NZ616504B2 - Organopolysilicone polyether drainage aid - Google Patents
Organopolysilicone polyether drainage aid Download PDFInfo
- Publication number
- NZ616504B2 NZ616504B2 NZ616504A NZ61650412A NZ616504B2 NZ 616504 B2 NZ616504 B2 NZ 616504B2 NZ 616504 A NZ616504 A NZ 616504A NZ 61650412 A NZ61650412 A NZ 61650412A NZ 616504 B2 NZ616504 B2 NZ 616504B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- polyether
- composition
- hydrocarbon
- moieties
- moiety
- Prior art date
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 78
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 claims abstract description 102
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001808 coupling Effects 0.000 claims abstract description 7
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- -1 1-n-butyl Chemical group 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 40
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 23
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 150000002431 hydrogen Chemical group 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000007792 addition Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- 239000007844 bleaching agent Substances 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 239000010703 silicon Substances 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 36
- 239000000835 fiber Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000002209 hydrophobic Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003197 catalytic Effects 0.000 description 5
- 125000005469 ethylenyl group Chemical group 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- PXWCUJRVSZCPHE-UHFFFAOYSA-N α-Butyl-ω-hydroxypoly(oxyethylene) poly(oxypropylene) Chemical compound CCCCOCCOCC(C)OCCCOC PXWCUJRVSZCPHE-UHFFFAOYSA-N 0.000 description 5
- WCYWZMWISLQXQU-UHFFFAOYSA-N Methyl radical Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920001451 Polypropylene glycol Polymers 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N Simethicone Chemical class C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- ZWRUINPWMLAQRD-UHFFFAOYSA-N 1-Nonanol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N Ethyl radical Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- IALUUOKJPBOFJL-UHFFFAOYSA-N [K+].[SiH3][O-] Chemical compound [K+].[SiH3][O-] IALUUOKJPBOFJL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5H-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L Zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- KLGZELKXQMTEMM-UHFFFAOYSA-N hydride Chemical compound [H-] KLGZELKXQMTEMM-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003219 poly( p-phenylene oxide) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-P rhodium;triphenylphosphanium;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-P 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940100888 zinc compounds Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
Abstract
The present disclosure relates to a drainage aid composition and its use in pulp washing process. More particularly, this disclosure relates to drainage aid composition of silicone polyethers prepared via zinc catalysed dehydrogenative coupling of alcohol terminated polyethers with silicone oligomers and polymers comprising of at least one silicon bonded hydrogen. The composition exhibits excellent drainage properties. s and polymers comprising of at least one silicon bonded hydrogen. The composition exhibits excellent drainage properties.
Description
Organopolysilicone Polyether Drainage Aid
This application claims the benefit of US provisional application number
61/479,110 filed April 26, 2011, the entire contents of which are hereby incorporated
by reference.
Background
Paper is manufactured predominantly from wood fibers as wood pulp. There
are three major processes for the production of pulp: wood digestion, brown stock
washing, and bleaching. Wood digestion is often referred to as “cooking” and it is the
process of using chemicals to dissolve approximately 50 % of the wood components
facilitating the liberation of wood fibers. Brown stock washing is the process where
the fibers are separated from non-fibrous wood components and spent cooking
chemicals by using recycled and or clean water and filtrates from other processes as
wash water. The non-fiber portion of this stream is referred to as black liquor and is
sent to a separate process where the chemicals are recovered. For fine grades of
paper, e.g. printing and writing, the fiber is bleached by treatments with oxidizing
chemicals to “brighten” the pulp.
Brown stock washing is a critical process in pulp mill operations. Its purpose
is to separate spent cooking liquors and undesired degraded wood components from
the wood fibers after the cooking process using a minimal amount of wash water.
The optimization of this process improves chemical recovery, mill energy
balance/usage, reduces unwanted chemical consumption in downstream
applications, and decreases environmental impact. When operated effectively, the
brown stock washers can be a source of considerable savings to a pulp mill.
It is common for a brown stock washing system to be run inefficiently. Many
of the NA operating pulp mills are antiquated and use original process equipment
instead of upgrading to newer more efficient washers. A global problem is that due to
the complexity of a washing process the operator’s are sometimes uncertain of how
to correctly respond to unfavorable wash conditions.
Many economically feasible chemical additives have been found to influence
the operation of brown stock washers in a positive way. By using filtration theory and
how it applies to a washer, it may be possible to better understand how certain
processes and chemicals influence a fiber washing process.
Many technologies exist for washing cellulosic fibers, but each design
incorporates the same basic principles. These basic principles are dilution and
displacement washing. Dilution washing is described as diluting a cellulosic material
with cleaner filtrates and wash waters then removing the filtrates and wash waters
through a filtration separation process under vacuum or pressure. Displacement
washing is done by replacing the liquid portion of cellulosic slurries with cleaner
filtrate or wash water under vacuum or pressure. Dilution washing is more effective,
but displacement washing uses less water. Typical equipment for washing cellulosic
slurries incorporates both dilution and displacement washing, or a series of
displacement washing zones. Cellulosic washer designs include perforated drums,
porous wires, extraction plates, and screw presses, all either under vacuum, under
pressure, or used to form nips for pressing.
Organopolysilicone defoamers functionalized with polyether have been used,
mainly, to aid in emulsifying and dispersing defoamer in incompatible mediums. The
addition of hydrophobic silica particles in the formulation is mandated by the fact that
they play an important roll, along with other ingredients, in foam suppression. The
following patents disclose the use of polyether functionalized silicone copolymers,
mainly a mixture of polydimethylsiloxane and polydimethylsiloxane-co-
polyhydromethylsiloxane copolymers with various molecular weights, as good
defoaming agents. The majority of patents use hydrosilylation as a mean to
incorporate allyl-functionalized polyethers onto silicone copolymer backbones
possessing randomly alternating dimethylsiloxane and methylhydrosiloxane
monomer units.
Dow Corning Co. (US Pat. No. 9230049.9) disclosed curable liquid
organopolysilicone compositions dispersed in a liquid continuous phase in the form of
an emulsion. The curable liquid comprised of organopolysilicone blends of
diorganopolysilicone possessing a silicone-bonded hydroxyl group and/or alkoxy
group having one to six carbon atoms and silicon resins containing a hydrolyzable
functionality. In Kulkarni et al. (US Pat. No. 4,509,532), the viscosity of the
dimethylpolysiloxanes oil was in the range of from 5000 to 30,000 cS at 25°C, which
improved efficiency in difficult to defoam aqueous systems. Keil et al., (US Patent
No. 3,784,479) disclosed a foam control composition of a base oil selected from
polyoxyprolene polymers, polyoxyproylene-polyoxyethylene copolymers or silicone-
glycol copolymers combined with dimethylpolysiloxane and silica filler. In another
closely related US patent number 3984347, Keil disclosed foam control compositions
which consisted mainly of base oil selected from polyoxypropylene polymers,
polyoxyproylene-polyoxyethylene copolymers or silicone-glycol copolymers, a foam
control agent comprising a liquid dimethylpolysiloxane, silica filler, and a silicone
copolymer dispersing agent. Similar composition containing higher molecular weight
polydimethylsiloxane was reported by Schiefer (US Pat. No. 4762640) was also
shown to be useful in defoaming of highly acidic aqueous systems. Aizawa et al.,
(US Pat. No. 463489 and 4749740) disclosed a method for producing silicone
defoamer compositions containing a mixture of filler, silicone resin and a catalyst to
promote reaction of the components at 50°C to 300°C. Starch, in United States
patent number 4983316, disclosed silicone antifoam emulsions particularly suited for
controlling foam in aqueous detergent systems. In this patent, the above mentioned
compositions of Aizawa et al. are used in conjunction with a secondary silicone
antifoam agent dispersed in a polypropylene glycol continuous phase. McGee et al.
(Aus. Pat. No. 34059/89), by combining the above mentioned compositions of
Aizawa et al. with particular silicone glycol compounds provided improved antifoams
for use in high pH aqueous systems, particularly pulp mill liquors.
Dow Corning Corp. (EUR Pat. No. 116-7502B1), disclosed silicone-based
foam control compositions where silicone antifoam/silica particles were dispersed in a
detergent compatible carrier. The composition consisted of a silicone-based
antifoam agent made from cross-linked silicone and branched silicone fluid. In
another patent Dow Corning Corp. revealed the former formulation that used vinyl
functionalized MQ resin, cross-linked polymethylhydrosiloxane fluid with a viscosity of
17,000 cSt. methylhydrosiloxane, and vinyl-terminated polymethylhydrosiloxane (450
cst) were cross-linked using a platinum catalyst. Dow Corning Corp. (EUR Pat. No.
1167456B1) revealed another formulation by using the same highly cross-linked
poly-organosiloxane fluid described in (US Pat. No. 4749740), adding mineral oil as
another component in the formulation.
Recently, a method for preparing a composition similar to that described by
Aizawa et aI. was disclosed by Miura (U.S. Patent No. 5,283,004). It is disclosed that
all the ingredients, including a catalyst, must be reacted at elevated temperatures to
obtain the desired antifoam agent. John et al. (US Pat. No. 217,501) disclosed a
foam control composition that improved performance in high foaming detergent
compositions. The defoamer comprised (I) a liquid siliconesili having a viscosity of at
least 7 x 10-3 m2/s at 25°C and prepared by mixing and heating a triorganosiloxane
end-blocked polydiorganosiloxane, the polydiorganosiloxane having at least one
terminal silanol group, and an organosiloxane resin comprised of monovalent and
tetravalent siloxy units that have at least one silanol group per molecule, and (II)
finely divided hydrophobic fillers. McGee et al. (U.S. Pat. No. 5,380,464) disclosed a
foam control composition containing a silicone defoamer and a silicone glycol
copolymer which is particularly effective in defoaming highly acidic or highly basic
aqueous systems. Union Carbide Corp., (EUR Pat. No. 273-4482) edify a foam
suppressant composition made by a free radical polymerization of a mixture of
diorganopolysilicones, silica particles, and a free radical initiator. A European patent
(EUR Pat. No. 0285391) disclosed organopolysilicone emulsions comprising a
hydroxyl end blocked organopolysilicone, an aminoxy group containing organosilicon
compound, a surfactant, and water. Dow Corning Co. (US Pat. No. 6207722 B1)
disclosed a defoamer composition made from polysiloxanes and a resin-filler
prepared from vinyl-functionalized silanol, trimethylsilyl functonalized silicone resin
(MQ resin). Elms et al. (US pat. No. 6,512,015 B1; Jan 28, 2003; Dow Corning Co.)
disclosed a foam control composition prepared by mixing trimethylsiloxane-
terminated polydimethylsiloxanes hydroxyl-terminated polydimethylsiloxanes
polysilicate resin, and a catalytic amount of potassium silanolate to promote cross-
linking between the added components. In addition to this formulation, Silwet L-77
silicone glycol, L-540 silicone polyglycol having block copolymer of PO:EO ratio
50/50, and mineral oil was added. Fey et al. (U.S. Pat. No. 5,908,891) disclosed a
dispersible silicone composition comprising (I) a silicone prepared by reacting a
trimethylsiloxane-terminated polydimethylsiloxane, a hydroxyl-terminated
polydimethylsiloxane, hydrophobic silica particle, and a catalytic amount of alkali
metal silinolate to promote the reaction of the other components and (II) mineral oil.
Fey et al. further discloses that the mineral oil is effective as a dispersing agent for
the silicone composition (I). Willibald et al, (US Pat. Application No. 2011/0021688
A1) owned by Wacker Chemie AG, issued in Aug, 21, 2008, disclosed defoamer
formulations using trimethylsiloxane-terminated polyhydromethylsiloxane mixed with
allyl polyether with PO/EO ratio of 4.0. The allyl polyether was hydrosilylated onto
PHMS using a platinum catalyst at 100 C. The resulting polymer surfactant had a
viscosity of 870 mm /s (25 C). The polymer was further cross-linked with
hexamethylene diisocyanate followed by the addition of Emulan HE 50 (BASF) to
give a final copolymer solution that has a viscosity of 2100 at 25 C. A defoamer
composition (EUR Pat. No. 0638346) was disclosed that comprised of a reaction
product prepared by heating a mixture of a polyorganosiloxane fluid, a silicon
compound, hydrophobic silica particles, and a catalytic amount of potassium
silanolate (for promoting the reaction of the other components) at a temperature of
50°C to 300°C. The patent further disclosed the use of the nonionic silicone
surfactants Silwet L-77 and L-540, and hydrophobic silica particles in the final
compositions. Kremer, (US Pat. No. 2005/01C19675 A1) disclosed a defoamer
composition consisting of polymethylhydrosiloxane resins cross-linked with alkyl
silicates emulsified in kerosene. This formulation is claimed to require lower amounts
of silicone. The final composition contains 90% kerosene and 8% 600,000
centistokes of a cross-linked linear polymethylhydrosiloxane and 2% of a cross-linked
branched polydimethylsiloxane and alkyl-silicate.
[0010a] In this specification where reference has been made to patent specifications,
other external documents, or other sources of information, this is generally for the
purpose of providing a context for discussing the features of the invention. Unless
specifically stated otherwise, reference to such external documents is not to be
construed as an admission that such documents, or such sources of information, in
any jurisdiction, are prior art, or form part of the common general knowledge in the
art.
Brief Description of the Invention
[0010b] In a first aspect, the present invention provides a composition comprising
functionalized organopolysiloxanes selected from the following structures;
Si Si
DA-1
wherein
R is, identically or differently, a phenyl, ethyl or methyl moiety,
m is an integer from 1 to 1000,
n is 0 or an integer from 1 to 2000,
f is identical or different, a divalent radical selected from the following: -S-, -NA -, -
COO-, and oxygen,
A is a hydrogen or a hydrocarbon having 1-3 carbon atoms,
x, identical or different, is selected from the group consisting of identical or different
polyether moieties, identical or different saturated or unsaturated hydrocarbon
radicals or mixtures thereof,
wherein the polyether moieties have the general formula
y-O-(CH CHR O) (CH CHR O) (CH ) -
2 v 2 z 2 w
and wherein the hydrocarbon radicals have the general formula
y-(CH ) -,
wherein
y is an aliphatic hydrocarbon moiety wherein the number of carbon atoms is between
1-18,
v is an integer from 1 to 1000,
z is a positive integer ranging from 0 to 1000,
w is a positive integer ranging from 1 to 18,
R is methyl, ethyl, or propyl,
R is hydrogen, methyl, ethyl, or propyl, and
R , identical or different, is selected from the group consisting of hydrogen, methyl,
ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, alkyl radicals with 5-
18 carbon atoms, substituted and unsubstituted aromatic hydrocarbon, fluorocarbon,
halocarbon, and cyclic hydrocarbons;
and wherein a finely divided zinc catalyst is used to promote the coupling of Si-H to
primary or secondary alcohols.
[0010c] In a second aspect, the present invention provides a method of making the
composition of the first aspect wherein the method comprises the steps of:
heating a polyether or aliphatic hydrocarbon, under inert conditions at a
temperature of from 90-160 C for at least two hours to reduce the water content
below 1000 microliter (µL),
adding an organosiloxane polymer to the polyether in the presence of a zinc
catalyst wherein the amount of catalyst added to the reaction vessel is from 0.5 -
1.0 wt% based on the amount of reactants,
allowing the components to react,
cooling the reaction vessel to ambient temperature after the completion of
siloxane addition to the reaction vessel.
[0010d] In a third aspect, the present invention provides a composition when made
by the method of the second aspect.
[0010e] In a fourth aspect, the present invention provides a method of improving
drainage and filtration rates in cellulosic washing and de-watering processes the
method comprising the steps of adding the composition of the first aspect to an
aqueous slurry containing cellulosic material wherein the composition is added at a
dosage of from 0.45 g to 1.8 kg (0.001 to 4 lb) for every 907 kg (2000 lb) of cellulosic
material in the aqueous slurry and wherein the solids content of the aqueous slurry is
from 0.01 to 30 % solids.
The present invention discloses dehydrogenative coupling (DC) to incorporate
polyether onto silicone copolymer backbone. Dehydrogenative coupling is a cost-
efficient alternative to hydrosilyation and does not require the used of allylated-
polyglycols, but instead takes advantage of a readily available hydroxyl-terminated
polyglycol. The dehydrogenative coupling reaction is assisted by transition metals in
the coupling of hydroxyl groups onto polysilicone backbones. One example of a
catalyst that can be used is Wilkinson’s catalyst ([(Ph P)] RhCl). This occurs at the
Si-H reactive site resulting in a Si-OR bond formation. The byproduct of this process
is hydrogen gas which is released into the atmosphere. We have discovered that by
using a unique combination of two particular Pluronics (L64 and L81) at a fixed ratio
resulted in significant improvement in drainage response comparable or slightly
exceeding the performance of the benchmark materials.
[0011a] The term “comprising” as used in this specification and claims means
“consisting at least in part of”. When interpreting statements in this specification and
claims which include the term “comprising”, other features besides the features
prefaced by this term in each statement can also be present. Related terms such as
“comprise”, “comprises”, and “comprised” are to be interpreted in similar manner.
[0011b] In the description in this specification reference may be made to subject
matter which is not within the scope of the appended claims. That subject matter
should be readily identifiable by a person skilled in the art and may assist in putting
into practice the invention as defined in the appended claims.
Detailed Description of the Invention
Silicone polyether compositions which improve drainage of pulp slurry in the
paper making process are disclosed.
Described herein is a drainage aid comprising functionalized
organopolysiloxanes comprising pendent polyethers and/or aliphatic hydrocarbons.
prepared by reacting
a) preferably polyethers of the general formula;
y-O-(CH CHR O ) (CH CHR O) (CH ) -f-H i
2 v 2 z 2 w
and / or
b) an aliphatic hydrocarbon of the formula
y-(CH ) -f-H ii
with
c) linear, cyclic or branched organopolysiloxanes.
In the general formula (i) or (ii): y can be hydrogen or is a monovalent
straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon
radical which has up to 100 carbon atoms. Preferably, y is an aliphatic hydrocarbon
moiety wherein the number of carbon atoms is between 1-18, more preferably 1 – 10
carbon atoms, more preferably between 1-4, or most preferably 1-2 carbon atoms. v
is an integer from 1 to 1000, preferably 1 to 500, more preferably 1 to 250, most
preferably 1-100 and z is a positive integer ranging from 0 to 1000, preferably from 0
to 500, more preferably 0 -250, more preferably 1-250, most preferably 1-100. w is a
positive integer ranging from 1 to 18, preferably from 1 to 10, more preferably 1-5,
1 2 1
most preferably 1-3. R and R can be identical or different. R can be methyl, ethyl,
1 1 2
or propyl, preferably R is methyl or ethyl, more preferably R is methyl group. R
can be hydrogen, methyl, ethyl, or propyl, preferably R is hydrogen, methyl or ethyl,
more preferably R is hydrogen or methyl group. Most preferably, R is a methyl and
R is a hydrogen. The structure in equation (i) can be block or random, preferably
random. f is a functional group that only exists if w is greater than zero. f is a
functional group selected from the group of B, Al, Sn, Si, Ge, O, S, N-A (where A is
hydrogen or a hydrocarbon having 1-3 carbon atoms), A -P (where A is hydrogen or
a hydrocarbon having 1-3 carbon atoms or any aromatic ring), phosphate, and –
COO-. Preferably, f is oxygen, S, or -COO-, most preferably, f is an oxygen.
The preferred structures of the polyether copolymer used for grafting onto
organopolysiloxanes are depicted in Chemical Structures 1. It is important to note
that, in the general formula (i), PPO (polypropylene glycol) and PEO (polyethylene
glycol) blocks can be distributed in any desired way. The PO (propylene glycol) and
EO (ethylene glycol) units can be randomly distributed (Chemical Structures 1,
compound 6 and 7). The most preferred polyether copolymer is a statistically
random copolymer 6.
The preferred the M (number average molecular weight) range for polyether
used to make drainage aid is from 200 to 100,000 Da, more preferably, from 200 to
,000 Da, most preferably, from 200 to 6000 Da
Chemical structures 1. Examples of polyethers
The p and q represent weight % of PO and EO units in the copolymer,
respectively. The preferred weight % value for q spans from 0-99 weight %, more
preferably, from 0-60%, most preferably, from 30-60 weight %. The most preferred
weight % value for q is between 40-55%. The total sum of p and q is 100%. The sum
of the total weight % of PO and EO in the polyether is 100%.
In the general formula (ii), y can be hydrogen or a monovalent straight-chain,
cyclic or branched, saturated, unsaturated or aromatic hydrocarbon moiety which has
up to 100 carbon atoms, preferably, y is preferably a straight-chain containing 1-18
carbon atoms, more preferably 1 – 10 carbon atoms, w is a positive integer ranging
from 1 to 18, preferably from 1 to 10, more preferably 1-5, most preferably 1-3. f is a
functional group selected from the group of B, Al, Sn, Si, Ge, O, S, N-A (where A is
hydrogen or a hydrocarbon having 1-3 carbon atoms), A -P (where A is hydrogen or
a hydrocarbon having 1-3 carbon atoms or any aromatic ring), phosphate, and –
COO-. Preferably, f is oxygen, S, or -COO-, most preferably, f is an oxygen.
In some embodiments when the alkyl hydrocarbon of the formula (ii) is used
to produce the composition of the present invention y can have from 6 to 9 carbon
atoms.
The preferred organopolysiloxanes that are used in making the drainage aid
of the present invention are linear, cyclic or branched organopolysiloxanes copolymer
(Chemical Structures 2). In Chemical Structure 2, R can be, identical or different, a
methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, alkyl
radicals with 5-18 carbon atoms, substituted and un-substituted aromatic
hydrocarbon, fluorocarbon, halocarbon, and cyclic hydrocarbons and mixtures
thereof. More preferably R is a phenyl, ethyl or methyl radical; most preferably R is a
methyl radical. In Chemical Structure 2, R denotes (R ) , and R , identical or
different, can be hydrogen, methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl,
isobutyl, tert-butyl, alkyl radicals with 5-18 carbon atoms, substituted and un-
substituted aromatic hydrocarbon, fluorocarbon, halocarbon, and cyclic
hydrocarbons. Preferably, R is selected from hydrogen, methyl, ethyl, and phenyl
radicals. The most preferred R is methyl.
Chemical Structures 2. Example of silicone
compounds
The most preferred organopolysiloxane copolymers are those having general
formula (iii).
6 3 4 5
H R SiO(R SiHO) (R SiO) SiR H (iii)
3-g g m 2 n h 3-h
wherein,
g is 2 or 3,
h is 2 or 3,
n is 0 or an integer from 1 to 2000 and
m is 0 or an integer from 1 to 1000
the sum of m and n is always at least one
R and R in the general formula (iii) are alkyl radicals and are identical or
different. R and R , identical or different, can be methyl, ethyl, n-propyl, isopropyl, 1-
n-butyl, 2-n-butyl, isobutyl, tert-butyl, alkyl radicals with 5-18 carbon atoms,
substituted and un-substituted aromatic hydrocarbon, fluorocarbon, halocarbon, and
cyclic hydrocarbons and mixtures thereof. Preferably R and R are selected from
methyl, ethyl, and phenyl radicals. R and R in the general formula (iii) are hydrogen
or alkyl radicals and are identical or different. R and R , identical or different, can
be hydrogen, methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-
butyl, alkyl radicals with 5-18 carbon atoms, substituted and un-substituted aromatic
hydrocarbon, fluorocarbon, halocarbon, and cyclic hydrocarbons. Preferably R and
6 5 6
R are selected from hydrogen, methyl, ethyl, and phenyl radicals. When R or R is
hydrogen, g or h, respectively is 3. The most preferred alkyl radicals in general
formula (iii) for organopolysiloxanes are methyl radicals.
The preferred organopolysiloxanes used in this invention are copolymers
comprising hydrogenalkylsiloxy and dialkylsiloxy units, more particularly copolymers
comprising hydrogenmethylsiloxy and dimethylsiloxy units, with the stipulation that
there exist at least one Si-bonded to hydrogen atom, preferably at least 2 Si-bonded
hydrogen atoms, per molecule, more preferably between 2 to 15.
In formula (iii) it is important to note that m -(SiRHO)- and n -(SiR O)-
repeating units can be distributed in any desired way in the molecule. With a
particular preference when g in formula (iii) is zero, the mole% for hydrogen-bonded-
silicon can range from 0 to 100 mole%. In one embodiment of the invention the
mole% of hydrogen-bonded-silicon is 1 to 10 mole%. In another embodiment
hydrogen-bonded-silicon is 10 to 20 mole%. In yet another embodiment hydrogen-
bonded-silicon is 20 to 60 mole%. In yet another embodiment the mole% of silicon-
bonded-hydrogen is 20-40 mole%. It is important to note that the sum of mole% for
hydrogen-bonded-silicon-bonded and dimethyl-bonded-silicon is always equal to
100%.
The organopolysiloxanes, in the general formula (iii), preferably possess an
average viscosity of 1 to 20,000 cSt (at 25° C), more preferably 1 to 10,000 cSt (at
° C), most preferably, 1 to 1000 cSt (at 25° C), and with particular preference for
values between 1 and 50 cSt (at 25° C).
It is preferred to use a catalytic amount of organometallic zinc compounds to
promote the coupling of Si-H to primary or secondary alcohols. It is possible in the
process described herein to employ any catalysts which promotes the addition of Si-
H to alcohol derivatives. The catalyst is preferably finely divided zinc particles which
may be present on supports such as silica, alumina or activated carbon, or
compounds or complexes of zinc, such as zinc halides, e.g., ZnCI ,Zinc(II)
acetylacetonate, ZnSO , Zinc Borate, Zn(C H O ) , ZnO, ZnCO , zinc acetate.
4 18 35 2 2 3
The silicone polyether drainage aid can be prepared by reacting polyether,
and or aliphatic hydrocarbons described above (Chemical Structures 1), with
organopolysiloxanes (Chemical Structures 2). The Si-H unit on the
organopolysiloxane polymers reacts with the polyether or aliphatic hydropcarbon
resulting in either pendant polyether groups or polyether end groups or aliphatic
groups on the silicone polymer depending on the original location of the Si-H unit on
the silicone polymer.
In one embodiment of the invention the organopolysiloxane is preferably,
comprised of 1-100 mole% MeSiHO with a viscosity of 1-100 cSt. This process is
catalyzed by zinc salt under inert anhydrous conditions, (such as a nitrogen purge)
and temperature range from about 80 C to about 160 C.
in one embodiment of the invention the drainage aid comprises the generic
structure shown in Chemical Structure 3.
Chemical Structure 3. Generic structure for
silicone polyether drainage aid.
In Chemical Structure 3, R is any of the hydrocarbon radicals of Formula (iii).
More preferably R is a phenyl, ethyl or methyl radical; most preferably R is a methyl
radical. R can be identical or different. In Chemical Structure 2, R denotes (R ) ,
and R is hydrogen or alkyl radicals and are identical or different. R , identical or
different, can be hydrogen, methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl,
isobutyl, tert-butyl, alkyl radicals with 5-18 carbon atoms, substituted and un-
substituted aromatic hydrocarbon, fluorocarbon, halocarbon, and cyclic
hydrocarbons. Preferably, R is selected from hydrogen, methyl, ethyl, and phenyl
radicals. The most preferred R is methyl. The functional group f is a divalent radical
covalently linked to the silicone backbone. f is a functional group selected from the
group of B, Al, Sn, Si, Ge, O, S, N-A (where A is hydrogen or a hydrocarbon having
1-3 carbon atoms), A -P (where A is hydrogen or a hydrocarbon having 1-3 carbon
atoms or any aromatic ring), phosphate, and –COO-. Preferably f is -S-, NH, -COO-,
or oxygen; most preferably f is an oxygen radical. The pendant group x, is the
hydrocarbon moiety resulted from the coupling reaction of the functional group, “ f ”,
on the polyether or aliphatic hydrocarbon with the hydrogen-bonded-silicon of the
silicone polymer backbone.
x can be:
y-O-(CH CHR O ) (CH CHR O) (CH ) - as described in formula (i)
2 v 2 z 2 w
and /or
y-(CH ) - as described in formula (ii)
Preferably, x is an aliphatic hydrocarbon having 1-18 carbon atoms, a polyether, or
any of the polyether copolymers described in Chemical Structures 1. The grafted
pendant group x can be identical or a mixture of multiple polyethers. Moreover, the
pendant group x can be a mixture of polyethers as described in the general formula
(i) and aliphatic hydrocarbon radicals as described in the general formula (ii).
Preferably, x is selected from the group of polyethers described in Chemical
Structures 1.
In one embodiment of the invention x comprises polyether-6 (Chemical
Structures 1) with EO wt% ranging from 0 to 99 wt% and M (number average
molecular weight) ranging from 100 to 100,000 Da. In another embodiment, x is
selected from polyether 6 (Chemical Structures 1) comprising of 35-55 wt% EO and a
Mn ~ 500-5000 Da.
The drainage aid of the invention can comprise at least one of the generic
structures shown in Chemical Structure 3.
wherein
R comprises phenyl, ethyl or methyl,
m is an integer from 1 to 1000,
n is 0 or an integer from 1 to 2000,
f comprises, identical or different, a divalent radical selected from the group
consisting of of B, Al, Sn, Si, Ge, O, S, N-A (where A is hydrogen or a hydrocarbon
having 1-3 carbon atoms), A -P (where A is hydrogen or a hydrocarbon having 1-3
carbon atoms or any aromatic ring), phosphate, and –COO-, preferably f is -S-, -NH-,
-COO-, or oxygen.
x comprises, identical or different, a polyether moiety, a mixture of moieties of
polyethers or a mixture of a polyether moiety and a saturated or un-saturated
hydrocarbon radical containing 1 to 18 carbon atoms,
the residue or the polyether comprising the formula
y-O-(CH CHR O ) (CH CHR O) (CH ) -
2 v 2 z 2 w
y is an aliphatic hydrocarbon moiety wherein the number of carbon atoms is between
1-18,
v is an integer from 1 to 1000,
z is a positive integer ranging from 0 to 1000,
w is a positive integer ranging from 1 to 18,
R is methyl, ethyl, or propyl,
R is hydrogen, methyl, ethyl, or propyl, and
R denotes (R ) , and R is hydrogen or alkyl radicals and are identical or different.
R , identical or different, can be hydrogen, methyl, ethyl, n-propyl, isopropyl, 1-n-
butyl, 2-n-butyl, isobutyl, tert-butyl, alkyl radicals with 5-18 carbon atoms, substituted
and un-substituted aromatic hydrocarbon, fluorocarbon, halocarbon, and cyclic
hydrocarbons. Preferably, R is selected from hydrogen, methyl, ethyl, and phenyl
radicals. The most preferred R is methyl.
In some embodiments of the invention the silicone polyether comprises DA-6
and x comprises a polyether-6 moiety, q is 45-50 wt%, y is a n-butyl radical and the
viscosity of DA-6 is from about 10,000cp to about 50,000cp(100% solids).
In one embodiment of the invention the viscosity of DA-6 is from about 15,000
to about 30,000 cp (100% solids).
In some embodiments x is a mixture of polyether moieties and hydrocarbon
radicals wherein at least one polyether moiety is a polyether-6 moiety and at least
one hydrocarbon radicals is a linear aliphatic hydrocarbon consisting of 1-18 carbon
atoms, preferebly1-9 carbons.
In some embodiments x is a mixture of polyether moieties and hydrocarbon
radicals wherein at least one polyether moiety is a polyether-6 moiety and at least
one hydrocarbon radicals is a linear aliphatic hydrocarbon consisting of 1-18 carbon
atoms, preferebly1-9 carbons, wherein and the linear aliphatic hydrocarbon
comprises from 10 to 90 mole % of the x moieties, preferably from 20 to 80, more
preferably from 30 to 65 mole % of the x moieties.
In some embodiments the wt% of polyether moiety in the composition is from
to 50 wt%.
The condition to synthesize the drainage aid requires the polyether to be
dried, under inert conditions, such as a nitrogen purge, prior to use. This is done by
heating the polyether in the reaction vessel at 90-120 C, preferably at 90-140 C,
more preferably from 90-160 C for at least 2 hours, or longer in order to lower the
water content below 1000 µL, preferably less than1.00 µL, preferably less than 0.005
µL, less than 0.0001 µL. The water content can be from 1000-1.00 µL, preferably
water content is as low as 1.0- 0.005 µL, more preferably as low as 0.005-0.0001 µL
most preferably lower than 0.0001 µL.
Following the drying process, a catalytic amount of zinc(II) acetylacetonate is
added to the reaction. Preferably, 1.0-0.5 wt% is added, more preferably, 0.5-0.1
wt%, most preferably 0.1-0.01 wt%.
Organosiloxane polymer is gradually added over a period of 15-120 min,
preferably 15-90 min, more preferably 15-60 min, most preferably 15-30 min.
It is preferred that the reaction be quenched by cooling the reaction to
ambient temperature. Generally the reaction is quenched 6-14 hours from the time
the addition of organosiloxane polymer was complete, more preferably 6- 10 hours,
most preferably 6-8 hours.
The mole percent of polyether used is dependant on the moles of Si-H bonds
in the silicone compounds. It is preferred that there be a molar excess of polyether
plus aliphatic hydrocarbon containing a functional group f, with respect to the moles
of Si-H bonds. If an aliphatic hydrocarbon containing a functional group is not used
then the molar amount of polyether to Si-H bonds is preferably 1:1 to 1.5:1, more
preferably from 1:1 to 1.25:1. If an aliphatic hydrocarbon containing a functional
group is used then the sum of the molar amount of aliphatic hydrocarbon and
polyether to Si-H bonds is preferably 1:1 to 1.5:1, more preferably from 1:1 to 1.25:1.
In general there will be a greater percent of polyether than aliphatic hydrocarbon
used. Maintaining a molar excess of reactants to Si-H bonds in the silicone is
preferred. The ratio of polyether to aliphatic hydrocarbon is chosen to maintain an
overall hydrophilic nature to the resulting silicone polyether polymer.
It was observed by Pelton et al. (New Insights into Dispersed Air Effects in
Brown Stock Washing. TAPPI Journal, 84 (1). 2001) that the size of air bubbles
entrained in a fiber mat can have a significant impact on drainage. Bleached fiber
and soap water was used in their studies, and through the use of a MacMaster
laboratory pulp washer they were able to capture this phenomenon on film. It was
concluded that air bubbles > 10 mm had less of an impact on filtration resistance
than bubbles < 2 mm. The bubbles > 10 mm rise to the surface of the mat relatively
unhindered, and through this create channels increasing the permeability of the mat.
The smaller air bubbles remain with the fiber in the mat, creating blockages and
increased surface area, adding to filtration resistance. They also demonstrated
through the use of defoamers, these smaller air bubbles would coalesce to a greater
degree before they became entrapped within the fiber mat, which decreased filtration
resistance. The natural surfactants present in black liquor results in smaller bubbles
which are stabilized against coalescence. Coalescence is further minimized by the
reduced mobility of the bubbles due to the physical barriers by the fibers. We believe
that bubbles are prone to being attached to the fibers in the slurry. Therefore, as the
fiber mat is formed under dynamic filtration conditions, air is entrapped within the mat
because of this bubble attachment. We also observed that larger bubbles do not
remain in the slurry but rise to the surface, but by increasing shear, which breaks up
the bubbles, increased the amount of air entrained. In our hypothesis we believe that
the drainage aids do not affect bubble size, but hinder the bubble attachment to the
fiber surfaces. Our data shows that there is a decrease in air entrainment in the pulp
slurry when the drainage aid is present. With less bubble attachment the mat
formation occurs with lower air entrainment and increases filtration rates.
The composition of the present invention is used to improve the filtration of
pulp and pulp mats in washing and thickening operations of a cellulosic processing
plant, more specifically a pulp mill. The composition of the invention is added to an
application either prior to pulp dilution, during pulp dilution, or shower water for mat
displacement washing. The composition of the invention is added in the range of
0.001 to 4.000 lbs for every 2000 lb of cellulosic material in the process. The
cellulosic slurries are generally aqueous. They can range from 0.01 to 30 % solids,
but are more preferably from 0.01 to 0.05 % solids. The addition of the composition
of the invention will have the effect of increasing the removal or wash through of the
liquid filtrates used in processing the cellulosic material.
The composition can be used for improving drainage and filtration rates in
cellulosic washing and de-watering processes. The composition is added to an
aqueous slurry containing cellulosic material. The composition is added at a dosage
of from 0.001 to 4 lb for every 2000 lb of cellulosic material in the aqueous slurry.
The solids content of the aqueous slurry is generally from 0.01 to 30 % solids.
The aqueous slurry preferably can have a pH in the range of from 10.5 to
13.5.
The aqueous slurry can be derived from a brown stock washing process, a
bleach plant process, a market pulp machine process or other processes.
Examples
Working example-1
To a 500 mL reaction vessel equipped with an overhead stirrer, 500g of
UCON 50-HB-5100 (Dow Chemicals, Midland, Michigan) was added. The reaction
vessel was gradually heated to 150 C and stirred at 150 C for 2 hours. Zinc(II)
acetylacetonate (Strem Chemicals, Newburyport, MA) (0.01 wt% was added to the
reaction vessel followed by gradually adding 2.0 wt% of polyhydromethylsiloxane
(Grelest, Inc., Morrisville, PA) over 1.4 hours. The reaction was allowed to stir at 150
C for an additional 4 hours before it was quenched by cooling the reactor to ambient
temperature Scheme-1.
Working example-2
To a 500 mL reaction vessel equipped with an overhead stirrer, 72.54g of
UCON 50-HB-5100 (Dow Chemicals) (polyether-6) was added. The reaction vessel
was gradually heated to 160 C using a heating mantle and stirred at 160 C for 2
hours. Zinc(II) acetylacetonate (Strem Chemicals)(0.04 wt%) was added to the
reactor in powder form. Hydride terminated polydimethylsiloxane (Gelest) 52 wt%
was then added to the reaction in three separate doses of 26.6g over a period of 1
hour. After the addition of silicone was complete, the reaction was allowed to stir at
160 C for an additional 5 hours. The reaction was quenched by cooling the reactor
to ambient temperature (Scheme-2).
Working example-3
To a 500 mL reaction vessel equipped with an overhead stirrer, 300g of
UCON 50-HB-5100 (Dow Chemicals) was added. The reaction vessel was gradually
heated to 160 C using a heating mantle and stirred at 160 C for 2 hours. 0.03 wt%
of Zinc(II) acetylacetonate (Strem Chemicals) was added to the reactor in powder
form. 15 wt% of tetramethylhydrocyclosiloxane (Gelest)) was injected into the
reaction over a period of 1 hour. After the injection of tetramethylhydrocyclosiloxane
was complete, the reaction was allowed to stir at 160 C for up to 5 hours. The
reaction was quenched by cooling the reactor to ambient temperature (Scheme-3).
Working example-4
To a 500 mL reaction vessel equipped with an overhead stirrer, 38g of
Pluronic L64 (BASF) (q=40 wt%) and 62g of Pluronic L81 (BASF) (q=10 wt%), were
added to the vessel. The reaction vessel was gradually heated to 135 C and stirred
at 135 C for 2 hours. 0.01wt% of Zn(II)acetylacetonate (Strem Chemicals) was then
added followed by a gradual addition of 15 wt% of polydimethysiloxane-co-
polyhydromethylsiloxane (25-Gelest; 30 mole% CH HSiO; 25-35 cSt) over 2h. After
the addition of silicone copolymer was complete, the reaction was stirred at 135 C
for an additional 30 min. The reaction was quenched by cooling the vessel to ambient
temperature. % yield was 95% (Scheme-4).
Working example-5
To a 500 mL reaction vessel equipped with an overhead stirrer, 300g of
UCON 50-HB-5100 (Dow Chemicals) was added. The reaction vessel was gradually
heated to 150 C using a heating mantle or oil bath and stirred at 150 C for 2 hour.
0.03 wt% of zinc(II) acetylacetonate (Strem Chemicals) was then added to the
reaction vessel followed by a gradual addition of 6.0 wt% of polydimethysiloxane-co-
polyhydromethylsiloxane (25-Gelest; 30 mole% CH HSiO; 25-35 cSt) over 1hour.
After the injection of the silicone copolymer was complete, the reaction was allowed
to stir at 150 C for 5 hours to insure complete consumption of Si-H for a total
reaction time of 6 hours. The reaction was quenched by cooling the product to
ambient temperature. % yield was 98%-90% (Scheme-5).
Working example-6
To a 500 mL reaction vessel equipped with an overhead stirrer, 200g of 1-
nonanol (Sigma-Aldrich, St. Louis, Missouri) was added. The reaction vessel was
gradually heated to 150 C using a heating mantle or oil bath and stirred at 150 C for
1 hour. 0.01g of zinc(II) acetylacetonate was then added to the reaction vessel
followed by gradual addition of 148g of polydimethysiloxane-co-
polyhydromethylsiloxane (25-Gelest; 30 mole% CH HSiO; 25-35 cSt) over 1 hour.
After the injection of the silicone copolymer was complete, the reaction was allowed
to stir at 150 C for 5 hours to insure complete consumption of Si-H for a total
reaction time of 7 hours. The reaction was quenched by cooling the product to
ambient temperature. % yield was about 90%.
Working example-7
To a 500 mL reaction vessel equipped with an overhead stirrer, 200g of
UCON 50-HB-5100 (Dow Chemicals) and 8.91g of 1-nonanol (Sigma-Aldrich) were
added. The reaction vessel was gradually heated to 150 C using a heating mantle
or oil bath and stirred at 150 C for 2 hour. 0.01g of zinc(II) acetylacetonate was then
added to the reaction vessel followed by a gradual addition of 65.67g of
polydimethysiloxane-co-polyhydromethylsiloxane (25-Gelest; 30 mole% CH HSiO;
-35 cSt) over 80 minutes. After the injection of the silicone copolymer was
complete, the reaction was allowed to stir at 150 C for 5 hours to insure complete
consumption of Si-H. The reaction was quenched by cooling the product to ambient
temperature. % yield was about 90-95%.
Example 8- Drainage test: Black liquor and pulp were mixed to obtain a pulp
consistency of 3% (based on dry pulp). The pulp slurry was then mixed under high
shear and ran in a drainage apparatus at 85 C°. After mixing, the slurry was filtered
with a screen, under moderate vacuum in the drainage apparatus. The screen was
sized to ensure that the path of greatest resistance was through the fibrous mat
during filtering. The flow rate of filtrate was then measured and used as the basis for
determining treatment efficacy.
The synthesized compounds of examples 1-5 and 7 were tested against black
liquor/cellulosic fibers having 3.0-2.5% consistency. The results are described in
Table 1. Shorter drainage times correspond to efficient drainage aid. Table 1
indicates that the shortest drainage time was observed with DA-5 and DA-6a. DA-5
was made from mixing two types of polyether having different HLBs, polyether-3a
(HLB~ 6) and polyether-3b (HLB ~ 15-18). By tuning the ratio of the two compounds
polyether the HLB of the compound can be adjust to optimize drainage time. In the
case with DA-5, a net HLB of ~ 9 was obtained by mixing 38g of polyether-3a and
62g of polyether-3b. Alternatively, by using a statistically random EO/PO copolymer
with 50 wt% EO also resulted in good drainage time which is also due to the right
balance between the hydrophilic and hydrophobic components of the copolymer.
Table 1: Drainage Times
Sample Drainage Time (sec) Increase in Drainage Rate
from Untreated
Untreated 30.8 n/a
DA-1 (from example 1) 27.4 11%
DA-2 (from example 2) 27.3 11%
DA-3 (from example 3) 30.1 2%
DA-5 (from example 4) 14.9 52%
DA-6a * (from example 5) 16.1 48%
DA-6b** (from example 7) 27.5*** 11%
*Silicone Polyether Compound of Structure DA-6
** Silicone Polyether and Aliphatic hydrocarbon Compound of Structure DA-6
*** Calculated drainage time based on measured drainage rate from a similar pulp
slurry.
DA-3 provided only a small improvement in drainage. It is theorized that
reducing the hydrophilicity of DA-3 will provide better drainage.
Claims (28)
1. A composition comprising functionalized organopolysiloxanes selected from the following structures; DA-1 wherein R is, identically or differently, a phenyl, ethyl or methyl moiety, m is an integer from 1 to 1000, n is 0 or an integer from 1 to 2000, f is identical or different, a divalent radical selected from the following: -S-, -NA -, - COO-, and oxygen, A is a hydrogen or a hydrocarbon having 1-3 carbon atoms, x, identical or different, is selected from the group consisting of identical or different polyether moieties, identical or different saturated or unsaturated hydrocarbon radicals or mixtures thereof, wherein the polyether moieties have the general formula y-O-(CH CHR O) (CH CHR O) (CH ) - 2 v 2 z 2 w and wherein the hydrocarbon radicals have the general formula y-(CH ) -, wherein y is an aliphatic hydrocarbon moiety wherein the number of carbon atoms is between 1-18, v is an integer from 1 to 1000, z is a positive integer ranging from 0 to 1000, w is a positive integer ranging from 1 to 18, R is methyl, ethyl, or propyl, R is hydrogen, methyl, ethyl, or propyl, and R , identical or different, is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, alkyl radicals with 5- 18 carbon atoms, substituted and unsubstituted aromatic hydrocarbon, fluorocarbon, halocarbon, and cyclic hydrocarbons; and wherein a finely divided zinc catalyst is used to promote the coupling of Si-H to primary or secondary alcohols.
2. The composition of claim 1 wherein R is methyl.
3. The composition of claim 1 or 2 wherein R is hydrogen or methyl.
4. The composition of claim 1, 2 or 3 wherein x comprises at least one polyether moiety.
5. The composition of any one of claims 1 to 4 wherein x comprises a mixture of moieties wherein the mixture comprises at least two polyether moieties derived from the group consisting of the following polyether-1, polyether-2, polyether-3, polyether-4, polyether-5, polyether-6, polyether-7, polyether-8, and polyether-9: wherein the polyether has a number average molecular weight range of from 200 to 100,000 Da and y is hydrogen or a monovalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 100 carbon atoms.
6. The composition of any one of claims 1 to 4 wherein x comprises a mixture of moieties wherein the mixture comprises at least one polyether moiety derived from the group consisting of polyether-1, polyether-2, polyether-3, polyether-4, polyether-5, polyether-6, polyether-7, polyether-8, and polyether-9, as defined in claim 5, and at least one aliphatic moiety derived from the following general formula (ii): y-(CH ) -f-H (ii) wherein y is hydrogen or a monovalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 100 carbon atoms, w is a positive integer ranging from 1 to 18, and f is a functional group selected from the group of B, Al, Sn, Si, Ge, O, S, N-A (where A is hydrogen or a hydrocarbon having 1-3 carbon atoms), A -P (where A is hydrogen or a hydrocarbon having 1-3 carbon atoms or any aromatic ring), phosphate, and -COO-.
7. The composition of any one of claims 1 to 4 wherein x comprises a mixture of polyether moieties and hydrocarbon moieties wherein at least one polyether moiety is derived from a polyether-6 moiety as defined in claim 5 and at least one hydrocarbon moiety is derived from a linear aliphatic hydrocarbon consisting of 1- 18 carbon atoms.
8. The composition of claim 7 wherein the hydrocarbon moiety is derived from a linear aliphatic hydrocarbon consisting of 1-9 carbon atoms.
9. The composition of claim 7 or 8 wherein the functionalized organopolysiloxane comprises DA-6.
10. The composition of any one of claims 1-9 wherein the aliphatic hydrocarbon comprises from 10 to 90 mole % of the x moieties.
11. The composition of any one of claims 1-10 wherein the aliphatic hydrocarbon comprises from 20 to 80 mole % of the x moieties.
12. The composition of any one of claims 1-11 wherein the aliphatic hydrocarbon comprises from 30 to 65 mole % of the x moieties.
13. The composition of any one of claims 1-12 wherein the functionalized organopolysiloxane further comprises DA-5 made from mixing a polyether-3a and a polyether-3b, wherein x is a mixture of moieties and comprises at least two polyether moieties wherein at least one of the polyethers is selected from the group consisting of , , , and mixtures thereof; wherein p and q are the weight % of propylene glycol and ethylene glycol units, respectively, of the organopolysilicones.
14. The composition of any one of of claims 1-12 wherein at least one polyether moiety is derived from polyether-3 as defined in claim 5, wherein the weight percent, “q”, of ethylene oxide units in the polyether is from 0 to 99%.
15. The composition of claim 14 wherein x comprises a mixture of at least two polyethers derived from a) polyether-3 with a q of from 30 to 40 wt%, and b) polyether-3 with a q of from 5 to 20 wt%.
16. The composition of claim 15 wherein wt% of polyether derived from polyether-3 with a q of from 30 to 40 wt% in the composition is from 30 to 40 wt% of the composition.
17. The composition of any one of claims 1 to 16 wherein the functionalized organopolysiloxane comprises DA-6 and wherein x comprises a polyether moiety derived from polyether-6 as defined in claim 5, wherein propylene glycol and ethylene glycol are randomly distributed and wherein weight percent of ethylene glycol in polyether-6 is from 10 to 90 wt%.
18. The composition of claim 17 wherein weight percent of ethylene glycol in polyether-6 is from 40 to 55 wt%.
19. The composition of any one of claims 1 to 17 wherein functionalized organopolysiloxane comprises DA-6 and wherein x is a mixture of moieties wherein the mixture comprises at least one polyether moiety derived from polyether-6 and at least one additional polyether moiety derived from the group consisting of polyether-1, polyether-2, polyether-3, polyether-4, polyether-5, polyether-7, polyether-8, polyether-9 and mixtures thereof as defined in claim 5.
20. The composition of any of claims 1 to 17 wherein functionalized organopolysiloxane comprises DA-6 and wherein x comprises polyether moiety derived from polyether-6 wherein weight percent of ethylene glycol in polyether-6 is from 45-50 wt%, and y is n-butyl radical.
21. A method of making the composition of any of claims 1 to 20 wherein the method comprises the steps of: heating a polyether or aliphatic hydrocarbon, under inert conditions at a temperature of from 90-160 C for at least two hours to reduce the water content below 1000 microliter (µL), adding an organosiloxane polymer to the polyether in the presence of a zinc catalyst wherein the amount of catalyst added to the reaction vessel is from 0.5 - 1.0 wt% based on the amount of reactants, allowing the components to react, cooling the reaction vessel to ambient temperature after the completion of siloxane addition to the reaction vessel.
22. A method of improving drainage and filtration rates in cellulosic washing and de- watering processes the method comprising the steps of adding the composition of any one of claims 1 to 20 to an aqueous slurry containing cellulosic material wherein the composition is added at a dosage of from 0.45 g to 1.8 kg (0.001 to 4 lb) for every 907 kg (2000 lb) of cellulosic material in the aqueous slurry and wherein the solids content of the aqueous slurry is from 0.01 to 30 % solids.
23. The method of claim 22 wherein the aqueous slurry has a pH in the range of from 10.5 to 13.5.
24. The method of claim 22 or 23 wherein the aqueous slurry is derived from the group consisting of a brown stock washing process, a bleach plant process, and a market pulp machine process.
25. A composition of any one of claims 1 to 20 substantially as herein described with reference to any example thereof.
26. A method of claim 21 substantially as herein described with reference to any example thereof.
27. A composition when made by the method of claim 21 or 26.
28. A method of any one of claims 22 to 24 substantially as herein described with reference to any example thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161479110P | 2011-04-26 | 2011-04-26 | |
US61/479,110 | 2011-04-26 | ||
PCT/US2012/034997 WO2012149019A1 (en) | 2011-04-26 | 2012-04-25 | Organopolysilicone polyether drainage aid |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ616504A NZ616504A (en) | 2015-10-30 |
NZ616504B2 true NZ616504B2 (en) | 2016-02-02 |
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