EP4065536A1 - Branched copolymers as dispersants for mineral binders - Google Patents
Branched copolymers as dispersants for mineral bindersInfo
- Publication number
- EP4065536A1 EP4065536A1 EP20808467.3A EP20808467A EP4065536A1 EP 4065536 A1 EP4065536 A1 EP 4065536A1 EP 20808467 A EP20808467 A EP 20808467A EP 4065536 A1 EP4065536 A1 EP 4065536A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- independently
- copolymers
- integer
- olefinically unsaturated
- mineral binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 108
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 84
- 239000011707 mineral Substances 0.000 title claims abstract description 84
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 25
- 229920005605 branched copolymer Polymers 0.000 title abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 83
- -1 vinyloxybutyl Chemical group 0.000 claims abstract description 69
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000005394 methallyl group Chemical group 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 16
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 12
- 229910052757 nitrogen Chemical group 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000004568 cement Substances 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 18
- 238000010526 radical polymerization reaction Methods 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- 239000011398 Portland cement Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052925 anhydrite Inorganic materials 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 239000004058 oil shale Substances 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000007858 starting material Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 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 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000028 Gradient copolymer Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000012987 RAFT agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LXEKPEMOWBOYRF-QDBORUFSSA-N AAPH Chemical compound Cl.Cl.NC(=N)C(C)(C)\N=N\C(C)(C)C(N)=N LXEKPEMOWBOYRF-QDBORUFSSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000004572 hydraulic lime Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
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- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/10—Mortars, concrete or artificial stone characterised by specific physical values for the viscosity
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2650/62—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the nature of monomer used
- C08G2650/64—Monomer containing functional groups not involved in polymerisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the invention relates to the use of branched copolymers as dispersants for mineral binders. Another aspect of the invention relates to a mineral binder composition and a cured molded body containing the branched copolymer.
- Dispersants or superplasticizers are used in the construction industry as liquefiers or water-reducing agents for mineral binders and / or mineral binder compositions such as concrete, mortar, cement, plaster and lime.
- the dispersants used are generally organic polymers which are added to the mixing water or added as a solid to the binder or the binder composition.
- both the consistency of the binder composition during processing and the properties in the cured state can advantageously be changed.
- the choice and dosage of a suitable dispersant depends in particular on the specific composition, the processing technique or the intended use of the binder or the binder composition.
- EP 2454296 describes copolymers which are built up from branched macromonomers. The use of such copolymers as thickeners, for example in detergents and cleaning agents, is also described.
- EP 2 964 586 describes copolymers as dispersants for mineral binders, the copolymers containing units which are derived from (i) an olefinically unsaturated acid and (ii) an olefinically unsaturated acid, branched polyether macromonomer with an alkyl terminus.
- These dispersants have the disadvantage that they are made using epichlorohydrin, which is difficult to handle.
- these copolymers often lead to an undesirable additional introduction of air. There is therefore still a need for improved dispersants for mineral binders which can overcome the disadvantages of the known prior art.
- the object of the present invention is to provide a method which enables mineral binders to be dispersed efficiently and thus the viscosity and / or the flow behavior of mineral binders
- R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
- A are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
- R 2 C1-C16 alkyl
- B each independently of one another is C1-C10 alkylene, preferably ethylene, propylene and / or butylene
- m each independently of one another is an integer in the range from 0-350, preferably 2-200, particularly preferably 5-150, especially 7-30
- n is an integer in the range 0-100, preferably 1-100, particularly preferably 2-75, very particularly preferably 5-55
- p is 0 or 1, preferably 0, o is an integer in the range from 1-50, preferably 3-40, particularly preferably 6-30, especially 8-20
- q is an integer in the range 1-10.
- An essential advantage of copolymers according to the invention is the presence of a large number of alkylene oxide-based side chains within a single macromonomer unit. This variety is achieved by introducing branches. As a result, an individual macromonomer unit has a greater steric demand than macromonomer units with purely linear side chains, such as those present in classic PCE, for example. This leads to a reduced interaction with side chains of other macromonomer units. In this way, a copolymer according to the invention can be used at the same time as a dispersant for mineral binders and to reduce the viscosity of mineral binder compositions, which is a significant advantage.
- copolymers according to the invention as dispersants in mineral binder compositions are less segregation or separation of the constituents of the mineral binder composition, and less undesired entry of air.
- the macromonomers which are required to build up copolymers according to the invention are distinguished by a simple synthesis which preferably does not require the use of epichlorohydrin. This is beneficial because epichlorohydrin is problematic due to its toxicity and carcinogenicity.
- Dispersant is understood here to mean an agent for improving the miscibility of mineral binders with a solvent, in particular with water. Dispersants in the context of the present invention lead in particular to mixtures of mineral binders or
- Binder compositions with water have greater flowability and / or less segregation than the same mixtures without the dispersant.
- the flowability of mixtures of mineral binders or binder compositions with water is increased by adding a dispersant.
- a measure of the flowability is in particular the slump measured in accordance with the DIN EN 12350-5 standard.
- a dispersant reduces the water requirement of a mineral binder in order to establish the same flowability as a mixture of the mineral binder with water but without the addition of a dispersant.
- the copolymers according to the invention act as dispersants and improve the flowability of a mineral binder composition modified therewith.
- the copolymers according to the invention also reduce the viscosity of a mineral binder composition modified therewith.
- a measure of the viscosity is in particular the funnel discharge time measured in accordance with the DIN EN 12350-9 standard.
- a first aspect of the invention relates to the use of copolymers as dispersants for mineral binders, the copolymers being built up from
- At least one olefinically unsaturated carboxylic acid monomer (2) at least one olefinically unsaturated macromonomer of the general
- R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
- R 2 C1-C16 alkyl
- B are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene
- m are each independently an integer in the range from 0-350, preferably 2-200, particularly preferably 5-150, especially 7-30
- n is an integer in the range from 0 - 100, preferably 1 - 100, particularly preferably 2 - 75, very particularly preferably 5 - 55
- p is 0 or 1, preferably 0, o is an integer in the range from 1 - 50, preferably 3-40, particularly preferably 6-30, especially 8-20
- q is an integer in the range 1-10.
- the number of linear structural units (BO) m in the general structure (I) depends on o and q.
- the number of structural units (BO) m is equal to oxq +1.
- the macromonomers according to the invention can contain different regioisomers. These are regioisomers that arise when the oxirane ring of the glycidol over the during the preparation of the macromonomers using, for example, glycidol different carbon atoms, according to one of the chemical reaction equations a) or b) as shown below. b) HO OH ° 'R
- regioisomer b) is shown in the present invention. What is meant, however, is always both regioisomers a) and b) or their mixtures.
- the structural elements (AO) and (BO) of the general structure (I) are polyalkylene oxide chains.
- a proportion of ethylene oxide units in the polyalkylene oxide chains (AO) m and (BO) m , based on all alkylene oxide units AO and BO present, is preferably more than 90 mol%, in particular more than 95 mol%, preferably more than 98 mol%, specifically 100 mol%.
- the polyalkylene oxide side chains have no hydrophobic groups, in particular no alkylene oxides with three or more
- Carbon atoms A high proportion of ethylene oxide units or a low content of alkylene oxides with three or more carbon atoms reduces the risk of undesired air entrainment.
- the weight average molecular weight (Mw) is determined in the present case by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art.
- Copolymers according to the invention can have a molar mass M w in the range from 250-100-0000 g / mol.
- the parameters n, m, o and p of the general structure (I) are chosen so that the mean molar mass M w of the copolymers is in the range from 100-10000, particularly preferably T500-50000, very particularly preferably 2-00-10000, in particular 3-75-00 or 3-50-00.
- the expression “mineral binder” is to be understood as meaning a binder which, in the presence of water, reacts in a hydration reaction to form solid hydrates or hydrate phases.
- This can, for example, be a hydraulic binder (e.g. cement or hydraulic lime), a latent hydraulic binding agent (e.g. slag), a pozzolanic binding agent (e.g. fly ash) or a non-hydraulic binding agent (gypsum or white lime).
- a mineral binder composition is accordingly a composition comprising at least one mineral binder.
- the mineral binder contains a hydraulic binder, preferably cement.
- a cement with a cement clinker content of> 35% by weight is particularly preferred.
- the cement is a Portland cement or Portland composite cement of the type CEM I, CEM II, CEM III, CEM IV or CEM V in accordance with standard EN 197-1, or an aluminate cement, in particular a high-alumina cement in accordance with DIN EN 14647, or mixtures of the cited cements.
- the mineral binder composition comprises at least one hydraulic binder, preferably cement, in at least 5% by weight, preferably in at least 20% by weight, particularly preferably in at least 35% by weight, very particularly preferably in at least 65% by weight, in particular> 95% by weight, based in each case on the dry matter of the mineral binder composition.
- the mineral binder or the mineral binder composition contains or essentially consists of other binders.
- these are in particular latent hydraulic binders and / or pozzolanic binders.
- Suitable latent hydraulic and / or pozzolanic binders are e.g. slag, fly ash, silica dust, microsilica, metakaolin, tuff, trass, volcanic, zeolites and / or burnt oil shale.
- the mineral binder can comprise or essentially consist of ⁇ -calcium sulfate hemihydrate, ⁇ -calcium sulfate hemihydrate, anhydrite and / or lime.
- the mineral binder composition can also contain inert substances such as limestone, quartz powder and / or pigments
- the mineral binder contains 5-95% by weight, in particular 5-65% by weight, particularly preferably 15-35% by weight, based in each case on the total dry matter of the mineral binder, latent hydraulic and / or pozzolanic Binder.
- Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.
- the mineral binder contains a hydraulic binder, in particular cement or cement clinker, and a latent hydraulic and / or pozzolanic binder, preferably slag and / or fly ash.
- the proportion of the latent hydraulic and / or pozzolanic binder is particularly preferably 5-65% by weight, particularly preferably 15-35% by weight, while at least 35% by weight, especially at least 65% by weight, in each case on the dry matter of the mineral binder.
- the mineral binder is accordingly selected from the group comprising cement, in particular portland cement and aluminum cement, ⁇ -calcium sulfate hemihydrate, ß-calcium sulfate hemihydrate, anhydrite, lime, industrial and synthetic slag, in particular blast furnace slag, blast furnace slag, blast furnace slag, electrothermal stainless steel phosphor slag, and copper slag , Pozzolans, in particular fly ash, microsilica, metakaolin, of course pozzolans, in particular tuff, trass and volcanic ash, natural and synthetic zeolites, burnt oil shale and mixtures thereof.
- the at least one olefinically unsaturated carboxylic acid monomer for forming copolymers of the present invention can be a monocarboxylic acid
- Monocarboxylic acid monomers are particularly preferred. It is possible to use different olefinically unsaturated carboxylic acid monomers to build up copolymers. Structural units of the copolymer derived from unsaturated carboxylic acid monomers can, independently of one another, be in their protonated form or partially or completely neutralized, e.g. by bases such as alkali metal or alkaline earth metal bases, ammonia, organic amines, etc.
- Particularly preferred unsaturated carboxylic acid monomers are acrylic acid and its salts, acrylamides, methacrylic acid and its salts, methacrylamides, maleic acid and its salts, maleic anhydride, maleic acid imides, crotonic acid and its salts, fumaric acid and its salts, and mixtures thereof.
- the at least one olefinically unsaturated macromonomer of the general structure (I) is a branched polyether macromonomer.
- a plurality of chemically and / or structurally different macromonomers of the general structure (I) can be used to build up copolymers according to the invention. Structurally different also includes, in particular, macromonomers of the general structure (I), which differ, for example, only with regard to their molar mass, e.g. through different choices of the parameters m, o and / or q.
- olefinically unsaturated macromonomers of the general structure (I) in which R 1 is a vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl or methacryloyl unit.
- either an (AO) m unit or an R 2 -X unit is present in the macromonomers.
- olefinically unsaturated macromonomers according to the invention of the general structure (I) are macromonomers in which
- R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
- A are each independently C1-C10 alkylene, preferably ethylene,
- Such monomers correspond to the general structure (III)
- olefinically unsaturated macromonomers according to the invention of the general structure (I) are macromonomers in which
- A are each independently ethylene, propylene and / or butylene, particularly preferably ethylene,
- Such macromonomers correspond to the general structure (IV) (iv), where x is an integer from 1-9, with the proviso that x ⁇ o.
- olefinically unsaturated macromonomers according to the invention of the general structure (I) are those macromonomers in which R 1 is an olefinically unsaturated radical having 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl , Vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
- B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
- olefinically unsaturated macromonomers according to the invention of the general structure (I) are those macromonomers in which R 1 is an olefinically unsaturated radical having 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl , Vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
- Such macromonomers correspond to the general structure (VI) (VI).
- the molar ratio of the at least one olefinically unsaturated carboxylic acid monomer to the at least one olefinically unsaturated macromonomer of the general structure (I) is in the range from 0.3-30, preferably 0.6-10, particularly preferably 1-4.5, in particular 1-3.
- copolymers according to the invention can contain one or more further copolymers Monomers M included.
- These further monomers M can be selected from styrene, ethylene, propylene, butylene, butadiene, isoprene, vinyl acetate, vinyl chloride, acrylonitrile, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylates and / or macromonomers of the general structures (VII) in which
- R 6 each independently of one another, is H, -CH 2 -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H or -CH 3 ,
- R 7 each independently of one another, is H or an alkyl group with 1 to 5 carbon atoms, preferably H,
- X is in each case, independently of one another, -O- or -NH-,
- R 9 independently of one another, is H, a C1 to C20 alkyl group, cyclohexyl group or alkylaryl group, and D is a C2 to C4 alkylene group, preferably ethylene.
- the additional monomers M are selected from linear polyethylene glycol ethers, in particular polyethylene glycol ethers of vinyl alcohol, allyl alcohol, methallyl alcohol, vinyl oxybutyl alcohol and / or isoprenol, and / or linear polyethylene glycol esters, in particular polyethylene glycol esters of acrylic acid and / or Methacrylic acid.
- the molar proportion of the one or more further monomers M is equal to or less than 66 mol%, preferably equal to or less than 50 mol%, more preferably equal to or less than 25 mol%, particularly preferably equal to or less than 10 mol% %, in particular equal to or less than 5 mol%, in each case based on all monomers making up the copolymer.
- Olefinically unsaturated macromonomers of the general structure (I) can be prepared in a multistep process comprising the steps
- the individual steps of the process are preferably carried out in succession without isolating or purifying the intermediate products.
- reaction conditions of steps 1) to 3) can vary.
- the reaction temperature, the pressure and / or the type and amount of catalyst used in steps 1) to 3) can be different. In general, however, it is preferred if the reaction temperature, the pressure and the type and amount of catalyst used in steps 1) to 3) are the same.
- the reaction temperature can vary in the range between 80.degree. C.-180.degree. C., in particular 100.degree. C.-140.degree.
- the pressure is preferably in the range from 1 to 5 bar, in particular in the range from 1 to 3 bar.
- the individual steps of the process are preferably carried out under catalysis.
- Suitable catalysts for the alkoxylations of steps 1) to 3) are known per se to the person skilled in the art.
- reaction steps 1) to 3) are catalyzed. It is particularly preferred to use the same catalyst for steps 1) to 3) without removing or deactivating it in the meantime.
- Alkali metal hydroxides and / or alkali metal alcoholates have proven to be particularly suitable catalysts.
- an alkali metal alcoholate of the alcohol which is also used as the starter S is used as the catalyst.
- sodium alcoholates in particular sodium methoxide or sodium ethoxide, as the catalyst.
- the starter S is selected from the group consisting of isoprenol, vinyl alcohol, allyl alcohol, methallyl alcohol, vinyloxybutyl alcohol, acrylic acid, methacrylic acid, acrylamide or methacrylamide.
- alkoxylating agents are compounds which can be converted to polyethers by polymerization. Alkoxylating agents thus cause alkoxylation or the formation of alkylene oxide or polyalkylene oxide units.
- alkoxylating agents for the purposes of the present invention contain oxirane, oxetane or oxolane structures.
- Particularly preferred alkoxylating agents are alkylene oxides selected from ethylene oxide, propylene oxide and / or 1,2-butylene oxide, and / or tetrahydrofuran.
- the alkoxylating agent is ethylene oxide and / or propylene oxide. It may be preferred to use only one alkoxylating agent in one of steps 1) to 3).
- steps 1) to 3 only one alkoxylating agent, in particular ethylene oxide, is used in steps 1) to 3).
- two or more alkoxylating agents in steps 1) to 3), either as a mixture or individually in each case in one of steps 1) to 3).
- macromonomers according to the invention are produced without the use of epichlorohydrin. The manufacturing process is therefore epichlorohydrin-free.
- steps 1) and 3 are not optional, but are mandatory.
- macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of an alcohol as the starter S.
- the manufacturing process is therefore epichlorohydrin-free.
- Macromonomers according to the invention can therefore be prepared particularly preferably in a process comprising the steps:
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- X O or NH
- Hal CI, Br or I
- R 2 is
- C1 - C16 is alkyl, 2) reaction of an alcohol R 1 -OH or the reaction product from step 1) with glycidol or a mixture of glycidol and an alkoxylating agent, 3) optional reaction of the reaction product from step 2) with an alkoxylating agent.
- steps 1) and 3 are not optional, but are mandatory.
- macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of an amine as the starter S.
- the manufacturing process is therefore epichlorohydrin-free.
- Copolymers according to the invention can therefore also be produced particularly preferably in a process comprising the steps:
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- X O or NH
- Hal CI, Br or I
- R 2 C1 - C16 alkyl
- step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
- step 3 is not optional, but rather is mandatory.
- macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of a carboxylic acid as starter S.
- the manufacturing process is therefore epichlorohydrin-free.
- Copolymers according to the invention can therefore also be produced particularly preferably in a process comprising the steps:
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen
- R 2 C1 - C16 alkyl
- step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
- steps 1) and 3 are not optional, but are mandatory.
- macromonomers according to the invention are prepared without the use of epichlorohydrin and using an alcohol as starter S, the starter alcohol first being reacted with an alkoxylating agent. The manufacturing process is therefore epichlorohydrin-free. Macromonomers according to the invention can consequently be prepared very particularly preferably in a process comprising the steps:
- step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
- step 3 is not optional, but rather is mandatory.
- Copolymers according to the invention can be random or non-random copolymers.
- Non-random copolymers are in particular alternating copolymers or block or gradient copolymers.
- Copolymers according to the invention which are random copolymers, can be obtained by free radical polymerization of mixtures comprising at least one olefinically unsaturated carboxylic acid monomer and at least one olefinically unsaturated monomer of general structure (I) can be prepared as described above. Suitable conditions for carrying out the free radical polymerization are known per se to the person skilled in the art and are described, for example, in EP 1 103570 (Nippon Shokubai).
- Copolymers according to the invention which are non-random copolymers, in particular block or gradient copolymers, can preferably be prepared by living free radical polymerization.
- Living free radical polymerization techniques include nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), or reversible addition-fragmentation chain transfer polymerization (RAFT).
- Living free radical polymerization essentially takes place in the absence of irreversible transfer or termination reactions.
- the number of active chain ends is low and remains essentially constant during the polymerization. This is achieved, for example, in RAFT polymerization through the use of a RAFT agent and only a small amount of initiator. This enables a substantially simultaneous and sustained growth of the chains during the entire polymerization process. This makes it possible to use this process to produce block or gradient copolymers and a correspondingly narrow molecular weight distribution or polydispersity of the polymer results. This is not possible in the case of conventional "free radical polymerization" or free radical polymerization which is not carried out alive.
- non-random copolymers of the present invention can be prepared by means of RAFT polymerization.
- Advantageous RAFT agents are dithioesters, dithiocarbamate, trithiocarbonate or xanthate.
- azobisisobutyronitrile AIBN
- AAPH a'-azodiisobutyramidine dihydrochloride
- AIBA azo-bis-isobutyramidine
- copolymers according to the invention by free radical polymerization or by living free radical polymerization takes place in a particularly preferred embodiment directly after the production of the at least one olefinically unsaturated macromonomer of the general structure (I).
- Another aspect of the present invention therefore relates to a multistage process for producing a copolymer for use as a dispersant for mineral binders.
- reaction product from step 2) optional reaction of the reaction product from step 2) with an alkoxylating agent, and 4) radical polymerization of a mixture of at least one olefinically unsaturated carboxylic acid monomer with the reaction product from step 3) or, if this is not part of the process, with the reaction product Step 2).
- steps 1) and 3 are not optional, but are mandatory.
- the process particularly preferably does not include any steps for working up and / or purifying intermediate products.
- catalysts and / or neutralization reagents which are used in steps 1) to 3) and which can hinder the free radical polymerization must be removed or reacted.
- these can be catalysts and / or neutralization reagents which interact with activators, initiators, and / or regulators, such as chain transfer agents or RAFT agents, of free-radical polymerization.
- the free-radical polymerization is carried out as a solution polymerization, in particular in a solvent containing water. It is very particularly preferred to carry out the polymerization in pure water. It is preferred to use the free-radical polymerization for the preparation of copolymers according to the invention up to a conversion of at least 75%, preferably at least 80%, more preferably at least 90%, very particularly preferably at least 95%, in particular at least 98% or more, based on the total amount of substance of the monomers present to drive.
- Copolymers according to the invention can be in liquid form, for example in the form of a solution or dispersion, in particular in the form of an aqueous solution. It is preferred if copolymers according to the invention have a proportion of a solution or dispersion, in particular an aqueous solution, of at least 30% by weight, preferably at least 40% by weight, particularly preferably at least 50% by weight, based in each case on the total weight the solution or dispersion.
- copolymers according to the invention into a solid form, preferably a powder form.
- Suitable methods are, for example, the application to a solid support and / or the drying of a solution or dispersion containing copolymers according to the invention.
- a suitable method for drying is, for example, spray drying.
- a multistage process for producing a copolymer according to the invention can therefore contain a step for drying, in particular spray drying, the copolymer.
- Powdered copolymers according to the invention can be added to a mineral binder or a mineral binder composition, for example to produce a dry mortar mixture.
- the copolymers according to the invention are used in mineral binders or mineral binder compositions for the purpose of improving their flow behavior and / or their viscosity.
- a mineral binder composition containing at least one copolymer according to the invention flows better, that is to say shows a higher slump measured according to DIN EN 12350-5, than the same mineral binder composition without the copolymer according to the invention.
- the use of a copolymer according to the invention in a mineral binder composition means that the amount of water required to set a certain slump is smaller than with a corresponding composition without the copolymer according to the invention.
- a copolymer according to the invention in a mineral binder composition leads to a reduction in viscosity, measured as a reduction in the funnel flow time according to standard DIN EN 12350-9, in comparison to a corresponding composition without a copolymer according to the invention. Both properties are equally important in order to achieve optimal processing properties of mineral binder compositions.
- a copolymer according to the invention in a mineral binder composition leads to particularly low air entrainment.
- the air intake is measured in accordance with the DIN EN 12350-7 standard. This is particularly important for achieving a high final strength.
- this property also means that copolymers according to the invention can be combined with common air-entraining agents without influencing their effectiveness. The entry of a desired amount of air and thus a certain air pore distribution is ensured in a simple manner without the need to match the type and amount of the air-entraining agent to the dispersant.
- a further aspect of the present invention is therefore a mineral binder or a mineral binder composition
- a mineral binder or a mineral binder composition comprising at least one mineral binder, preferably cement, and at least one copolymer according to the invention.
- the mineral binders and copolymers according to the invention are as described above. It is possible and in some cases also preferred that mixtures of two or more copolymers according to the invention which differ chemically and / or structurally are used.
- the mineral binder composition is preferably a mortar or concrete composition.
- the mineral binder composition can be made up with water and / or contain water.
- the ratio of water to mineral binder is in the range from 0.18-0.7, preferably 0.2-0.6, particularly preferably 0.25-0.5, very particularly preferably 0.3-0.45.
- the mineral binder is a cement, the ratio of water to mineral binder then corresponds to the w / c value.
- the copolymer according to the invention is advantageously whole in a proportion of 0.01-10% by weight, preferably 0.05-7% by weight, particularly preferably 0.1-5% by weight particularly preferably 0.2-3% by weight, in particular 0.2-1% by weight, based in each case on the mineral binder content.
- a copolymer according to the invention it is possible to add a copolymer according to the invention as such, for example in powder form, to a mineral binder composition.
- a copolymer according to the invention it is also possible to add a copolymer according to the invention as an aqueous solution or dispersion in water to a mineral binder composition. It is also possible to dissolve or disperse a copolymer according to the invention in an additive, in particular an aqueous additive.
- Another aspect of the present invention is therefore an additive comprising at least one copolymer according to the invention.
- the additive can contain other common additives for mineral binder compositions.
- common additives are advantageously selected from the list consisting of liquefiers, air-entraining agents, defoamers, accelerators, retarders, shrinkage reducers, activators, sealants, stabilizers, thickeners, chromate reducers, corrosion inhibitors, hydrophobizing agents, pigments, fibers and biocides.
- At least one copolymer according to the invention is used with one or more conventional plasticizers based on polycarboxylate ethers (PCE) in an additive.
- PCE polycarboxylate ethers
- Suitable PCEs are described, for example, in EP0753488, EP1138697, EP1179517 and EP1966258. It is possible to mix the at least one copolymer according to the invention with one or more plasticizers based on PCE to form a component and to add this to a mineral binder composition. However, it is also possible to add the at least one copolymer according to the invention and one or more plasticizers based on PCE to a mineral binder composition each separately.
- a final aspect of the present invention is a shaped body obtainable by curing a mineral binder or a mineral binder composition comprising at least one copolymer according to the invention.
- the shaped body can for example be a concrete part, for example a precast concrete part or a concrete block, a hardened mortar mixture, for example joint mortar or a screed, and / or part of a structure, for example a bridge or a tunnel.
- the invention is explained in more detail below by means of examples. However, the examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.
- Step 1 4 g (0.074 mol) of sodium methylate are dissolved in 464 g (8 mol) of allyl alcohol in a reactor which has been rendered inert with 1 h gas and the mixture is heated to 100.degree. Then 1760 g (40 mol) of ethylene oxide are metered in over 5 hours. The temperature is kept at 100 to 140 ° C and the pressure at 1 to 3 bar.
- reaction mixture is stirred at 140 ° C. for 2 hours. The mixture is then cooled to 30.degree.
- Step 2 In a reactor rendered inert with N2 gas, 117 g (0.42 mol) of the mixture from step 1) are mixed with 0.54 g (0.01 mol) of sodium methylate and heated to 130.degree. Then 93 g (1.26 mol) of glycidol are metered in over a period of 30 minutes.
- the temperature is kept at 130 to 140 ° C and the pressure at 1 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 2 hours. It is allowed to cool to 50 ° C.
- Step 3 After cooling to 50 ° C., 2.2 g (0.04 mol) of sodium methylate are added to the mixture from step 2). The reactor is again rendered inert with N2 gas and heated to 130.degree. Then 628 g (14.27 mol) of ethylene oxide are metered in over 4 hours. The temperature is kept at 130 to 140 ° C and the pressure at 0 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 3 hours. The mixture is then cooled to 50 ° C. and neutralized with 3.2 g (0.054 mol) of acetic acid. The resulting mixture is macromonomer M-1.
- a dry mix was prepared consisting of 150 g cement (CEM I).
- the slump was measured on the mortar obtained in accordance with DIN EN 12350-5.
- the funnel discharge time was measured in accordance with DIN EN 12350-9.
- the air content was determined 30 minutes after mixing in accordance with the DIN EN 12350-7 standard.
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Abstract
The invention relates to the use of branched copolymers as dispersants of mineral binders, the copolymers being constituted of (1) at least one olefinically unsaturated carbonic acid monomer; and (2) at least one olefinically unsaturated macromonomer of the general structure (I), wherein R1 is an olefinically unsaturated group with 2 - 10 C atoms, which can optionally be substituted by oxygen and/or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and/or methacryloyl, X = O or NH, A independently represents C1-C10 alkylene, preferably ethylene, propylene and/or butylene, R2 = C1-C16 alkyl, B independently represents C1-C10 alkylene, preferably ethylene, propylene and/or butylene, m independently stands for an integer in the range of 0 – 350, preferably 2 – 200, more preferred 5 – 150, specifically 7 – 30, n stands for an integer in the range of 0 – 100, preferably 1 – 100, more preferred 2 – 75, most preferred 5 – 55, p is 0 or 1, preferably 0, o stands for an integer in the range of 1 – 50, preferably 3 – 40, more preferred 6 – 30, specifically 8 – 20, and q stands for an integer in the range of 1 – 10.
Description
Verzweigte Copolymere als Dispergiermittel für mineralische Bindemittel Branched copolymers as dispersants for mineral binders
Technisches Gebiet Technical area
Die Erfindung betrifft die Verwendung verzweigter Copolymere als Dispergiermittel von mineralischen Bindemittel. Ein weiterer Aspekt der Erfindung betrifft eine mineralische Bindemittelzusammensetzung sowie einen ausgehärteten Formkörper enthaltend das verzweigte Copolymer. The invention relates to the use of branched copolymers as dispersants for mineral binders. Another aspect of the invention relates to a mineral binder composition and a cured molded body containing the branched copolymer.
Hintergrund background
Dispergiermittel oder Fliessmittel werden in der Bauindustrie als Verflüssiger oder wasserreduzierende Mittel für mineralische Bindemittel und/oder mineralische Bindemittelzusammensetzungen, wie z.B. Beton, Mörtel, Zemente, Gipse und Kalk, eingesetzt. Als Dispergiermittel werden im Allgemeinen organische Polymere eingesetzt, welche dem Anmachwasser zugesetzt oder als Feststoff dem Bindemittel bzw. der Bindemittelzusammensetzung beigefügt werden. Dadurch können sowohl die Konsistenz der Bindemittelzusammensetzung während der Verarbeitung als auch die Eigenschaften in ausgehärtetem Zustand in vorteilhafter Weise verändert werden. Die Wahl und Dosierung eines geeigneten Dispergiermittels hängt insbesondere von der spezifischen Zusammensetzung, der Verarbeitungstechnik oder dem Einsatzzweck des Bindemittels bzw. der Bindemittelzusammensetzung ab. Dispersants or superplasticizers are used in the construction industry as liquefiers or water-reducing agents for mineral binders and / or mineral binder compositions such as concrete, mortar, cement, plaster and lime. The dispersants used are generally organic polymers which are added to the mixing water or added as a solid to the binder or the binder composition. As a result, both the consistency of the binder composition during processing and the properties in the cured state can advantageously be changed. The choice and dosage of a suitable dispersant depends in particular on the specific composition, the processing technique or the intended use of the binder or the binder composition.
In der Praxis werden häufig Hochleistungsverflüssiger in Form von Polycarboxylatethern (PCE) als Dispergiermittel für mineralische Bindemittel eingesetzt, beispielsweise um das Fliessverhalten von mineralischen Bindemittelzusammensetzungen zu verbessern. Zwar zeigen herkömmliche PCE normalerweise eine starke Wasserreduktion und verringern die Fliessgrenze von mineralischen Bindemittelzusammensetzungen, haben aber keinen oder nur geringen Einfluss auf die Viskosität. In practice, high-performance plasticizers in the form of polycarboxylate ethers (PCE) are often used as dispersants for mineral binders, for example to improve the flow behavior of mineral binder compositions. Although conventional PCE normally show a strong reduction in water and lower the yield point of mineral binder compositions, they have little or no influence on the viscosity.
Die EP 2454296 beschreibt Copolymere welche aus verzweigten Makromonomeren aufgebaut sind. Die Verwendung solcher Copolymere als Verdicker, beispielsweise in Wasch- und Reinigungsmitteln wird ebenfalls beschrieben. EP 2454296 describes copolymers which are built up from branched macromonomers. The use of such copolymers as thickeners, for example in detergents and cleaning agents, is also described.
Die EP 2 964 586 beschreibt Copolymere als Dispergiermittel für mineralische Bindemittel, wobei die Copolymere Einheiten enthalten, die abgeleitet sind aus (i) einer olefinisch ungesättigten Säure und (ii) einem olefinisch ungesättigten,
verzweigten Polyethermakromonomer mit einem Alkyl-Terminus. Diese Dispergiermittel haben den Nachteil, dass sie unter Verwendung von Epichlorhydrin hergestellt werden, welches schwer zu handhaben ist. Ausserdem führen diese Copolymere oft zu einem unerwünschten zusätzlichen Lufteintrag. Es besteht also weiterhin ein Bedarf an verbesserten Dispergiermitteln für mineralische Bindemittel, welche die Nachteile des bekannten Stands der Technik überwinden können. EP 2 964 586 describes copolymers as dispersants for mineral binders, the copolymers containing units which are derived from (i) an olefinically unsaturated acid and (ii) an olefinically unsaturated acid, branched polyether macromonomer with an alkyl terminus. These dispersants have the disadvantage that they are made using epichlorohydrin, which is difficult to handle. In addition, these copolymers often lead to an undesirable additional introduction of air. There is therefore still a need for improved dispersants for mineral binders which can overcome the disadvantages of the known prior art.
Zusammenfassung der Erfindung Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Verfügung zu stellen, welches es ermöglicht, mineralische Bindemittel effizient zu dispergieren und so die Viskosität und/oder das Fliessverhalten mineralischerSUMMARY OF THE INVENTION The object of the present invention is to provide a method which enables mineral binders to be dispersed efficiently and thus the viscosity and / or the flow behavior of mineral binders
Bindemittelzusammensetzungen zu verbessern, insbesondere ohne zusätzlichen Lufteintrag. Überraschenderweise wurde gefunden, dass diese Aufgabe gelöst werden kann durch die Verwendung von Copolymeren als Dispergiermittel für mineralische Bindemittel, wobei die Copolymere aufgebaut sind aus To improve binder compositions, in particular without additional air entrainment. It has surprisingly been found that this object can be achieved through the use of copolymers as dispersants for mineral binders, the copolymers being composed of
(1) mindestens einem olefinisch ungesättigten Carbonsäure-Monomer (1) at least one olefinically unsaturated carboxylic acid monomer
(2) mindestens einem olefinisch ungesättigten Makromonomer der allgemeinen Struktur (I)
wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff du/oder Stickstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, (2) at least one olefinically unsaturated macromonomer of the general structure (I) where R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O oder NH ist, X = O or NH,
A jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen und/oder Butylen sind, A are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
R2 = C1-C16 Alkyl ist, B jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen und/oder Butylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, bevorzugt
2 - 200, besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind, n eine ganze Zahl im Bereich von 0 - 100, bevorzugt 1 - 100, besonders bevorzugt 2 - 75, ganz besonders bevorzugt 5 - 55 ist, p gleich 0 oder 1, bevorzugt 0 ist, o eine ganze Zahl im Bereich von 1 - 50, bevorzugt 3 - 40, besonders bevorzugt 6 - 30, im Speziellen 8 - 20 ist, und q eine ganze Zahl im Bereich von 1 - 10 ist. R 2 = C1-C16 alkyl, B each independently of one another is C1-C10 alkylene, preferably ethylene, propylene and / or butylene, m each independently of one another is an integer in the range from 0-350, preferably 2-200, particularly preferably 5-150, especially 7-30, n is an integer in the range 0-100, preferably 1-100, particularly preferably 2-75, very particularly preferably 5-55, p is 0 or 1, preferably 0, o is an integer in the range from 1-50, preferably 3-40, particularly preferably 6-30, especially 8-20, and q is an integer in the range 1-10.
Ein wesentlicher Vorteil erfindungsgemässer Copolymere ist das Vorliegen einer Vielzahl von Alkylenoxid-basierten Seitenketten innerhalb einer einzelnen Makromonomer-Einheit. Diese Vielzahl wird durch die Einführung von Verzweigungen erreicht. Dadurch besitzt eine einzelne Makromonomereinheit einen grösseren sterischen Anspruch als Makromonomereinheiten mit rein linearen Seitenketten, wie sie beispielsweise in klassischen PCE vorliegen. Dies führt zu einer verminderten Wechselwirkung mit Seitenketten anderer Makromonomereinheiten. Auf diese Weise kann ein erfindungsgemässes Copolymer gleichzeitig als Dispergiermittel für mineralische Bindemittel und zur Herabsetzung der Viskosität mineralischer Bindemittelzusammensetzungen verwendet werden, was einen wesentlichen Vorteil darstellt. An essential advantage of copolymers according to the invention is the presence of a large number of alkylene oxide-based side chains within a single macromonomer unit. This variety is achieved by introducing branches. As a result, an individual macromonomer unit has a greater steric demand than macromonomer units with purely linear side chains, such as those present in classic PCE, for example. This leads to a reduced interaction with side chains of other macromonomer units. In this way, a copolymer according to the invention can be used at the same time as a dispersant for mineral binders and to reduce the viscosity of mineral binder compositions, which is a significant advantage.
Weitere Vorteile der Verwendung erfindungsgemässer Copolymere als Dispergiermittel in mineralischen Bindemittelzusammensetzungen sind weniger Entmischung bzw. Separation der Bestandteile der mineralischen Bindemittelzusammensetzung, sowie weniger unerwünschter Lufteintrag. Further advantages of the use of copolymers according to the invention as dispersants in mineral binder compositions are less segregation or separation of the constituents of the mineral binder composition, and less undesired entry of air.
Schliesslich zeichnen sich die Makromonomere, welche zum Aufbau erfindungsgemässer Copolymere benötigt werden durch eine einfache Synthese aus, welche bevorzugt ohne die Verwendung von Epichlorhydrin auskommt. Dies ist von Vorteil, da Epichlorhydrin aufgrund seiner Toxizität und Karzinogenität problematisch ist. Finally, the macromonomers which are required to build up copolymers according to the invention are distinguished by a simple synthesis which preferably does not require the use of epichlorohydrin. This is beneficial because epichlorohydrin is problematic due to its toxicity and carcinogenicity.
Weitere Aspekte der Erfindung sind Gegenstand anderer unabhängiger Ansprüche. Besonders bevorzugte Ausführungsformen der Erfindung sind Gegenstand der abhängigen Ansprüche.
Wege zur Ausführung der Erfindung Further aspects of the invention are the subject of other independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways of Carrying Out the Invention
Unter dem Begriff „Dispergiermittel“ versteht man vorliegend ein Mittel zur Verbesserung der Mischbarkeit mineralischer Bindemittel mit einem Lösungsmittel, insbesondere mit Wasser. Dispergiermittel im Sinne der vorliegenden Erfindung führen insbesondere dazu, dass Mischungen mineralischer Bindemittel oderThe term “dispersant” is understood here to mean an agent for improving the miscibility of mineral binders with a solvent, in particular with water. Dispersants in the context of the present invention lead in particular to mixtures of mineral binders or
Bindemittelzusammensetzungen mit Wasser eine grössere Fliessfähigkeit und/oder eine geringere Entmischung aufweisen, als dieselben Mischungen ohne das Dispergiermittel. Im Speziellen wird die Fliessfähigkeit von Mischungen mineralischer Bindemittel oder Bindemittelzusammensetzungen mit Wasser durch Zugabe eines Dispergiermittels erhöht. Ein Mass für die Fliessfähigkeit ist dabei insbesondere das Ausbreitmass gemessen nach Norm DIN EN 12350-5. Alternativ bewirkt ein Dispergiermittel eine Verringerung des Wasseranspruches eines mineralischen Bindemittels zur Einstellung derselben Fliessfähigkeit wie eine Mischung des mineralischen Bindemittels mit Wasser aber ohne Zusatz von Dispergiermittel. Die erfindungsgemässen Copolymere wirken als Dispergiermittel und verbessern die Fliessfähigkeit einer damit modifizierten mineralischen Bindemittelzusammensetzung. Die erfindungsgemässen Copolymere reduzieren darüber hinaus auch die Viskosität einer damit modifizierten mineralischen Bindemittelzusammensetzung. Ein Mass für die Viskosität ist dabei insbesondere die Trichterauslaufzeit gemessen nach Norm DIN EN 12350-9. Binder compositions with water have greater flowability and / or less segregation than the same mixtures without the dispersant. In particular, the flowability of mixtures of mineral binders or binder compositions with water is increased by adding a dispersant. A measure of the flowability is in particular the slump measured in accordance with the DIN EN 12350-5 standard. Alternatively, a dispersant reduces the water requirement of a mineral binder in order to establish the same flowability as a mixture of the mineral binder with water but without the addition of a dispersant. The copolymers according to the invention act as dispersants and improve the flowability of a mineral binder composition modified therewith. The copolymers according to the invention also reduce the viscosity of a mineral binder composition modified therewith. A measure of the viscosity is in particular the funnel discharge time measured in accordance with the DIN EN 12350-9 standard.
Ein erster Aspekt der Erfindung betrifft die Verwendung von Copolymeren als Dispergiermittel für mineralische Bindemittel, wobei die Copolymere aufgebaut sind aus A first aspect of the invention relates to the use of copolymers as dispersants for mineral binders, the copolymers being built up from
(1) mindestens einem olefinisch ungesättigten Carbonsäure-Monomer (2) mindestens einem olefinisch ungesättigten Makromonomer der allgemeinen(1) at least one olefinically unsaturated carboxylic acid monomer (2) at least one olefinically unsaturated macromonomer of the general
Struktur (I)
wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff und/oder Stickstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, Structure (I) where R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O oder NH ist, X = O or NH,
A jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen
und/oder Butylen sind, A in each case independently of one another C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
R2 = C1-C16 Alkyl ist, R 2 = C1-C16 alkyl,
B jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen und/oder Butylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, bevorzugt 2 - 200, besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind, n eine ganze Zahl im Bereich von 0 - 100, bevorzugt 1 - 100, besonders bevorzugt 2 - 75, ganz besonders bevorzugt 5 - 55 ist, p gleich 0 oder 1, bevorzugt 0 ist, o eine ganze Zahl im Bereich von 1 - 50, bevorzugt 3 - 40, besonders bevorzugt 6 - 30, im Speziellen 8 - 20 ist, und q eine ganze Zahl im Bereich von 1 - 10 ist. B are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene, m are each independently an integer in the range from 0-350, preferably 2-200, particularly preferably 5-150, especially 7-30 , n is an integer in the range from 0 - 100, preferably 1 - 100, particularly preferably 2 - 75, very particularly preferably 5 - 55, p is 0 or 1, preferably 0, o is an integer in the range from 1 - 50, preferably 3-40, particularly preferably 6-30, especially 8-20, and q is an integer in the range 1-10.
Wenn q = 1 ist, so ist o eine ganze Zahl im Bereich von 1 - 50. Wenn q > 1 ist, so sind alle o jeweils unabhängig voneinander eine ganze Zahl im Bereich von 1 - 50. Es ist besonders bevorzugt, dass p = 0 ist, wenn n > 0 ist. If q = 1, then o is an integer in the range from 1 to 50. If q> 1, then all o are each, independently of one another, an integer in the range from 1 to 50. It is particularly preferred that p = Is 0 when n> 0.
Die Anzahl linearer Struktureinheiten (BO)m in der allgemein Struktur (I) ist abhängig von o und q. Die Anzahl der Struktureinheiten (BO)m ist gleich o x q +1. The number of linear structural units (BO) m in the general structure (I) depends on o and q. The number of structural units (BO) m is equal to oxq +1.
Zur besseren Verdeutlichung werden im Folgenden einige Beispielstrukturen abgeleitet aus der allgemeinen Struktur (I) mit definierten Kombinationen von o und q dargestellt. Diese Beispielstrukturen sollen in keiner Weise als einschränkend für die erfindungsgemässen Makromonomere gelten. For better clarity, some example structures derived from the general structure (I) with defined combinations of o and q are shown below. These example structures are in no way intended to be regarded as restrictive for the macromonomers according to the invention.
Für den Fall o = 2 und q = 1 ergeben sich Makromonomere der folgenden allgemeinen Struktur (la)
For the case o = 2 and q = 1 there are macromonomers of the following general structure (la)
Für den Fall o = 3 und q = 1 ergeben sich Makromonomere der folgenden allgemeinen Struktur (Ib)
Für den Fall o = 1 und q = 2 ergeben sich Makromonomere der folgenden allgemeinen Struktur (Ic)
For the case o = 3 and q = 1 there are macromonomers of the following general structure (Ib) For the case o = 1 and q = 2 there are macromonomers of the following general structure (Ic)
Für den Fall o = 2 und q = 3 ergeben sich Makromonomere der folgenden allgemeinen Struktur (Id)
For the case o = 2 and q = 3 there are macromonomers of the following general structure (Id)
Dem Fachmann ist klar, dass die erfindungsgemässen Makromonomere unterschiedliche Regioisomere enthalten können. Dabei handelt es sich um Regioisomere, die entstehen wenn bei der Herstellung der Makromonomere unter Verwendung von beispielsweise Glycidol der Oxiran-Ring des Glycidols über die
verschiedenen C-Atome, gemäss einer der chemischen Reaktionsgleichungen a) bzw. b) wie im Folgenden dargestellt geöffnet wird.
b) HO OH °'R It is clear to the person skilled in the art that the macromonomers according to the invention can contain different regioisomers. These are regioisomers that arise when the oxirane ring of the glycidol over the during the preparation of the macromonomers using, for example, glycidol different carbon atoms, according to one of the chemical reaction equations a) or b) as shown below. b) HO OH ° 'R
Zur Vereinfachung wird in der vorliegenden Erfindung stets nur das Regioisomer b) abgebildet. Gemeint sind aber stets beide Regioisomere a) und b) bzw. deren Gemische. For the sake of simplicity, only the regioisomer b) is shown in the present invention. What is meant, however, is always both regioisomers a) and b) or their mixtures.
Die Strukturelemente (AO) sowie (BO) der allgemeinen Struktur (I) sind Polyalkylenoxidketten. Bevorzugt beträgt ein Anteil an Ethylenoxideinheiten in den Polyalkylenoxid-Ketten (AO)m und (BO)m, bezogen auf sämtliche vorhandenen Alkylenoxid-Einheiten AO und BO, mehr als 90 Mol-%, insbesondere mehr als 95 Mol- %, bevorzugt mehr als 98 Mol-%, im Speziellen 100 Mol-% beträgt. In einer besonderen Ausführungsform weisen die Polyalkylenoxid-Seitenketten keine hydrophoben Gruppen, insbesondere keine Alkylenoxide mit drei oder mehrThe structural elements (AO) and (BO) of the general structure (I) are polyalkylene oxide chains. A proportion of ethylene oxide units in the polyalkylene oxide chains (AO) m and (BO) m , based on all alkylene oxide units AO and BO present, is preferably more than 90 mol%, in particular more than 95 mol%, preferably more than 98 mol%, specifically 100 mol%. In a particular embodiment, the polyalkylene oxide side chains have no hydrophobic groups, in particular no alkylene oxides with three or more
Kohlenstoffatomen, auf. Ein hoher Anteil an Ethylenoxideinheiten oder ein geringer Gehalt an Alkylenoxiden mit drei oder mehr Kohlenstoffatomen reduziert die Gefahr von unerwünschtem Lufteintrag. Carbon atoms. A high proportion of ethylene oxide units or a low content of alkylene oxides with three or more carbon atoms reduces the risk of undesired air entrainment.
Das durchschnittliche gewichtsgemittelte Molekulargewicht (Mw) wird vorliegend durch Gel-Permeations-Chromatographie (GPC) mit Polyethylenglycol (PEG) als Standard bestimmt. Diese Technik ist dem Fachmann an sich bekannt. Erfindungsgemässe Copolymere können eine Molmasse Mw im Bereich von 250 - 1Ό00Ό00 g/mol haben. Bei bevorzugten Copolymeren sind die Parameter n, m, o und p der allgemeinen Struktur (I) so gewählt, dass die mittlere Molmasse Mw der Copolymere im Bereich von 1Ό00 - 1Ό00Ό00, besonders bevorzugt T500 - 500Ό00, ganz besonders bevorzugt 2Ό00 - 100Ό00, insbesondere 3Ό00 - 75Ό00 oder 3Ό00 - 50Ό00 liegt.The weight average molecular weight (Mw) is determined in the present case by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art. Copolymers according to the invention can have a molar mass M w in the range from 250-100-0000 g / mol. In the case of preferred copolymers, the parameters n, m, o and p of the general structure (I) are chosen so that the mean molar mass M w of the copolymers is in the range from 100-10000, particularly preferably T500-50000, very particularly preferably 2-00-10000, in particular 3-75-00 or 3-50-00.
Unter dem Ausdruck "mineralisches Bindemittel" ist vorliegend ein Bindemittel zu verstehen, welches in Anwesenheit von Wasser in einer Hydratationsreaktion zu festen Hydraten oder Hydratphasen reagiert. Dies kann beispielsweise ein hydraulisches Bindemittel (z.B. Zement oder hydraulischer Kalk), ein latent
hydraulisches Bindemittel (z.B. Schlacke), ein puzzolanisches Bindemittel (z.B. Flugasche) oder ein nicht hydraulisches Bindemittel (Gips oder Weisskalk) sein. In the present context, the expression “mineral binder” is to be understood as meaning a binder which, in the presence of water, reacts in a hydration reaction to form solid hydrates or hydrate phases. This can, for example, be a hydraulic binder (e.g. cement or hydraulic lime), a latent hydraulic binding agent (e.g. slag), a pozzolanic binding agent (e.g. fly ash) or a non-hydraulic binding agent (gypsum or white lime).
Eine mineralische Bindemittelzusammensetzung ist dementsprechend eine Zusammensetzung umfassend mindestens ein mineralisches Bindemittel. A mineral binder composition is accordingly a composition comprising at least one mineral binder.
Insbesondere enthält das mineralische Bindemittel ein hydraulisches Bindemittel, bevorzugt Zement. Besonders bevorzugt ist ein Zement mit einem Zementklinkeranteil von > 35 Gew.-%. Insbesondere ist der Zement ein Portlandzement oder Portlandkompositzement vom Typ CEM I, CEM II, CEM III, CEM IV oder CEM V gemäss Norm EN 197-1, oder ein Aluminatzement, insbesondere ein Tonerdezement nach DIN EN 14647, oder Mischungen der genannten Zemente. In particular, the mineral binder contains a hydraulic binder, preferably cement. A cement with a cement clinker content of> 35% by weight is particularly preferred. In particular, the cement is a Portland cement or Portland composite cement of the type CEM I, CEM II, CEM III, CEM IV or CEM V in accordance with standard EN 197-1, or an aluminate cement, in particular a high-alumina cement in accordance with DIN EN 14647, or mixtures of the cited cements.
Die mineralische Bindemittelzusammensetzung umfasst mindestens ein hydraulisches Bindemittel, bevorzugt Zement, in wenigstens 5 Gew.-%, bevorzugt in wenigstens 20 Gew.-%, besonders bevorzugt in wenigstens 35 Gew.-%, ganz besonders bevorzugt in wenigstens 65 Gew.-%, im Speziellen > 95 Gew.-%, jeweils bezogen auf die Trockenmasse der mineralischen Bindemittelzusammensetzung. The mineral binder composition comprises at least one hydraulic binder, preferably cement, in at least 5% by weight, preferably in at least 20% by weight, particularly preferably in at least 35% by weight, very particularly preferably in at least 65% by weight, in particular> 95% by weight, based in each case on the dry matter of the mineral binder composition.
Es kann aber auch vorteilhaft sein, wenn das mineralische Bindemittel oder die mineralische Bindemittelzusammensetzung andere Bindemittel enthält oder im Wesentlichen daraus besteht. Dies sind insbesondere latent hydraulische Bindemittel und/oder puzzolanische Bindemittel. Geeignete latenthydraulische und/oder puzzolanische Bindemittel sind z.B. Schlacke, Flugasche, Silicastaub, Mikrosilika, Metakaolin, Tuff, Trass, Vulkansche, Zeolithe, und/oder gebrannten Ölschiefer. However, it can also be advantageous if the mineral binder or the mineral binder composition contains or essentially consists of other binders. These are in particular latent hydraulic binders and / or pozzolanic binders. Suitable latent hydraulic and / or pozzolanic binders are e.g. slag, fly ash, silica dust, microsilica, metakaolin, tuff, trass, volcanic, zeolites and / or burnt oil shale.
In einerweiteren Ausführungsform kann das mineralische Bindemittel a- Claciumsulfathemihydrat, ß-Calciumsulfathemihydrat, Anhydrit und/oder Kalk umfassen oder im Wesentlichen daraus bestehen. In a further embodiment, the mineral binder can comprise or essentially consist of α-calcium sulfate hemihydrate, β-calcium sulfate hemihydrate, anhydrite and / or lime.
Ebenso kann die mineralische Bindemittelzusammensetzung inerte Stoffe wie z.B. Kalkstein, Quarzmehle und/oder Pigmente enthalten The mineral binder composition can also contain inert substances such as limestone, quartz powder and / or pigments
In einer vorteilhaften Ausführungsform enthält das mineralische Bindemittel 5 - 95 Gew.-%, insbesondere 5 - 65 Gew.-%, besonders bevorzugt 15 - 35 Gew.-%, jeweils bezogen auf die gesamte Trockenmasse des mineralischen Bindemittels, latenthydraulische und/oder puzzolanische Bindemittel. Vorteilhafte latenthydraulische und/oder puzzolanische Bindemittel sind Schlacke und/oder Flugasche. In an advantageous embodiment, the mineral binder contains 5-95% by weight, in particular 5-65% by weight, particularly preferably 15-35% by weight, based in each case on the total dry matter of the mineral binder, latent hydraulic and / or pozzolanic Binder. Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.
In einer besonders bevorzugten Ausführungsform enthält das mineralische Bindemittel ein hydraulisches Bindemittel, insbesondere Zement oder Zementklinker, und ein
latenthydraulisches und/oder puzzolanisches Bindemittel, bevorzugt Schlacke und/oder Flugasche. Der Anteil des latenthydraulischen und/oder puzzolanischen Bindemittels beträgt dabei besonders bevorzugt 5 - 65 Gew.-%, besonders bevorzugt 15 - 35 Gew.-%, während wenigstens 35 Gew.-%, im Speziellen wenigstens 65 Gew.- %, jeweils bezogen auf die Trockenmasse des mineralischen Bindemittels. In a particularly preferred embodiment, the mineral binder contains a hydraulic binder, in particular cement or cement clinker, and a latent hydraulic and / or pozzolanic binder, preferably slag and / or fly ash. The proportion of the latent hydraulic and / or pozzolanic binder is particularly preferably 5-65% by weight, particularly preferably 15-35% by weight, while at least 35% by weight, especially at least 65% by weight, in each case on the dry matter of the mineral binder.
Gemäss bevorzugter Ausführungsformen ist das mineralische Bindemittel demnach ausgewählt aus der Gruppe umfassend Zement, insbesondere Portlandzement und Aluminatzement, a-Calciumsulfathemihydrat, ß-Calciumsulfathyemihydrat, Anhydrit, Kalk, industrielle und synthetische Schlacken, insbesondere Hochofenschlacken, Hüttensand, Hüttensandmehl, elektrothermische Phosphorschlacke, Kupferschlacke und Edelstahlschlacke, Puzzolane, insbesondere Flugaschen, Mikrosilika, Metakaolin, natürlich Puzzolane, insbesondere Tuff, Trass und Vulkansche, natürliche und synthetische Zeolithe, gebrannten Ölschiefer sowie Mischungen davon. According to preferred embodiments, the mineral binder is accordingly selected from the group comprising cement, in particular portland cement and aluminum cement, α-calcium sulfate hemihydrate, ß-calcium sulfate hemihydrate, anhydrite, lime, industrial and synthetic slag, in particular blast furnace slag, blast furnace slag, blast furnace slag, electrothermal stainless steel phosphor slag, and copper slag , Pozzolans, in particular fly ash, microsilica, metakaolin, of course pozzolans, in particular tuff, trass and volcanic ash, natural and synthetic zeolites, burnt oil shale and mixtures thereof.
Das mindestens eine olefinisch ungesättigte Carbonsäure-Monomer zum Aufbau von Copolymeren der vorliegenden Erfindung kann ein Monocarbonsäure-, einThe at least one olefinically unsaturated carboxylic acid monomer for forming copolymers of the present invention can be a monocarboxylic acid
Dicarbonsäure- oder ein Carbonsäureanhydrid-Monomer sein. Monocarbonsäure- Monomere sind besonders bevorzugt. Es ist möglich, unterschiedliche olefinisch ungesättigte Carbonsäure-Monomere zum Aufbau von Copolymeren zu verwenden. Von ungesättigten Carbonsäure-Monomeren abgeleitete Struktureinheiten des Copolymeren können unabhängig voneinander in ihrer protonierten Form vorliegen oder teilweise oder ganz neutralisiert, z.B. durch Basen wie Alkalimetall- oder Erdalkalimetallbasen, Ammoniak, organische Amine, etc. Be dicarboxylic acid or a carboxylic acid anhydride monomer. Monocarboxylic acid monomers are particularly preferred. It is possible to use different olefinically unsaturated carboxylic acid monomers to build up copolymers. Structural units of the copolymer derived from unsaturated carboxylic acid monomers can, independently of one another, be in their protonated form or partially or completely neutralized, e.g. by bases such as alkali metal or alkaline earth metal bases, ammonia, organic amines, etc.
Das mindestens eine olefinisch ungesättigte Carbonsäure-Monomer zum Aufbau von Copolymeren der vorliegenden Erfindung kann ausgewählt werden aus Strukturen der allgemeinen Strukturen (lla) und/oder (Mb)
wobei R3 = H oder eine C1-C6-Alkylkette ist, R4 = H, C(Ö)Y, oder eine C1-C6-Alkylkette ist, bevorzugt H ist, und The at least one olefinically unsaturated carboxylic acid monomer for the construction of copolymers of the present invention can be selected from structures of the general structures (Ila) and / or (Mb) where R 3 = H or a C1-C6-alkyl chain, R 4 = H, C (O) Y, or a C1-C6-alkyl chain, is preferably H, and
Y = OM, mit M ausgewählt aus H, Alkalimetallen, Erdalkalimetallen oder organischem
Ammonium, oder Y = NR4R5, mit R4 und R5 unabhängig voneinander gleich H oder eine C1-C6-Alkylkette, ist;
wobei Z = O oder NR5 ist und R3 die vorstehenden Bedeutungen hat, und R5 = H oder eine C1-C6-Alkylkette ist. Y = OM, with M selected from H, alkali metals, alkaline earth metals or organic Ammonium, or Y = NR 4 R 5 , with R 4 and R 5 independently of one another being H or a C1-C6-alkyl chain; where Z = O or NR 5 and R 3 has the above meanings, and R 5 = H or a C1-C6-alkyl chain.
Besonders bevorzugte ungesättigte Carbonsäure-Monomere sind Acrylsäure und ihre Salze, Acrylamide, Methacrylsäure und ihre Salze, Methacrylamide, Maleinsäure und ihre Salze, Maleinsäureanhydrid, Maleinsäureimide, Crotonsäure und ihre Salze, Fumarsäure und ihre Salze, sowie Mischungen davon. Particularly preferred unsaturated carboxylic acid monomers are acrylic acid and its salts, acrylamides, methacrylic acid and its salts, methacrylamides, maleic acid and its salts, maleic anhydride, maleic acid imides, crotonic acid and its salts, fumaric acid and its salts, and mixtures thereof.
Das mindestens eine olefinisch ungesättigte Makromonomer der allgemeinen Struktur (I) ist ein verzweigtes Polyether Makromonomer. Es können mehrere chemisch und/oder strukturell unterschiedliche Makromonomere der allgemeinen Struktur (I) zum Aufbau von erfindungsgemässen Copolymeren verwendet werden. Strukturell unterschiedlich schliesst dabei insbesondere auch Makromonomere der allgemeinen Struktur (I) ein, die sich beispielsweise nur hinsichtlich ihrer Molmasse, z.B. durch unterschiedliche Wahl der Parameter m, o und/oder q, unterscheiden. The at least one olefinically unsaturated macromonomer of the general structure (I) is a branched polyether macromonomer. A plurality of chemically and / or structurally different macromonomers of the general structure (I) can be used to build up copolymers according to the invention. Structurally different also includes, in particular, macromonomers of the general structure (I), which differ, for example, only with regard to their molar mass, e.g. through different choices of the parameters m, o and / or q.
Besonders bevorzugt sind olefinisch ungesättigte Makromonomer der allgemeinen Struktur (I), bei denen R1 eine Vinyl-, Allyl-, Methallyl-, Vinyloxybutyl, Isoprenyl-, Acryloyl- oder Methacryloyl-Einheit ist. Particularly preferred are olefinically unsaturated macromonomers of the general structure (I) in which R 1 is a vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl or methacryloyl unit.
In einer bevorzugten Ausführungsform sind erfindungsgemässe olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) solche Makromonomere, bei denen p = 0 ist, falls n > 0 ist und bei denen p = 1 ist, falls n = 0 ist. In dieser Ausführungsform ist in den Makromonomeren also jeweils entweder eine (AO)m- Einheit oder eine Einheit R2-X vorhanden. In a preferred embodiment, olefinically unsaturated macromonomers according to the invention of the general structure (I) are those macromonomers in which p = 0 if n> 0 and in which p = 1 if n = 0. In this embodiment, either an (AO) m unit or an R 2 -X unit is present in the macromonomers.
Gemäss einer weiteren bevorzugten Ausführungsform sind alle m so gewählt, dass die mittlere Anzahl (BO)-Einheiten an allen o x q +1 linearen Strukturen jeweils gleich ist.
Entsprechend einer bevorzugten Ausführungsform sind erfindungsgemässe olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) solche Makromonomere, bei denen According to a further preferred embodiment, all m are chosen such that the average number (BO) units on all oxq +1 linear structures is the same in each case. According to a preferred embodiment, olefinically unsaturated macromonomers according to the invention of the general structure (I) are macromonomers in which
R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O ist, X = O,
A jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen sind, A are each independently C1-C10 alkylene, preferably ethylene,
B jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich 5 - 150 ist, n eine ganze Zahl im Bereich von 5 - 55 ist, p = 0 ist, o eine ganze Zahl im Bereich von 8 - 50 ist, und q eine ganze Zahl im Bereich von 1 - 10, insbesondere 1 ist. Solche Monomere entsprechen der allgemeinen Struktur (III)
B are each independently C1-C10 alkylene, preferably ethylene, m each independently of one another is an integer in the range from 5 to 150, n is an integer in the range from 5 to 55, p = 0, o is an integer in the range from 8 to 50, and q is an integer in the range from 1 to 10, in particular 1. Such monomers correspond to the general structure (III)
Entsprechend einer weiteren bevorzugten Ausführungsform sind erfindungsgemässe olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) solche Makromonomere, bei denen According to a further preferred embodiment, olefinically unsaturated macromonomers according to the invention of the general structure (I) are macromonomers in which
R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, X = O ist, R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, X = O,
A jeweils unabhängig voneinander Ethylen, Propylen und/oder Butylen, besonders bevorzugt Ethylen sind, A are each independently ethylene, propylene and / or butylene, particularly preferably ethylene,
B jeweils unabhängig voneinander Ethylen, Propylen und/oder Butylen, besonders bevorzugt Ethylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, besonders bevorzugt 2 - 200, ganz besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind,
n eine ganze Zahl im Bereich von 1 - 100, besonders bevorzugt 2 - 75, ganz besonders bevorzugt 5 - 55 ist, p = 0 ist, und o eine ganze Zahl im Bereich von 1 - 50, besonders bevorzugt 3 - 40, ganz besonders bevorzugt 6 - 30, im Speziellen 8 - 20 ist, und q mindestens 2 ist. B are each independently ethylene, propylene and / or butylene, particularly preferably ethylene, m each independently an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, especially 7-30 , n is an integer in the range from 1-100, particularly preferably 2-75, very particularly preferably 5-55, p = 0, and o is an integer in the range 1-50, particularly preferably 3-40, very particularly is preferably 6-30, especially 8-20, and q is at least 2.
Solche Makromonomere entsprechen der allgemeinen Struktur (IV)
(iv), wobei x eine ganze Zahl von 1-9 ist, mit der Massgabe, dass x < o. Such macromonomers correspond to the general structure (IV) (iv), where x is an integer from 1-9, with the proviso that x <o.
Entsprechend einer weiteren bevorzugten Ausführungsform sind erfindungsgemässe olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) solche Makromonomere, bei denen R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, According to a further preferred embodiment, olefinically unsaturated macromonomers according to the invention of the general structure (I) are those macromonomers in which R 1 is an olefinically unsaturated radical having 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl , Vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O ist, X = O,
B jeweils unabhängig voneinander Ethylen, Propylen und/oder Butylen, besonders bevorzugt Ethylen sind, B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
R2 gleich C1-C16 Alkyl, besonders bevorzugt C2-C4 Alkyl, insbesondere Butyl ist, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, besonders bevorzugt 2 - 200, ganz besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind, n = 0 ist, p = 1 ist, o eine ganze Zahl im Bereich von 1 - 50, besonders bevorzugt 3 - 40, ganz besonders bevorzugt 6 - 30, im Speziellen 8 - 20 ist, und q mindestens 2 ist. Solche Makromonomere entsprechen der allgemeinen Struktur (V)
Entsprechend einer weiteren bevorzugten Ausführungsform sind erfindungsgemässe olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) solche Makromonomere, bei denen R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, R 2 is C1-C16 alkyl, particularly preferably C2-C4 alkyl, in particular butyl, m is, independently of one another, an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, especially 7- 30, n = 0, p = 1, o is an integer in the range from 1-50, particularly preferably 3-40, very particularly preferably 6-30, especially 8-20, and q is at least 2. Such macromonomers correspond to the general structure (V) According to a further preferred embodiment, olefinically unsaturated macromonomers according to the invention of the general structure (I) are those macromonomers in which R 1 is an olefinically unsaturated radical having 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl , Vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O ist, X = O,
B jeweils unabhängig voneinander Ethylen, Propylen und/oder Butylen, besonders bevorzugt Ethylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, besonders bevorzugt 2 - 200, ganz besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind, n = 0 ist, p = 0 ist, q eine ganze Zahl im Bereich von 1 - 10 ist, und o jeweils unabhängig voneinander eine ganze Zahl im Bereich von 1 - 50, besonders bevorzugt 3 - 40, ganz besonders bevorzugt 6 - 30, im Speziellen 8 - 20 sind. Solche Makromonomere entsprechen der allgemeinen Struktur (VI)
(VI). B are each independently ethylene, propylene and / or butylene, particularly preferably ethylene, m each independently an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, especially 7-30 , n = 0, p = 0, q is an integer in the range from 1 to 10, and o is in each case, independently of one another, an integer in the range from 1 to 50, particularly preferably 3 to 40, very particularly preferably 6 to 30 , specifically 8-20. Such macromonomers correspond to the general structure (VI) (VI).
Das molare Verhältnis des mindestens einen olefinisch ungesättigten Carbonsäure- Monomers zu dem mindestens einen olefinisch ungesättigten Makromonomer der allgemeinen Struktur (I) liegt im Bereich von 0.3 - 30, bevorzugt 0.6 - 10, besonders bevorzugt 1 - 4.5, insbesondere 1 - 3. The molar ratio of the at least one olefinically unsaturated carboxylic acid monomer to the at least one olefinically unsaturated macromonomer of the general structure (I) is in the range from 0.3-30, preferably 0.6-10, particularly preferably 1-4.5, in particular 1-3.
Zusätzlich zu dem mindestens einen olefinisch ungesättigten Carbonsäure-Monomer und dem mindestens einen olefinisch ungesättigten Makromonomer der allgemeinen Struktur (I) können erfindungsgemässe Copolymere ein oder mehrere weitere
Monomere M enthalten. Diese weiteren Monomere M können ausgewählt sein aus Styrol, Ethylen, Propylen, Butylen, Butadien, Isopren, Vinylacetat, Vinylchlorid, Acrylonitril, N-Vinylpyrrolidon, Hydroxyalkyl(meth)acrylaten und/oder Makromonomeren der allgemeinen Strukturen (VII)
wobei In addition to the at least one olefinically unsaturated carboxylic acid monomer and the at least one olefinically unsaturated macromonomer of the general structure (I), copolymers according to the invention can contain one or more further copolymers Monomers M included. These further monomers M can be selected from styrene, ethylene, propylene, butylene, butadiene, isoprene, vinyl acetate, vinyl chloride, acrylonitrile, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylates and / or macromonomers of the general structures (VII) in which
R6, jeweils unabhängig voneinander H, -CH2-COOM oder eine Alkylgruppe mit 1 bis 5 C-Atomen, bevorzugt H oder -CH3, ist, R 6 , each independently of one another, is H, -CH 2 -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H or -CH 3 ,
R7, jeweils unabhängig voneinander H oder eine Alkylgruppe mit 1 bis 5 C-Atomen, bevorzugt H, ist, R 7 , each independently of one another, is H or an alkyl group with 1 to 5 carbon atoms, preferably H,
R8, jeweils unabhängig voneinander H, -COOM oder eine Alkylgruppe mit 1 bis 5 C- Atomen, bevorzugt H, ist, r = 0, 1 oder 2 ist, s = 0 oder 1 ist, t = 0, oder eine ganze Zahl von 1 bis 4 ist, u = 2 - 250, insbesondere 10 - 200 ist, R 8 , each independently of one another, is H, -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H, r = 0, 1 or 2, s = 0 or 1, t = 0, or an integer is from 1 to 4, u = 2-250, in particular 10-200,
X jeweils unabhängig voneinander -O- oder -NH- ist, X is in each case, independently of one another, -O- or -NH-,
R9, jeweils unabhängig voneinander H, eine C1- bis C20-Alkylgruppe, - Cyclohexylgruppe oder -Alkylarylgruppe ist, und D eine C2- bis C4-Alkylen-Gruppe, bevorzugt Ethylen ist. R 9 , independently of one another, is H, a C1 to C20 alkyl group, cyclohexyl group or alkylaryl group, and D is a C2 to C4 alkylene group, preferably ethylene.
In einer ganz besonders bevorzugten Ausführungsform sind die zusätzlichen Monomere M ausgewählt aus linearen Polyethylenglykol-Ethern, insbesondere Polyethylenglykolether von Vinylalkohol, Allylalkohol, Methallylalkohol, Vinyl- oxybutylalkohol und/oder Isoprenol, und/oder linearen Polyethylenglykol-Estern, insbesondere Polyethylenglykolester der Acrylsäure und/oder Methacrylsäure. In a very particularly preferred embodiment, the additional monomers M are selected from linear polyethylene glycol ethers, in particular polyethylene glycol ethers of vinyl alcohol, allyl alcohol, methallyl alcohol, vinyl oxybutyl alcohol and / or isoprenol, and / or linear polyethylene glycol esters, in particular polyethylene glycol esters of acrylic acid and / or Methacrylic acid.
Es ist bevorzugt, dass der molare Anteil des einen oder der mehreren weiteren Monomeren M gleich oder kleiner 66 mol%, bevorzugt gleich oder kleiner 50 mol-%, mehr bevorzugt gleich oder kleiner 25 mol-%, besonders bevorzugt gleich oder kleiner 10 mol-%, insbesondere gleich oder kleiner 5 mol-%, jeweils bezogen auf alle das Copolymere aufbauenden Monomere, ist.
Olefinisch ungesättigte Makromonomere der allgemeinen Struktur (I) können hergestellt werden in einem mehrstufigen Verfahren, umfassend die Schritte It is preferred that the molar proportion of the one or more further monomers M is equal to or less than 66 mol%, preferably equal to or less than 50 mol%, more preferably equal to or less than 25 mol%, particularly preferably equal to or less than 10 mol% %, in particular equal to or less than 5 mol%, in each case based on all monomers making up the copolymer. Olefinically unsaturated macromonomers of the general structure (I) can be prepared in a multistep process comprising the steps
1) optional Umsetzung eines Starters S, ausgewählt aus der Gruppe bestehend aus Alkoholen, Aminen, Carbonsäuren oder Carbonsäureamiden der allgemeinen Formel R1-XH, mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, X = O oder NH, Hai = CI, Br oder I, und R2 = C1 - C16 Alkyl ist, 1) optional reaction of a starter S, selected from the group consisting of alcohols, amines, carboxylic acids or carboxamides of the general formula R 1 -XH, with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, X = O or NH, Hal = CI , Br or I, and R 2 = C1 - C16 alkyl,
2) Umsetzung eines Startes S oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder Epichlorhydrin oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel oder einer Mischung aus Epichlorhydrin und einem Alkoxylierungsmittel, 3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem2) Implementation of a start S or the reaction product from step 1) with glycidol or epichlorohydrin or a mixture of glycidol and an alkoxylating agent or a mixture of epichlorohydrin and an alkoxylating agent, 3) optional reaction of the reaction product from step 2) with a
Alkoxylierungsmittel. Alkoxylating agents.
Vorzugsweise werden die einzelnen Schritte des Verfahrens aufeinanderfolgend, ohne Isolierung oder Aufreinigung der Zwischenprodukte durchgeführt. The individual steps of the process are preferably carried out in succession without isolating or purifying the intermediate products.
Die Reaktionsbedingungen der Schritte 1) bis 3) können variieren. So können beispielsweise die Reaktionstemperatur, der Druck, und/oder die Art und Menge an eingesetztem Katalysator der Schritte 1) bis 3) unterschiedlich sein. Im Allgemeinen ist es jedoch bevorzugt, wenn die Reaktionstemperatur, der Druck, sowie die Art und Menge an eingesetztem Katalysator in den Schritten 1) bis 3) dieselben sind. The reaction conditions of steps 1) to 3) can vary. For example, the reaction temperature, the pressure and / or the type and amount of catalyst used in steps 1) to 3) can be different. In general, however, it is preferred if the reaction temperature, the pressure and the type and amount of catalyst used in steps 1) to 3) are the same.
Die Reaktionstemperatur kann im Bereich zwischen 80°C - 180°C, insbesondere 100°C - 140°C variieren. Der Druck liegt vorzugsweise im Bereich von 1 - 5 bar, insbesondere im Bereich von 1 - 3 bar. The reaction temperature can vary in the range between 80.degree. C.-180.degree. C., in particular 100.degree. C.-140.degree. The pressure is preferably in the range from 1 to 5 bar, in particular in the range from 1 to 3 bar.
Die einzelnen Schritte des Verfahrens werden vorzugsweise unter Katalyse durchgeführt. Geeignete Katalysatoren für die Alkoxylierungen der Schritte 1) bis 3) sind dem Fachmann an sich bekannt. In bevorzugten Ausführungsformen werden die Reaktionsschritte 1) bis 3) katalysiert. Es ist insbesondere bevorzugt, denselben Katalysator für die Schritte 1) bis 3) zu nutzen, ohne diesen zwischenzeitlich zu entfernen oder zu deaktivieren. Als besonders geeignete Katalysatoren haben sich Alkalimetallhydroxide und/oder Alkalimetallalkoholate herausgestellt. In einer
bevorzugten Ausführungsform wird als Katalysator ein Alkalimetallalkoholat desjenigen Alkohols eingesetzt wird, der auch als Starter S verwendet wird. Es kann auch bevorzugt sein, Natriumalkoholate, im Speziellen Natriummethanolat oder Natriumethanolat als Katalysator einzusetzen. The individual steps of the process are preferably carried out under catalysis. Suitable catalysts for the alkoxylations of steps 1) to 3) are known per se to the person skilled in the art. In preferred embodiments, reaction steps 1) to 3) are catalyzed. It is particularly preferred to use the same catalyst for steps 1) to 3) without removing or deactivating it in the meantime. Alkali metal hydroxides and / or alkali metal alcoholates have proven to be particularly suitable catalysts. In a In a preferred embodiment, an alkali metal alcoholate of the alcohol which is also used as the starter S is used as the catalyst. It can also be preferred to use sodium alcoholates, in particular sodium methoxide or sodium ethoxide, as the catalyst.
Ein geeignetes Verfahren zur Herstellung von erfindungsgemässen Makromonomeren wird beispielsweise in der EP 0 116 978 angegeben. A suitable process for the production of macromonomers according to the invention is given in EP 0 116 978, for example.
Der Starter S ist vorliegend eine Verbindung ausgewählt aus der Gruppe bestehend aus Alkoholen, Aminen, Carbonsäuren oder Carbonsäureamiden der allgemeinen Formel R1-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist und X = O oder NH ist. Es ist besonders bevorzugt, dass der Starter S ausser der Gruppe XH keine weiteren nucleophilen Gruppen enthält. Wenn der Starter S ein Alkohol ist, so handelt es sich um ein Monool, also um einen Alkohol mit nur einer OH-Gruppe. Wenn der Starter S ein Amin ist, so handelt es sich um ein primäres Amin, also um ein Amin mit einer NH2-Gruppe. Es handelt sich bei dem Starter S nicht um ein sekundäres oder tertiäres Amin. In the present case, the starter S is a compound selected from the group consisting of alcohols, amines, carboxylic acids or carboxylic acid amides of the general formula R 1 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which may be substituted by oxygen can, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, and X = O or NH. It is particularly preferred that the starter S contains no further nucleophilic groups apart from the group XH. If the starter S is an alcohol, it is a monool, i.e. an alcohol with only one OH group. If the starter S is an amine, it is a primary amine, i.e. an amine with an NH2 group. The starter S is not a secondary or tertiary amine.
In besonders bevorzugten Ausführungsformen ist der Starter S ausgewählt aus der Gruppe bestehend aus Isoprenol, Vinylalkohol, Allylalkohol, Methallylalkohol, Vinyloxybutylalkohol, Acrylsäure, Methacrylsäure, Acrylamid oder Methacrylamid.In particularly preferred embodiments, the starter S is selected from the group consisting of isoprenol, vinyl alcohol, allyl alcohol, methallyl alcohol, vinyloxybutyl alcohol, acrylic acid, methacrylic acid, acrylamide or methacrylamide.
Alkoxylierungsmittel im Sinne der vorlegenden Erfindung sind Verbindungen, die durch Polymerisation zu Polyethern umgesetzt werden können. Alkoxylierungsmittel bewirken also eine Alkoxylierung, bzw. den Aufbau von Alkylenoxid- bzw. Polyalkylenoxid-Einheiten. Insbesondere enthalten Alkoxylierungsmittel im Sinne der vorliegenden Erfindung Oxiran-, Oxetan- oder Oxolan-Strukturen. Besonders bevorzugte Alkoxylierungsmittel sind Alkylenoxide ausgewählt aus Ethylenoxid, Propylenoxid und/oder 1,2-Butylenoxid, und/oder Tetrahydrofuran. Im Speziellen ist das Alkoxylierungsmittel Ethylenoxid und/oder Propylenoxid. Es kann bevorzugt sein, nur ein Alkoxylierungsmittel in einem der Schritte 1) bis 3) zu verwenden. In einer ganz bevorzugten Ausführungsform wird nur ein Alkoxylierungsmittel, insbesondere Ethylenoxid, in den Schritten 1) bis 3) verwendet. Es ist aber auch möglich zwei oder mehr Alkoxylierungsmittel in den Schritten 1) bis 3) zu verwenden, entweder als Gemisch oder jeweils einzeln in jeweils einem der Schritte 1) bis 3).
In einer bevorzugten Ausführungsform werden erfindungsgemässe Makromonomere ohne die Verwendung von Epichlorhydrin hergestellt. Das Verfahren zur Herstellung ist also Epichlorhydrin-frei. Erfindungsgemässe Makromonomere können demzufolge bevorzugt hergestellt werden in einem Verfahren umfassend die Schritte: 1) optional Umsetzung eines Starters S, ausgewählt aus der Gruppe bestehend aus Alkoholen, Aminen, Carbonsäuren oder Amiden der allgemeinen Formel R1-XH, mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, X = O oder NH, Hai = CI, Br oder I, und R2 = C1 - C16 Alkyl ist, For the purposes of the present invention, alkoxylating agents are compounds which can be converted to polyethers by polymerization. Alkoxylating agents thus cause alkoxylation or the formation of alkylene oxide or polyalkylene oxide units. In particular, alkoxylating agents for the purposes of the present invention contain oxirane, oxetane or oxolane structures. Particularly preferred alkoxylating agents are alkylene oxides selected from ethylene oxide, propylene oxide and / or 1,2-butylene oxide, and / or tetrahydrofuran. In particular, the alkoxylating agent is ethylene oxide and / or propylene oxide. It may be preferred to use only one alkoxylating agent in one of steps 1) to 3). In a very preferred embodiment, only one alkoxylating agent, in particular ethylene oxide, is used in steps 1) to 3). However, it is also possible to use two or more alkoxylating agents in steps 1) to 3), either as a mixture or individually in each case in one of steps 1) to 3). In a preferred embodiment, macromonomers according to the invention are produced without the use of epichlorohydrin. The manufacturing process is therefore epichlorohydrin-free. Macromonomers according to the invention can therefore preferably be prepared in a process comprising the steps: 1) optionally reaction of a starter S, selected from the group consisting of alcohols, amines, carboxylic acids or amides of the general formula R 1 -XH, with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, X = O or NH, Hai = CI, Br or I, and R 2 = C1 - C16 alkyl,
2) Umsetzung eines Startes S oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel, 3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem2) reaction of a start S or the reaction product from step 1) with glycidol or a mixture of glycidol and an alkoxylating agent, 3) optionally reaction of the reaction product from step 2) with a
Alkoxylierungsmittel. Alkoxylating agents.
Dabei ist es insbesondere bevorzugt, wenn das Verfahren die Schritte 1) und 3) umfasst, Schritte 1) und 3) also nicht optional sind, sondern zwingend vorhanden sind.It is particularly preferred if the method comprises steps 1) and 3), ie steps 1) and 3) are not optional, but are mandatory.
In einer besonders bevorzugten Ausführungsform werden erfindungsgemässe Makromonomere ohne die Verwendung von Epichlorhydrin und unter Verwendung eines Alkohols als Starter S hergestellt. Das Verfahren zur Herstellung ist also Epichlorhydrin-frei. Erfindungsgemässe Makromonomere können demzufolge besonders bevorzugt hergestellt werden in einem Verfahren umfassend die Schritte: In a particularly preferred embodiment, macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of an alcohol as the starter S. The manufacturing process is therefore epichlorohydrin-free. Macromonomers according to the invention can therefore be prepared particularly preferably in a process comprising the steps:
1) optional Umsetzung eines Alkohols R1-OH mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl oder Isoprenyl ist, X = O oder NH, Hai = CI, Br oder I, und R2 =1) optional reaction of an alcohol R 1 -OH with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen can be, preferably vinyl, allyl, methallyl, vinyloxybutyl or isoprenyl, X = O or NH, Hal = CI, Br or I, and R 2 =
C1 - C16 Alkyl ist, 2) Umsetzung eines Alkohols R1-OH oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel,
3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem Alkoxylierungsmittel. C1 - C16 is alkyl, 2) reaction of an alcohol R 1 -OH or the reaction product from step 1) with glycidol or a mixture of glycidol and an alkoxylating agent, 3) optional reaction of the reaction product from step 2) with an alkoxylating agent.
Dabei ist es insbesondere bevorzugt, wenn das Verfahren die Schritte 1) und 3) umfasst, Schritte 1) und 3) also nicht optional sind, sondern zwingend vorhanden sind.It is particularly preferred if the method comprises steps 1) and 3), ie steps 1) and 3) are not optional, but are mandatory.
In einerweiteren besonders bevorzugten Ausführungsform werden erfindungsgemässe Makromonomere ohne die Verwendung von Epichlorhydrin und unter Verwendung eines Amins als Starter S hergestellt. Das Verfahren zur Herstellung ist also Epichlorhydrin-frei. Erfindungsgemässe Copolymere können demzufolge weiterhin besonders bevorzugt hergestellt werden in einem Verfahren umfassend die Schritte: In a further particularly preferred embodiment, macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of an amine as the starter S. The manufacturing process is therefore epichlorohydrin-free. Copolymers according to the invention can therefore also be produced particularly preferably in a process comprising the steps:
1) optional Umsetzung eines Amins R1-NH2 mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, oder Isoprenyl, ist, X = O oder NH, Hai = CI, Br oder I, und R2 = C1 - C16 Alkyl ist, 1) optional reaction of an amine R 1 -NH2 with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen can be, preferably vinyl, allyl, methallyl, vinyloxybutyl, or isoprenyl, X = O or NH, Hal = CI, Br or I, and R 2 = C1 - C16 alkyl,
2) Umsetzung eines Amins R1-NH2 oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel,2) Reaction of an amine R 1 -NH2 or the reaction product from step 1) with glycidol or a mixture of glycidol and an alkoxylating agent,
3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem Alkoxylierungsmittel. 3) optional reaction of the reaction product from step 2) with an alkoxylating agent.
Dabei ist es insbesondere bevorzugt, wenn das Verfahren Schritt 3) umfasst, Schritt 3) also nicht optional ist, sondern zwingend vorhanden ist. It is particularly preferred if the method comprises step 3), that is to say step 3) is not optional, but rather is mandatory.
In einerweiteren besonders bevorzugten Ausführungsform werden erfindungsgemässe Makromonomere ohne die Verwendung von Epichlorhydrin und unter Verwendung einer Carbonsäure als Starter S hergestellt. Das Verfahren zur Herstellung ist also Epichlorhydrin-frei. Erfindungsgemässe Copolymere können demzufolge weiterhin besonders bevorzugt hergestellt werden in einem Verfahren umfassend die Schritte: In a further particularly preferred embodiment, macromonomers according to the invention are prepared without the use of epichlorohydrin and with the use of a carboxylic acid as starter S. The manufacturing process is therefore epichlorohydrin-free. Copolymers according to the invention can therefore also be produced particularly preferably in a process comprising the steps:
1) optional Umsetzung einer Carbonsäure R1-OH mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Acryloyl und/oder
Methacryloyl, ist, X = O oder NH, Hai = CI, Br oder I, und R2 = C1 - C16 Alkyl ist, 1) optional reaction of a carboxylic acid R 1 -OH with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally substituted by oxygen can be, preferably acryloyl and / or Methacryloyl, is, X = O or NH, Hai = CI, Br or I, and R 2 = C1 - C16 alkyl,
2) Umsetzung einer Carbonsäure R1-OH oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel, 2) Reaction of a carboxylic acid R 1 -OH or the reaction product from step 1) with glycidol or a mixture of glycidol and an alkoxylating agent,
3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem Alkoxylierungsmittel. 3) optional reaction of the reaction product from step 2) with an alkoxylating agent.
Dabei ist es insbesondere bevorzugt, wenn das Verfahren die Schritte 1) und 3) umfasst, Schritte 1) und 3) also nicht optional sind, sondern zwingend vorhanden sind. In einer ganz besonders bevorzugten Ausführungsform werden erfindungsgemässe Makromonomere ohne die Verwendung von Epichlorhydrin und unter Verwendung eines Alkohols als Starter S hergestellt, wobei der Starter-Akohol zunächst mit einem Alkoxylierungsmittel umgesetzt wird. Das Verfahren zur Herstellung ist also Epichlorhydrin-frei. Erfindungsgemässe Makromonomere können demzufolge ganz besonders bevorzugt hergestellt werden in einem Verfahren umfassend die Schritte: It is particularly preferred if the method comprises steps 1) and 3), ie steps 1) and 3) are not optional, but are mandatory. In a very particularly preferred embodiment, macromonomers according to the invention are prepared without the use of epichlorohydrin and using an alcohol as starter S, the starter alcohol first being reacted with an alkoxylating agent. The manufacturing process is therefore epichlorohydrin-free. Macromonomers according to the invention can consequently be prepared very particularly preferably in a process comprising the steps:
1) Umsetzung eines Alkohols R1-OH mit einem Alkoxylierungsmittel, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl oder Isoprenyl, ist, 2) Umsetzung des Reaktionsproduktes aus Schritt 1) mit Glycidol oder einer1) Reaction of an alcohol R 1 -OH with an alkoxylating agent, where R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl or isoprenyl, 2) Reaction of the reaction product from step 1) with glycidol or a
Mischung aus Glycidol und einem Alkoxylierungsmittel, Mixture of glycidol and an alkoxylating agent,
3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem Alkoxylierungsmittel. 3) optional reaction of the reaction product from step 2) with an alkoxylating agent.
Dabei ist es insbesondere bevorzugt, wenn das Verfahren Schritt 3) umfasst, Schritt 3) also nicht optional ist, sondern zwingend vorhanden ist. It is particularly preferred if the method comprises step 3), that is to say step 3) is not optional, but rather is mandatory.
Erfindungsgemässe Copolymere können statistische oder nicht-statistische Copolymere sein. Nicht-statistische Copolymere sind insbesondere alternierende Copolymere oder Block- oder Gradienten-Copolymere. Copolymers according to the invention can be random or non-random copolymers. Non-random copolymers are in particular alternating copolymers or block or gradient copolymers.
Erfindungsgemässe Copolymere, welche statistische Copolymere sind, können durch freie radikalische Polymerisation von Mischungen umfassend mindestens ein olefinisch ungesättigtes Carbonsäure-Monomer sowie mindestens ein olefinisch
ungesättigtes Monomer der allgemeine Struktur (I) wie oben beschrieben hergestellt werden. Geeignete Bedingungen zur Durchführung der freien radikalischen Polymerisation sind dem Fachmann an sich bekannt und beispielsweise beschreiben in EP 1 103570 (Nippon Shokubai). Copolymers according to the invention, which are random copolymers, can be obtained by free radical polymerization of mixtures comprising at least one olefinically unsaturated carboxylic acid monomer and at least one olefinically unsaturated monomer of general structure (I) can be prepared as described above. Suitable conditions for carrying out the free radical polymerization are known per se to the person skilled in the art and are described, for example, in EP 1 103570 (Nippon Shokubai).
Erfindungsgemässe Copolymere, welche nicht-statistische Copolymere sind, insbesondere Block- oder Gradienten-Copolymere, können bevorzugt durch lebende freie radikalische Polymerisation hergestellt werden. Die Techniken der lebenden freien radikalischen Polymerisation sind unter anderem die Nitroxid-vermittelte- Polymerisation (NMP), die Atom-Transfer-Radikalpolymerisation (ATRP) oder die Reversible Additions-Fragmentierungs Kettenübertragungs-Polymerisation (RAFT).Copolymers according to the invention which are non-random copolymers, in particular block or gradient copolymers, can preferably be prepared by living free radical polymerization. Living free radical polymerization techniques include nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), or reversible addition-fragmentation chain transfer polymerization (RAFT).
Die lebende freie radikalische Polymerisation erfolgt im Wesentlichen unter Abwesenheit von irreversiblen Übertragungs- oder Abbruchreaktionen. Die Zahl der aktiven Kettenenden ist gering und bleibt während der Polymerisation im Wesentlichen konstant. Dies wird beispielsweise bei der RAFT-Polymerisation durch die Verwendung eines RAFT-Agens und einer nur geringen Menge an Initiator erreicht. Dadurch wird ein im Wesentlichen zeitgleiches und während des gesamten Polymerisationsprozesses anhaltendes Wachstum der Ketten ermöglicht. Dadurch ergibt sich die Möglichkeit, mit diesem Prozess Block- oder Gradienten- Copolymere herzustellen und es ergibt sich entsprechend eine enge Molekulargewichtsverteilung bzw. Polydispersität des Polymers. Dies ist bei der herkömmlichen "freien radikalischen Polymerisation" bzw. der nicht lebend durchgeführten freien radikalischen Polymerisation nicht möglich. Besonders vorteilhaft können nicht statistische Copolymere der vorliegenden Erfindung mittels RAFT-Polymerisation hergestellt werden. Vorteilhafte RAFT-Agentien sind Dithioester, Dithiocarbamat, Trithiocarbonat oder Xanthat. Living free radical polymerization essentially takes place in the absence of irreversible transfer or termination reactions. The number of active chain ends is low and remains essentially constant during the polymerization. This is achieved, for example, in RAFT polymerization through the use of a RAFT agent and only a small amount of initiator. This enables a substantially simultaneous and sustained growth of the chains during the entire polymerization process. This makes it possible to use this process to produce block or gradient copolymers and a correspondingly narrow molecular weight distribution or polydispersity of the polymer results. This is not possible in the case of conventional "free radical polymerization" or free radical polymerization which is not carried out alive. Particularly advantageously, non-random copolymers of the present invention can be prepared by means of RAFT polymerization. Advantageous RAFT agents are dithioesters, dithiocarbamate, trithiocarbonate or xanthate.
Vorteilhafte Initiatoren sind Azobisisobutyronitril (AIBN), a,a'-Azodiisobutyramidine dihydrochloride (AAPH) oder Azo-bis-isobutyramidin (AIBA). Advantageous initiators are azobisisobutyronitrile (AIBN), a, a'-azodiisobutyramidine dihydrochloride (AAPH) or azo-bis-isobutyramidine (AIBA).
Die Herstellung erfindungsgemässer Copolymere durch freie radikalische Polymerisation oder durch lebende freie radikalische Polymerisation erfolgt in einer besonders bevorzugten Ausführungsform direkt im Anschluss an die Herstellung des mindestens einen olefinisch ungesättigten Makromonomeren der allgemeinen Struktur (I). Ein weiterer Aspekt der vorliegenden Erfindung betrifft daher einen mehrstufigen Prozess zur Herstellung eines Copolymer zur Verwendung als Dispergiermittel von mineralischen Bindemitteln. Ein besonders bevorzugtes Verfahren zur Herstellung von erfindungsgemässen Copolymeren umfasst daher die Schritte:
1) optional Umsetzung eines Starters S, ausgewählt aus der Gruppe bestehend aus Alkoholen, Aminen, Carbonsäuren oder Amiden der allgemeinen Formel R1-XH, mit einem Alkoxylierungsmittel und/oder einem halogenierten Alkohol oder halogenierten Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, X = O oder NH, Hai = CI, Br oder I, und R2 = C1 - C16 Alkyl ist, The production of copolymers according to the invention by free radical polymerization or by living free radical polymerization takes place in a particularly preferred embodiment directly after the production of the at least one olefinically unsaturated macromonomer of the general structure (I). Another aspect of the present invention therefore relates to a multistage process for producing a copolymer for use as a dispersant for mineral binders. A particularly preferred process for the preparation of copolymers according to the invention therefore comprises the steps: 1) optional reaction of a starter S, selected from the group consisting of alcohols, amines, carboxylic acids or amides of the general formula R 1 -XH, with an alkoxylating agent and / or a halogenated alcohol or halogenated amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which can optionally be substituted by oxygen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, X = O or NH, Hal = CI , Br or I, and R 2 = C1 - C16 alkyl,
2) Umsetzung eines Startes S oder des Reaktionsproduktes aus Schritt 1) mit Glycidol oder Epichlorhydrin oder einer Mischung aus Glycidol und einem Alkoxylierungsmittel oder einer Mischung aus Epichlorhydrin und einem Alkoxylierungsmittel, 2) Implementation of a start S or the reaction product from step 1) with glycidol or epichlorohydrin or a mixture of glycidol and an alkoxylating agent or a mixture of epichlorohydrin and an alkoxylating agent,
3) optional Umsetzung des Reaktionsproduktes aus Schritt 2) mit einem Alkoxylierungsmittel, und 4) radikalische Polymerisation eines Gemisches aus mindestens einem olefinisch ungesättigen Carbonsäure-Monomer mit dem Reaktionsprodukt aus Schritt 3) oder, falls dieser nicht Teil des Verfahrens ist, mit dem Reaktionsprodukt aus Schritt 2). 3) optional reaction of the reaction product from step 2) with an alkoxylating agent, and 4) radical polymerization of a mixture of at least one olefinically unsaturated carboxylic acid monomer with the reaction product from step 3) or, if this is not part of the process, with the reaction product Step 2).
Dabei ist es insbesondere bevorzugt, wenn das Verfahren die Schritte 1) und 3) umfasst, Schritte 1) und 3) also nicht optional sind, sondern zwingend vorhanden sind.It is particularly preferred if the method comprises steps 1) and 3), ie steps 1) and 3) are not optional, but are mandatory.
Besonders bevorzugt umfasst das Verfahren keine Schritte zur Aufarbeitung und/oder Reinigung von Zwischenprodukten. Allerdings müssen Katalysatoren und/oder Neutralisationsreagentien, welche in den Schritten 1) bis 3) eingesetzt werden und welche die radikalische Polymerisation behindern können entfernt oder abreagiert werden. Insbesondere können dies solche Katalysatoren und/oder Neutralisationsreagentien sein, welche mit Aktivatoren, Initiatoren, und/oder Regulatoren, wie Kettenübertragungsragentien oder RAFT-Agentien, der radikalischen Polymerisation wechselwirken. The process particularly preferably does not include any steps for working up and / or purifying intermediate products. However, catalysts and / or neutralization reagents which are used in steps 1) to 3) and which can hinder the free radical polymerization must be removed or reacted. In particular, these can be catalysts and / or neutralization reagents which interact with activators, initiators, and / or regulators, such as chain transfer agents or RAFT agents, of free-radical polymerization.
Entsprechend einer besonders bevorzugten Ausführungsform wird die radikalische Polymerisation als Lösungspolymerisation, insbesondere in einem Lösemittel enthaltend Wasser, durchgeführt. Es ist ganz besonders bevorzugt, die Polymerisation in reinem Wasser durchzuführen.
Es ist bevorzugt, die radikalische Polymerisation zur Herstellung von erfindungsgemässen Copolymeren bis zu einem Umsatz von mindestens 75%, bevorzugt mindestens 80 %, mehr bevorzugt mindestens 90%, ganz besonders bevorzugt mindestens 95%, im Speziellen mindestens 98% oder mehr, jeweils bezogen auf die gesamte Stoffmenge der vorhandenen Monomeren, zu fahren. According to a particularly preferred embodiment, the free-radical polymerization is carried out as a solution polymerization, in particular in a solvent containing water. It is very particularly preferred to carry out the polymerization in pure water. It is preferred to use the free-radical polymerization for the preparation of copolymers according to the invention up to a conversion of at least 75%, preferably at least 80%, more preferably at least 90%, very particularly preferably at least 95%, in particular at least 98% or more, based on the total amount of substance of the monomers present to drive.
Erfindungsgemässe Copolymere können in flüssiger Form, beispielsweise in Form einer Lösung oder Dispersion, insbesondere in Form einer wässrigen Lösung vorliegen. Es ist bevorzugt, wenn erfindungsgemässe Copolymere einen Anteil an einer Lösung oder Dispersion, insbesondere einer wässrigen Lösung, von wenigstens 30 Gew.-%, bevorzugt wenigstens 40 Gew.-%, besonders bevorzugt wenigstens 50 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Lösung oder Dispersion, haben.Copolymers according to the invention can be in liquid form, for example in the form of a solution or dispersion, in particular in the form of an aqueous solution. It is preferred if copolymers according to the invention have a proportion of a solution or dispersion, in particular an aqueous solution, of at least 30% by weight, preferably at least 40% by weight, particularly preferably at least 50% by weight, based in each case on the total weight the solution or dispersion.
Es ist ebenfalls möglich, erfindungsgemässe Copolymere in eine feste Form, bevorzugt eine Pulverform, zu überführen. Geeignete Methoden sind beispielsweise das Aufziehen auf einen festen Träger und/oder die Trocknung einer Lösung oder Dispersion enthaltend erfindungsgemässe Copolymere. Ein geeignetes Verfahren zur Trocknung ist beispielsweise die Sprühtrocknung. Ein mehrstufiger Prozess zur Herstellung eines erfindungsgemässen Copolymeren kann daher einen Schritt zur Trocknung, insbesondere Sprühtrocknung des Copolymeren enthalten. Pulverförmige erfindungsgemässe Copolymere können einem mineralischen Bindemittel oder einer mineralischen Bindemittelzusammensetzung beigegeben werden, beispielsweise zur Herstellung einer Trockenmörtelmischung. It is also possible to convert copolymers according to the invention into a solid form, preferably a powder form. Suitable methods are, for example, the application to a solid support and / or the drying of a solution or dispersion containing copolymers according to the invention. A suitable method for drying is, for example, spray drying. A multistage process for producing a copolymer according to the invention can therefore contain a step for drying, in particular spray drying, the copolymer. Powdered copolymers according to the invention can be added to a mineral binder or a mineral binder composition, for example to produce a dry mortar mixture.
Die Verwendung erfindungsgemässer Copolymere in mineralischen Bindemitteln oder mineralischen Bindemittelzusammensetzungen erfolgt zum Zwecke der Verbesserung deren Fliessverhalten und/oder deren Viskosität. Dies bedeutet, dass eine mineralische Bindemittelzusammensetzung enthaltend mindestens ein erfindungsgemässes Copolymer besser fliesst, also ein höheres Ausbreitmass gemessen nach DIN EN 12350-5 zeigt, als dieselbe mineralische Bindemittelzusammensetzung ohne erfindungsgemässes Copolymer. Dies bedeutet gleichzeitig, dass durch die Verwendung eines erfindungsgemässen Copolymeren in einer mineralischen Bindemittelzusammensetzung die Menge an Wasser, die zur Einstellung eines bestimmten Ausbreitmasses benötigt wird, kleiner ist, als bei einer entsprechenden Zusammensetzung ohne erfindungsgemässes Copolymer. Weiter führt die Verwendung eines erfindungsgemässen Copolymers in einer mineralischen Bindemittelzusammensetzung zu einer Verringerung der Viskosität, gemessen als eine Verringerung der Trichterauslaufzeit nach Norm DIN EN 12350-9, im Vergleich
zu einer entsprechenden Zusammensetzung ohne erfindungsgemässes Copolymer. Beide Eigenschaften sind gleichermassen wichtig, um optimale Verarbeitungseigenschaften von mineralischen Bindemittelzusammensetzungen zu erreichen. The copolymers according to the invention are used in mineral binders or mineral binder compositions for the purpose of improving their flow behavior and / or their viscosity. This means that a mineral binder composition containing at least one copolymer according to the invention flows better, that is to say shows a higher slump measured according to DIN EN 12350-5, than the same mineral binder composition without the copolymer according to the invention. At the same time, this means that the use of a copolymer according to the invention in a mineral binder composition means that the amount of water required to set a certain slump is smaller than with a corresponding composition without the copolymer according to the invention. Furthermore, the use of a copolymer according to the invention in a mineral binder composition leads to a reduction in viscosity, measured as a reduction in the funnel flow time according to standard DIN EN 12350-9, in comparison to a corresponding composition without a copolymer according to the invention. Both properties are equally important in order to achieve optimal processing properties of mineral binder compositions.
Desweiteren führt die Verwendung eines erfindungsgemässen Copolymers in einer mineralischen Bindemittelzusammensetzung zu einem besonders niedrigen Lufteintrag. Der Lufteintrag wird gemessen nach Norm DIN EN 12350-7. Dies ist insbesondere für die Erreichung einer hohen Endfestigkeit wichtig. Darüber hinaus führt diese Eigenschaft auch dazu, dass erfindungsgemässe Copolymere mit gängigen Luftporenbildnern kombiniert werden können, ohne deren Wirksamkeit zu beeinflussen. Der Eintrag einer gewünschten Menge an Luft und damit einer bestimmten Luftporenverteilung wird dadurch auf einfache Weise gewährleistet, ohne dass eine Abstimmung der Art und Menge des Luftporenbildners auf das Dispergiermittel erfolgen muss. Furthermore, the use of a copolymer according to the invention in a mineral binder composition leads to particularly low air entrainment. The air intake is measured in accordance with the DIN EN 12350-7 standard. This is particularly important for achieving a high final strength. In addition, this property also means that copolymers according to the invention can be combined with common air-entraining agents without influencing their effectiveness. The entry of a desired amount of air and thus a certain air pore distribution is ensured in a simple manner without the need to match the type and amount of the air-entraining agent to the dispersant.
Ein weiterer Aspekt der vorliegenden Erfindung ist daher ein mineralisches Bindemittel oder eine mineralische Bindemittelzusammensetzung umfassend mindestens ein mineralisches Bindemittel, bevorzugt Zement, sowie mindestens ein erfindungsgemässes Copolymer. A further aspect of the present invention is therefore a mineral binder or a mineral binder composition comprising at least one mineral binder, preferably cement, and at least one copolymer according to the invention.
Die mineralischen Bindemittel sowie erfindungsgemässe Copolymere sind wie oben beschreiben. Es ist möglich und in manchen Fällen auch bevorzugt, dass Mischungen aus zwei oder mehr erfindungsgemässen Copolymeren, welche sich chemisch und/oder strukturell unterscheiden, verwendet werden. The mineral binders and copolymers according to the invention are as described above. It is possible and in some cases also preferred that mixtures of two or more copolymers according to the invention which differ chemically and / or structurally are used.
Bei der mineralischen Bindemittelzusammensetzung handelt es sich bevorzugt um eine Mörtel- oder Betonzusammensetzung. The mineral binder composition is preferably a mortar or concrete composition.
Die mineralische Bindemittelzusammensetzung kann mit Wasser angemacht werden und/oder Wasser enthalten. Das Verhältnis von Wasser zu mineralischem Bindemittel liegt im Bereich von 0.18 - 0.7, bevorzugt 0.2 - 0.6, besonders bevorzugt 0.25 - 0.5, ganz besonders bevorzugt 0.3 - 0.45. In ganz besonders bevorzugten Ausführungsformen ist das mineralische Bindemittel ein Zement, das Verhältnis von Wasser zu mineralischem Bindemittel entspricht dann dem w/z-Wert. The mineral binder composition can be made up with water and / or contain water. The ratio of water to mineral binder is in the range from 0.18-0.7, preferably 0.2-0.6, particularly preferably 0.25-0.5, very particularly preferably 0.3-0.45. In very particularly preferred embodiments, the mineral binder is a cement, the ratio of water to mineral binder then corresponds to the w / c value.
Das erfindungsgemässe Copolymer ist in einem mineralischen Bindemittel oder einer mineralischen Bindemittelzusammensetzung mit Vorteil mit einem Anteil von 0.01 - 10 Gew.-%, bevorzugt 0.05 - 7 Gew.-%, besonders bevorzugt 0.1 - 5 Gew.-%, ganz
besonders bevorzugt 0.2 - 3 Gew.-%, insbesondere 0.2 - 1 Gew.-%, jeweils bezogen auf den Gehalt an mineralischem Bindemittel, vorhanden. In a mineral binder or a mineral binder composition, the copolymer according to the invention is advantageously whole in a proportion of 0.01-10% by weight, preferably 0.05-7% by weight, particularly preferably 0.1-5% by weight particularly preferably 0.2-3% by weight, in particular 0.2-1% by weight, based in each case on the mineral binder content.
Es ist möglich, ein erfindungsgemässes Copolymer als solches, beispielsweise in Pulverform, zu einer mineralischen Bindemittelzusammensetzung zu geben. Es ist aber auch möglich, ein erfindungsgemässes Copolymer als wässrige Lösung oder Dispersion in Wasser zu einer mineralischen Bindemittelzusammensetzung zu geben. Weiter ist es möglich, ein erfindungsgemässes Copolymer in einem Zusatzmittel, insbesondere einem wässrigen Zusatzmittel, zu lösen oder zu dispergieren. It is possible to add a copolymer according to the invention as such, for example in powder form, to a mineral binder composition. However, it is also possible to add a copolymer according to the invention as an aqueous solution or dispersion in water to a mineral binder composition. It is also possible to dissolve or disperse a copolymer according to the invention in an additive, in particular an aqueous additive.
Ein weiterer Aspekt der vorliegenden Erfindung ist daher ein Zusatzmittel umfassend mindestens ein erfindungsgemässes Copolymer. Zusätzlich kann das Zusatzmittel weitere gängige Zusatzmittel für mineralische Bindemittelzusammensetzungen enthalten. Solche gängigen Zusatzmittel sind vorteilhaft ausgewählt aus der Liste bestehend aus Verflüssigern, Luftporenbildnern, Entschäumern, Beschleunigern, Verzögerern, Schwundreduzierern, Aktivatoren, Dichtungsmittel, Stabilisierer, Verdicker, Chromatreduzierer, Korrosionsinhibitoren, Hydrophobisierungsmitteln, Pigmenten, Fasern und Bioziden. Another aspect of the present invention is therefore an additive comprising at least one copolymer according to the invention. In addition, the additive can contain other common additives for mineral binder compositions. Such common additives are advantageously selected from the list consisting of liquefiers, air-entraining agents, defoamers, accelerators, retarders, shrinkage reducers, activators, sealants, stabilizers, thickeners, chromate reducers, corrosion inhibitors, hydrophobizing agents, pigments, fibers and biocides.
In einer besonderen Ausführungsform wird mindestens ein erfindungsgemässes Copolymere mit einem oder mehreren herkömmlichen Verflüssigern auf Basis Polycarboxylatether (PCE) in einem Zusatzmittel verwendet. Geeignete PCE werden beispielsweise beschrieben in EP0753488, EP1138697, EP1179517 und EP1966258. Es ist möglich, das mindestens eine erfindungsgemässe Copolymere mit einem oder mehreren Verflüssigern auf Basis PCE zu einer Komponenten zu vermischen und diese einer mineralischen Bindemittelzusammensetzung zuzugeben. Es ist aber auch möglich, das mindestens eine erfindungsgemässe Copolymere und einen oder mehrere Verflüssiger auf Basis PCE einer mineralischen Bindemittelzusammensetzung jeweils separat zuzugeben. In a particular embodiment, at least one copolymer according to the invention is used with one or more conventional plasticizers based on polycarboxylate ethers (PCE) in an additive. Suitable PCEs are described, for example, in EP0753488, EP1138697, EP1179517 and EP1966258. It is possible to mix the at least one copolymer according to the invention with one or more plasticizers based on PCE to form a component and to add this to a mineral binder composition. However, it is also possible to add the at least one copolymer according to the invention and one or more plasticizers based on PCE to a mineral binder composition each separately.
Ein letzter Aspekt der vorliegenden Erfindung ist ein Formkörper, erhältlich durch Aushärten eines mineralischen Bindemittels oder einer mineralischen Bindemittelzusammensetzung umfassend mindestens ein erfindungsgemässes Copolymer. Der Formkörper kann beispielsweise ein Betonteil, z.B. ein Betonfertigteil oder ein Betonstein, sein, eine ausgehärtete Mörtelmischung, z.B. Fugenmörtel oder ein Estrich, sein und/oder Teil eines Bauwerkes, z.B. einer Brücke oder eines Tunnels, sein.
Im Folgenden wird die Erfindung durch Beispiele näher erläutert. Die Beispiele dienen jedoch nur der Veranschaulichung und sind nicht als Einschränkung des Umfangs der Erfindung anzusehen. BEISPIELE A final aspect of the present invention is a shaped body obtainable by curing a mineral binder or a mineral binder composition comprising at least one copolymer according to the invention. The shaped body can for example be a concrete part, for example a precast concrete part or a concrete block, a hardened mortar mixture, for example joint mortar or a screed, and / or part of a structure, for example a bridge or a tunnel. The invention is explained in more detail below by means of examples. However, the examples are for illustrative purposes only and should not be construed as limiting the scope of the invention. EXAMPLES
Svnthesebeispiel 1: Herstellung des Makromonomeren M-1 Synthesis Example 1: Preparation of Macromonomer M-1
Schritt 1: In einem mit I h-Gas inertisierten Reaktor werden 4 g (0.074 mol) Natriummethylat in 464 g (8 mol) Allylalkohol gelöst und auf 100°C geheizt. Danach werden während 5 Stunden 1760 g (40 mol) Ethylenoxid zudosiert. Dabei wird die Temperatur bei 100 bis 140°C und der Druck bei 1 bis 3 bar gehalten. NachStep 1: 4 g (0.074 mol) of sodium methylate are dissolved in 464 g (8 mol) of allyl alcohol in a reactor which has been rendered inert with 1 h gas and the mixture is heated to 100.degree. Then 1760 g (40 mol) of ethylene oxide are metered in over 5 hours. The temperature is kept at 100 to 140 ° C and the pressure at 1 to 3 bar. To
Beendigung der Dosierung wird das Reaktionsgemisch 2 Stunden bei 140°C gerührt. Anschliessend wird das Gemisch auf 30°C gekühlt. At the end of the metering, the reaction mixture is stirred at 140 ° C. for 2 hours. The mixture is then cooled to 30.degree.
Schritt 2: In einem mit N2-Gas inertisierten Reaktor werden 117 g (0.42 mol) des Gemisches aus Schritt 1) mit 0.54 g (0.01 mol) Natriummethylat versetzt und auf 130°C erhitzt. Danach werden während 30 Minuten 93 g (1.26 mol) Glycidol zudosiert.Step 2: In a reactor rendered inert with N2 gas, 117 g (0.42 mol) of the mixture from step 1) are mixed with 0.54 g (0.01 mol) of sodium methylate and heated to 130.degree. Then 93 g (1.26 mol) of glycidol are metered in over a period of 30 minutes.
Dabei werden die Temperatur bei 130 bis 140°C und der Druck bei 1 bis 3 bar gehalten. Nach Beendigung der Dosierung wird das Reaktionsgemisch 2 Stunden bei 140°C gerührt. Man lässt auf 50 °C abkühlen. The temperature is kept at 130 to 140 ° C and the pressure at 1 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 2 hours. It is allowed to cool to 50 ° C.
Schritt 3: Nach dem Abkühlen auf 50°C werden zu dem Gemisch aus Schritt 2) 2.2 g (0.04 mol) Natriummethylat zugegeben. Der Reaktor wird erneut mit N2-Gas inertisiert und auf 130°C geheizt. Danach werden während 4 Stunden 628 g (14.27 mol) Ethylenoxid zudosiert. Dabei werden die Temperatur bei 130 bis 140°C und der Druck bei 0 bis 3 bar gehalten. Nach Beendigung der Dosierung wird das Reaktionsgemisch 3 Stunden bei 140°C gerührt. Anschliessend wird das Gemisch auf 50°C gekühlt und mit 3.2 g (0.054 mol) Essigsäure neutralisiert. Die erhaltene Mischung ist das Makromonomer M-1. Step 3: After cooling to 50 ° C., 2.2 g (0.04 mol) of sodium methylate are added to the mixture from step 2). The reactor is again rendered inert with N2 gas and heated to 130.degree. Then 628 g (14.27 mol) of ethylene oxide are metered in over 4 hours. The temperature is kept at 130 to 140 ° C and the pressure at 0 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 3 hours. The mixture is then cooled to 50 ° C. and neutralized with 3.2 g (0.054 mol) of acetic acid. The resulting mixture is macromonomer M-1.
Svnthesebeispiel 2: Herstellung des Copolymeren C-1 Synthesis Example 2: Preparation of Copolymer C-1
In einem mit N2-Gas inertisierten Reaktor werden 70 g Wasser, 57 g (0.05 mol) des Makromonomeren M-1, 27 g (0.05 mol) eines Allylalkohol-gestarteten Polyethylenglykols (11 EO-Einheiten), 26 g (0.36 mol) Acrylsäure, 50 g einer 16% wässrigen NaOH-Lösung, 0.8 g einer 10% wässrigen Lösung von Fe(ll)S04 7 H2O und 1.1 g Natriumhypophosphit vorgelegt. Unter Rühren werden tropfenweise 5.5 g einer 30% wässrigen Wasserstoffperoxidlösung und 2.3 g einer 5% wässrigen
Rongalitlösung innerhalb von 70 min bei einer Temperatur von 20 - 35 °C gleichzeitig zugegeben. 120 min nach Beginn der Zugabe erhält man eine klare Lösung des Copolymeren C-1. In a reactor rendered inert with N2 gas, 70 g of water, 57 g (0.05 mol) of the macromonomer M-1, 27 g (0.05 mol) of an allyl alcohol-started polyethylene glycol (11 EO units), 26 g (0.36 mol) of acrylic acid are added , 50 g of a 16% aqueous NaOH solution, 0.8 g of a 10% aqueous solution of Fe (II) S0 4 7 H2O and 1.1 g of sodium hypophosphite. 5.5 g of a 30% aqueous hydrogen peroxide solution and 2.3 g of a 5% aqueous solution are added dropwise with stirring Rongalit solution was added simultaneously within 70 min at a temperature of 20 - 35 ° C. A clear solution of the copolymer C-1 is obtained 120 minutes after the start of the addition.
Die folgende Tabelle gibt einen Überblick über die verwendeten Copolymere. Tabelle 1: Verwendete Copolymere
The following table gives an overview of the copolymers used. Table 1: Copolymers used
Anwendunqsbeispiel 1: Mörtelprüfunq Application example 1: Mortar test
Es wurde eine Trockenmischung hergestellt bestehend aus 150 g Zement (CEM IA dry mix was prepared consisting of 150 g cement (CEM I
42.5 N von Vigier Holding AG), 5.8 g Mikrosilika (SikaFume® -HR/-TU, erhältlich von Sika Schweiz AG), 69.2 g Hochofenschlacke (Regen GGBS von Hanson UK) und42.5 N from Vigier Holding AG), 5.8 g microsilica (SikaFume® -HR / -TU, available from Sika Schweiz AG), 69.2 g blast furnace slag (Regen GGBS from Hanson UK) and
41.5 g Kalkstein (Nekafill 15 von Kalkfabrik Netstal AG). Zur Herstellung der Trockenmischung wurden die Bestandteile in einem Hobartmischer trocken für 30 Sekunden vermischt. Zu dieser Trockenmischung wurden die in Tabelle 2 angegebenen Zusatzmittel, jeweils gelöst in 60 g Wasser gegeben. Es wurde für 30 Sekunden auf Stufe 1 weitergemischt, abschliessend wurde für 3.5 Minuten auf Stufe 2 weitergemischt. 41.5 g limestone (Nekafill 15 from Kalkfabrik Netstal AG). To prepare the dry mix, the ingredients were dry blended in a Hobart mixer for 30 seconds. The additives indicated in Table 2, each dissolved in 60 g of water, were added to this dry mixture. Mixing was continued for 30 seconds at level 1, then mixing was continued for 3.5 minutes at level 2.
An den erhaltenen Mörtel wurden das Ausbreitmass gemäss DIN EN 12350-5 gemessen. Ausserdem wurde die Trichterauslaufzeit gemäss DIN EN 12350-9 gemessen. Der Luftgehalt wurde 30 Minuten nach dem Anmachen gemäss Norm DIN EN 12350- 7 ermittelt. The slump was measured on the mortar obtained in accordance with DIN EN 12350-5. In addition, the funnel discharge time was measured in accordance with DIN EN 12350-9. The air content was determined 30 minutes after mixing in accordance with the DIN EN 12350-7 standard.
Die folgende Tabelle gibt einen Überblick über die Ergebnisse.
Tabelle 2: Ergebnisse der Mörtelprüfungen
The following table gives an overview of the results. Table 2: Results of the mortar tests
* Dosierung in Gew.-% relativ zum Trockengewicht des Zementes * Dosage in% by weight relative to the dry weight of the cement
LP: Luftporenbildner bestehend aus 1 Gew.-% Aluminiumpulver (Partikelgrösse D50 = 5 pm, Siebrückstand bei 45 pm von < 0.1 Gew.-%), 0.5 Gew.-% destilliertes T allöl, 98.5 Gew.-% Calciumcarbonat-Pulver.
LP: Air-entraining agent consisting of 1% by weight aluminum powder (particle size D50 = 5 μm, sieve residue at 45 μm of <0.1% by weight), 0.5% by weight distilled tale oil, 98.5% by weight calcium carbonate powder.
Claims
1. Verwendung von Copolymeren als Dispergiermittel für mineralische Bindemittel, wobei die Copolymere aufgebaut sind aus (1) mindestens einem olefinisch ungesättigten Carbonsäure-Monomer 1. Use of copolymers as dispersants for mineral binders, the copolymers being built up from (1) at least one olefinically unsaturated carboxylic acid monomer
(2) mindestens einem olefinisch ungesättigten Makromonomer der allgemeinen Struktur (I)
wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff und/oder Stickstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, (2) at least one olefinically unsaturated macromonomer of the general structure (I) where R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O oder NH ist, X = O or NH,
A jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen und/oder Butylen sind, A are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
R2 = C1-C16 Alkyl ist, R 2 = C1-C16 alkyl,
B jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen, Propylen und/oder Butylen sind, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 0 - 350, bevorzugt 2 - 200, besonders bevorzugt 5 - 150, im Speziellen 7 - 30 sind, n eine ganze Zahl im Bereich von 0 - 100, bevorzugt 1 - 100, besonders bevorzugt 2 - 75, ganz besonders bevorzugt 5 - 55 ist, p gleich 0 oder 1, bevorzugt 0 ist, o eine ganze Zahl im Bereich von 1 - 50, bevorzugt 3 - 40, besonders bevorzugt 6 - 30, im Speziellen 8 - 20 ist, und q eine ganze Zahl im Bereich von 1 - 10 ist. B are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene, m are each independently an integer in the range from 0-350, preferably 2-200, particularly preferably 5-150, especially 7-30 , n is an integer in the range from 0 - 100, preferably 1 - 100, particularly preferably 2 - 75, very particularly preferably 5 - 55, p is 0 or 1, preferably 0, o is an integer in the range from 1 - 50, preferably 3-40, particularly preferably 6-30, especially 8-20, and q is an integer in the range 1-10.
2. Verwendung von Copolymeren gemäss Anspruch 1, dadurch gekennzeichnet, dass das mindestens eine ungesättigte Carbonsäure-Monomer ein Monomer der allgemeinen Strukturen (lla) oder (Mb) ist
wobei R3 = H oder eine C1-C6-Alkylkette ist, R4 = H, C(0)Y, oder eine C1-C6-Alkylkette ist, bevorzugt H ist, und 2. Use of copolymers according to claim 1, characterized in that the at least one unsaturated carboxylic acid monomer is a monomer of the general structures (Ila) or (Mb) where R 3 = H or a C1-C6-alkyl chain, R 4 = H, C (0) Y, or a C1-C6-alkyl chain, is preferably H, and
Y = OM, mit M ausgewählt aus H, Alkalimetallen, Erdalkalimetallen oder organischem Ammonium, oder Y = NR4R5, mit R4 und R5 unabhängig voneinander gleich H oder eine C1-C6-Alkylkette, ist;
wobei Z = O oder NR5 ist und R3 die vorstehenden Bedeutungen hat, und R5 = H oder eine C1-C6-Alkylkette ist. Y = OM, with M selected from H, alkali metals, alkaline earth metals or organic ammonium, or Y = NR 4 R 5 , with R 4 and R 5 independently of one another being H or a C1-C6-alkyl chain; where Z = O or NR 5 and R 3 has the above meanings, and R 5 = H or a C1-C6-alkyl chain.
3. Verwendung von Copolymeren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass in der allgemeinen Struktur (I) 3. Use of copolymers according to claim 1 or 2, characterized in that in the general structure (I)
R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff und/oder Stickstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, R 1 is an olefinically unsaturated radical with 2 - 10 carbon atoms, which can optionally be substituted by oxygen and / or nitrogen, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl,
X = O ist, A jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen sind,X = O, A are each independently C1-C10 alkylene, preferably ethylene,
B jeweils unabhängig voneinander C1-C10 Alkylen, bevorzugt Ethylen sind, p = 0 ist, m jeweils unabhängig voneinander eine ganze Zahl im Bereich von 5 - 150 sind, n eine ganze Zahl im Bereich von 5 - 55 ist, o eine ganze Zahl im Bereich von 8 - 50 ist, und q eine ganze Zahl im Bereich von 1 - 10 ist.
B are each independently C1-C10 alkylene, preferably ethylene, p = 0, m are each independently an integer in the range from 5 to 150, n is an integer in the range from 5 to 55, o is an integer im Is the range 8-50 and q is an integer in the range 1-10.
4. Verwendung von Copolymeren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Anteil an Ethylenoxid-Einheiten in den Polyalkylenoxid-Ketten (AO)m und (BO)m, bezogen auf sämtliche vorhandenen Alkylenoxid-Einheiten AO und BO, mehr als 90 Mol-%, insbesondere mehr als 95 Mol-%, bevorzugt mehr als 98 Mol-%, im Speziellen 100 Mol-% beträgt. 4. Use of copolymers according to one of the preceding claims, characterized in that the proportion of ethylene oxide units in the polyalkylene oxide chains (AO) m and (BO) m , based on all alkylene oxide units AO and BO present, is more than 90 Mol%, in particular more than 95 mol%, preferably more than 98 mol%, in particular 100 mol%.
5. Verwendung von Copolymeren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das molare Verhältnis des mindestens einen olefinisch ungesättigten Carbonsäure-Monomers zu dem mindestens einen olefinisch ungesättigten Makromonomer der allgemeinen Struktur (I) im Bereich von 0.3 - 30, bevorzugt 0.6 - 10, besonders bevorzugt 1 - 4.5, insbesondere 1 - 3 liegt. 5. Use of copolymers according to one of the preceding claims, characterized in that the molar ratio of the at least one olefinically unsaturated carboxylic acid monomer to the at least one olefinically unsaturated macromonomer of the general structure (I) is in the range from 0.3-30, preferably 0.6-10 , particularly preferably 1-4.5, in particular 1-3.
6. Verwendung von Copolymeren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Copolymere weitere Monomere M umfassen, welche ausgewählt sind aus der Gruppe umfassend Styrol, Ethylen, Propylen, Butylen, Butadien, Isopren, Vinylacetat, Vinylchlorid, Acrylonitril, N- Vinylpyrrolidon, Hydroxyalkyl(meth)acrylaten und/oder Monomeren der allgemeinen Strukturen (VI)
wobei 6. Use of copolymers according to one of the preceding claims, characterized in that the copolymers comprise further monomers M which are selected from the group comprising styrene, ethylene, propylene, butylene, butadiene, isoprene, vinyl acetate, vinyl chloride, acrylonitrile, N-vinylpyrrolidone , Hydroxyalkyl (meth) acrylates and / or monomers of the general structures (VI) in which
R6, jeweils unabhängig voneinander H, -CH2-COOM oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, bevorzugt H oder -CH3, ist, R 6 , each independently of one another, is H, -CH 2 -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H or -CH 3 ,
R7, jeweils unabhängig voneinander H oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, bevorzugt H, ist, R 7 , each independently of one another, is H or an alkyl group having 1 to 5 carbon atoms, preferably H,
R8, jeweils unabhängig voneinander H, -COOM oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, bevorzugt H, ist, r = 0, 1 oder 2 ist, s = 0 oder 1 ist, t = 0, oder eine ganze Zahl von 1 bis 4 ist, u = 2 - 250, insbesondere 10 - 200 ist,
X, jeweils unabhängig voneinander -O- oder -NH- ist, R 8 , each independently of one another, is H, -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H, r = 0, 1 or 2, s = 0 or 1, t = 0, or an integer of 1 to 4, u = 2 - 250, in particular 10 - 200, X, in each case independently of one another, is -O- or -NH-,
R9, jeweils unabhängig voneinander H, eine Cr bis C2o-Alkylgruppe, - Cyclohexylgruppe oder -Alkylarylgruppe ist, und D = C2- bis C4-Alkylen, bevorzugt Ethylen ist. R 9 is , independently of one another, H, a C1 to C2o-alkyl group, - cyclohexyl group or -alkylaryl group, and D = C2- to C4-alkylene, preferably ethylene.
7. Verwendung von Copolymeren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das olefinisch ungesättigte Monomer der allgemeinen Struktur (I) eine mittlere Molmasse Mw der Copolymere im Bereich von 1Ό00 - 1Ό00Ό00, besonders bevorzugt 1‘500 - 500Ό00, ganz besonders bevorzugt 2Ό00 - 100Ό00, insbesondere 3Ό00 - 75Ό00 oder 3Ό00 - 50Ό00 hat. 7. Use of copolymers according to one of the preceding claims, characterized in that the olefinically unsaturated monomer of the general structure (I) has an average molar mass Mw of the copolymers in the range from 1Ό00-1 --00Ό00, particularly preferably 1,500–500,000, very particularly preferably 2,000 - 100,000, in particular 3,000-75,000 or 3,000-50,000.
8. Verwendung gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das mineralische Bindemittel ausgewählt ist aus der Gruppe umfassend Zement, insbesondere Portlandzement und Aluminatzement, a-Calciumsulfathemihydrat, ß-Calciumsulfathemihydrat, Anhydrit, Kalk, industrielle und synthetische Schlacken, insbesondere Hochofenschlacken, Hüttensand, Hüttensandmehl, elektrothermische Phosphorschlacke, Kupferschlacke und Edelstahlschlacke, Puzzolane, insbesondere Flugaschen, Mikrosilika, Metakaolin, natürlich Puzzolane, insbesondere Tuff, Trass und8. Use according to one of the preceding claims, characterized in that the mineral binder is selected from the group comprising cement, in particular portland cement and aluminate cement, α-calcium sulfate hemihydrate, ß-calcium sulfate hemihydrate, anhydrite, lime, industrial and synthetic slag, especially blast furnace slag, blast furnace slag , Granulated blast furnace slag, electrothermal phosphorus slag, copper slag and stainless steel slag, pozzolans, in particular fly ash, microsilica, metakaolin, of course pozzolans, in particular tuff, trass and
Vulkansche, natürliche und synthetische Zeolithe, gebrannten Ölschiefer sowie Mischungen davon. Volcanic, natural and synthetic zeolites, burnt oil shale and mixtures thereof.
9. Verwendung gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Copolymere in einer Menge von 0.01 - 10 Gew.-%, bevorzugt 0.05 - 7 Gew.-%, besonders bevorzugt 0.1 - 5 Gew.-%, ganz besonders bevorzugt 0.2 - 3 Gew.-%, insbesondere 0.2 - 1 Gew.-%, jeweils bezogen auf den Gehalt an mineralischen Bindemittel, vorhanden ist. 9. Use according to one of the preceding claims, characterized in that the copolymer in an amount of 0.01-10% by weight, preferably 0.05-7% by weight, particularly preferably 0.1-5% by weight, very particularly preferably 0.2 - 3 wt .-%, in particular 0.2-1 wt .-%, each based on the content of mineral binder, is present.
10. Mehrstufiger Prozess zur Herstellung eines Copolymer zur Verwendung gemäss10. Multi-stage process for the production of a copolymer for use according to
Anspruch 1, umfassend die Schritte Claim 1 comprising the steps
1) Umsetzung eines Alkohols oder Amins R1-XH mit Alkylenoxid und/oder einem halogenierten Alkohol oder Amin Hal-R2-XH, wobei R1 ein olefinisch ungesättigter Rest mit 2 - 10 C-Atomen, welcher ggf. durch Sauerstoff
und/oder Stickstoff substituiert sein kann, bevorzugt Vinyl, Allyl, Methallyl, Vinyloxybutyl, Isoprenyl, Acryloyl und/oder Methacryloyl, ist, X = O oder NH, Hai = Halogenid und R2 = Ci - Cie Alkyl, 1) Reaction of an alcohol or amine R 1 -XH with alkylene oxide and / or a halogenated alcohol or amine Hal-R 2 -XH, where R 1 is an olefinically unsaturated radical with 2-10 carbon atoms, which is optionally replaced by oxygen and / or nitrogen can be substituted, preferably vinyl, allyl, methallyl, vinyloxybutyl, isoprenyl, acryloyl and / or methacryloyl, X = O or NH, Hal = halide and R 2 = Ci - Cie alkyl,
2) Umsetzung des Reaktionsproduktes aus Schritt 1) mit Glycidol oder Epichlorhydrin oder einer Mischung aus Glycidol und Alkylenoxid bzw. Epichlorhydrin und Alkylenoxid, 2) Reaction of the reaction product from step 1) with glycidol or epichlorohydrin or a mixture of glycidol and alkylene oxide or epichlorohydrin and alkylene oxide,
3) Umsetzung des Reaktionsproduktes aus Schritt 2) mit Alkylenoxid, und3) reaction of the reaction product from step 2) with alkylene oxide, and
4) radikalische Polymerisation eines Gemisches aus mindestens einem olefinisch ungesättigen Carbonsäure-Monomer mit dem Reaktionsproduktes aus Schritt 3). 4) radical polymerization of a mixture of at least one olefinically unsaturated carboxylic acid monomer with the reaction product from step 3).
11. Mehrstufiger Prozess gemäss Anspruch 10, gekennzeichnet durch einen weiteren Schritt 11. Multi-stage process according to claim 10, characterized by a further step
5) Trocknung, insbesondere Sprühtrocknung des Reaktionsproduktes aus Schritt 4). 5) Drying, in particular spray drying, of the reaction product from step 4).
12. Mineralisches Bindemittel oder mineralische Bindemittelzusammensetzung umfassend mindestens ein mineralisches Bindemittel, bevorzugt Zement, sowie mindestens ein Copolymer erhältlich aus einem Prozess gemäss Anspruch 10. 12. Mineral binder or mineral binder composition comprising at least one mineral binder, preferably cement, and at least one copolymer obtainable from a process according to claim 10.
13. Mineralisches Bindemittel oder mineralische Bindemittelzusammensetzung gemäss Anspruch 12, umfassend 0.01 - 10 Gew.-%, bevorzugt 0.05 - 7 Gew.- %, besonders bevorzugt 0.1 - 5 Gew.-%, ganz besonders bevorzugt 0.2 -2 Gew.-%, insbesondere 0.2 - 1 Gew.-%, jeweils bezogen auf den Gehalt an mineralischem Bindemittel, mindestens eines Copolymer erhältlich aus einem13. Mineral binder or mineral binder composition according to claim 12, comprising 0.01-10% by weight, preferably 0.05-7% by weight, particularly preferably 0.1-5% by weight, very particularly preferably 0.2-2% by weight, in particular 0.2-1% by weight, based in each case on the content of mineral binder, of at least one copolymer obtainable from one
Prozess gemäss Anspruch 10. Process according to claim 10.
14. Zusatzmittel für mineralische Bindemittelzusammensetzungen umfassend mindestens ein Copolymer erhältlich aus einem Prozess gemäss Anspruch 10. 14. Additive for mineral binder compositions comprising at least one copolymer obtainable from a process according to claim 10.
15. Zusatzmittel gemäss Anspruch 14, weiterhin umfassend einen oder mehrere Polycarboxylatether.
15. An additive according to claim 14, further comprising one or more polycarboxylate ethers.
16. Formkörper, erhältlich durch Aushärten eines mineralischen Bindemittels oder einer mineralischen Bindemittelzusammensetzung gemäss Anspruch 12.
16. Shaped bodies obtainable by curing a mineral binder or a mineral binder composition according to claim 12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19212571.4A EP3828153A1 (en) | 2019-11-29 | 2019-11-29 | Branched copolymers as dispersants for mineral binders |
PCT/EP2020/083326 WO2021105188A1 (en) | 2019-11-29 | 2020-11-25 | Branched copolymers as dispersants for mineral binders |
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EP4065536A1 true EP4065536A1 (en) | 2022-10-05 |
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EP19212571.4A Withdrawn EP3828153A1 (en) | 2019-11-29 | 2019-11-29 | Branched copolymers as dispersants for mineral binders |
EP20808467.3A Pending EP4065536A1 (en) | 2019-11-29 | 2020-11-25 | Branched copolymers as dispersants for mineral binders |
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EP19212571.4A Withdrawn EP3828153A1 (en) | 2019-11-29 | 2019-11-29 | Branched copolymers as dispersants for mineral binders |
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US (1) | US20240059612A1 (en) |
EP (2) | EP3828153A1 (en) |
JP (1) | JP2023503538A (en) |
KR (1) | KR20220112242A (en) |
CN (1) | CN114585594B (en) |
AU (1) | AU2020393503A1 (en) |
WO (1) | WO2021105188A1 (en) |
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CN114316155B (en) * | 2022-01-24 | 2023-09-12 | 武汉三源特种建材有限责任公司 | Dendritic early-strength polycarboxylate superplasticizer and preparation method thereof |
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EP0116978A3 (en) | 1983-02-22 | 1986-04-30 | Union Carbide Corporation | Connected branch copolymers and method for their production |
MY114306A (en) | 1995-07-13 | 2002-09-30 | Mbt Holding Ag | Cement dispersant method for production thereof and cement composition using dispersant |
MY135684A (en) | 1999-11-29 | 2008-06-30 | Nippon Catalytic Chem Ind | Copolymer for cement admixtures and its production process and use |
EP1138696A1 (en) | 2000-03-29 | 2001-10-04 | Sika AG, vorm. Kaspar Winkler & Co. | Polymers for cement dispersing admixtures |
SG101990A1 (en) | 2000-08-11 | 2004-02-27 | Nippon Catalytic Chem Ind | Cement dispersant and cement composition comprising this |
EP1707542A2 (en) * | 2005-03-31 | 2006-10-04 | Nippon Shokubai Co.,Ltd. | Powdery cement dispersant |
DE102005061153A1 (en) | 2005-12-21 | 2007-06-28 | Construction Research & Technology Gmbh | New copolymers for use as additive in aqueous suspension of mineral or bituminous binder e.g. cement, lime or gypsum or dispersion binder powder comprise unsaturated mono- or dicarboxylic acid derivative and oxyalkylene glycol alkenyl ether |
CN101712755B (en) * | 2009-05-18 | 2011-11-23 | 江苏博特新材料有限公司 | Alkoxy polyether containing double bonds at tail end and preparation method thereof |
WO2011006837A1 (en) * | 2009-07-15 | 2011-01-20 | Basf Se | Mixtures comprising branched oligomer or polymer compounds, the production and use thereof |
WO2011006838A2 (en) * | 2009-07-15 | 2011-01-20 | Basf Se | Copolymers, their use as thickeners and method for producing the same |
CN102993432B (en) * | 2012-10-19 | 2015-05-20 | 江苏苏博特新材料股份有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
EP2774899A1 (en) | 2013-03-06 | 2014-09-10 | Construction Research & Technology GmbH | Polycarboxylate ether with branched side chains |
EP3018108A1 (en) * | 2014-11-10 | 2016-05-11 | Basf Se | Polymer with polyether side chains |
CN105542147B (en) * | 2016-01-27 | 2017-11-03 | 江苏苏博特新材料股份有限公司 | The preparation method and applications of water reducer with hyperbranched topological structure |
CN107573511A (en) * | 2017-10-18 | 2018-01-12 | 江苏苏博特新材料股份有限公司 | A kind of aminated polyethers intermediate, the preparation method and application of its Phosphorylated products |
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- 2019-11-29 EP EP19212571.4A patent/EP3828153A1/en not_active Withdrawn
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AU2020393503A1 (en) | 2022-04-07 |
CN114585594B (en) | 2023-10-27 |
CN114585594A (en) | 2022-06-03 |
JP2023503538A (en) | 2023-01-31 |
WO2021105188A1 (en) | 2021-06-03 |
US20240059612A1 (en) | 2024-02-22 |
KR20220112242A (en) | 2022-08-10 |
EP3828153A1 (en) | 2021-06-02 |
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