MXPA01007124A - Modified vinyl polymers containing amphiphilic hydrocarbon moieties - Google Patents
Modified vinyl polymers containing amphiphilic hydrocarbon moietiesInfo
- Publication number
- MXPA01007124A MXPA01007124A MXPA/A/2001/007124A MXPA01007124A MXPA01007124A MX PA01007124 A MXPA01007124 A MX PA01007124A MX PA01007124 A MXPA01007124 A MX PA01007124A MX PA01007124 A MXPA01007124 A MX PA01007124A
- Authority
- MX
- Mexico
- Prior art keywords
- clause
- group
- polymer
- paper
- sheet
- Prior art date
Links
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 114
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 41
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 35
- 229920002678 cellulose Polymers 0.000 claims abstract description 32
- 239000001913 cellulose Substances 0.000 claims abstract description 32
- 210000001519 tissues Anatomy 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920001888 polyacrylic acid Polymers 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 54
- 150000002430 hydrocarbons Chemical group 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 41
- 229920001400 block copolymer Polymers 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229920000578 graft polymer Polymers 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 239000000835 fiber Substances 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 24
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000007900 aqueous suspension Substances 0.000 claims description 12
- 238000011068 load Methods 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- -1 aliphatic amines Chemical class 0.000 description 42
- 125000002091 cationic group Chemical group 0.000 description 35
- 229920001223 polyethylene glycol Polymers 0.000 description 22
- 238000010348 incorporation Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 18
- 125000000129 anionic group Chemical group 0.000 description 17
- 238000007334 copolymerization reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 229920001451 Polypropylene glycol Polymers 0.000 description 8
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N Glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229940015043 Glyoxal Drugs 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 230000000996 additive Effects 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000006011 modification reaction Methods 0.000 description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000002194 synthesizing Effects 0.000 description 6
- 102100001279 PAM Human genes 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 238000006266 etherification reaction Methods 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 230000002378 acidificating Effects 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000000640 hydroxylating Effects 0.000 description 4
- 238000005805 hydroxylation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 210000004872 soft tissue Anatomy 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 230000001419 dependent Effects 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000002209 hydrophobic Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1-octoxyoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- RRAQGPNOVYEVCW-UHFFFAOYSA-N OC(=O)C=C.C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 Chemical compound OC(=O)C=C.C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 RRAQGPNOVYEVCW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000266 alpha-aminoacyl group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000035618 desquamation Effects 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001815 facial Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LCDOENXNMQXGFS-UHFFFAOYSA-N phenoxybenzene;prop-2-enoic acid Chemical compound OC(=O)C=C.C=1C=CC=CC=1OC1=CC=CC=C1 LCDOENXNMQXGFS-UHFFFAOYSA-N 0.000 description 1
- 239000003211 photoinitiator Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GHVWODLSARFZKM-UHFFFAOYSA-N trimethyl-[3-methyl-3-(prop-2-enoylamino)butyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC(C)(C)NC(=O)C=C GHVWODLSARFZKM-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Synthetic polymers having moieties capable of covalent or hydrogenbonding to cellulose and one or more amphiphilic moieties are disclosed. These polymers are capable of providing two distinct properties to paper products, such as tissues, which properties heretofore have been imparted through the use of at least two different molecules. The backbone of these synthetic polymers is based on modified vinyl polymers, such as polyvinyl alcohol, polyacrylamides and polyacrylic acids.
Description
VINYL POLYMERS MODIFIED CONTAINING ANTIPHYLIC HYDROCARBON MITES
Background of the Invention
In the manufacture of paper products, such as facial tissue, tissue for bathroom, paper towels, paper napkins and the like, a wide variety of product properties are imparted to the final product through the use of chemical additives. Examples of such additives include softeners, debonders, wet strength agents, dry strength agents, sizing agents, opacifiers and the like. In many cases more than one chemical additive is added to the product at some point in the manufacturing process. Unfortunately, there are cases where certain chemical additives may not be compatible with each other or may be detrimental to the efficiency of the papermaking process, as may be the case with the effect of wet end chemicals on downstream efficiency of creping adhesives. Another limitation which is associated with the addition of wet end chemical is the limited availability of suitable bonding sites on the paper fibers to which the chemicals themselves can be attached. Under such circumstances, more than one chemical functionality competes with limited available binding sites, sometimes resulting in insufficient retention of one or both chemicals on the fibers.
Therefore, there is a need for means to apply more than one chemical functionality to the paper web which mitigate the limitations created by the limited number of binding sites.
Synthesis of the Invention
In certain cases, two or more chemical functionalities can be combined in a single molecule, so that the combined molecule imparts at least two different product properties to the final paper product that has been imparted through the use of two or more. more different molecules. More specifically, synthetic polymers, which are commonly used in the paper industry as dry strength resins, wet strength resins, auxiliary resins, can be combined into a single molecule with amphiphilic hydrocarbons which are used in the industry. of the paper with surface modifiers, release agent, antifoams, softeners, lubricant binder. The resulting molecule is a synthetic polymer which has halves capable of binding to the amphiphilic hydrocarbon and cellulose moieties which can provide several potential benefits, depending on the specific combination employed, including: softness imparting strength aids; softeners that do not reduce the resistance; wet strength with improved dry / wet strength ratio; surface sensing modifiers with reduced desquamation and fraying; auxiliary resistance with controlled absorbency; retention aids that soften; and the improved retention of the amphiphilic hydrocarbon when added as a wet end additive.
The "synthetic polymers" as described herein, have a part of their structure derived from the polymerization of ethylenically unsaturated compounds which contain pendant groups that can form hydrogen bonds, ionic bonds or covalent bonds with cellulose molecules in fibers, increasing by both the union of entrefibra. These may include polyacrylamide, polyvinyl alcohol, polyacrylic acid, polymaleic anhydride, polymaleic acid, polyitaconic acid, cationic polyacrylamides, anionic polyacrylamides and the like. The synthetic polymers as described herein can be water soluble, organic soluble or soluble in mixtures of water and organic compounds miscible in water. Preferably these are water soluble or water dispersible but this is not a necessity of the invention. Also included within the definition are the salts of the aforementioned acidic polymers. The substances which can be combined with the acidic part of the polymers to make the salts include the alkali metals such as potassium and sodium usually added in the form of their hydroxides. The aliphatic amines and the alkanol amines, such salts and method for preparing such salts are well known to those skilled in the art.
Also as used herein, the phrase "amphiphilic hydrocarbon moieties" are organic compounds that include alkanes, alkenes, alkynes, cyclic aliphatic aromatic hydrocarbons that contain surfactants or are capable of acting as a surfactant. The hydrocarbon portion of such materials may be linear or branched, saturated or unsaturated, substituted or unsubstituted.
Depending on the chemical and the desired impact on the paper sheet, the synthetic polymers of this invention can be applied to the paper fabric by any means known to those skilled in the art. Such means include the addition of wet end, the spraying addition onto the wet fabric, and a creping chemical sprayed onto the Yankee dryer, or as a post addition treatment including spraying, printing or coating.
Therefore, in one aspect, the invention resides in a synthetic polymer having halves capable of binding cellulose and containing one or more amphiphilic hydrocarbon moieties, said synthetic polymer having the following structure:
where
a, b,
c, d = 0 so that c + d > 0;
w > 1;
Qj = a block or graft monomer or copolymer unit containing a pendant group capable of forming hydrogen bonds or covalent bonds with cellulose. Suitable pendant groups for the hydrogen bonds are -C0NH2, -COOH, -COO "M +, -OH and mixtures of said groups.The preferred pendant groups for the covalent bond are aldehydes and anhydrides, M + can be any suitable counterion including Na +. , J +, Ca + 2 and the like.
Q2 = a block or graft copolymer unit in which the amphiphilic functionality is constructed. This may be alkyl hydrocarbons with hydrophilic functionality (such as -OH, ethoxy and propoxy groups) or aliphatic hydrocarbons with a
hydrophilic functionality. The hydrocarbons may be linear or branched, saturated or unsaturated, substituted or unsubstituted, with two or more hydrocarbons. Q, it can take the form of
Wherein Z, is any bridging radical whose purpose is to provide the incorporation into the polymer column and Q, is as previously defined. Q3 = a monomer unit or a block or graft copolymer containing a loading functionality. Such charging functionality is preferably cationic but
can be anionic or amphoteric; and Q4 = a monomer unit or block or graft copolymer containing a hydrophilic moiety, which is desirable to make the material in a form suitable for papermaking. Q4 can take the form of -Z: -Q4-Z2 'where Z :, Z2' are any bridge radicals, the same or different whose purposes are to provide incorporation into the polymer column and Q4 is as previously defined . Q4 can be incorporated to decentralize the increased polymer hydrophobicity caused by the introduction of the amphiphilic hydrocarbon moieties. Examples of suitable halves Q4 are (but not limited to) the aliphatic polyether derivatives of the formula [(CR1R2) xO] and -R3, where R, R2 is H or CH3, x = 2, y = 1 and R3 is a suitable terminal group including -CH3, -H, -C2H5, -NH2.
It should be noted that when Q3 or another charged half is present in the synthetic polymer, which will require an adequate counter-ion. Such counterions may or may not be represented in the formulas. Where such counterions are not represented in the formulas, it should be understood that such an ion will exist. The specific counter ion is not critical to invention, such a counter ion is only necessary to provide load balance. For the cationically charged groups, the most common anions are those of the halides and the alkyl sulfat. For the anionically charged groups on polymer the most common counterions will be those of the alkaline earth metals and alkali as well as the amine and cationic ammonium derivatives.
More specifically, the invention resides in a synthetic polymer having the following structure:
where :
w > 1;
R1, R, ', R2, R3 = H, C, _4 alkyl:
a, b, > 0;
c, d = 0 so that c + d > 0;
w = 1;
Q4 = a unit of block or graft monomer or copolymer containing one half
hydrophilic, which is desirable to make the material in a suitable form for making paper. Q4 can take the form of -Z2-Q4-Z2 '- where Z2, Z2' are bridge radicals, the same or different ones whose purpose is to
provide the incorporation into the polymer column and Q4 is as previously defined. Q4 can be incorporated to decentralize the hydrophobicity of the increased polymer caused by the introduction of
the amphiphilic moieties.
R0 = any group capable of forming hydrogen bonds or covalent with cellulose. Preferred groups are -CONH ,, -COOH, COO "M +, -20 OH, -CONCHCHOHCHO and mixtures of said groups;
A, = -H, -COOH;
R4 = Z - R6 radical where: 25 Z = aryl, -CH2-, -COO-, -CONR'-, -O-, -S-, - OS020-, -CONHCO-, -CONHCHOHCHOO- or any other radical able to bypass the R6 group to the vinyl column part
of the molecule. (R '= H, alkyl);
R6 = an amphiphilic hydrocarbon; this may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or
ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality. Hydrocarbons can be linear or branched, saturated or unsaturated, substituted or unsubstituted
with two or more hydrocarbons.
R5 = Z2-R10-W;
Z2 = aryl, -CH2-, -COO-, -CONH, - -0-, -S-, -20 OS020-, any radical capable of bridging the Ri0 group to the vinyl column part of the molecule;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of two or more carbons preferably - (CH2CH2) -, C (CH3) 2CH2CH2-; Y
W = where alkyl group -N + Rp, R12, R, 3 wherein R ^ R ^ R ^ is a C.
- [CH2CR3Rj] c- can also be the residue formed by the copolymerization with dimethyldiallylammonium chloride. In this case the waste containing charge [CH; CR3R5j c- will be in the form of the monomers with repeating units of the structure:
In another aspect, the invention resides in a sheet of paper, such as a tissue sheet comprising a synthetic polymer having halves capable of binding cellulose and containing an amphiphilic hydrocarbon moiety, said polymer having the following structure:
QHrt Q-fr where:
a, b, > 0;
c, d = 0 so that c + d > 0;
w > 1;
Qi = a unit of monomer or copolymer d
block or graft containing a hanging group capable of forming covalent or hydrogen bonds with cellulose. The preferred pendant groups for hydrogen bonding are -CONH2, -COOH, -COO "M", -OH
mixtures of said groups. The preferred pendant groups for the covalent linkage are aldehydes and anhydrides, M + can be any suitable counterion including Na +, J +, Ca + 2 and the like. Q2 = a unit of block copolymer or graft copolymer where the ampliclic functionality is constructed. This can be alkyl hydrocarbons with functional
hydrophilic (such as -OH, ethoxy propoxy groups) or aliphatic hydrocarbons with a hydrophilic functionality. The hydrocarbons may be linear or branched, saturated or unsaturated, substituted or unsubstituted, with two or more hydrocarbons. Q, can take the form of -Z ^ Qj-Z, - where Z, is a bridge radical whose purpose is to provide the incorporation into the polymer column and Q, is as previously defined. 10 Q3 = a monomer unit or a block or graft copolymer containing a loading functionality. Such charging functionality is preferably cationic but
can be anionic or amphoteric; Y
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable to make
the material in a form suitable for papermaking. Q4 can take the form of -Z2-Q4-Z2 'where Z2, Z2' are bridging radicals, the same or different ones whose purpose is to
provide incorporation into the polymer column and Q4 is as previously defined. Q4 can be incorporated to offset the hydrophobicity of the increased polymer caused by the introduction of the amphiphilic hydrocarbon moieties. Examples of suitable halves Q (but not limited to these) are the aliphatic polyether derivatives of the formula f (CR, R2) .0] and -R3, where R, R2 is H or CH3, xa2, and > 1 and R3 is any suitable terminal group including -CH3, -H, -CH5, -NH2.
More specifically, the invention resides in a sheet of paper, such as a tissue sheet, comprising a synthetic polymer having a hydrogen binding capacity and containing an amphiphilic hydrocarbon moiety, said polymer having the following structure:
eCR, CR, ir- CH2CR: - tCH2CR3 tt Q4I3- A, or * 4 R5
wherein w = 1, -R,, R, R2, R3-H, C, _4 alkyl a, b, > O;
c, d O so that c + d > O;
w > 1;
Q4 = a monomer unit or a graft or block copolymer containing a hydrophilic mite, which is desirable for making
the material in a form suitable for papermaking. Q4 can take the form of -Z2-Q4-Z2 '- where Z2, Z2' s are bridging radicals, the same ones whose purpose is the d
provide incorporation into the polymer column and Q4 is as previously defined. Q4 can be incorporated to decentralize the hydrophobicity of the polymer increased by the introduction of the
amphiphilic halves. Examples of suitable halves Q4 are (but are not limited to) these are the aliphatic polyether derivatives of the formula - [(CR, R2) .0] and -R3, where R, R2 is H or CH3, x = 2, y = ly and R3 e
Any suitable terminal group including -CH3, -H, -C2H5, -NH2;
Ro = any group capable of forming hydrogen bonds or covalent with cellulose. Suitable groups are -CONH, -COOH, COO "M +, - OH, -CONHCHOHCHO and anhydride including
mixtures of said groups;
A, = -H, -COOH;
R4 = Z - R6 radical wherein: Z Z = aryl, -CH2-, -COO-, -CONR'-, -O-, -S-, -OS020-, -CONHCO-, -CONHCHOHCHOO- or any radical capable of bridging group R6 to the vinyl column part of
the molecule. (R '= H, alkyl);
R6 = an amphiphilic hydrocarbon radical; this may be an alkyl hydrocarbon radical with hydrophilic functionality such
as the -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality. The hydrocarbons can be linear or branched, saturated or unsaturated,
substituted or unsubstituted with two or more hydrocarbons.
R, = Z2-R10-W;
Z, = aryl, -CH2-, -COO-, -CONH, - -O-, -S-, -OS020-, or any radical capable of bridging the group R10 to the vinyl column part of the molecule;
Rio _ any aliphatic or aromatic hydrocarbon, linear or branched, of two or more carbons, preferably - (CH2CH2) -, C (CH3), CH2CH2-; Y
W = -N * R ,,, R?;, R, 3 wherein Rp, R, 2, R13 alkyl group.
- [CH2CR3R5] c- can also be the residue formed by the copolymerization with dimethyldiallylammonium chloride. In this case the waste containing the charge [CH2CR3R5] C- will be to the shape of the monomers with the repeating units of the structure:
In another aspect, the invention resides in a method for making a sheet of paper, such as a tissue sheet comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of fibers to make paper on a forming fabric to form a fabric; and (c) draining and drying the fabric to form a sheet of paper, wherein a synthetic polymeric additive is added to the aqueous fiber suspension or to the fabric, said polymeric additive having the following structure:
-h QI-JG tQrtr 1 QHr +
where :
a, b, 0;
c, d = 0 so that c + d > 0, - w = 1;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen bonds or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonds are -CONH2, -COOH, -COO "M +, -OH and mixtures of said groups.The preferred pendant groups for covalent attachment 5 are aldehydes and anhydrides, M + can be any suitable counter-ion. including Na +, J +, Ca + 2 and the like.
Q2 = a block or graft copolymer unit where the amphiphilic functionality is constructed. This may be alkyl hydrocarbons with hydrophilic functionality (such as -OH, ethoxy and propoxy groups) or aliphatic hydrocarbons with hydrophilic functionality. The hydrocarbons may be linear or branched, saturated or unsaturated, substituted or unsubstituted, with two or more hydrocarbons. Q, can take the form of 20 where Z, is a bridge radical whose purpose is to provide incorporation into the polymer column and Q! it is as previously defined.
Q3 = a unit of block or graft monomer or copolymer containing a loading functionality. Such a load functional is preferably cationic but can be anionic or amphoteric; Y
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for making paper. Q4 can take the form of -Z2-Q4- 10 Z2 'where Z2, Z2' are any bridging radicals, the same or different ones whose purpose is to provide the incorporation into the polymer column and Q4 is as previously defined . Q4 can be
incorporated to de-stress the increased polymer hydrophobicity caused by the introduction of the amphiphilic hydrocarbon moieties. Examples of the appropriate Q4 halves are (but not
limited a) the aliphatic polyether derivatives of the formula - [(CR, R2) .0] V-R3, wherein Rl t R2 is H or CH3, x > 2, y = l and R3 is any suitable terminal group including -CH3, -H, -C2H5, -NH2. More specifically, the invention resides in a method for making a sheet of paper, such as a sheet of tissue, m comprising the steps of: (a) forming an aqueous suspension or fibers for making paper; (b) depositing the aqueous suspension of the fibers to make paper on a forming fabric to form a fabric; and (c) draining and drying the fabric to form a sheet of paper, wherein the synthetic polymeric additive is added to the aqueous fiber suspension or to the fabric, said polymeric additive having the following structure:
where:
w > 1;
R ,, R? ', R2, R] = H, C alkyl:
a, b, 0; C, d = 0;
Q4 = a unit of block or graft monomer or copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for making paper. Q4 can take the form of -Z2-Q4-Z2 '- where Z2, Z2' are any bridging radicals, the same or different ones whose purpose is to provide incorporation into the polymer column and Q4 is as defined previously. Q4 can be incorporated to decentralize the
hydrophobicity of the polymer caused by the introduction of the amphiphilic hydrocarbon moieties. Examples of suitable Q4 moieties are (but are not limited to, the aliphatic polyether derivatives of the
Formula - [(CR, R2) xO] y -R3, wherein R, R2 is H or CH3 x > 2, y = 1 and R 3 is any suitable terminal group including -CH 3, -H, -C 2 H 5, -NH 2;
RQ = any group capable of forming covalent hydrogen bonds with cellulose. Preferred are -CONH2, -COOH, COO ", -OH, CONHCHOHCHO anhydride including mixtures of said groups; A, = -H, -COOH;
R4 = Z - R6 radical where:
Z = aryl, - -CH2-, -COO-, -CONR'-, -0-, -S-, - 0S020-, -C0NHC0-, -CONHCHOHCHOO- or
Any radical capable of bridging the R6 group with the vinyl column part of the molecule. (R '= H, alkyl);
R6 = an amphiphilic hydrocarbon radical; this may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with the hydrophilic functionality. The hydrocarbons may be linear or branched, saturated or unsaturated, substituted or unsubstituted with two or more hydrocarbons.
R5 = Z2-R10-W;
Z2 = aryl, -CH2-, -COO-, -CONH, - -O-, -S-,-OS020-, any radical capable of bridging group R10 to the vinyl column part 25 of the molecule;
R10 = any aliphatic or aromatic hydrocarbon, linear or branched, of two or more carbons, preferably - (CH2CH2) -, C (CH3) 2CH2CH2-; Y
W = -N + Ru, R12, R, 3 wherein Rp / R?; / Rl3 is a C alkyl group.
- [CH2CR3R5] c- can also be the residue formed by copolymerization with dimethyldiallylammonium chloride. In this case the waste containing charge [CH2CR3R5] C- will be in the form of monomers with the repeating units of the structure:
The amount of modified vinyl polymer containing amphiphilic hydrocarbon moieties added to the papermaking fibers can be from 0.02 to about 4 percent by weight, on a dry fiber basis, more specifically from about 0.05 to about 3 percent by weight and even more specifically from about 0.1 to about 2 percent by weight. The modified vinyl polymer can be added to the fibers at any point in the process where the fibers are suspended in water.
Methods for making paper products that can benefit from the various aspects of this invention are well known to those skilled in the art of papermaking. Examples of patents include U.S. Patents Nos. 5,785,813 issued July 28, 1998 to Smith et al and entitled "Method for Treating a Supply to Make Paper to Make Soft Tissue"; U.S. Patent No. 5,772,845 issued June 30, 1998 to Farrington, Jr., et al., entitled "Soft Tissue"; U.S. Patent No. 5,746,887 issued May 5, 1998 to Wendt et al entitled "Method for Making Soft Tissue Products"; and U.S. Patent No. 5,591,306 issued January 7, 1997 to Kaun and entitled "Method for Making Soft Tissue Using Cationic Silicones," all of which are incorporated herein by reference.
Detailed description of the invention
To further describe the invention, examples of the synthesis of some of the various chemical species are given below.
Vinyl Polymers
With regard to the modified vinyl polymers, these can be done through the free radical polymerization of the vinyl monomers of the form:
wherein R, R2, R3, R4 can be H, halogen, alkyl, functional alkyl, aryl, functional aryl. For papermaking polyacrylamides (R4 = -C0NH :), polyvinyl alcohols
(R4 = -OH), and polyacrylates (R4 = -COOR ', R' = H, Me) are the most widely used.
Of the modified vinyl polymers, polyacrylamides (PAM) are used as dry strength additives in addition to their widespread use as drainage and retention aids. These are water-soluble polymers containing primary amide groups that can form hydrogen bonds with the cellulose molecules in the fibers thus increasing the interfiber bond. These are synthesized by the free radical polymerization or the photoinitiated polymerization of acrylamide as shown in Figure 1. Any free radical initiator or photoinitiator can be used. Polymerization can be done through a variety of processes including solution, volume, suspension and emulsion polymerizations.
Ficrura
PAMs are non-ionic materials and have very little attraction for papermaking fibers. It is therefore necessary to incorporate charged groups in the polymer structure to make them useful for papermaking. Both anionic and cationic polyacrylamides are known in the art.
The anionic polyacrylamides can be produced by: (1) copolymerization of acrylamide with acrylic acid; and (2) hydrolysis of some of the amine groups on the polyacrylamide chain. The resulting polymer will contain a mixture of acrylic acid and acrylamide groups. The anionic polyacrylamides were first produced in 1950 through the copolymerization of acrylamide with acrylic acid. The acrylic acid groups introduced an ionizable carboxyl group onto the polymer column. The ionization of these carboxyl groups is highly dependent on the pH where above a pH of 7 essentially 100% of the carboxyl groups are ionized. Since the anionic polyacrylamides are negatively charged, they are not directly attracted to the charged cellulose fibers. A cationic substance such as alum should be used in conjunction with these to promote its retention.
To avoid the need for a cationic promoter, another approach is to incorporate cationic groups directly into the polymer column. Having been commercially produced in the 1960s, these cationically charged polyacrylamides are the most common form of dry strength PAMs. The cationic polyacrylamides are produced by the copolymerization of acrylamide with cationic monomers or by modification of some amine groups. A typical reaction is illustrated in Figure 2 for copolymerization with methacryloyloxyethyl trimethyl ammonium methosulfate (METAMS). Cationic monomers typically include: (1) methacryloyloxyethyltrimethyl ammonium methosulfate; (2) dimethyldiallylammonium chloride (DMDAAC); (3) 3-acryloamido-3-methyl butyl trimethyl ammonium chloride (AMBTAC); (4) trimethylamino methacrylate; and (5) vinyl benzyl trimethylammonium chloride (VBTAC). Such materials have structures similar to those shown in Figure 2 for METAMS copolymerized with PAM.
CHa O ^ O H2C = - C-O-C 'C -mCHs *' SO4CH3 + H2C-CHCNH METAMS
Figure
The incorporation of the cationic groups through the modification of nonionic polyacrylamide is most often achieved by the Mannich reaction as illustrated in Figure 3. Generally, cationic polyacrylamides will contain from about 5 to about 70 mole% by weight. hundred of cationic groups.
Figure Generally dry strength PAMs are supplied as ready to use aqueous solutions or as water soluble powders which must be dissolved before use. These can be added to a thin or thick supply at a point of good mixing for good results. Addition rates of 0.1% to 0.5% of dry fiber typically give good results. The high addition rates can cause the supply to be overqualified and reduce the effectiveness of other additives.
When they are used as resistance additives usually around 5-10 mol% of the monomers will contain charged groups. Unlike anionic PAMs, cationic PAMs are effectively charged throughout the entire pH range. Typical molecular weights for cationic PAM dry strength auxiliaries are in the range of 10,000 to 500,000. The molecular weight is important to be low enough not to bridge between the particles and cause flocculation, but still high enough to retard the migration of the polymer into the pores of the fibers. Such emigration can cause a reduction to a dry resistance activity.
When used as retention aids, a wider range of molecular weights and load densities can be employed. The key features of polyacrylamide retention aids include the molecular weight, the type of charge, the charge density and the form of delivery. For the average molecular weight the range can be: low (1,000 - 100,000); medium (100,000 - 1,000,000); high (1,000,000 - 5, 000, 000); very high (> 5,000, 000). The type of charge can be non-ionic, cationic, anionic or amphoteric. The charge density can sr: low (1-10%); medium (10-40%), high (40-80%, or very high (80-100%). Delivery can be either through an emulsion, an aqueous solution or a dry solid.
Low density / high molecular weight flocculants are most frequently used for the retention of fine particles in turbulent and high-cut environments. High density / low molecular weight loading products are used for their load modification capabilities and for retention in low cut environments.
A second class of charged polyacrylamides which has found wide use in the manufacture of tissue and paper is the so-called "glyoxylated" polyacrylamides. Coscia et al., U.S. Patent No. 3,556,932, assigned to American Cyanamid Company, describes the preparation and properties of glyoxylated polyacryl amides in detail. These polymers are nonionic or ionic water soluble polyvinyl amides having sufficient glyoxal substituents to be thermosettable. When a cationic charge is employed, the amount of cationic component in the polymers should be sufficient to make the polymer substantive to the cellulose fibers in aqueous suspensions. The amount of cationic charge in these polymers may vary. This can be from less than 10 mol percent to as high as about 50 mol percent. In truth many commercial versions are sold with a charge density of around 5 mol percent. Incorporation of the filler into the polymer column can be accomplished through any of the methods known in the art. A preferred approach is to incorporate a cationic vinyl monomer with acrylamide or other vinyl monomers during the polymerization of the base polymer. As with the non-glyoxylated polyacrylamides, the specific monomer used to introduce the cationic charge onto the polyacrylamide is not very critical and can be chosen from any monomers known to be capable of incorporating a cationic charge in a polyacrylamide column. Dimethyldiallylammonium chloride is an especially preferred monomer for introducing the cationic charge. Where the substantivity to cellulose fibers in an aqueous solution is not required, half of the cationic charge may be absent from the polymer column. The anionic versions of the polymers can be easily prepared from the appropriate raw materials, these anionic polymers capable of being deposited on fibers with the use of alum or other various cationic retention aids.
The minimum amount of pendant amide groups that need to be reacted with the glyoxal for the polymer to be thermosetted is about 2 mole percent of the total number of available amide groups. This is usually preferred to have an even higher degree of reaction, such as to promote a development of greater wet strength, even when above a certain additional level the glyoxal provides only a minimum wet strength improvement. The optimal ratio of glyoxylated to non-glyoxylated acrylamide groups is about 10 to 20 mole percent, of the total number of reactive amide groups available on the parent polymer. The reaction can be easily carried out in diluted solution by stirring the glyoxal with the polyacrylamide base polymer at temperatures of about 25 ° C to 100 ° C at a neutral or slightly alkaline pH. Generally, the reaction is run until a slight increase in viscosity is noted. Most of the glyoxal reacts in only one of its functionalities giving the desired functional aldehyde acrylamide. The molecular weight of the acrylamide-based polymer is not very critical to the ability to react with glyoxal and the polymers generally of molecular weight less than 2,000,000 are suitably water soluble and dilutable so as not to severely impair the reactivity. In practice, lower molecular weight polymers having a molecular weight of less than 25,000 are generally preferred because of their lower solution viscosity and ease at which they can be diluted in water. The molecular weight and the degree of glyoxylationHowever, it can have an impact on the level of resistance development and the ability to easily disperse in water. It could be expected that certain operating characteristics could be made by mixing polymers of different molecular weights and substitution levels. For example, Dauplaise et al., In U.S. Patent No. 5,723,022 discloses the unique performance gained by mixing the high and low molecular weight acrylamides having different levels of glyoxylation. The glyoxylated polyacrylamides are generally delivered as dilute aqueous solutions having a solids content of 10% or less. The most highly concentrated solutions can be prepared but the risk of gel formation increasing as the solids content increases. The shelf life is also reduced to high temperatures.
A structure for the typical cationic glyoxylated polyacrylamide is shown in Figure 4. The polymer is retained on the fiber by the cationic quaternary amine group which is attracted to the anionic sites on the cellulose. In terms of chemical reactivity, only the amide and the aldehyde functionalities are reactive. Approximately 2-30 mol% of the complete glyoxylated PAM copolymer exists as the active aldehyde group. The amide groups suspended on this polymer form hydrogen bonds with the cellulose increasing the dry strength of the sheet. The aldehyde group can be either crosslinked with amide groups on another part of the polymer or reacted with a hydroxyl group on cellulose fibers.
Figure
where :
= 1 x, y, z > 1
If the aldehyde is bonded to the amide, a permanent covalent cross bond is formed which increases the permanent wet strength. If the aldehyde forms a covalent hemi-acetal bond to the cellulose, the wet strength is also increased. However, this union is not permanent and will break when submerged in water resulting in temporary rather than permanent moisture resistance. Therefore, the Parez is normally used to increase the dry strength and temporarily the wet strength, as desired for the bathroom tissue.
Glyoxylated polyacrylamides have many beneficial properties. These increase both the wet and dry strength of the paper. Even when slightly acidic conditions are preferred, they are thermosetted or "cured" at a pH in the approximate range of 4-8 and at moderately high temperatures that are common to most papermaking systems. Since these can be cured over a wide pH range including a neutral pH, precise control of the pH in the papermaking system is not required. Polymers develop the vast majority of their wet and dry strength as they pass through the drying section of the paper process with leaf temperatures as low as 70 ° F to 90 ° F being adequate. An additional advantage for glyoxylated polyacrylamides is that they possess what is called a "temporary moisture resistance". A part of the wet strength developed within the tissue of paper is lost when it is soaked in water for a moderate period of time. This feature allows the use of these materials and products such as bath tissue where breaking in water is a required product attribute. In addition all the resistance in the humidity can be lost quickly under alkaline conditions. This makes these materials very docile for the operations of breaking and re-pulping, not requiring additional chemicals or processes which increase the paper manufacturing costs in general.
Amphiphilic Hydrocarbon Halves
The amphiphilic hydrocarbon moieties are a group of surfactants (surfactants) capable of modifying the interface between the phases. Surfactants are widely used by the industry for cleaning
(detergency), solubilization, dispersion, suspension, emulsification, wetting and foam control. In the papermaking industry these are frequently used for de-inking, dispersion and foam control. They have an amphiphilic molecular structure containing at least one hydrophilic polar region and at least one lipophilic (non-polar, hydrophobic) region within the same molecule. When placed in a given interface, the hydrophilic end is inclined towards the polar phase while the lipophilic end is oriented towards the polar phase.
Surfactant
Polar Phase Non-Polar Phase F-
Lipophilic Extreme Hydrophilic End The hydrophilic end can be added to the hydrophobe synthetically to create an amphiphilic molecular structure. Figure 5 shows a schematically possible trajectory for making a variety of surfactants:
Add R-CHj-OH Fundonacity OH 0 R-CH, R 'CHfOH) - R "- CHj Etñrib? On
Sulfonation Carboxi be ion Ctorínación
RCHJOSOJH RCHjCOOH R-CHjCl
Add Ampholic Functionality RCH3S03H
Figure
Based on the charge, the surfactants can be grouped as anopheromeric, anionic, cationic and nonionic.
First, in relation to amphoteric surfactants, the charges on the hydrophilic end change with the ambient pH; positive at acidic pH, negative at high pH and zwitterionic at an intermediate pH. Surfactants included in this category include acrylamido alkylamides and substituted amino alkyl acids.
The structure commonly shared by alkylamido alkyl amines:
RoCONH - (CH2) n - N - (CH,) "- COOZ i i Ri
where :
Ro = an aliphatic hydrocarbon of C4 or higher, normal or branched, saturated or unsaturated, substituted or unsubstituted alkyl;
n = 2;
R, = hydroxyalkyl or hydroxy or carboxy end alkyl groups, C = 2C chains, with or without ethoxylation, propoxylation or other substitution; Y
Z = H or another cationic counterion.
The structure commonly shared by the substituted alkyl amino acids:
R, - NR'2Z
where :
R, = an alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, C chain > of 4C;
n = 2;
Z = H or another cationic counterion; Y
R '= carboxylic end of the amino acid.
With respect to the anionics, the hydrophilic end of the surfactant molecule is negatively charged. The anionics consist of five main chemical structures: acylated amino acids / acyl peptides, carboxylic acids and salts, sulfonic acid derivatives, sulfuric acid derivatives and phosphoric acid derivatives.
The structure commonly shared by the acylated amino acids and the acyl peptides is shown as follows:
RQOCO - R, - COOZ
HOOC - R, - COOZ
where :
Ro = alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, C chain = 4C;
R, = half of substituted alkyl amino acid; or - (NH-CHX-CO) -NH-CHX- wherein n > 1, X = amino acid side chain, or alkyl-NHCOR 'wherein R' = aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, C chain > 4C; Y
Z = H or another cationic counterion.
The structure commonly shared by carboxylic acids and salts is shown as follows:
R - COOZ
where :
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, chain C = 4C; Y
Z = H or another cationic counterion.
The structure commonly shared by sulfonic acid derivatives is shown as follows:
RCO - NR, - (CH2) n - S03Z or alkyl aryl - S03Z or R - S03Z or ROOC - (CH2) n - CH S03 - COOZ or [RCO - NH - (OCH2) "- OOC - CH S03 - COO] 2 Z or R (OCH2CH2) n - S03Z
where
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, C chain = 4C;
R [= alkyl or hydroxyalkyl, C chain > 1 C;
n 1;
Z = H or another counterion.
The structure commonly shared by the sulfuric acid derivatives is as shown as follows:
R - O S03Z
wherein R = aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, with or without ethoxylation or propoxylation, chain C > 4C;
Z = H or another counterion.
The structure commonly shared by the phosphoric acid derivatives are shown as follows:
R 0 P03Z
where
R = aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, with or without ethoxylation or propoxylation, C chain> 4C; Y
Z = H or another counterion.
In relation to cationics, these are surfactants with a positively charged atom, more commonly nitrogen, on the hydrophobic end. The charge may be permanent and non-pH dependent (such as quaternary ammonium compounds) or pH dependent (such as cationic amines). These include the substituted alkyl ammonium salts, the heterocyclic ammonium salts, the substituted alkyl imidazoline salts and the alkyl amines.
The structure commonly shared by this group is shown as follows:
N + R4Z "
where:
R = H, alkyl, hydroxyalkyl, alkyl ethoxylated and / or propoxylation, benzyl, or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, with or without carboxylation, with or without ethoxylation or propoxylation, chain C = 4C. The R groups can be the same or different; Y
Z = Counterion that includes halide, hydroxide, etc.
Regarding non-ionics, in this group the molecule has no charge. The hydrophilic end frequently contains a polyether (polyoxyethylene) or one or more hydroxyl groups. These generally include alcohols, alkyl phenols, esters, ethers, amine oxides, alkylamines, alkylamides, polyalkylene oxide block copolymers.
Modified Vinyl Polymers Containing Amphiphilic Hydrocarbon Halves
There are several predicted trajectories in which modified vinyl polymers and amphiphilic hydrocarbons can be combined on a single molecule for purposes of this invention. These include, but are not limited to: (1) direct monomer incorporation or copolymerization; (2) derivation of functional groups on the polymer column; and (3) block copolymerization.
The molar and weight ratios of the various functional groups on the polymer will largely depend on the specific application of the material and is not a critical aspect of the invention. However, the portion of the synthetic polymer [Q,] capable of forming hydrogen bonds, covalent and ionic can constitute from about 10 to about 95 mol% of the total polymer, more specifically from about 20 to about 90 % mol of the total polymer and even more specifically from about 30 to about 85% mol of the total polymer. The amphiphilic hydrocarbon portion [Q2] of the synthetic polymer can constitute from about 1 to about 90 mol% of the synthetic polymer, more specifically from about 2 to about 80 mol% of the synthetic polymer and even more specifically from about 3 to about 70% mol of the synthetic polymer. The charge-containing part [Q3] of the synthetic polymer can be composed of monomer units constituting from 0 to about 80 mol% of the total monomer units in the synthetic polymer, more specifically from 0 to about 30% mol of the synthetic polymer and even more specifically from about 2 to about 20 mol%. The functionality [Q4] will be comprised of monomer units constituting from 0 to about 80 mole% of the total number of monomer units in the synthetic polymer, more specifically from 0 to about 40 mole% and even more specifically from 0 to about 20% mol.
Similarly, the molecular weights of the synthetic polymers of the present invention will greatly depend on the specific application of the material and are not very critical to the invention. The weight average molecular weight range can be from 1,000 to about 5,000,000, more specifically from about 10,000 to about 2,000,000 and even more specifically from about 20,000 to about 1,000. 000, 000. Where these polymers are aggregated for dry strength it is important that the molecular weight of the polymer is sufficiently low so as not to bridge between the particles and cause flocculation and still high enough to retard the migration of the polymer inside the pores of the fibers. These materials can have average molecular weight weights in the range of about 5, 000 to about 2 '000, 000, more specifically from about 10,000 to about 1' 500,000 and even more specifically from around 20,000 to around 1'000, 000.
Incorporation of Direct Monomer
The incorporation of the amphiphilic moieties can be achieved through copolymerization with vinyl type monomers containing amphiphilic groups. Almost any vinyl monomer containing a pendant amphiphilic moiety can be copolymerized with acrylamide or a similar vinyl monomer containing a pendant hydrogen bonding moiety to be incorporated in the polymer column. Generally the synthesis can be described in figure 7.
1- R.-CR, T-G-CH2CR, - jr -r-CH2CR, • fr- -t-CHjCR, 'Ai Ro R R5 R14 w
Figure
where
'R, R, = H, C 1-4 alkyl'
a, b = 1;
C, d, = 0;
w = 1;
r, S = 1;
t, U > 0;
a * w = r; b * w = s; c * w = t; d * w = u;
RQ = any group capable of forming hydrogen bonds. They are preferred but not limited to CONH2, COOH, COO- including mixtures of said groups;
A, = H, COOH;
R4 = amphiphilic hydrocarbon radical; this may be an alkyl hydrocarbon radical with a hydrophilic functionality
such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality. The hydrocarbons can be linear or branched, saturated or unsaturated,
substituted or unsubstituted, with two or more hydrocarbons.
R5 = Z2-R10-W, where:
Z2 = Ar, CH2, COO-, CONH-, - 0 -, - S -, -0S020-, any radical capable of bridging the group R10 to the vinyl column part of the molecule RI0 = any aromatic or aliphatic hydrocarbon linear or branched of two or more carbons, preferably - (CH2CH2) -, -C (CH3) 2CH2CH2-;
W = -N + R ,,, Rl2, R13, where Rp, R12, R, 3 is a group of alkyl CM.
R5 can also be the residue form by copolymerization with dimethyldiallylammonium chloride. In this case the residue will be in the form of monomers with the repeating units of the structure:
R14 = hydrophilic moiety which is desirable to make the material in a form suitable for papermaking to compensate for any increased hydrophobicity that can be introduced through the incorporation of the amphiphilic hydrocarbon moiety.
A wide variety of ethylenically unsaturated vinyl monomers containing amphiphilic moieties are known in the art. Acrylates based on poly (ethylene glycol) and poly (propylene glycol), methacrylates and derivatives including poly (ethylene glycol) acrylate, poly (propylene glycol) acrylate, poly (ethylene glycol) methacrylate, poly (propylene glycol) methacrylate, poly (ethylene glycol) mono-ether acrylates and methacrylates including methyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, as well as the poly (propylene glycol) analogues and the like are commercially available materials known. Also known are mono-aryl ether derivatives which include poly (ethylene glycol) 4-nonylphenyl ether acrylate, poly (ethylene glycol) phenyl ether acrylate, poly (ethylene glycol) 2,4,6-tris (l-phenylethyl) phenyl ether methacrylate and the like. Such monomers can be easily derived from the esterification of acrylic acid, methacrylic acid, and the like with poly (ethylene glycol) and poly (propylene) glycol and the corresponding monoethers including but not limited to such materials as poly (ethylene glycol) mono butyl ether, poly (ethylene glycol) mono octyl ether, poly (ethylene glycol) mono decyl ether, poly (ethylene glycol) mono dodecyl ether, poly (ethylene glycol) mono lauryl ether, poly (ethylene glycol) mono octadecyl ether, poly (propylene glycol) and the mixed poly (propylene glycol) and poly (ethylene glycol) mono ether derivatives.
The corresponding alkyl ether derivatives of polyethylene glycol and propylene glycol are also known. Such materials are generally synthesized from the reaction of any allyl halide and hydroxyl compound in the presence of sodium hydroxide. Examples of such monomers include allyl polyethylene glycol, methallyl polyethylene glycol, methoxy allyl polyethylene glycol, butoxy allyl polyethylene glycol, and the like. Such allyl ether materials generally conform to the formula:
CH2 = CHR -R '- O - R "
where :
R = H, C 1-4 alkyl
R '= polyethylene glycol, polypropylene glycol, or mixed polyethylene / polypropylene glycol radical.
R '= alkyl or aryl radical C, -30-
These could be expected to be incorporated into any vinyl type polymer such as PAM, PVA, etc. Evani et al., In the patent of the United States of America No.
No. 4,921,902 describes the incorporation of such monomers in a non-ionic polyacrylamide column, such materials being useful for the control of mobility and fracturing of fluids in oil recovery operations.
Other examples of the amphiphilic monomers that could be incorporated through these processes include the carboxyethaines and the sulfobetaines as described by Samour et al. In U.S. Patent No. 3,671,502. Copolymers of these materials with hydroxyalkyl acrylates were found to be useful for binders in various applications. Additional examples include but are not limited to such materials as those described by Valint et al., In U.S. Patent No. 5,177,165 and Robinson in U.S. Patent No. 5,874,495.
The examples mentioned above are not intended to limit the scope of the invention. Indeed, any of the generic amphoteric materials previously described can be incorporated through the aforementioned copolymerization technique as long as there is a single ethylenically unsaturated site with the amphoteric molecule. These would be incorporated directly into the polymer during the polymerization process as described in Figure 7. When they were incorporated into the polymer in this manner the amphiphilic hydrocarbons are arranged in a hanging form outside the polymer column. Polymers of the type shown in Figure 7, which do not have an amide functionality will not replace pendant, they can further be modified to produce materials that temporarily exhibit wet strength as well as dry strength. Most notably this can be achieved through the reaction with glyoxal. A specific reaction scheme is given in Figure 8.
lioxal
PO »- (CH2CHCH3?) - g i güira 8 EtO- ^ CHjCHiO).
It should be appreciated that several different polymeric structures are possible when polymers are integrated in the aforementioned manner. Such characteristics can be made in the polymer depending on the synthesis path chosen. If the polymers are mixed concurrently, a type of copolymer A-B-A-B-A-B will be randomized. If the monomers are consecutively mixed, the block copolymers of type AAAAA-BBBB-AAAAA-BBBB can be formed. The size of the individual blocks can be controlled through any of the means known in the art. While not critical to the invention those skilled in the art will recognize the potential for different behaviors depending on the specific structure of the copolymer. When more than one comonomer is used the mixtures of random and block copolymers can be designed depending on the synthetic approach used.
Derivation of Functional Groups of the Polymer Column
The second approach to the synthesis of materials of this invention is the modification of the functional groups on the polymer column. Vinyl type polymers include the modified polyacrylamides, acrylic acid and polyvinyl alcohol contain functional groups that can be further derivatized to produce the materials of Figure 4. Polymer functional groups which can be reacted include but are not limited to : amide, carboxyl, hydroxyl, cyano and aldehyde (from the glyoxylation reaction or a similar reaction). The general scheme for the synthesis is shown in Figure 9.
H, r-fr o3 -fcf-Q4 a -
Z5-R6 Figure
where :
= H, C 1-4 alkyl
a, b = 1;
c, d, 0;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen bonds or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are -CONH2, -COO "'M, -OH and mixtures of said groups.The preferred pendant groups for covalent attachment are aldehydes and anhydrides.M + may be any suitable counterion including Na +. , K +, Ca + 2 and the like;
Q3 = a monomer unit or a block or graft copolymer containing a loading functionality. Such charging functionality is preferably cationic but may be anionic or amphoteric;
Z4 = -CONHCHOHCHO, -CHO, -C0NH2, -COOH, -CN, -OH, -SH, -NH2, -R'OH, -R'CHO, -R'CONH ,, -R'COOH, -R 'CN, -R'OH, -T'SH, -R'NH2, -RS03H, - ROS03H, or any other functional group capable of being reacted in a manner such as
to incorporate the amphiphilic hydrocarbon moiety in the polymer and R 'can be any bridging radical whose purpose is to hold the functional group to the polymer; and Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for
make paper. Q4 can take the form of -Z2-Q4-Z2 '- where Z2, Z2' are any bridge radicals, the same or different ones whose purpose is to provide incorporation into the column
of polymer and Q4 is as previously defined. Q4 can be incorporated to decentralize the increased polymer hydrophobicity caused by the introduction of the aliphatic hydrocarbon moieties.
Examples of suitable Q4 halves are (but are not limited to) the aliphatic polyether derivatives of the formula - [(CR, R2) x0] and -R3, where R, R2 is H or CH3, x = 2, y = 2 and R3 is any group
suitable terminal including -CH3, -H, -C2H5, -NH2;
Z5 = HOOC-, CIOC-, HO-, HS-, -COOOC-, H2N-, HCO-, CIS020-, XOC- (X = halo), CICOO-, or
Any other functional group capable of reacting with the functional group of type Z4 to bind the residue -Rft in the polymer;
R1 = an amphiphilic hydrocarbon radical.
If the end block functional groups (Z4 and / or RQ) are not sufficiently reactive, a further modification may be made prior to the incorporation of the amphiphilic moieties to ensure better performance. The general scheme for such modification is shown in Figure 10.
Acylation of the PDKero Column of Vinyl: -
Figure 10
Some specific examples of such reactions are given in figures 11-12.
Figure 11
where :
R = H, alkyl, aliphatic hydrocarbon, substituted or unsubstituted, linear or branched or cyclic, C > , = 6.
OR -C, O-RO-OCR x, y. > . «L z > , «0 Figure 12 where:
R = alkyl, aliphatic, branched or linear or cyclic hydrocarbon, substituted or unsubstituted, with or without ethoxylation;
R '= ethoxylated alkyl or aliphatic, branched or linear or substituted or unsubstituted cyclic hydrocarbon.
Block Copolymerization
Block copolymers containing polyethylene PAM's, polytetrafluoroethylene, or any other substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbons, wherein such copolymers are incorporated either as block copolymers or as grafts on the vinyl column. Note that since these polymers maintain the amide pendant functionality they are capable of being glyoxylated to form materials that possess a temporary wetting resistance. A general example of such materials is shown in Figure 13.
- Ktt.yR * Q-fc f-cHjCRj-fe "
Rl, R, R3-C1-4 Alkyl a, b > 0 C > s0 Figure 13 where:
Ro = any group capable of forming hydrogen bonds or covalent with cellulose. Preferred are - CONH2, COOH, COO-, -OH, - CONHCHOHCHO including mixtures of said groups;
A, = H, COOH; 10 Q = radical form -Z-R2-Z;
R2 = a block or graft copolymer wherein the amphiphilic functionality is
built. This may be alkyl hydrocarbons with hydrophilic functionality (such as -OH, or ethoxy groups), or aliphatic hydrocarbons with hydrophilic functionality. The hydrocarbons can be
linear or branched, saturated or unsaturated, substituted or unsubstituted, with 4 or more hydrocarbons.
Z = any bridging radical or whose purpose is to provide incorporation into the polymer column;
R5 = Z2-R10-W, where:
Z, = Ar, CH2, COO-, CONH-, - 0 -, - S -, -0S020-, any radical capable of bridging the group R10 to the vinyl column part of the molecule;
R10 = any linear or branched aromatic or aliphatic hydrocarbon of two or more carbons, preferably - (CH2CH,) -, C (CH3) 2CH2CH; -;
W = -N + R ,,, R12, R13, where Rn, R12, R13 is a C-alkyl group.
R5 can also be the residue formed by the copolymerization with dimethyldiallylammonium chloride. In this case the residue may be in the form of monomers with repeating units of the structure:
It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be construed as limiting the scope of this invention, which is defined by the claims that follow and all equivalents thereof.
Claims (72)
1. A synthetic polymer containing one or more amphiphilic hydrocarbon moieties, said synthetic polymer has the following structure: 4 + Q? -is f-onj; f Qrir-f-Q4-J < r w where : a, b, 0; c, d = 0 such as c + d > 0; w = 1; Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen bonds or covalent with cellulose; Q2 = a block or graft copolymer containing an amphiphilic moiety. Q3 = a monomer unit or a block or graft copolymer containing a loading functionality; Y Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for making paper.
2. The polymer as claimed in clause 1, characterized in that the pendant group in Q, capable of forming hydrogen or covalent bonds is selected from the group consisting of -C0NH2, -COOH, -COO-M +, -OH, - CONHCHOHCHO and mixtures thereof, wherein M + is a counter ion.
3. The polymer as claimed in clause 1, characterized in that Q2 is of the form of -ZI-Q2-Z1'-wherein Z, Zx 'are bridging radicals, which may be the same or different.
4. The polymer as claimed in clause 1, characterized in that Q4 is of the form of -Z2-Q4-Z '-where Z2, Z2' are bridging radicals, which may be the same or different.
5. The polymer as claimed in clause 1, characterized in that Q4 is a radical of the form -CHR ^ RoR, '- wherein RQ is an aliphatic polyether derivative of the formula - [(CR, R2') -0 ] y-R3, where : R,, R, 'is H, C alkyl; R ,, R2 'is H or -CH3; x > 2; R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5, and -NH.
6. The polymer as claimed in clause 1, characterized in that Q3 is CH, -
7. The polymer as claimed in clause 1, characterized in that Q3 is a radical of the form -CHR ^ RoRi '- where: R0 = is a pendant group of the form Z, -R, 0-W, where Z, is a radical that joins the group R, 0 to the polymer; R ,, R, '= H or a C, 4 alkyl group; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; Y W = -N + Ru, R12, R13 where Rn, Rl2, R13 is a group of alkyl CM.
8. The polymer as claimed in clause 7, characterized in that Z is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, -0-, -S-, and -0S020-.
9. The polymer as claimed in clause 7, characterized in that R 10 is - (CH 2 CH 2) - or -C (CH 3) 2 CH 2 CH 2 -.
10. The polymer as claimed in clause 1, characterized in that "c" is 0.
11. The polymer as claimed in clause 1, characterized in that "d" is 0.
12. The polymer as claimed in clause 1, characterized in that the pendant group on Q, capable of forming hydrogen bonds is -CONH2.
13. The polymer as claimed in clause 1, characterized in that the hanging group on Q! capable of forming covalent bonds of -CONHCHOHCHO.
14. The polymer as claimed in clause 1, characterized in that Qi has pendant groups -C0NH2 and -CONHCHOHCHO.
15. A synthetic polymer having one half capable of forming covalent or hydrogen bonds with cellulose and containing one or more amphiphilic hydrocarbon moieties, said polymer having the following structure: where : w = 1; R1 / R ,,, R2, R3 = H or C, ^ alkyl; a, b, > O; c, d = O so that c + d > OR, - 5 RQ - a group capable of forming covalent hydrogen bonds with cellulose; Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety; A, = -H, -COOH; R4 = a radical of Z, - R6; 15 where: Z] = any radical capable of binding the R6 group to the polymer; R6 = a block or graft copolymer containing the amphiphilic hydrocarbon; R5 = Z, -R10-W; 25 where: Z, = any radical capable of binding the group R, 0 to the polymer; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of two or more hydrocarbons; Y = -N + Ru, R12, R13 where Rp, R | 2, R13 are alkyl groups CM.
16. The polymer as claimed in clause 15, characterized in that Ro is selected from the group consisting of -CONH2, COOH, -COO "M +, -CONHCHOHCHO, and mixtures thereof, wherein M + is a counter ion.
17. The polymer as claimed in clause 15, characterized in that Q4 is of the form -Z2-Q4-Z2 '- wherein Z2, Z2' are bridging radicals, which may be the same or different.
18. The polymer as claimed in clause 15, characterized in that Z is selected from the group consisting of aryl, -CH2-, -COO-, -CONR'-, -0-, -S-, -0S020-, -C0NHC0-, and -CONHCHOHCHOO-, and wherein R 'is H or C-alkyl.
19. The polymer as claimed in clause 15, characterized in that Z, is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, -O-, -S-, and -OS020-.
20. The polymer as claimed in clause 15, characterized in that R10 is - (CH2CH2) - or -C (CH3) 2CH2CH2.
21. The polymer as claimed in clause 15, characterized in that A, is -H and RQ is -CONH, -.
22. The polymer as claimed in clause 15, characterized in that A] is -H and R "is -CONHCHOHCHOO-.
23. The polymer as claimed in clause 15, characterized in that Rg consists of both groups -CONH2- and -CONHCHOHCHOO-.
24. A synthetic polymer having one half capable of forming covalent or hydrogen bonds with cellulose and containing one or more amphiphilic hydrocarbon moieties, said polymer having the following structure: Tf nfr-ts8r + CB -ram for Qa tr A, Ro H, C? CH2 tv H, C CH, where: w > 1; R ,, R, ', R2 / R3 = H or alkyl CM; a, b, > 0; c, d = 0 so that c + d > 0; 10 Ro = a group capable of forming covalent hydrogen bonds with cellulose; Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety; TO! = -H, -COOH; R4 = a radical of Z, - R6; where : Z, = any radical capable of linking the group R6 to the polymer; R6 = an amphiphilic hydrocarbon radical;
25. A sheet of paper comprising a synthetic polymer having a half capable of forming covalent or hydrogen bonds with cellulose and containing one or more amphiphilic hydrocarbon moieties, said polymer having the following structure: where : a, b > 0; c, d = 0; w = 1; Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen bonds or covalent with cellulose; Q2 = a block or graft copolymer containing half the amphiphilic hydrocarbon; Q3 = a monomer unit or a block or graft copolymer containing a loading functionality; Y Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for making paper.
26. The sheet of paper as claimed in clause 25, characterized in that the pendant group on Q, is capable of forming hydrogen or covalent bonds is selected from the group consisting of -CONH2, -COOH, -COO "M ~, - OH, CONHCHOHCHO and mixtures thereof, wherein M + is a counter ion.
27. The sheet of paper as claimed in clause 25, characterized in that Q2 is of the form of -Z, -Q2-Z, '- where Z ,, Z [' are bridging radicals, which may be the same or different.
28. The sheet of paper as claimed in clause 25, characterized in that Q4 is of the form of -Z2-Q4-Z2 '- where Z2, Z2' are bridging radicals, which may be the same or different.
29. The sheet of paper as claimed in clause 25, characterized in that Q4 is a radical of the form -CHR ^ RQR! '- wherein RQ is an aliphatic polyether derivative of the formula - [(CR, R2') x0] y-R3, where : R,, R, 'is -H, alkyl CM; ^ 2 'R2' is -H or -CH3; X = 2; y = 2; Y R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5, and -NH2.
30. The sheet of paper as claimed in clause 25, characterized in that Q3 is
31. The sheet of paper as claimed in clause 25, characterized in that Q3 is a radical of the form -CHR ^ RoR, '- where: Ro = is a pendant group of the form Z, -Ri0-W, where Z, is a radical capable of binding the group R10 to the polymer; R1 # R, '= H or a C 1-4 alkyl group R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; Y W = -N + Rn, R12, R13 where Rp, R12, R13 is a C, ^ alkyl group.
32. The sheet of paper as claimed in clause 31, characterized in that Z, is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, -0-, -S-, and -0S020 -
33. The sheet of paper as claimed in clause 31, characterized in that R10 is - (CH2CH2) - or C (CH3) 2CH2CH2-.
34. The sheet of paper as claimed in clause 25, characterized in that "c" is 0.
35. The sheet of paper as claimed in clause 25, characterized by "d" is 0.
36. The sheet of paper as claimed in clause 25, characterized in that the hanging group on Q, is capable of forming hydrogen bonds is -C0NH2.
37. The sheet of paper as claimed in clause 25, characterized in that the hanging group on Q, capable of forming covalent bonds is -CONHCHOHCHO.
38. The sheet of paper as claimed in clause 25, characterized in that Q has pendant groups -C0NH2 and -CONHCHOHCHO.
39. A sheet of paper comprising a synthetic polymer having a half capable of forming covalent or hydrogen bonds with cellulose and containing one or more amphiphilic hydrocarbon moieties, said polymer having the following structure: where : = 1; R ,, R1 ', R2, R3 = H or C-alkyl; a, b, > 0; c, d = 0; Ro = a group capable of forming covalent hydrogen bonds with cellulose; Q4 = a unit of monomer or block or graft copolymer containing a hydrophilic moiety; A, = -H, -COOH; R4 = a radical Z, - R6; 5 where: Zx = any radical capable of linking the group R6 to the polymer; R6 = a block or graft copolymer containing half amphiphilic hydrocarbon; R5 = Z, -RI0-W, 15 where: Z, = any radical capable of binding the R10 group to the polymer; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; Y 25 = where -N + Ru, R12, R13 where R ,,, R12, R13 are C, _4 alkyl groups.
40. The sheet of paper as claimed in clause 39, characterized in that RQ is selected from the group consisting of CONH2, -COOH, -COO "M +, -OH, -CONHCHOHCHO, mixtures thereof, wherein M + is a counterion.
41. The sheet of paper as claimed in clause 39, characterized in that Q4 is of the form -Z2-Q4-Z2 'where Z2, Z2' are bridging radicals, they may be the same or different.
42. The sheet of paper as claimed in clause 39, characterized in that Z, is selected from the group consisting of aryl -CH2-, -COO-, -CONR'-, -O-, -S-, -0S020- , -CONHCO- and -CONHCHOHCHOO-, and wherein R 'is H or C, 4 alkyl.
43. The sheet of paper as claimed in clause 39, characterized in that Z, is selected from the group consisting of aryl CH2-, -COO-, -CONH-, -O-, -S-, and -OS020-.
44. The sheet of paper as claimed in clause 39, characterized in that R10 is - (CH2CH2) - or C (CH3) 2CH2CH2-.
45. The sheet of paper as claimed in clause 39, characterized in that Aj is -H and R "is -C0NH2.
46. The sheet of paper as claimed in clause 39, characterized in that A, is -H and Ro is CONHCHOHCHO.
47. The sheet of paper as claimed in clause 39, characterized in that R "consists of both groups of -CONH2 and -CONHCHOHCHO.
48. A sheet of paper comprising a synthetic polymer having a group capable of forming covalent or hydrogen bonds with cellulose containing one or more amphiphilic hydrocarbon moieties, said polymer having the structure: Q »KJ where : W = 1; R,, RI ', R2, R3 = H or C-alkyl, a, b 0; c, d, = O Ro = a group capable of forming hydrogen bonds or covalent with cellulose; Q4 = a monomer unit or a graft or block copolymer containing a hydrophilic moiety; A, = -H, -COOH; R4 a radical Z, R? ' where : Z, = any radical capable of binding the Rg group down to the polymer; R6 = a block or graft copolymer containing the siloxane bonds (-Si-O-);
49. A method for making a sheet of paper comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of fibers to make paper on a forming fabric to form a fabric; (c) draining and drying the fabric to form a sheet of paper, wherein the synthetic polymer is added to the aqueous fiber suspension and / or the fabric, said polymer having the following structure: + f-Qrfc r? rt í Qrtr + k-? r w where a, b c, d z 0; w = 1; Q, = a unit of block or graft monomer or copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose; Q2 = a graft block copolymer containing half amphiphilic hydrocarbon; Q3 = a monomer unit or a block or graft copolymer containing a loading functionality; Q4 = a monomer unit or a graft or block copolymer containing a hydrophilic moiety, which is desirable to make the material in a suitable form for making paper.
50. The method as claimed in clause 49, characterized in that the pendant group on Q, capable of forming hydrogen or covalent bonds is selected from the group consisting of -CONH2, -COOH, -COO, M +, -OH, CONHCHOHCHO and mixtures thereof, wherein M + is a counter ion.
51. The method as claimed in clause 49, characterized in that Q2 is of the form -Z, -Q2-Z, 'where Z ,, Z,' are bridging radicals, which may be the same or different.
52. The method as claimed in clause 29, characterized in that Q4 is of the form -Z2-Q2-Z2 'where Z2, Z2' are bridging radicals, which may be the same or different.
53. The method as claimed in clause 49, characterized in that Q4 is a radical of the form CHR | CRoR | ' wherein RQ is an aliphatic polyether derivative of the formula - [(CR2R2) x0] y -R3. where : R ,, R, 'is -H, alkyl CM; R2, R2 'is -H or CH3 x = 2; y = 2; Y R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5; and -NH2.
54. The method as claimed in clause 49, characterized in that Q, is
55. The method as claimed in clause 49, characterized in that Q3 is a radical of the form -CHRjCRoR, '- where Ro = a pendant group of the form Z, -R10-W, where Z, is a radical capable of binding the group R10 to the polymer; R, R, '= H or a C alkyl group; RI0 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; Y W = -N + RU, R12, R13 wherein Rn, R12 / R13 is a group of alkyl CM.
56. The method as claimed in clause 55, characterized in that Z, is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, -O-, -S-, -OS020-.
57. The method as claimed in clause 55, characterized in that R10 is - (CH2CH2) - or -C (CH3) 2CH2CH2-
58. The method as claimed in clause 49, characterized in that "c" is 0.
59. The method as claimed in clause 49, characterized in that "d" is 0.
60. The method as claimed in clause 49, characterized in that the pendant group on Q, is capable of forming hydrogen bonds is -CONH ,.
61. The method as claimed in clause 49, characterized in that the pendant group on Q, capable of forming covalent bonds is -CONHCHOHCHO.
62. The method as claimed in clause 49, characterized in that Q has pendant groups -CONH, and -CONHCHOHCHO.
63. A method for making a sheet of paper comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of fibers to make paper on a forming fabric to form a fabric; (c) draining and drying the fabric to form the paper sheet, wherein the synthetic polymer is added to the aqueous fiber suspension and / or the fabric, said polymer has the following structure: -j-tp, p, trtcH2fR2r-fCHJCRJttQ «arJ- A, Ro« 4 «9 where: w = 1; R1, R1 ', R2, R3 = H or alkyl CM; 5 a, b > 0; c, d, = 0 Ro = a group capable of forming hydrogen bonds or covalent bonds with cellulose; Q4 = a unit of graft or block monomer or copolymer containing a hydrophilic moiety; 15 R4 = a radical Z, - R6, where : 20 Z, = any radical capable of binding the R6 group to the polymer; R1 = a block or graft copolymer containing half the amphiphilic hydrocarbon. R5 = Z, -R10-W, where : Z, = any radical capable of binding the R10 group to the polymer; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; Y W = -N + RH, R12, R13 wherein R ,,, R12, R13 are C alkyl groups.
64. The method as claimed in clause 63, characterized in that RQ is selected from the group consisting of C0NH2, -COOH, -COO "M +, -OH, -CONHCHOHCHO, and mixtures thereof, wherein M + is a counter ion .
65. The method as claimed in clause 63, characterized in that Q4 is of the form -Z2-Q4-Z2 'where Z2, Z2' are bridging radicals, which may be the same or different.
66. The method as claimed in clause 63, characterized in that Zx is selected from the group consisting of aryl -CH2-, -COO-, -CONR'-, -O-, -S-, -OS020-, -CONHCO - and -CONHCHOHCHOO-, and wherein R 'is H or alkyl CM.
67. The method as claimed in clause 63, characterized in that Z, is selected from the group consisting of aryl CH2-, -COO-, -CONH-, -O-, -S-, and -0S020-.
68. The method as claimed in clause 63, characterized in that R 10 is - (CH 2 CH 2) - or C (CH 3) 2 CH 2 CH 2 -.
69. The method as claimed in clause 63, characterized in that A, is -H and Ro is -CONH2.
70. The method as claimed in clause 63, characterized in that A, is -H and Rg is -CONHCHOHCHO.
71. The method as claimed in clause 63, characterized in that RQ consists of both groups of -CONH2 and -CONHCHOHCHO.
72. A method for making a sheet of paper comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of fibers to make paper on a forming fabric to form a fabric; and (c) draining and drying the fabric to form a sheet of paper, wherein a synthetic polymer is added to the aqueous suspension of fibers and / or to the fabric, said polymer having the following structure: where w = 1; R ,, R, ', R2, R3 = H O alkyl C i-a a, b > O; c, d, = O Ro =. a group capable of forming hydrogen bonds or covalent with cellulose; Q_4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety; TO! = -H, -COOH; R4 = a radical Z, - R6, 5 where: Z, = any radical capable of binding the R6 group down to the polymer; R6 = a block or graft copolymer containing half the amphiphilic hydrocarbon. R E S U E N Synthetic polymers are described which have moieties capable of the covalent attachment of hydrogen to cellulose and one or more amphiphilic moieties. These polymers are capable of providing two different properties to paper products such as tissue, whose properties hitherto had been imparted through the use of at least two different molecules. The column of these synthetic polymers is based on modified vinyl polymers, such as polyvinyl alcohol, polyacrylamides and polyacrylic acids.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/117,165 | 1999-01-25 | ||
| US09449260 | 1999-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA01007124A true MXPA01007124A (en) | 2002-03-05 |
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