TWI767951B - 以鈉及鈣離子中和且具有窄分子量分佈之丙烯酸聚合物 - Google Patents
以鈉及鈣離子中和且具有窄分子量分佈之丙烯酸聚合物 Download PDFInfo
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- TWI767951B TWI767951B TW106137767A TW106137767A TWI767951B TW I767951 B TWI767951 B TW I767951B TW 106137767 A TW106137767 A TW 106137767A TW 106137767 A TW106137767 A TW 106137767A TW I767951 B TWI767951 B TW I767951B
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- Prior art keywords
- neutralized
- acrylic
- acid groups
- acrylic acid
- acid
- Prior art date
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 23
- 238000009826 distribution Methods 0.000 title description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title description 4
- 239000011734 sodium Substances 0.000 title description 4
- 239000002253 acid Substances 0.000 claims abstract description 37
- 229920000058 polyacrylate Polymers 0.000 claims description 66
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 50
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 49
- 239000012986 chain transfer agent Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000000920 calcium hydroxide Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 description 24
- 239000002002 slurry Substances 0.000 description 19
- 238000007792 addition Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 14
- 235000011116 calcium hydroxide Nutrition 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000005385 peroxodisulfate group Chemical group 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical group OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/02—Low molecular weight, e.g. <100,000 Da.
-
- C—CHEMISTRY; METALLURGY
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Abstract
本發明係關於一種丙烯酸聚合物,其重量平均分子量Mw
在3500至12 000 g/mol範圍內且多分散性指數Mw
/Mn
≤ 2.5,其中該等丙烯酸聚合物之30%至60%酸基已經鈣離子中和,30%至70%之該等丙烯酸聚合物已經鈉離子中和,且該等丙烯酸聚合物之0%至10%酸基未被中和。
Description
本發明係關於以鈉及鈣離子中和且具有窄分子量分佈之丙烯酸聚合物,係關於製備丙烯酸聚合物之製程,且係關於其作為固體之水性懸浮液中之分散劑之用途。
碳酸鈣水性懸浮液通常係藉由碳酸鈣之濕法研磨使用聚羧基鹽作為研磨輔助劑來製備。該等碳酸鈣懸浮液用作造紙及染料工業中之填充劑及白色顏料。為了良好的性能性質,經研磨顏料需要高細度,且此應在最短研磨時間內達成。為保證廣泛工業用途,懸浮液(亦稱為漿液)需要具有良好可泵性及儲存穩定性二者,同時具有高固體含量。儲存穩定性很重要,此乃因在研磨操作與進一步處理之間,儲存及運輸階段通常持續數天至數周,且懸浮液在此時間階段內必須保持可泵性。 已知藉由自由基聚合製備之低分子量聚丙烯酸具有良好分散性質。為了良好效能,該等聚合物之平均分子量(Mw
)應< 50 000 g/mol。Mw
< 20 000 g/mol之聚丙烯酸通常尤其有效。 DE 40 04 953 A1闡述製備丙烯酸聚合物之製程,其中在實施聚合前丙烯酸之一部分以氫氧化鈣中和。 DE 103 11 617 A1闡述已至少部分以鹼金屬氫氧化物或氨中和之具有5000至30 000 g/mol之平均分子量及含硫有機端基之聚丙烯酸作為碳酸鈣之研磨輔助劑之用途。 US 4,840,985闡述部分中和之丙烯酸聚合物,其作為研磨輔助劑用於製備用作顏料懸浮液之礦物質水性懸浮液。丙烯酸聚合物中40%至80%之酸基已經鹼金屬離子、銨離子或多價陽離子中和。 US 5,432,238及US 5,432,239闡述已經鎂離子及鈉離子中和之丙烯酸之聚合物及共聚物,其作為研磨及分散輔助劑用於製備礦物質懸浮液。根據US 5,432,238,出於此目的,使用藉由分級分離獲得且比黏度為0.3至0.8且重量平均分子量為1000-10 000 g/mol之聚合物部分。 US 7,956,211揭示使用含硫有機分子量調節劑藉由RAFT聚合製備具有低多分散性指數(PDI)之聚丙烯酸。產物可用作礦物質水性懸浮液之研磨助劑。 EP-A 1 074 293揭示分子量Mw
為2000至5800 g/mol之膦酸酯封端之聚丙烯酸,其作為分散劑用於產生碳酸鈣、高嶺土、黏土、滑石粉及金屬氧化物之水性漿液,固體含量為至少60 wt%。 WO 2012/104401闡述藉由在次磷酸鹽存在下在作為溶劑之水中,用過氧二硫酸鹽作為起始劑以進料模式使丙烯酸聚合,來製備丙烯酸聚合物水溶液之製程,其中首先裝填水及視情況一或多種烯系未飽和共聚單體,且連續添加呈酸性、未經中和形式之丙烯酸、視情況一或多種烯系未飽和共聚單體、過氧二硫酸鹽水溶液及次磷酸鹽水溶液,其中基於總單體含量,共聚單體含量不超過30 wt%。所獲得丙烯酸聚合物之特有特徵為,總磷含量之至少76%呈聚合物鏈內鍵結之亞膦酸酯基形式。 WO 2012/104304闡述藉由在次磷酸鹽存在下在作為溶劑之水中,在進料操作中用自由基起始劑使丙烯酸聚合,來製備丙烯酸聚合物水溶液之製程,該製程包含 (i) 首先裝填水及視情況一或多種烯系未飽和共聚單體, (ii) 連續添加呈酸性、未經中和形式之丙烯酸、視情況一或多種烯系未飽和共聚單體、自由基起始劑水溶液及次磷酸鹽水溶液, (iii) 在丙烯酸進料終止後向水溶液添加鹼, 其中基於總單體含量,共聚單體含量不超過30 wt%,其中次磷酸鹽水溶液係在由三個連續進料時間間隔ΔtI
、ΔtII
及ΔtIII
構成之總進料時間期間添加,其中第二進料時間間隔ΔtII
中之平均進料速率大於第一及第三進料時間間隔ΔtI
、ΔtIII
之平均進料速率。 根據WO 2012/104401及WO 2012/104304獲得之水溶液及自其獲得之丙烯酸聚合物用作CaCO3
、高嶺土、滑石粉、TiO2
、ZnO、ZrO2
、Al2
O3
或MgO之水性固體分散液中之分散劑。 儘管使用聚合物,但懸浮液之儲存穩定性仍有限。在僅幾天後且尤其在1至2周後,黏度顯著升高,使得懸浮液之泵送及進一步處理(若進行)可極難。同時,懸浮液可因固體沉降而分離並形成沈澱。更長儲存穩定性階段可顯著簡化與礦物質懸浮液相關之邏輯。 所解決問題係為製備礦物質懸浮液、尤其碳酸鈣懸浮液提供分散及研磨輔助劑之問題,其產生低黏度、儲存穩定的懸浮液,其即使在數周儲存時間後仍可泵送。
該問題由重量平均分子量Mw
在3500至12 000 g/mol範圍內且多分散性指數Mw
/Mn
≤ 2.5之丙烯酸聚合物來解決,其中丙烯酸聚合物中30%至60%酸基已經鈣離子中和,丙烯酸聚合物中30%至70%酸基已經鈉離子中和,且丙烯酸聚合物中0%至10%酸基尚未被中和。 較佳地,丙烯酸聚合物中40%至60%酸基已經鈣離子中和,丙烯酸聚合物中40%至60%酸基已經鈉離子中和,且丙烯酸聚合物中0%至10%酸基尚未被中和。較佳地,多分散性指數Mw
/Mn
≤ 2.3,更佳為1.5至2.2。丙烯酸聚合物之酸基包括藉由丙烯酸引入聚合物中之酸基以及彼等藉由任何酸性共聚單體引入之酸基。 已令人驚訝地發現,使用其中30%至60%酸基已經鈣離子中和,30%至70%酸基已經鈉離子中和,且不多於10%酸基尚未被中和之重量平均分子量為3500至12,000 g/mol且具有窄分子量分佈之丙烯酸聚合物作為分散劑,獲得即使在三周儲存時間後仍具有低黏度及極佳可泵性之碳酸鈣懸浮液。 本發明丙烯酸聚合物係藉由丙烯酸視情況與共聚單體之自由基聚合來獲得。可能藉由用於製備聚丙烯酸之任何已知自由基聚合方法來進行。較佳者係在水中、在有機溶劑中或在水與有機溶劑之混合物中溶液聚合。尤佳者係在水中聚合。具有窄分子量分佈之丙烯酸聚合物可藉由所獲得丙烯酸聚合物之分級分離、例如藉由沈澱來獲得。根據本發明中和之丙烯酸聚合物係藉由將包含鈉離子之鹼及包含鈣離子之鹼添加至藉由呈酸性形式之丙烯酸之自由基聚合製備之未中和丙烯酸聚合物之溶液中來獲得,添加量使得30%至60%酸基已經鈣離子中和,30%至70%酸基已經鈉離子中和,且不多於10%酸基尚未被中和。 通常,具有窄分子量分佈之丙烯酸聚合物之水溶液係藉由在鏈轉移劑存在下在作為溶劑之水中,以進料模式用自由基起始劑進行丙烯酸之聚合來獲得。 本申請案亦提供製備重量平均分子量Mw
在3500至12 000 g/mol範圍內且多分散性指數Mw
/Mn
≤ 2.5之丙烯酸聚合物之水溶液之製程,其中丙烯酸聚合物中30%至60%酸基已經鈣離子中和,丙烯酸聚合物中30%至70%酸基已經鈉離子中和,且丙烯酸聚合物中0%至10%酸基尚未被中和,其係藉由在鏈轉移劑存在下在作為溶劑之水中,以進料模式用自由基起始劑進行丙烯酸之聚合來製備,該製程包含 (i) 首先裝填水及視情況呈酸性、未經中和形式之丙烯酸、視情況一或多種烯系未飽和共聚單體、視情況鏈轉移劑及視情況起始劑, (ii) 添加丙烯酸、視情況一或多種烯系未飽和共聚單體、自由基起始劑水溶液及鏈轉移劑, (iii) 在丙烯酸進料終止後將鹼添加至該水溶液, 其中,在步驟(iii)中,包含鈉離子之鹼及包含鈣離子之鹼之添加量使得丙烯酸聚合物中30%至60%酸基經鈣離子中和,丙烯酸聚合物中30%至70%酸基經鈉離子中和,且丙烯酸聚合物中0%至10%酸基未經中和。 較佳地,在步驟(iii)中,首先添加包含鈣離子之鹼,隨後添加包含鈉離子之鹼。 較佳包含鈉離子之鹼係氫氧化鈉及碳酸鈉。尤佳者係氫氧化鈉。 較佳包含鈣離子之鹼係氫氧化鈣及碳酸鈣。尤佳者係氫氧化鈣。氫氧化鈣較佳以「石灰乳」形式使用,其係氫氧化鈣水性懸浮液,固體含量為例如20 wt%。 適宜聚合起始劑係已知起始劑,例如無機或有機過化合物(per compound),例如過氧二硫酸鹽、過氧化物、氫過氧化物及過酸酯;偶氮化合物,例如2,2'-偶氮二異丁腈;及具有有機及無機組分之氧化還原系統。較佳起始劑係過氧二硫酸鹽及過氧化氫。 用於製備丙烯酸聚合物中之鏈轉移劑係含硫及含磷鏈轉移劑。較佳者係巰基乙醇、亞硫酸氫鹽及次磷酸鹽。尤佳鏈轉移劑係次磷酸鹽。 次磷酸鹽可以次磷酸形式或以次磷酸鹽形式使用。較佳者係以進料模式聚合,其使得能將鏈轉移劑在聚合物溶液中之殘留含量降至最低。適宜進料方法闡述於WO 2012/104401及WO 2012/104304中。 在進料方法中,在階段(t1-t1.0)期間以恆定或變化計量速率向包含溶劑(通常為水)之熱初始罐填充料中添加總量m1之丙烯酸,在階段(t2-t2.0)期間添加總量m2之自由基起始劑溶液,且在階段(t3-t3.0)期間添加總量m3之鏈轉移劑溶液。聚合在時間階段(t4-t4.0)內發生在攪拌罐中,其中t1.0、t2.0及t3.0確定各別進料之開始且t4.0確定聚合之開始。時間t1係丙烯酸之計量添加之結束,t2係起始劑之計量添加之結束,t3係鏈轉移劑之計量添加之結束,且t4係聚合(包括自t1至t4發生之後聚合)之結束。 具有極窄分子量分佈之丙烯酸聚合物之水溶液可藉由在次磷酸鹽存在下在作為溶劑之水中,以進料模式用自由基起始劑進行丙烯酸聚合來獲得,其包含 (i) 首先裝填水及視情況呈酸性、未經中和形式之丙烯酸、視情況一或多種烯系未飽和共聚單體、視情況次磷酸鹽水溶液及視情況起始劑, (ii) 添加丙烯酸、視情況一或多種烯系未飽和共聚單體、自由基起始劑水溶液及次磷酸鹽水溶液, (iii) 在丙烯酸進料終止後向水溶液添加鹼, 其中基於總單體含量,共聚單體含量不超過30 wt%,其中添加丙烯酸、自由基起始劑水溶液及次磷酸鹽水溶液,使得丙烯酸對自由基可提取之結合磷之氫之莫耳比x[AA]/[P-H]在其中至少75%丙烯酸經轉化之時間階段期間之值x恆定為在± 0.5內且在0.8至2範圍內。 因此,根據本發明,丙烯酸對自由基可提取之結合磷之氫之莫耳比x[AA]/[P-H]在其中至少75%丙烯酸經轉化之時間階段期間不小於0.8 ± 0.5 (即在此時間階段期間可自0.3至1.1變化)且不大於2.0 ± 0.5 (即在此時間階段期間可自1.5至2.5變化)。在本發明之較佳實施例中,丙烯酸對自由基可提取之結合磷之氫之莫耳比x[AA]/[P-H]為1.5 ± 0.5。自由基可提取之結合磷之氫理解為意指存於所用次磷酸鈉中或存於鍵結至聚合物鏈末端之次磷酸鹽中之共價氫-磷鍵。次磷酸鈉及所納入次磷酸鹽可以解離形式(在無作為相對離子之鈉的情況下)及以質子化形式存於水中。 通常,在時間階段(t1-t1.0)期間將總量m1之丙烯酸以恆定或變化計量速率連續地或間斷地(分批)添加至包含水作為溶劑之初始裝填料中,在時間階段(t2-t2.0)期間添加總量m2之自由基起始溶液,且在時間階段(t3-t3.0)期間添加總量m3之次磷酸鹽水溶液。聚合在時間階段(t4-t4.0)內發生於攪拌反應器皿中,其中時間t4.0確定聚合之開始。時間t1確定丙烯酸添加之結束,t2確定起始劑添加之結束,t3確定鏈轉移劑添加之結束,且t4確定聚合反應(包括在時間階段t1至t4中之後聚合)之結束。 鏈轉移劑之殘留量m3'不具有與聚合物之共價鍵(C-P鍵),且因此在下文中稱為無機磷。其可以所用鏈轉移劑之形式或以次磷酸鹽之其他氧化態(例如膦酸、磷酸)存在。亦可能係各別氧化態之解離、質子化及結構異構化形式。無機磷之量m3'及比例m3'/m3隨所選用於次磷酸鹽鏈轉移劑之進料時間t3-t3.0縮短而減小。無機磷之量m3'亦隨在總鏈轉移劑計量時間t3-t3.0內早期添加之次磷酸鹽鏈轉移劑之比例增加而減小。在調配中計量之鏈轉移劑之總量m3減小時,m3'亦減小。隨時間平均化之鏈轉移劑之計量添加之接點的適宜量度係以下參數:其中t係自t3.0至t3之時間,d(t)係在接點t,鏈轉移劑之計量添加之速率(單位質量/時間)。隨時間平均化之計量添加之接點將鏈轉移劑之總量之添加闡述為隨時間之平均值。 在本發明之較佳實施例中,所有進料在相同時間t0開始,即t1.0 = t2.0 = t3.0 = t0。在此特定情形中,隨時間平均化之鏈轉移劑之計量添加之接點對丙烯酸之總計量時間(t1-t1.0)之比率< 0.49,更佳 < 0.47且尤佳為0.3至0.47。另外,鏈轉移劑之計量添加之平均接點對鏈轉移劑之總計量時間之比率較佳< 0.5,更佳≤ 0.45且尤佳為0.3至0.45。 次磷酸鹽鏈轉移劑之進料可連續地實現,或在不連續時間t31、t32、t33等,直至時間t3為止,以不連續量m31、m32、m33等間斷地實現。 已發現,當藉由控制製程參數使在任何時刻存於反應器皿中之自由基可提取之結合磷之氫與丙烯酸之濃度之莫耳比[AA]/[P-H]在其中實現至少75%單體轉化之時間階段期間保持恆定為(0.8至2.0) ± 0.5、較佳1.5 ± 0.5時,儘管無機磷之量(m3')減小,分子量分佈係保守的。在此期間丙烯酸對結合磷之氫之比率保持恆定之轉化範圍之減小導致分子量分佈加寬。即使超出至少75%之單體轉化極限,自較佳值[AA]/[P-H] = 1.5 ± 0.5之偏移亦應極小,以獲得極窄分子量分佈。超出75%轉化範圍之[AA]/[P-H]之值應始終小於[AA]/[P-H] = 4.5。 所存在丙烯酸之濃度可藉由HPLC、NMR光譜法或GC來測定。所存在P-H官能基之濃度可藉由31-P {1H} NMR光譜法來測定。 通常,進料方法中丙烯酸之總進料時間通常為80至500 min,較佳100至400 min。 共聚單體可首先於反應混合物中裝填,首先部分裝填且部分作為進料添加,或僅作為進料添加。在該等共聚單體部分或全部作為進料添加時,其通常與丙烯酸同時添加。 通常添加水並將其加熱至至少75℃、較佳90℃至115℃、更佳95℃至105℃之反應溫度。另外,初始裝填料中可能包括磷酸水溶液作為腐蝕抑制劑。然後開始丙烯酸及視情況烯系未飽和共聚單體、起始劑及鏈轉移劑之連續進料。丙烯酸係以未中和酸性形式添加。進料通常同時開始。作為起始劑之過氧二硫酸鹽及作為鏈轉移劑之次磷酸鹽二者皆以其水溶液形式使用。尤佳者係以次磷酸或鈉鹽形式使用次磷酸鹽。次磷酸鹽較佳基於單體總量以3至14 wt%、較佳4至10 wt%、更佳5至8 wt%之量使用。 較佳自由基起始劑係過氧二硫酸鹽。過氧二硫酸鹽通常係以鈉、鉀或銨鹽形式使用。過氧二硫酸鹽較佳基於單體總量(丙烯酸及視情況共聚單體)以0.5至10 wt%、較佳0.8至5 wt%之量使用。另外可例如以50%水溶液形式使用過氧化氫作為自由基起始劑。亦適宜者係在硫酸鐵(II)及/或羥基甲烷亞磺酸鈉存在下之基於過氧化物及氫過氧化物及還原性化合物(例如過氧化氫)之氧化還原起始劑。 起始劑進料之持續時間通常較丙烯酸進料之持續時間長至多50%。起始劑進料之持續時間較佳較丙烯酸進料之持續時間長約3至20%。鏈轉移劑進料之總持續時間較佳等於丙烯酸進料之持續時間。通常,鏈轉移劑進料之總持續時間等於丙烯酸進料之持續時間至較丙烯酸進料之持續時間短或長至多50%。 基於所有烯系未飽和單體,丙烯酸聚合物可包含至多30 wt%、較佳至多20%、更佳至多10 wt%之共聚化烯系未飽和共聚單體。適宜烯系未飽和共聚單體之實例係甲基丙烯酸、馬來酸、馬來酸酐、乙烯基磺酸、烯丙基磺酸及2-丙烯醯胺基-2-甲基丙烷磺酸(AMPS)及其鹽。該等共聚單體之混合物亦可存在。 單體進料或(在使用共聚單體時)單體進料之持續時間為例如2至5 h。舉例而言,在所有進料同時開始時,鏈轉移劑進料在單體進料結束前10至30 min結束,且起始劑進料在單體進料結束後10至30 min結束。 尤佳者係無共聚單體含量之丙烯酸均聚物。根據本發明,丙烯酸聚合物之分子量係3500至12 000 g/mol,較佳3500至12 000 g/mol,且更佳3500至8000 g/mol,更佳3500至6500 g/mol,且尤佳4000至6500 g/mol。可經由所用鏈轉移劑之量將分子量控制在該等範圍內。 根據本發明,丙烯酸聚合物之多分散性指數(PDI)Mw
/Mn
≤ 2.5,較佳≤ 2.3,更佳為1.5至2.2,例如2.1。 最後,將包含鈉離子之鹼及包含鈣離子之鹼添加至所獲得之酸性丙烯酸聚合物,添加量使得丙烯酸聚合物中30%至60%酸基經鈣離子中和,丙烯酸聚合物中30%至70%酸基經鈉離子中和,且丙烯酸聚合物中0%至10%酸基未經中和。 酸性丙烯酸聚合物較佳經氫氧化鈣及氫氧化鈉中和。中和可以添加包含鈣離子之鹼或包含鈉離子之鹼開始。較佳者係以添加包含鈣離子之鹼開始。 氫氧化鈣較佳以石灰乳形式使用,即固體含量為例如20 wt%之氫氧化鈣水性懸浮液,且氫氧化鈉較佳以固體含量為例如50 wt%之水溶液形式使用。 對於中和,在攪拌的同時將計算量之氫氧化鈣水性懸浮液泵送至可冷卻攪拌罐中之酸性丙烯酸聚合物之水溶液中。此係在冷卻的同時進行,以吸收所產生之中和熱量。在第二步驟中,將計算量之50%氫氧化鈉溶液泵送至丙烯酸聚合物溶液中。此亦係在冷卻的同時進行,以吸收所產生之中和熱量。持續攪拌直至所散發之熱量減少且形成透明溶液為止。隨後,用水建立期望最終濃度。 獲得固體含量為30至60 wt%之丙烯酸聚合物水溶液。較佳者係固體含量為35至50 wt%。該等可用於藉由噴霧乾燥或噴霧粒化獲得經中和丙烯酸聚合物固體。 本發明亦係關於丙烯酸聚合物作為水性固體分散液中之分散劑及研磨輔助劑之用途,尤其係關於在CaCO3
、高嶺土、滑石粉、TiO2
、ZnO、ZrO2
、Al2
O3
或MgO之水性分散液中之用途。 自其獲得之漿液用作繪圖紙及油漆之白色顏料,用作陶瓷建築材料之解絮凝劑或用作熱塑性塑膠之填充劑。 本發明丙烯酸聚合物用於其之尤佳分散液(漿液)係研磨碳酸鈣漿液。研磨係在水性懸浮液中連續或分批實施,且較佳在球磨機中進行。該等懸浮液之碳酸鈣含量通常≥ 50 wt%,較佳≥ 60 wt%且更佳≥ 70 wt%。通常,在每一情形中基於存於懸浮液中之碳酸鈣,使用0.1至2 wt%、較佳0.3至1.5 wt%之本發明丙烯酸聚合物。較佳地,在研磨後在該等碳酸鈣漿液中,90%至95%之顆粒之粒徑小於2 µm,且70%至75%之顆粒之粒徑小於1 µm。所獲得碳酸鈣懸浮液具有優良流變性質,且即使在儲存數周後仍具有極佳可泵性。 藉由以下實例詳細闡釋本發明。 實例 實例1至8及比較實例C1至C5 實例中所用聚合物係聚丙烯酸,其係藉由進料方法在作為溶劑之水中自丙烯酸製備,以過硫酸鈉作為起始劑且以次磷酸鈉作為鏈轉移劑。隨後,酸性聚丙烯酸酯已經氫氧化鈣、氫氧化鎂及/或氫氧化鈉中和或部分中和。 中和係在可冷卻攪拌罐中實施。出於此目的,首先將計算量之約20%氫氧化鈣懸浮液或氫氧化鎂懸浮液泵送至存於攪拌罐中之酸性聚丙烯酸水溶液中,之後將計算量之約50%氫氧化鈉溶液泵送至存於攪拌罐中之酸性聚丙烯酸水溶液中。在操作期間使混合物冷卻,以移除所釋放之中和熱量。持續冷卻直至所散發之熱量減少且形成透明溶液為止。為建立期望最終濃度,添加水。 本發明丙烯酸聚合物首先經氫氧化鈣中和,隨後經氫氧化鈉中和。 聚丙烯酸之中和程度係藉助滴定來測定。 聚合物之分子量分佈之分子量及數目平均Mn
及重量平均Mw
係藉助凝膠滲透層析(GPC)來測定。分子量分佈係藉助對緩衝至pH 7之丙烯酸聚合物水溶液之GPC來測定,使用羥乙基甲基丙烯酸酯共聚物網絡(HEMA)作為固定相,針對聚丙烯酸鈉標準來進行。實例中製備且使用之(部分)中和之丙烯酸聚合物顯示於表1中。 表1
測試聚丙烯酸酯溶液作為用於產生漿液之分散劑之適合性。出於此目的,在每一情形中在Dispermat中實施碳酸鈣(Marple Flour, Imerys)之研磨。出於此目的,在每一情形中混合300 g碳酸鈣及600 g陶瓷珠粒且首先將其裝填於1 L夾套罐中。隨後,添加欲測試之聚丙烯酸酯之100 g稀水溶液。使用具有交叉樑攪拌器之Dispermat AE04-C1型研磨總成(來自Getzmann GmbH)以1300 rpm之速度實施研磨。一旦73%顏料之粒徑(PSD)小於1 µm (Malvern Mastersizer 3000),結束研磨(在約60 min後)。在研磨後,在瓷吸濾漏斗幫助下經由780 µm過濾器過濾漿液以移除陶瓷珠粒,且將漿液之固體含量調節至77%。在一天、一周、兩周及三周後量測漿液黏度。 以基於固體碳酸鈣(wt/wt%)之活性分散劑wt%報告聚合物之起始重量。結果顯示於表2中。 表2
在整個三周階段期間,用本發明丙烯酸聚合物產生之碳酸鈣漿液之黏度顯著低於用比較聚合物及等量分散劑產生之碳酸鈣漿液之黏度。 實例9及比較實例C10、C11 在儲存過程中,鹼性碳酸鈣分散液自空氣吸收二氧化碳。二氧化碳與溶解碳酸鈣反應產生碳酸氫鈣,其降低分散液之pH且導致黏度增加。為模擬在吸收CO2
時分散劑對碳酸鈣分散液黏度之效應,將不同量之碳酸氫鈉添加至經不同聚丙烯酸酯穩定之漿液。添加後立即量測漿液黏度。碳酸氫鈉係作為10重量%溶液添加;其量在表中以基於漿液中固體碳酸鈣之固體NaHCO3
之wt%來報告。漿液各自經0.8% (wt/wt%)聚丙烯酸酯穩定。結果顯示於表3中。 表3
發明性聚合物7及比較聚合物3及5具有窄分子量分佈(PDI = 2.1)。添加NaHCO3
溶液後,經以鈣及鈉離子中和之聚丙烯酸酯(聚合物7)穩定之碳酸鈣漿液展現最小黏度增加。 因此,與僅經鈉離子中和之聚丙烯酸酯(聚合物3)或經鈉及鎂離子中和之聚丙烯酸酯(聚合物5)相比,經鈣及鈉離子中和之聚丙烯酸酯更佳地穩定碳酸鈣漿液以抵抗漿液由於吸收CO2
之陳化。
Claims (9)
- 一種製備丙烯酸聚合物之水溶液之方法,該丙烯酸聚合物具有重量平均分子量Mw在3500至12 000g/mol範圍內且多分散性指數Mw/Mn 2.5,其中該丙烯酸聚合物之30%至60%酸基已經鈣離子中和,該丙烯酸聚合物之30%至70%酸基已經鈉離子中和,且該等丙烯酸聚合物之0%至10%酸基未被中和,其係藉由在鏈轉移劑存在下在作為溶劑之水中,用自由基起始劑以進料模式聚合丙烯酸來進行,該方法包含(i)首先裝填水及視情況呈酸性、未經中和形式之丙烯酸、視情況一或多種烯系未飽和共聚單體、視情況該鏈轉移劑及視情況起始劑,(ii)添加丙烯酸、視情況一或多種烯系未飽和共聚單體、自由基起始劑水溶液及鏈轉移劑,(iii)在該丙烯酸進料終止後向該水溶液添加鹼,其中,在步驟(iii)中,包含鈉離子之鹼及包含鈣離子之鹼之添加量使得該等丙烯酸聚合物之30%至60%酸基經鈣離子中和,該等丙烯酸聚合物之30%至70%酸基經鈉離子中和,且該等丙烯酸聚合物之0%至10%酸基未經中和,且其中該鏈轉移劑係次磷酸鹽。
- 如請求項1之方法,其中該等丙烯酸聚合物之40%至60%酸基已經鈣離子中和,該等丙烯酸聚合物之40%至60%酸基已經鈉離子中和且該等丙烯酸聚合物之0%至10%酸基未被中和。
- 如請求項1之方法,其中該多分散性指數Mw/Mn係1.5至2.2。
- 如請求項1之方法,其中,在步驟(iii)中,首先添加該包含鈣離子之鹼,隨後添加該包含鈉離子之鹼。
- 如請求項1至4中任一項之方法,其中該包含鈉離子之鹼選自氫氧化鈉及碳酸鈉。
- 如請求項1至4中任一項之方法,其中該包含鈣離子之鹼選自氫氧化鈣及碳酸鈣。
- 一種如請求項7之丙烯酸聚合物之用途,其用作固體之水性分散液中之分散劑及研磨輔助劑。
- 如請求項8之用途,其用於CaCO3、高嶺土、滑石粉、TiO2、ZnO、ZrO2、Al2O3或MgO之水性分散液中。
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