticles as additives in papermaking - Google Patents
Vinylamine containing copolymer microparticles as additives in papermaking Download PDFInfo
- Publication number
- NZ622454B2 NZ622454B2 NZ622454A NZ62245412A NZ622454B2 NZ 622454 B2 NZ622454 B2 NZ 622454B2 NZ 622454 A NZ622454 A NZ 622454A NZ 62245412 A NZ62245412 A NZ 62245412A NZ 622454 B2 NZ622454 B2 NZ 622454B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- polymer product
- styrene
- vinylformamide
- vinylamine
- range
- Prior art date
Links
- 239000000654 additive Substances 0.000 title claims abstract description 53
- 229920001577 copolymer Polymers 0.000 title claims abstract description 46
- 239000011859 microparticle Substances 0.000 title claims description 20
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 title description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229920000642 polymer Polymers 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 37
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N N-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002091 cationic group Chemical group 0.000 claims abstract description 15
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 claims description 43
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 230000000996 additive Effects 0.000 claims description 28
- DDVIXBCBHPDYMS-UHFFFAOYSA-N ethenamine;N-ethenylformamide;styrene Chemical compound NC=C.C=CNC=O.C=CC1=CC=CC=C1 DDVIXBCBHPDYMS-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 150000003440 styrenes Chemical class 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 150000003222 pyridines Chemical class 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical group [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000001475 halogen functional group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000003301 hydrolyzing Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 25
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 239000004094 surface-active agent Substances 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 6
- 238000004513 sizing Methods 0.000 abstract description 5
- 230000001404 mediated Effects 0.000 abstract description 4
- 239000004815 dispersion polymerization Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000004970 Chain extender Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000003141 primary amines Chemical group 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- -1 vinyl amine Chemical class 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- LXEKPEMOWBOYRF-UHFFFAOYSA-N V-50 Substances Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 3
- 150000001409 amidines Chemical group 0.000 description 3
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000001965 increased Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-Dichlorophenoxyacetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N N-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N cdcl3 Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002829 reduced Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (Z)-octadec-9-en-1-amine Polymers CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 230000036499 Half live Effects 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- UWMAJDZFMJMYFZ-UHFFFAOYSA-N N-ethenylformamide;styrene Chemical compound C=CNC=O.C=CC1=CC=CC=C1 UWMAJDZFMJMYFZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920003118 cationic copolymer Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulant Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SFBPZEATETXZRK-UHFFFAOYSA-N ethenamine;styrene Chemical compound NC=C.C=CC1=CC=CC=C1 SFBPZEATETXZRK-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical compound NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000004450 types of analysis Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- 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
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
Abstract
Disclosed herein is a surfactant mediated, free radical initiated emulsion/dispersion polymerization of n-vinylformamide with styrene or substituted styrene copolymers, and its subsequently hydrolyzed products bearing formamide, amine and styrenic functionality. Also disclosed are processes for polymerization, polymer composition, and hydrolysis of the polymers. The polymers bearing cationic functionality can be used in papermaking applications as dry strength additives, wet strength additives, retention aids, drainage aids, sizing agent, sizing promoter and pitch and stickies control agents. merization, polymer composition, and hydrolysis of the polymers. The polymers bearing cationic functionality can be used in papermaking applications as dry strength additives, wet strength additives, retention aids, drainage aids, sizing agent, sizing promoter and pitch and stickies control agents.
Description
VINYLAMINE CONTAINING COPOLYMER MICROPARTICLES AS
ADDITIVES IN PAPERMAKING
FIELD OF THE INVENTION
This invention relates to a process for making vinylamine-vinylformamide-
styrene terpolymer additives comprising reacting n-vinylformamide (VFA) with styrene or
substituted styrene or vinyl pyridine, and subsequent hydrolysis to form vinylamine
(VAm)-styrene terpolymers. The resulting aqueous dispersion containing microparticles
of vinylamine-vinylformamide-styrene terpolymers can be used as a cost effective paper
making additive to improve paper making process and paper dry strength properties.
BACKGROUND OF THE INVENTION
Due to the ability of cationic functionality of polymer to hydrogen bond with
cellulose fibers, polymers containing amine functionality are well studied in paper
industry. Use of cationic polymer has proven improvement in paper strength, drainage,
retention and several other properties. Several patents and research articles discusses use
of polyvinylamine as a paper making additive. U.S. Patent No. 2,721,140 discloses use of
polyvinylamine as an additive to make papers having high wet strength, while U.S. Patent
No. 5,961,782 discloses use of polyvinylamine to make crosslinkable creping adhesive
formulations.
Among the polymers with amine functionality, the cost effective synthesis of
polymer containing primary amine functionality has been a challenge for generations. The
monomers that can introduce primary amine functionality, on polymerization are
allylamine and vinylamine (VAm) or, on hydrolysis are vinylformamide (VFA) and vinyl
acetamide. Due to lack of conjugation in allylamine and presence of free amine
functionality, polymerization of allylamine is relatively sluggish and also leads in several
side reactions like inhibition or chain transfer. Therefore, it is challenging to synthesize
allylamine containing polymers with high molecular weight. Whereas, vinyl amine
monomer does not exist in free state, and hence it was not possible to synthesize
polyvinylamine. The significant efforts by the Air Products and Chemicals Inc., BASF
and DiaNitrix resulted in vinylformamide monomer. BASF launched the industrial
production of vinylformamide (VFA) momomer that can be effectively polymerized by
using radical initiators to synthesize materials with high molecular weight. VFA
homopolymers as well VFA copolymers with vinyl monomers offers a material with
distinctive chemical and physical properties. The hydrolysis of poly(VFA) results in a
material with pendant primary amine functionality that makes these polymers highly
cationic in nature. The introduction of primary amine functionality on alternate carbon
atoms yields the material with a relatively high charge density and cationicity that makes
this material as an attractive and viable candidate for variety of commercial applications.
U.S. Patent No. 4,421,602 discloses a partially hydrolyzed, water-soluble polymer of n-
vinylformamide that contains n-vinylformamide units and vinylamine units. It also
discloses use of polyvinylamine and a 50% hydrolyzed polyvinylformamide to increase
flocculation efficiencies, fines retention, and the drainage rate of pulp fiber in
papermaking processes, while U.S. Patent No. 6,159,340 discloses the use of such
polymers as dry and wet strength additives in paper and paperboard production. U.S.
Patent Nos. 6,616,807 and 6,797,785 disclose use of polyvinylamines as drainage aids,
flocculants, and retention aids in the paper making.
Vinylformamide copolymers and their subsequently hydrolyzed products are also
known additives for paper applications. U.S. Patent No. 4,774,285 discloses that n-
vinylformamide monomer may be copolymerized with an additional vinyl monomer, e.g.,
vinyl acetate, and subsequently hydrolyzed to produce a water-soluble copolymer of
vinylamine and vinyl alcohol, which may be used as wet and dry strength additives for
papermaking. U.S. Patent No. 5,630,907 discloses copolymer compositions containing
vinyl amine and acrylic acid units, as well as their applications. U.S. Patent No. 6,797,785
discloses copolymers containing vinylamine units in combination with either
diallyldimethylammonium (chloride) (DADMAC) or acrylamide units via reverse
emulsion polymerization, and their use as flocculants and coagulants in papermaking. EP
0251182 discloses copolymers containing vinylamine and acrylonitrile units for use in
papermaking as drainage aids, retention aids, as well as wet end additives for increasing
the dry strength of paper products.
Styrene containing polymers are also well utilized in a variety of applications,
due to their relatively low cost, and compatibility with other polymers. The aromatic
group of styrene offers unique properties to the material namely, better hydrophobicity,
higher thermal stability, and resistance to acid or base conditions during hydrolysis. U.S.
Patent No. 4,328,579 discloses copolymerization of n-vinyl acetamide with styrene and
substituted styrene and its subsequent hydrolysis to form styrene-vinyl amine copolymer.
However, the copolymerization reactions are slow and need almost 57 hours to achieve
96% conversion. Additionally the polymer needs to be purified by precipitation in a non-
solvent to remove residual monomer, and the soluble nature of the material suggests the
obtained polymers have a relatively low molecular weight. On the other hand attempts to
copolymerize styrene with VFA resulted in lower conversions and lower molecular weight
material. (Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48, 2257-2283).
Therefore, it is desirable to develop a polymerization process to copolymerize
styrene with VFA with high efficiency of shorter reaction time resulting in high
conversion of the monomers into the polymer products without further purification. It is
also desirable to produce a cationic copolymer containing VAm, VFA, and styrene groups,
which can be used as a cost effective dry strength additive in papermaking and has many
other potential applications. It is an object of the present invention to go some way to
satisfying one or more of these desiderata; and/or to at least provide the public with a
useful choice.
In this specification where reference has been made to patent specifications,
other external documents, or other sources of information, this is generally for the purpose
of providing a context for discussing the features of the invention. Unless specifically
stated otherwise, reference to such external documents is not to be construed as an
admission that such documents, or such sources of information, in any jurisdiction, are
prior art, or form part of the common general knowledge in the art.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a process for making vinylamine-
vinylformamide-styrene terpolymer additives comprising:
a) reacting vinylformamide with styrene or substituted styrene under free radical,
emulsion polymerization reaction conditions;
b) producing a first polymer product which comprises randomly distributed repeating
units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
c) hydrolyzing the first polymer product using an acid or base treatment;
d) producing a second polymer product comprising randomly distributed repeating
monomer units having at least two of the formula (III), (IV), (V) and (VI):
wherein,
R and R are H;
R is H or alkyl;
m and m independently is a positive mole percent, and m and m independently may be 0
1 2 3 4
to 99 mole percent, and the sum of m , m m and m is equal to or less than x mole
1 2, 3 4
percent of formula (I).
In another aspect, the present invention provides an aqueous dispersion
comprising the resulting polymer product from a process which comprises:
a) reacting vinylformamide with styrene or substituted styrene under free
radical, emulsion polymerization reaction conditions;
b) producing a polymer product which comprises randomly distributed
repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
wherein, the polymer product in said aqueous dispersion is in a form of
microparticles, and the particle size of the polymer product is in the range of from 30
nanometer to 2000 nanometer.
In another aspect, the present invention provides a vinylamine-vinylformamide-
styrene terpolymer additive comprising the resulting second polymer product from a
process which comprises:
a) reacting vinylformamide with styrene or substituted styrene under free
radical, emulsion polymerization reaction conditions;
b) producing a first polymer product which comprises randomly distributed
repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
c) hydrolyzing the first polymer product using and acid or base treatment;
d) producing a second polymer product comprising randomly distributed
repeating monomer units having at least two of the formulae (III), (IV), (V) and (VI):
wherein,
R and R are H;
R is H or alkyl;
m and m independently is a positive mole percent, and m and m independently
1 2 3 4
may be 0 to 99 mole percent, and the sum of m , m m and m is equal to or less than x
1 2, 3 4
mole percent of formula (I),
wherein, the first polymer product is in a form of microparticles, and the particle
size of the first polymer product is in the range of from 30 nanometer to 2000 nanometer,
and the second polymer product is vinylamine-vinylformamide-styrene terpolymer,
and wherein, said vinylamine-vinylformamide-styrene terpolymer additive is in a
form of microparticles in aqueous dispersion, and the viscosity measured at ambient
temperature (about 20ºC to about 25ºC) of active solids in the range of from 13.0% to
18.0% of vinylamine-vinylformamide-styrene terpolymer is in the range of from 100 to
500 cP.
In another aspect, the present invention provides a second polymer product
produced by a process of the present invention.
Described herein is a radically initiated, surfactant mediated emulsion
copolymerization of VFA with styrene or substituted styrene, and its subsequent
hydrolysis to form micro particulate VAm, VFA and styrene terpolymer. The ratio of
VFA to styrene or substituted styrene in copolymer can be varied from 99:1 to 50:50, can
be 80:20 to 51:49, and may be 80:20 to 70:30. The micro particulate VFA-styrene
copolymers can be subsequently hydrolyzed by acids or bases treatment to introduce
vinylamine functionality to form vinylamine, n-vinylformamide and styrene terpolymer.
The partially hydrolyzed terpolymer micro particles described in this invention can be
used to enhance the dry strength, wet strength, drainage, fixative, and sizing properties of
paper when used as additives in the papermaking process and has many other potential
applications.
DETAILED DESCRIPTION OF THE INVENTION
The term “comprising” as used in this specification and claims means “consisting
at least in part of”. When interpreting statements in this specification and claims which
include the term “comprising”, other features besides the features prefaced by this term in
each statement can also be present. Related terms such as “comprise” and “comprised”
are to be interpreted in similar manner.
As used herein and unless otherwise stated: (1) all percentages, parts, ratios, etc.,
are by weight; (2) when an amount, concentration, or other value or parameter, is given as
a list of upper preferable values and lower preferable values, this is to be understood as
specifically disclosing all ranges formed from any pair of an upper preferred value and a
lower preferred value, regardless whether ranges are separately disclosed; (3) the term
"total solids" refers to the solids that remain after the volatiles (e.g., solvents) have been
removed from styrene-vinylformamide resin or composition thereof; (4) the term "active
solids" refers to the at least one styrene-vinylamine resin portion of the total solids
remaining after subtraction of inorganic content from the styrene-VFA polymer used in
the feed.
Described herein is a radically initiated, surfactant mediated emulsion
polymerization process to polymerize N-vinylformamide (VFA) and styrene or substituted
styrene or vinyl pyridine. The polymerization reaction results in quantitative conversions
(> 99%) and obtained material are micro particles in nature and can be used without any
purification. Subsequent hydrolysis of resulting material introduces vinylamine (VAm)
functionality, forming terpolymer containing VAm, VFA, and styrene groups. Also, VFA
on hydrolysis readily forms amidine functionality, whereas the presence of methyl
functionality in vinylacetamide significantly delays or limits amidine formation. The
obtained polymer can be used as a cost effective dry strength additive in papermaking and
has many other potential applications.
Described is a process to produce a water dispersible additive which contains
vinylamine units, vinyl aromatic units, has micro particulate structure, is cationic in
nature, and when used as a paper making additive in the wet end of a paper making
process, it helps to improve strength properties of the paper. According to this process,
VFA is polymerized with styrene or substituted styrene by free radical initiated, surfactant
mediated emulsion polymerization and its subsequent hydrolysis. The hydrolyzed product
maintains micro particulate structure, is cationic in nature, is easily dispersible in water,
and helps to improve paper making process and paper strength properties. Whereas, the
vinylacetamide and styrene copolymers and their subsequently hydrolyzed materials
disclosed in U. S. Patent 4,238,579 need longer reaction time, are semi-quantitative in
conversion and needs a purification step, the soluble nature of the obtained material
suggest lower molecular weight polymers. The VFA based copolymer additives are cost
effective compared with n-vinyl acetamide and styrene or substituted styrene copolymers,
VFA homopolymers, and have improved performance to enhance strength properties of
the paper when compared with vinylamine homopolymers.
The present invention provides a process for making vinylamine-
vinylformamide-styrene terpolymer additives comprising:
a) reacting vinylformamide for a period of time with styrene or substituted
styrene under a free radical, emulsion polymerization reaction conditions;
b) producing a first polymer product which comprises randomly distributed
repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
c) hydrolyzing the first polymer product using an acid or base treatment;
d) producing a second polymer product comprising randomly distributed
repeating monomer units having at least two of the formula (III), (IV), (V) and (VI):
wherein,
R and R are H;
R is H or alkyl;
m and m independently is a positive mole percent and, m and m independently
1 2 3 4
may be 0 to 99 mole percent, and the sum of m , m m and m is equal to or less than x
1 2, 3 4
mole percent of formula (I).
In one embodiment of the present invention, the amount of each of the employed
monomers should be determined by fully considering performance and stability of the
resulting terpolymer. The ratio of VFA to styrene or substituted styrene in copolymer can
be varied from 99:1 to 50:50, can be 80:20 to 51:49, and may be 80:20 to 70:30, the sum
of percentages of monomer feed in reaction is always 100.
At above mentioned feed ratio VFA and styrene monomers are miscible with
each other, and may be added as a mixture of monomers in reaction feed or can be added
separately as neat solution.
In the present invention, surfactant for polymerization may be selected based on
its, Hydrophile-Lipophile Balance (HLB) number, functionality that does not poison free
radical or react with monomers. The HLB values for the surfactant of interest can be less
than 10 or more than 10, can be between 4 to 16, and may be between 10 to 14. The
amount of surfactant in the polymerization is employed in conventional amounts, for
example 0.1% to 4%, can be 0.15% to 2%, and may be 0.3% to 1% by weight, based on
the monomers.
In one embodiment of the present invention, the hydrophobic monomer
employed for copolymerization is selected from one or more than one of the following
aromatic monomers, styrene, α-methyl styrene, halogenated styrene, alkoxy styrene,
sulfonated styrene and pyridine or substituted pyridine.
In one embodiment of the present invention, the polymerization is carried out in
a solvent or diluents. The choice of solvent depends on compatibility of monomers and
end use of final product. The polymerization can be performed in aqueous solvents, or
organic solvents, or mixtures of both. The preferable solvent for polymerization is water,
in which resulting VFA-styrene polymer forms as a micro particulate structure. The pH
during polymerization is from 4 to 10, can be from 5 to 8, and may be 6 to 7.
In one embodiment of the present invention, a polymerization reaction is initiated
using free radical initiators or other materials known in the art for this purpose, for
example peroxides, hydroperoxides, redox catalysts, or azo compounds which decompose
to give free radicals. The preferable radical initiator for polymerization is water soluble
azo compounds. The initiators are employed in conventional amounts, and by controlling
the monomer to initiator ratio, molecular weight of the polymer can be altered; a technique
well known to those skilled in the art. Other chain extender or chain transfer agents that
can regulate VFA copolymer molecular weight can be employed.
The present invention also provides an aqueous dispersion comprising the
resulting polymer product from a process which comprises:
a) reacting vinylformamide with styrene or substituted styrene under a free
radical, emulsion polymerization reaction conditions;
b) producing a polymer product which comprises randomly distributed
repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
wherein, the polymer product in said aqueous dispersion is in a form of micro
particles, and the particle size of the polymer product is in the range of from 30
nanometer to 2000 nanometer.
In one embodiment of the present invention, obtained emulsions are well
dispersed emulsions of VFA and styrene or substituted styrene copolymer and are micro
particles in nature, wherein the particle size is from 30 nanometer to 2000 nanometer, can
be from 50 nanometer to 1000 nanometer, and may be from 70 nanometer to 200
nanometer. The particle size and size distribution of polymeric micro particles can be
controlled by polymerization conditions, surfactant concentration, and ratio of co-
monomers.
In one embodiment of the present invention, chain extenders that introduce a
branched structure in VFA and styrene copolymers may be used. These chain extenders
include, but are not limited to, divinylbenzene, ethylene glycol di(meth)acrylate,
diethyleneglycol di(meth)acrylate, methylenebisacrylamide, methylene-bis-(meth)
acrylamide, ethylene-bis-(meth) acrylamide, and hexamethylene-bis-(meth) acrylamide.
These may be used in an amount of 0.005 to 3 molar percent, can be 0.01 to 1 molar
percent, and may be 0.02 to 0.5 molar percent.
In the present invention, the polymerization temperature may depend on type of
initiator employed and its half life period at decomposition temperature. The
polymerizations of the present invention are performed at temperatures of from about 25ºC
to about 125ºC, temperatures can be between 30ºC to 90ºC, and may be between 60ºC to
85ºC.
In one embodiment of the present invention, polymerization reactions may be
performed under atmospheric, reduced, or super atmospheric pressure. The preferable
pressure for polymerization is reduced atmospheric pressure.
The obtained VFA and styrene or substituted styrene polymer micro particles
rich in VFA content are insoluble in common organic solvents and are easily dispersible in
water. In a very specialized solvent system comprising 1,1,1,3,3,3-hexafluoropropanol
and inorganic salts, VFA and styrene copolymers shows maximum solubility.
Formation of a copolymer is confirmed by different spectroscopic techniques and
is discussed in the experimental section. Without wishing to be bound by theory it is
believed that the VFA and styrene or substituted styrene units in obtained copolymers are
randomly distributed which offers desired material properties.
Described herein is a vinylamine-vinylformamide-styrene terpolymer additive
comprising the resulting second polymer product from a process which comprises:
a) reacting vinylformamide with styrene or substituted styrene in a free
radical, emulsion polymerization reaction;
b) producing a first polymer product which comprises randomly distributed
repeating units of formula (I) and (II);
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl
substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is
hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x
and y is 100 mole percent, and the ratio of x:y is in the range of from 99:1 to 50:50;
c) hydrolyzing the first polymer product with an acid or base treatment;
d) producing a second polymer product comprising randomly distributed
repeating monomer units having at least two of the formula (III), (IV), (V) and (VI):
wherein,
R and R are H;
R is H or alkyl;
m and m are independently a positive mole percent, m and m independently may
1 2 3 4
be 0 to 99 mole percent, and the sum of m , m m and m is equal to or less than x mole
1 2, 3 4
percent of formula (I),
wherein, the first polymer product is in the form of microparticles, and the particle
size of the first polymer product is in the range of from 30 nanometer to 2000 nanometer.
In one embodiment of the present invention, the VFA-Styrene or substituted
styrene copolymers are subjected to hydrolysis to introduce amine functionality. The
formamide group of VFA-styrene copolymer can be hydrolyzed by acid or base treatments
and vinylamine groups can be introduced, as described in U. S. Pat. No. 4,421,602 and
4,774,285. However, in addition to vinylamine functionality, hydrolysis of formamide can
also introduce amidine functionality to the resulting polymer. (see U. S. Pat. Appl. No.
2010/0193148 A1). The acid or base treatment on VFA-styrene copolymer does not alter
the structure of styrenic moiety. The degree of hydrolysis of formamide groups can be
altered by the amount of acid or base used, reaction temperature, and length of hydrolysis
reaction. Polymers obtained by a base treatment have a degree of hydrolysis from 10 to
99%, can be 20 to 80%, and may be 30 to 70%. The temperature for the hydrolysis
reaction may be from about 25ºC to 100ºC, can be between 40ºC to 90ºC, and may be
between 60ºC to 80ºC. The degree of hydrolysis is controlled by the amount of base
addition to the VFA-styrene copolymer, and is monitored by FT-IR analysis.
In another embodiment of the present invention, the hydrolyzed VFA-styrene
polymer, in which 10 to 99%, can be 20 to 80%, and may be 30 to 70% of the VFA units
are converted to vinylamine functionality resulting in a VAm-VFA-styrene terpolymer,
and are employed in papermaking processes to improve paper dry strength and wet
strength properties. The hydrolyzed micro particle dispersion of terpolymers was added to
the paper stock, prior to sheet formation, in an amount of from 0.05 to 2% by weight and
can be 0.1 to 1% by weight based on dry fiber. The invention can be employed to make
various grades of paper that benefit from enhanced dry strength including copy paper,
container board, corrugating medium, file folder, newsprint, paper board, packaging
board, printing and writing, and publication grade. These paper grades can be comprised
of any typical pulp fibers including groundwood, Kraft, sulfate, mechanical, and recycled.
The aqueous dispersion of the hydrolyzed terpolymers may also be applied to the surface
of the paper, and may help to improve strength as well as water hold out properties of the
paper.
In one embodiment of the present invention, partially hydrolyzed terpolymers
bearing styrene between 20 to 30 weight percent greatly improves strength properties of
the paper in comparison to its fully hydrolyzed analogues or polymers bearing different
styrene content, or hydrolyzed VFA homopolymers (Hercobond® 6350 and 6363
papermaking additives available from Ashland Inc).
The following examples further explain the invention and demonstrates that the
micro particle nature of the polymer helps to improve dry strength, wet strength, retention,
drainage properties of the paper when used during paper making process. The examples
and data presented below better illustrate the benefits of the claimed invention and are not
meant to be limiting.
Example 1- Synthesis of n-vinylformamide and styrene polymer (Table 1, Example 1-3)
A series of copolymers of n-vinylformamide with styrene as exemplified in
Example 1-3, were prepared as follows: to a 1 liter resin kettle equipped with overhead
stirrer, thermocouple, condenser, nitrogen inlet-outlet, and pressure gauge was added
445.81 g of deionized water, 1.22 grams of 75 wt % aqueous phosphoric acid, 1.79 grams
of 25 wt % aqueous sodium hydroxide and 0.5 g of Rhodameen PN-430 surfactant
(available from Rhodia, France). The resultant solution pH was adjusted to 6.5 +/- 0.3.
The kettle was heated to 80ºC while stirring at 250 RPM. The pressure was slowly
lowered to about 320 torr.
A mixture of n-vinylformamide (VFA, 90.4 grams), Styrene (33.12 g), and 3.0
wt % aqueous V-50 (18.47 grams) initiator (available from Wako Chemicals USA, Inc.,
Richmond, USA) are added concurrently over 90 minutes for the monomers and 170
minutes for the initiator respectively. After the VFA addition was complete, 10 grams of
boiled (deaerated) deionized water was used to rinse the VFA line. The polymerization
temperature was controlled at 78 +/- 2ºC. After the V-50 addition was complete, the kettle
vacuum was dropped to about 350 torr. After a total time of 260 minutes the vacuum was
released and the reactor was flushed with nitrogen (3 cycles of vacuum and nitrogen
refill). Then 18.47 g of 3 wt% V-50 solution was added slowly over a period of 1 hour at
78 +/- 2ºC, after complete addition reaction was continued for additional 2 hours. After
completion reactor was cooled to room temperature. The viscosity of the composition was
measured using a Brookfield Viscometer LV unit with spindle # 62 (unit of centipoise
(cP)).
The solid state 13C NMR analysis of the obtained polymers was performed by
grinding the polymers into fine powder in a cryogenic freezer mill and packing the powder
into 4-mm NMR rotors. The solid state 13C NMR analysis of VFA-styrene copolymer
sample in which VFA to styrene feed ratio was maintained at 73.2 to 26.8 shows random
distribution of the comonomer. Furthermore, the ratio of VFA to styrene calculated by
NMR analysis is in close agreement with feed ratio. A solvent extraction experiment was
also performed to further confirm copolymer formation. The VFA-styrene copolymer
was thoroughly washed with deuterated chloroform dissolving any atactic polystyrene.
The CDCl fraction was concentrated and analyzed by proton NMR, which did not show
any peaks corresponding to polystyrene homopolymer. Also, the FT-IR analysis showed a
strong absorbance at 1684 cm corresponding to a carbonyl group of amide and peaks in
the finger print region corresponding to styrene units. For SEC analysis, polymers were
dissolved in hexafluoroisopropanol and inorganic salts in which quantitative amounts of
polymer were soluble. The SEC analysis of the soluble fraction using both an RI and UV
detector showed a monomodal peak, supporting the above claim for formation of
copolymer. Further, the SEC analysis using UV detection of different fractions collected
at different time intervals suggest styrene is uniformly distributed through out the polymer
chain. Particle size was measured by light scattering, using Horiba LA900 and showed a
median particle size of 90 nanometer. For thermal analyses, polymers were precipitated in
methanol and dried under vacuum. The glass transition temperature (Tg) analysis of the
copolymers by Differential Scanning Calorimetry analysis are recorded from the second
heating cycle and are reported in Table 1. Glass transition temperatures were between
50ºC to 98ºC, and increased with lowering styrene content from 49 wt % to 7 wt %.
Polymers of Examples 1-1, 1-2, 1-4 and 1-5 were prepared following a similar
process, except that different ratios of VFA to styrene were used and are listed in Table 1.
Table 1: Effect of VFA to styrene ratio on polymer properties
Example % Total Styrene Brookfield Mean Particle Size Tg (ºC)
Solid Viscosity, (μm)
Mol% Wt%
centipoise (cP)
1-1 20.1 5 7.2 2819 13 98.5
1-2 20.2 10 14 1539 0.08 75.7
1-3 19.7 20 26.8 626 0.09 71.0
1-4 19.6 30 38.6 194 0.12 54.7
1-5 20.3 40 49.4 156 0.13 51.7
These experiments were performed at equal surfactant concentration, and
different VFA to styrene ratio suggest viscosity of copolymer emulsion and micro particle
size is dependent on VFA to styrene ratio. Additionally, glass transition temperature of
copolymers decreased from 98.5 ºC to 51.7 ºC, with an increase in styrene content from
7.2 wt% to 49.4 wt%, respectively.
Example 2- Effect of surfactant and chain extender on polymer properties
Example 1 is repeated, except that the concentration and type of surfactant were
varied. Polyoxyethylated oleyl amine (PN-430) with HLB 14.2, and Peroxyethylated
tallow amine (T-15, available from Rhodia, France) with HLB 10 were employed as
surfactant and divinylbenzene was used as chain extender.
Table 2: Effect of surfactant on polymer properties
Example Surfactant DVB %Total Brookfield Mean Particle Tg (ºC)
(wt %) (wt %) Solid Viscosity, cP Size, (μm)
2-1 PN-430(0.4) 0 19.7 626 0.09 71
2-2 T-15 (0.4) 0 19.1 907 0.08 70.6
2-3 PN-430(0.8) 0 18.6 299 0.09 71.7
2-4 T-15(0.8) 0 19.1 667 0.08 74.9
2-5 PN-430(0.4) 0.4 19.4 458 0.11 70.7
2-6 PN-430(0.6) 0 18.9 222 0.16 -
2-7 T-15(0.4) 0.4 18.6 534 0.07 71.1
2-8 PN-430(0.8) 0.4 19.3 338 0.1 67.6
2-9 T-15(0.8) 0.4 20.2 595 0.08 71.5
2-10 PN-430(0.6) 0.8 19.2 328 0.11 -
These results show surfactant type, and surfactant concentration impacts
viscosity of copolymer emulsion properties. Whereas, polymer chain extender has
minimal impact on emulsion viscosity and also copolymer properties.
Example 3- Hydrolysis of n-vinylformamide and styrene polymer
Hydrolysis of NVF/Styrene polymer was performed using a caustic treatment.
The amount of caustic used and reaction time can be varied depending on the desired
hydrolysis level (see Table 3). In a typical example, a 500-mL round-bottom flask was
fitted with a condenser, pH and temperature probes, a temperature controlled heating
mantle, an addition funnel, and a mechanical stirrer. To the flask was added 200 grams of
polymer intermediate, to this 3.2 g of 20% sodium bisulfite solution was added and stirred
for 10 min. The reaction mixture was heated to 80 C and then 32 grams of 25 wt %
aqueous sodium hydroxide solution (caustic) was added over 15 minutes. After 3 hours at
80 C, the reaction mixture was cooled to 40 C and then 30 wt % aqueous hydrochloric
acid was added over 5 minutes to adjust the pH to 9. The degree of hydrolysis is
monitored by FTIR analysis, in which intensity of the 1684 cm peak decreased, and
intensity of the new broad peak at 3400 cm due to primary amine group increased.
Similarly in one example, the zeta potential measured on VFA-styrene copolymer
particles, showed a particle charge of 1.92 and 1.30 mV, at pH 4 and 6, respectively.
Upon hydrolysis, the resulting VAm-VFA-styrene copolymer showed a particle charge of
86.04 and 41.96 mV, at pH 4 and 6, respectively, suggesting formation of primary amine
functionality. The glass transition temperatures of hydrolyzed polymers containing VAm
functionality are comparatively lower than their corresponding prepolymers.
Table 3: Hydrolysis of n-vinylformamide and styrene copolymer
Example Sample % Hydrolysis %Active Brookfield
ID Solid Viscosity, cP
3-1 1-1 99 15.6 395
3-2 1-2 99 15.9 477
3-3 1-3 99 16.1 181
3-4 1-4 99 16.6 388
3-5 1-5 99 17.4 294
3-6 2-2 50 15.9 398
3-7 2-2 99 13.7 195
3-8 2-3 50 15.5 300
3-9 2-3 99 13.4 182
3-10 2-4 50 15.9 345
3-11 2-4 99 13.7 198
3-12 2-5 50 16.1 280
3-13 2-5 99 13.9 135
3-14 2-6 30 16.6 335
3-15 2-6 65 14.7 268
3-16 2-6 99 13.4 228
3-17 2-7 50 15.5 296
3-18 2-7 99 13.4 163
3-19 2-8 50 15.9 250
3-20 2-8 99 13.6 120
3-21 2-9 50 16.6 195
3-22 2-9 99 14.3 143
3-23 2-10 30 17.3 420
3-24 2-10 65 15.1 190
3-25 2-10 99 13.4 146
Table 3 suggests hydrolyzed copolymer emulsions are less viscous when
compared with VFA-styrene copolymer emulsions.
Example 4 - Evaluation of terpolymers as dry strength additives in papermaking
applications
The dry strengths of papers made with the vinyl amine-vinylformamide-styrene
terpolymer additives of the above examples were compared with the dry strengths of paper
made with a benchmark dry strength resin polyvinylamine (Hercobond® 6350 paper
performance additive, available from Ashland Inc.).
Linerboard paper was made using a papermaking machine. The paper pulp was a
100 % recycled medium with 50 ppm hardness, 25 ppm alkalinity, 2.5 % GPC D15F
oxidized starch, 0.5% Stalok 300 cationic starch and 2000 µS/cm conductivity. The
system pH was 7.0 and the pulp freeness was 350-420 Canadian Standard Freeness (CSF)
with the stock temperature at 52°C. The basis weight was 100 lbs per 3000 ft . VAm-
VFA-styrene terpolymer additives prepared in the above examples were added as dry
strength agents to the wet end of the papermaking machine at the level of 0.3 weight % of
polymer active versus dry paper pulp. Ring crush, dry Mullen burst, dry tensile, and wet
tensile tests were used to measure the dry strength effects.
The dry strength test results are shown below in Table 4. Performance of the
vinylamine-vinylformamide-styrene terpolymer additives are expressed as a percentage of
the dry strength of paper made without a dry strength resin.
Table 4: Strength testing of linerboard made using vinyl amine-vinylformamide-styrene
terpolymer additives and wet end starch
Example Additive Ring Crush Dry Mullen Wet Tensile
4-1 - 100 100 100
4-2 3-1 104 103.5 447.8
4-3 3-2 104.1 104.7 409
4-4 3-3 104.9 107.4 403
4-5 3-4 101.9 103.9 306.9
4-6 3-5 101.4 100.3 263
These data illustrate that the dry strength of the paper can be improved by using
VAm-VFA-styrene copolymer as wet end dry strength additive.
Linerboard paper was made using paper making conditions mentioned in
Example 4 except Stalok 300 was not used. VAm-VFA-styrene terpolymer additives
prepared in Example 3 were added as dry strength agents to the wet end of the
papermaking machine at a level of 0.3 weight % of polymer active versus dry paper pulp.
Ring crush, dry Mullen burst, dry tensile, and wet tensile tests were used to measure the
dry strength effects.
The dry strength test results are shown below in Table 5. Performances of the
vinylamine-vinylformamide-styrene terpolymer additives are expressed as a percentage of
the dry strength of paper made without a dry strength resin.
Table 5: Strength testing of linerboard made using vinyl amine-vinylformamide-styrene
terpolymer additives and no wet end starch
Example Additive Ring Dry Mullen Dry Wet
Crush Tensile Tensile
-1 - 100.0 100.0 100.0 100.0
-2 Hercobond® 6350 108.2 106.8 103.3 509.0
-3 3-6 109.4 121.2 103.8 330.4
-4 3-7 107.5 109.1 102.1 390.6
-5 3-8 108.8 110.1 107.2 267.1
-6 3-9 111.2 106.8 96.1 319.7
-7 3-10 108.9 118.4 103.6 318.2
-8 3-11 107.8 107.7 98.9 386.8
-9 3-12 108.6 116.9 103.9 296.9
-10 3-13 110.9 116.5 106.5 384.0
-11 3-14 112.1 124.3 111.9 320.1
-12 3-15 111.5 110.3 104.7 403.1
-13 3-16 108.1 117.6 107.2 488.2
-14 3-17 111.0 113.6 109.5 325.0
-15 3-18 110.1 109.5 103.6 381.0
-16 3-19 109.5 110.3 109.5 290.0
-17 3-20 109.4 111.2 105.3 354.4
-18 3-21 111.1 114.6 108.3 294.2
-19 3-22 104.5 115.3 104.5 357.8
-20 3-24 110.9 118.1 113.7 359.5
-21 3-25 105.6 103.7 104.7 413.0
-22 3-26 112.1 104.4 103.6 487.1
These data illustrate that partially hydrolyzed VFA-styrene copolymers have
better performance compared with Hercobond® 6350. At equal addition levels,
hydrolyzed VFA-styrene copolymers offer a lower cost additive and also provides
improved dry strength when compared with polyvinylamine. Wet tensile of paper made
with hydrolyzed VFA-styrene copolymer micro particles was expected to be lower when
compared with polyvinylamine.
The vinylamine-vinylformamide-styrene terpolymer additive of the present
invention, is added to the wet end of the paper making system to improve paper making
processes and paper wet and dry strength, and it can be applied on an already formed
paper to improve paper finish properties. Thus, the present invention provides a paper
product which comprises a second polymer product prepared by the process of the
present invention, or a paper product which comprises the vinylamine-vinylformamide-
styrene terpolymer additive of the present invention.
In the description in this specification reference may be made to subject matter
which is not within the scope of the claims of the current application. That subject matter
should be readily identifiable by a person skilled in the art and may assist in putting into
practice the invention as defined in the claims of this application.
Claims (23)
1. A process for making vinylamine-vinylformamide-styrene terpolymer additives comprising: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a first polymer product which comprises randomly distributed repeating units by the formula (I) and (II): wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; c) hydrolyzing the first polymer product using an acid or base treatment; d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formula (III), (IV), (V) and (VI): wherein, R and R are H; R is H or alkyl; m and m independently is a positive mole percent, and m and m independently 1 2 3 4 may be 0 to 99 mole percent, and the sum of m , m m and m is equal to or less than x 1 2, 3 4 mole percent of formula (I).
2. The process of claim 1, wherein Ar is phenyl and R is H.
3. The process of claim 1, wherein the first polymer product is vinylformamide-styrene copolymer.
4. The process of claim 1, wherein the emulsion polymerization reaction is carried out at temperature in the range of from about 25ºC to about 125ºC, can be carried out at temperature in the range of from about 30ºC to about 90ºC, and may be carried out at temperature in the range of from about 60ºC to about 85ºC.
5. The process of claim 1, wherein the ratio of x:y is in the range of from 80:20 to 51:49, and may be in the range of from 80:20 to 70:30.
6. The process of claim 1, wherein about 10% to 99% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
7. The process of claim 1, wherein about 20% to 80% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d), and can be 30% to 70% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
8. The process of claim 1, wherein the second polymer product is a cationic, and water dispersible polymer.
9. An aqueous dispersion comprising the resulting polymer product from a process which comprises: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a polymer product which comprises randomly distributed repeating units by the formula (I) and (II): wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; wherein, the polymer product in said aqueous dispersion is in a form of microparticles, and the particle size of the polymer product is in the range of from 30 nanometer to 2000 nanometer.
10. The aqueous dispersion of claim 9, wherein the particle size of the polymer product is in the range of from 50 nm to 1000 nanometer, and can be in the range of from 70 nanometer to 200 nanometer.
11. A vinylamine-vinylformamide-styrene terpolymer additive comprising the resulting second polymer product from a process which comprises: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a first polymer product which comprises randomly distributed repeating units by the formula (I) and (II): wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; c) hydrolyzing the first polymer product using and acid or base treatment; d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formulae (III), (IV), (V) and (VI): wherein, R and R are H; R is H or alkyl; m and m independently is a positive mole percent, and m and m independently 1 2 3 4 may be 0 to 99 mole percent, and the sum of m , m m and m is equal to or less than x 1 2, 3 4 mole percent of formula (I), wherein, the first polymer product is in a form of microparticles, and the particle size of the first polymer product is in the range of from 30 nanometer to 2000 nanometer, and the second polymer product is vinylamine-vinylformamide-styrene terpolymer, and wherein, said vinylamine-vinylformamide-styrene terpolymer additive is in a form of microparticles in aqueous dispersion, and the viscosity measured at ambient temperature (about 20ºC to about 25ºC) of active solids in the range of from 13.0% to 18.0% of vinylamine-vinylformamide-styrene terpolymer is in the range of from 100 to 500 cP.
12. The vinylamine-vinylformamide-styrene terpolymer additive of claim 11, wherein the particle size of the first polymer product is in the range of from 50 nm to 1000 nanometer, and can be in the range of from 70 nanometer to 200 nanometer.
13. The vinylamine-vinylformamide-styrene terpolymer additive of claim 11, wherein about 10% to 99% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
14. The vinylamine-vinylformamide-styrene terpolymer additive of claim 11, wherein about 20% to 80% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d), and can be about 30% to 70% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
15. The vinylamine-vinylformamide-styrene terpolymer additive of claim 11, wherein the vinylamine-vinylformamide-styrene terpolymer additive is added to the wet end of the paper making system to improve paper making process and paper wet and dry strength.
16. The vinylamine-vinylformamide-styrene terpolymer additive of claim 11, wherein the vinylamine-vinylformamide-styrene terpolymer additive is applied on already formed paper to improve paper finish properties.
17. A paper product comprising the second polymer product of claim 1.
18. A paper product comprising the vinylamine-vinylformamide-styrene terpolymer additive of claim 11.
19. A process according to claim 1, substantially as herein described with reference to any example thereof.
20. An aqueous dispersion according to claim 9, substantially as herein described with reference to any example thereof.
21. A vinylamine-vinylformamide-styrene terpolymer additive according to claim 11, substantially as herein described with reference to any example thereof.
22. A second polymer product produced by the process of any one of claims 1 to 8.
23. A second polymer product according to claim 22, substantially as herein described with reference to any example thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161557949P | 2011-11-10 | 2011-11-10 | |
US61/557,949 | 2011-11-10 | ||
PCT/US2012/063020 WO2013070489A1 (en) | 2011-11-10 | 2012-11-01 | Vinylamine containing copolymer microparticles as additives in papermaking |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ622454A NZ622454A (en) | 2015-12-24 |
NZ622454B2 true NZ622454B2 (en) | 2016-03-30 |
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