US20030177690A1 - Vinylamine compounds - Google Patents
Vinylamine compounds Download PDFInfo
- Publication number
- US20030177690A1 US20030177690A1 US10/363,659 US36365903A US2003177690A1 US 20030177690 A1 US20030177690 A1 US 20030177690A1 US 36365903 A US36365903 A US 36365903A US 2003177690 A1 US2003177690 A1 US 2003177690A1
- Authority
- US
- United States
- Prior art keywords
- building blocks
- copolymer
- copolymers
- formula
- combustion
- 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.)
- Abandoned
Links
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 title claims description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 10
- 238000006268 reductive amination reaction Methods 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000002480 mineral oil Substances 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 21
- 239000000446 fuel Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000002485 combustion reaction Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- 235000010446 mineral oil Nutrition 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000976 ink Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 239000003921 oil Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229920001897 terpolymer Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- -1 aminoalkyl vinyl ethers Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VOCDJQSAMZARGX-UHFFFAOYSA-N 1-ethenylpyrrolidine-2,5-dione Chemical compound C=CN1C(=O)CCC1=O VOCDJQSAMZARGX-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- IGDLZDCWMRPMGL-UHFFFAOYSA-N 2-ethenylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C=C)C(=O)C2=C1 IGDLZDCWMRPMGL-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920001145 Poly(N-vinylacetamide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- QEGNUYASOUJEHD-UHFFFAOYSA-N gem-dimethylcyclohexane Natural products CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Definitions
- the present invention relates to compounds, in particular copolymers, which contain vinylamine building blocks.
- the present invention furthermore relates to a process for the preparation of such compounds of copolymers, their use as assistants in mineral oils, mineral oil distillates, combustion fuels and power fuels and in other areas, and concentrates and combustion fuel and power fuel compositions containing them.
- Vinylamine polymers can be obtained only indirectly by polymer-analogous reactions since the base monomer, vinylamine, cannot be isolated.
- Vinylamine polymers are prepared, for example, by hydrolysis of poly-N-vinylamides, such as poly-N-vinylformamide or poly-N-vinylacetamide, poly-N-vinylimides, such as poly-N-vinylsuccinimide or poly-N-vinylphthalimide and by Hoffmann degradation of polyacrylamide under the action of basic hypochlorite.
- poly-N-vinylamides such as poly-N-vinylformamide or poly-N-vinylacetamide
- poly-N-vinylimides such as poly-N-vinylsuccinimide or poly-N-vinylphthalimide
- Hoffmann degradation of polyacrylamide under the action of basic hypochlorite These synthesis routes start from poorly obtainable or expensive monomers and include complicated reaction or working-up steps. They have been used to date only in a few special
- Mineral oil distillates in particular middle distillates, such as gas oils, diesel oils or heating oils, which are obtained from mineral oils by distillation and the further processing stages of the refineries, have, depending on the origin of the crude oil, different contents of n-paraffins, which may crystallize on cooling. This point is referred to as the cloud point (CP).
- the lamellar paraffin crystals form a sort of house-of-cards structure, so that a middle distillate (MD) sets although the predominant part is still liquid.
- MD middle distillate
- the flowability in particular of power fuels, is considerably impaired by the precipitated paraffins in the temperature range between cloud point and pour point.
- the paraffins block filters and, in the case of power fuels, cause an uneven fuel supply to the engine or completely stop said supply. Similar problems arise in the case of heating oils.
- these additives result in the formation of fine, well crystallized, separate paraffin crystals which do not settle out and which cannot pass through the filters, so that trouble-free fuel transport is ensured.
- WASA wax-anti-settling additives
- Copolymers which are derived from ethylene and vinyl acetate have widely been described as flow improvers for mineral oil middle distillates (cf. for example DE-A-196 24 861).
- the copolymers described furthermore contain (meth)acrylate building blocks which are derived from amino alcohols which may be alkoxylated.
- EP-A-0 964 052 relates to the use of nitrogen-containing ethylene copolymers for the preparation of fuel oils having an improved lubricating effect.
- the copolymers also contain those structural units which are derived from ethylenically unsaturated compounds which have at least one aromatically or aliphatically bonded nitrogen atom.
- Alkylamino (meth)acrylates, alkyl(meth)acrylamides, vinylamides, aminoalkyl vinyl ethers, allylamines and heterocycles containing a vinyl group are mentioned as such comonomers.
- terpolymers which are derived from ethylene, vinyl acetate and 1-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide or dimethylaminoethyl methacrylate are used.
- the nitrogen-containing vinylic comonomers have in some cases a complicated structure and as a rule cannot be prepared in a simple manner and from economical raw materials.
- EP-A-0 405 270 relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding a mixture of an ethylene/vinyl acetate copolymer and an ethylene/vinyl acetate/N-vinyl-pyrrolidone terpolymer.
- WO 96/18706 relates to combustion and power fuel compositions which have a low sulfur content and whose flowability is increased by adding nitrogen-containing compounds.
- amine salts or amides which are obtained by reacting hydrocarbon-substituted amines with alkanoic acids, are used.
- copolymers which have a number of advantageous properties as assistants in mineral oil, mineral oil distillates and combustion and power fuels.
- R 1 and R 2 independently of one another, are each hydrogen, C 1-20 -alkyl, C 6-18 -aryl, C 7-20 -alkaryl, C 7-20 -aralkyl or a polyamine radical, by reductive amination of compounds which contain one or more groups of the formula (II)
- R 3 is hydrogen, C 1-20 -alkyl, C 6-18 -aryl, C 7-20 -alkaryl or C 7-20 -aralkyl,
- the compounds which contain the structures of the formula (I) or (II) may be low molecular weight, oligomeric or polymeric structures. They may accordingly have 1, 2, 3, 4, 5, 6 or more of the structures of the formulae (I) and (II).
- the compounds having the structures of the formula (I) have altogether 4 to 100,000, particularly preferably 10 to 10,000, in particular 10 to 1000, carbon atoms if they are low molecular weight or oligomeric compounds.
- the compounds are polymers which contain vinylamine building blocks of the formula (I) in the main chain.
- the polymers contain 1 or 2, 3, 4, 5, 6 or more of the building blocks of the formula (I).
- They may be completely composed of building blocks of the formula (I). In this case, they are homopolymers. Frequently, they are copolymers which contain unconverted structures of the formula (II) in addition to the structures of the formula (I). Moreover, further building blocks as described below may be present.
- the compounds are polymers which contain one or more vinylamine building blocks of the formula (I) in the main chain and are obtained by reductive amination of polymers which contain one or more vinyl ester building blocks of the formula (II) in the main chain.
- the polymers to be aminated are copolymers which contain C 2 -C 12 -olefin building blocks and vinyl esters of C 1-12 -monocarboxylic acids as building blocks.
- the copolymers to be aminated are ethylene/vinyl acetate copolymers.
- R 1 and R 2 are each preferably hydrogen or C 1-12 -alkyl, particularly preferably hydrogen or C 1-4 -alkyl, in particular hydrogen.
- ammonia is used as a compound of the formula (III).
- R 3 is preferably hydrogen or C 1-12 -alkyl, particularly preferably C 1-4 -alkyl, in particular methyl. These are therefore in particular vinyl acetate building blocks.
- Particularly preferred compounds which contain the structures of the formula (I) or (II) are polymers having a number average molecular weight of from 100 to 10,000,000, particular preferably from 500 to 100,000.
- the novel reductive amination can be carried out analogously to known processes for the reductive amination of, for example, aldehydes, ketones or esters and alcohols. It is preferably carried out using suitable catalysts. Suitable catalysts are known and are described, for example, in the non-prior-published DE-A-199 10 960 with the earlier priority.
- Catalysts customary for the reductive amination are, for example, those based on Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Al, Si, Ti, Zr, Nb, Mg, Zn or a combination thereof.
- Typical reaction conditions are temperatures of from 50 to 300° C. and pressures of up to about 600 bar.
- a preferred catalyst contains as catalytically active material, before the reduction with hydrogen,
- a particularly preferred catalyst is composed of 51% by weight of NiO, 17% by weight of CuO, 30.5% by weight of ZrO 2 and 1.5% by weight of MoO 3 .
- the catalyst is preferably composed only of catalytically active material and, if required, a molding assistant, such as graphite or stearic acid.
- the catalyst may be used in any suitable form, for example as pellets, beads, rings or extrudates.
- the catalytically active material can, if required, furthermore contain one or more elements, or inorganic or organic compounds thereof, selected from groups IA to IVA and IB to VIIB and VIII of the Periodic Table of the Elements. Catalysts which, after the final heat treatment and before the reduction with hydrogen, contain less than 20, preferably less than 10, in particular less than 5, very particularly less than 1, % by weight of cobalt, calculated as CoO, are particularly preferred. Very particularly preferably, the catalytically active material contains no catalytically active amounts of cobalt or compounds thereof.
- the catalysts can be prepared by various processes, for example by peptization of pulverulent mixtures of the hydroxides, carbonates, oxides and/or other salts of the components with water and subsequent extrusion and heating of the material thus obtained.
- known precipitation methods are used for preparing the catalysts.
- the individual components can be precipitated individually or together as a coprecipitate.
- the precipitation products are dried in general at from 80 to 200° C., preferably from 100 to 150° C. and then calcined at from 300 to 800° C., preferably from 400 to 600° C., in particular from 450 to 500° C.
- the amines of the formula (III) can be used in stoichiometric amounts, based on the ester groups to be reacted. Preferably, however, an excess of the amines is used, for example more than a 5 molar excess.
- ammonia is generally used in a 5- to 250-fold, preferably 10- to 100-fold, in particular 25- to 80-fold, molar excess.
- the novel process can be carried out batchwise or continuously, the catalyst preferably being arranged as a fixed bed in the reactor.
- the reaction can be carried out in the liquid phase or in the gas phase.
- the reaction is effected at from 50 to 300° C., preferably from 80 to 250° C., particularly preferably from 80 to 230° C., in particular from 100 to 220° C.
- reaction is carried out at from 1 to 400, preferably from 10 to 250, in particular from 20 to 200, bar.
- the hydrogen is generally introduced in an amount of from 5 to 400, preferably from 50 to 250, l(S.T.P.) per mol of ester component to be reacted.
- the reaction may be carried out without additional solvent.
- the reaction involving high molecular weight starting compounds or products which are highly viscous or which are solid at room temperature is advantageously effected in a solvent which is inert under reaction conditions, for example in tetrahydrofuran, dioxane, N-methylpyrrolidone, mihagol, ethylene glycol dimethyl ether, cyclohexane or hexane or generally aliphatic or aromatic solvents.
- the present invention also relates to the copolymers prepared by the novel process, particularly preferably a copolymer containing copolymerized vinylamine building blocks of the formula (I)
- R 1 and R 2 independently of one another, are each hydrogen, C 1-20 -alkyl, C 6-18 -aryl, C 7-20 -alkaryl, C 7-20 -aralkyl or a polyamine radical,
- R 4 is hydrogen or C 1-4 -alkyl
- R 5 is R 6 or
- R 7 is hydrogen or C 1-4 -alkyl and n has a mean value of 1 to 100
- R 6 is hydrogen, C 1-20 -alkyl, C 6-18 -aryl, C 7-20 -alkaryl, C 7-20 -aralkyl, which may be unsubstituted or substituted by
- R 8 and R 9 independently of one another, are each hydrogen or C 1-4 -alkyl.
- R 1 and R 2 have the preferred meanings stated above.
- R 6 has the preferred meanings stated above for R 3 .
- R 4 is preferably hydrogen or methyl, in particular methyl.
- R 5 is preferably R 6 or —O—C(O)—R 6 .
- R 1 is R 6
- R 6 is preferably hydrogen, C 1-12 -alkyl, phenyl or C 7-10 -alkaryl, particularly preferably hydrogen, methyl, ethyl or phenyl.
- the copolymer particularly preferably contains building blocks of the formula (IVa)
- R 5 is hydrogen, C 1-20 -alkyl or C 6-18 -aryl.
- the copolymers have the building blocks of the formulae (I), (IVa) and (IVb).
- Such copolymers may also contain up to 20% by weight, based on the total copolymer, of further building blocks; particularly preferably, they are composed essentially or only of the building blocks of the formulae (I), (IVa) and (IVb). Particularly preferably, they are ethylene/vinyl acetate/vinylamine terpolymers.
- the copolymers or terpolymers preferably have a number average molecular weight of from 100 to 10,000,000, particularly preferably from 500 to 100,000.
- novel copolymers can be prepared by any desired suitable process. Particularly preferably, the preparation of the copolymers is carried out by free radical copolymerization of vinyl esters of the formula (V)
- R 3 is hydrogen, C 1-20 -alkyl, C 6-18 -aryl, C 7-20 -alkaryl or C 7-20 -aralkyl,
- R 4 and R 5 have the stated meanings, and, if required, further vinylic comonomers to give a copolymer and subsequent reductive amination by the above process.
- the ethylene/vinyl acetate copolymers are prepared, for example, by free radical polymerization by the high-pressure mass polymerization method, alternatively in stirred autoclaves, tubular reactors or segmented tubular reactors. Such processes are described, for example, in DE-A-197 54 039, DE-A-197 19 689 and M. Recksch, Erdöl und Kohle-Erdgas-Petrochemie in combination with Brennstoff-Chemie, 42(4) 1989.
- the novel copolymers can be used in a large number of applications.
- the copolymers are suitable for optimizing the retention and drainage and for fixing anionic substances in papermaking (retention aids, drainage aids, flocculants and fixing compositions).
- the polymers improve the dry and wet paper strength (cf. also Weinbl. Textilfabr. (1999), 127(8), 511-518).
- the copolymers are suitable for colorizing wastewaters from papermaking or for removing dye from said wastewaters (according to U.S. Pat. No. 5,476,594).
- the polymers are suitable as water-soluble or water-swellable, cationic polyelectrolytes for aqueous adhesive dispersions for the production of multilayer paper or paper materials (according to DE 198 29 757).
- copolymers are suitable for modifying cleaned or chemically pretreated metal surfaces, which are then suitable in particular for electrodip coating (according to EP 0 672 467).
- copolymers are suitable as dye transfer inhibitors for detergents (according to DE 441 3 720).
- the copolymers are suitable as a starting substance for the preparation of polymers containing carbamate units. These polymers are suitable as retention aids, drainage aids and flocculants and as fixing compositions in the production of paper, as protective colloids for the preparation of aqueous alkyldiketene dispersions and as dispersants for the preparation of aqueous filler suspensions (according to WO 98/35999).
- copolymers are suitable for the treatment and preparation of viscose products with cationic polymers (according to WO 99/36604).
- the copolymers are suitable as water-soluble amine-based polymer components in multilayer membranes for separating acidic gases from gaseous mixtures (according to DE 196 00 954).
- the copolymers are suitable for the preparation of aqueous and organic dispersions, emulsions or solutions of amine-based polymers.
- the amine-based polymers, dispersions, emulsions or solutions are particularly suitable for coating and imparting water repellency to surfaces (finish surfaces, packaging coating, building material impregnation, particle boards, stone, metal, textiles, plastics, leather, wood, paper), for the treatment of various materials (stone, metal, textiles, plastics, leather, wood, paper), as process chemicals in the textile industry, as additives in printing inks and finishes, and as mold release agents.
- the copolymers are suitable as effective corrosion inhibitors in radiation protection mixtures.
- the copolymers are particularly preferably used as flow improvers, wax-anti-settling-additives and lubricity additives, for reducing fretting, as corrosion inhibitors and/or as internal combustion engine intake system cleaners in mineral oils, mineral oil distillates and combustion and power fuels.
- the novel copolymers are preferably employed in combustion and power fuel compositions, in particular in middle distillates, such as diesel fuels and light heating oils. They can be used together with further conventional additives.
- the novel copolymers can be incorporated into the mineral oils, mineral oil distillates and combustion and power fuels, in particular into a middle distillate, directly but preferably as 20 to 70% strength by weight solutions.
- solvents are hydrocarbon solvents. Suitable solvents are described, for example, in DE-A-196 24 861 and DE-A-43 41 528.
- the novel copolymers may be dissolved in a large amount in a hydrocarbon solvent; preferably, the solutions contain from 5 to 80, particularly preferably from 20 to 70, particularly from 40 to 60, % by weight of one or more novel copolymers alone or together with other assistants, for example according to the abovementioned applications.
- the present invention also relates to such concentrates or mixtures.
- the concentrates may be further used, for example, for the preparation of combustion and power fuel compositions (cf DE-A-196 24 861).
- the present invention also relates to combustion and power fuel compositions which contain from 5 to 5000, preferably from 10 to 500, ppm by weight, based on the total weight of the composition, of the copolymer, alone or together with other assistants.
- the content of ethylene, vinyl acetate and vinylamine was determined by NMR spectroscopy.
- the terpolymer contained 75.6% by weight of ethylene, 14.7% by weight of vinyl acetate and 9.7% by weight of vinylamine.
- test oils had the following characteristic data.
- TABLE 1 Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Initial boiling point [° C.] 173 182 168 195 178 5% [° C.] 206 223 186 222 194 10% [° C.] 219 236 192 233 200 50% [° C.] 285 287 233 275 243 95% [° C.] 369 354 353 343 343 Final boiling point [° C.] 380 365 367 354 355 90%-20% [° C.] 115 87 127 80 115 FPB-90% [° C.] 27 25 39 27 30 Cloud point [° C.] 2.8 2 ⁇ 6.4 ⁇ 8.9 ⁇ 7.7 CFPP [° C.] 0 0 ⁇ 9 ⁇ 12 ⁇ 9 Sulfur [ppm] 2000 1800 450 310 45
- the novel terpolymers were introduced into the test oils, and the cold filter plugging point (CFPP) was determined according to EN 116. In addition, the cloud point (CP) was determined according to ISO 3015.
- the CFPP is shown in Table 2 below. TABLE 2 Test oil Dose/ppm CFPP [° C.] 1 100 ⁇ 7 2 250 ⁇ 2 3 50 ⁇ 11 3 125 ⁇ 18 4 25 ⁇ 15
- Substances which lead to the results of case (A) and case (B) in the test are efficient wax-anti-settling additives.
- the cloud point (CP) and the CFPP are determined for the lower 20%.
- a positive effect on the low-temperature behavior of the test oil is present when the cloud point of the 20% lower phase is slightly (1-2° C.) above the cloud point before the storage test at ⁇ 13° C.
- Test oil 3 without additive Visual CP: ⁇ 6.4° C. assessment 20% lower phase CFPP: ⁇ 9° C. CFPP/° C. Lower phase Upper phase CP/° C. CFPP/° C.
- Table 4 shows that the ethylene/vinyl acetate copolymer used for the preparation of the ethylene/vinyl acetate/vinylamine terpolymer has no effect on the paraffin sedimentation. A positive effect on the paraffin sedimentation is achieved by adding the ethylene/vinyl acetate/vinylamine terpolymer to the ethylene/vinyl acetate copolymer.
Abstract
Compounds which contain one or more groups of the formula (I)
—CH2—CH(NR1R2)— (I)
where
R1 and R2, independently of one another, are each hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl or a polyamine radical,
are prepared by reductive amination of compounds which contain one or more groups of the formula (II)
—CH2—CH(O—C(O)—R3)— (II)
where
R3 is hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl or C7-20-aralkyl, with amines of the formula (III)
HNR1R2 (III)
and hydrogen.
Description
- The present invention relates to compounds, in particular copolymers, which contain vinylamine building blocks. The present invention furthermore relates to a process for the preparation of such compounds of copolymers, their use as assistants in mineral oils, mineral oil distillates, combustion fuels and power fuels and in other areas, and concentrates and combustion fuel and power fuel compositions containing them.
- Vinylamine polymers can be obtained only indirectly by polymer-analogous reactions since the base monomer, vinylamine, cannot be isolated. Vinylamine polymers are prepared, for example, by hydrolysis of poly-N-vinylamides, such as poly-N-vinylformamide or poly-N-vinylacetamide, poly-N-vinylimides, such as poly-N-vinylsuccinimide or poly-N-vinylphthalimide and by Hoffmann degradation of polyacrylamide under the action of basic hypochlorite. These synthesis routes start from poorly obtainable or expensive monomers and include complicated reaction or working-up steps. They have been used to date only in a few special applications, for example flocculants and retention aids.
- Mineral oil distillates, in particular middle distillates, such as gas oils, diesel oils or heating oils, which are obtained from mineral oils by distillation and the further processing stages of the refineries, have, depending on the origin of the crude oil, different contents of n-paraffins, which may crystallize on cooling. This point is referred to as the cloud point (CP). On further cooling, the lamellar paraffin crystals form a sort of house-of-cards structure, so that a middle distillate (MD) sets although the predominant part is still liquid. This point is referred to as the pour point. The flowability, in particular of power fuels, is considerably impaired by the precipitated paraffins in the temperature range between cloud point and pour point. The paraffins block filters and, in the case of power fuels, cause an uneven fuel supply to the engine or completely stop said supply. Similar problems arise in the case of heating oils.
- It is known that the crystal growth of the paraffins in middle distillates and kerosene middle distillate mixtures can be modified by introducing suitable additives into the mineral oil distillate. Effective additives prevent paraffins in middle distillates from forming such structures resembling a house of cards and the middle distillates from becoming solid at temperatures only a few ° C. below the temperature at which the first crystals are precipitated. They thus act as flow improvers. The improvement of the flow properties of middle distillates is frequently determined as a reduction of the cold filter plugging point (CFPP), for example according to DIN EN 116. On the other hand, these additives result in the formation of fine, well crystallized, separate paraffin crystals which do not settle out and which cannot pass through the filters, so that trouble-free fuel transport is ensured. Here, they act as wax-anti-settling additives (WASA).
- Copolymers which are derived from ethylene and vinyl acetate have widely been described as flow improvers for mineral oil middle distillates (cf. for example DE-A-196 24 861). The copolymers described furthermore contain (meth)acrylate building blocks which are derived from amino alcohols which may be alkoxylated.
- EP-A-0 964 052 relates to the use of nitrogen-containing ethylene copolymers for the preparation of fuel oils having an improved lubricating effect. In addition to structural units which are derived from ethylene, the copolymers also contain those structural units which are derived from ethylenically unsaturated compounds which have at least one aromatically or aliphatically bonded nitrogen atom. Alkylamino (meth)acrylates, alkyl(meth)acrylamides, vinylamides, aminoalkyl vinyl ethers, allylamines and heterocycles containing a vinyl group are mentioned as such comonomers. In particular, terpolymers which are derived from ethylene, vinyl acetate and 1-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide or dimethylaminoethyl methacrylate are used.
- The nitrogen-containing vinylic comonomers have in some cases a complicated structure and as a rule cannot be prepared in a simple manner and from economical raw materials.
- EP-A-0 405 270 relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding a mixture of an ethylene/vinyl acetate copolymer and an ethylene/vinyl acetate/N-vinyl-pyrrolidone terpolymer.
- WO 96/18706 relates to combustion and power fuel compositions which have a low sulfur content and whose flowability is increased by adding nitrogen-containing compounds. In particular, amine salts or amides, which are obtained by reacting hydrocarbon-substituted amines with alkanoic acids, are used.
- It is an object of the present invention to provide a process for the preparation of compounds which contain structural elements derived from vinylamine, it being intended that the amino group be capable of being introduced simply and economically.
- In addition, it is intended to provide copolymers which have a number of advantageous properties as assistants in mineral oil, mineral oil distillates and combustion and power fuels.
- We have found that this object is achieved, according to the invention, by a process for the preparation of a compound which contains one or more groups of the formula (I)
- —CH2—CH(NR1R2)— (I)
- where
- R1 and R2, independently of one another, are each hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl or a polyamine radical, by reductive amination of compounds which contain one or more groups of the formula (II)
- —CH2—CH(O—C(O)—R3)— (II)
- where
- R3 is hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl or C7-20-aralkyl,
- with amines of the formula (III)
- HNR1R2 (III)
- and hydrogen.
- It was found, according to the invention, that structural elements derived from vinyl esters and present in chemical compounds, for example polymers, can be converted into structures derived from vinylamine by reductive amination with amines and hydrogen.
- The compounds which contain the structures of the formula (I) or (II) may be low molecular weight, oligomeric or polymeric structures. They may accordingly have 1, 2, 3, 4, 5, 6 or more of the structures of the formulae (I) and (II). Preferably, the compounds having the structures of the formula (I) have altogether 4 to 100,000, particularly preferably 10 to 10,000, in particular 10 to 1000, carbon atoms if they are low molecular weight or oligomeric compounds.
- Particularly preferably, the compounds are polymers which contain vinylamine building blocks of the formula (I) in the main chain. The polymers contain 1 or 2, 3, 4, 5, 6 or more of the building blocks of the formula (I).
- They may be completely composed of building blocks of the formula (I). In this case, they are homopolymers. Frequently, they are copolymers which contain unconverted structures of the formula (II) in addition to the structures of the formula (I). Moreover, further building blocks as described below may be present.
- Preferably, the compounds are polymers which contain one or more vinylamine building blocks of the formula (I) in the main chain and are obtained by reductive amination of polymers which contain one or more vinyl ester building blocks of the formula (II) in the main chain.
- Particularly preferably, the polymers to be aminated are copolymers which contain C2-C12-olefin building blocks and vinyl esters of C1-12-monocarboxylic acids as building blocks.
- In particular, the copolymers to be aminated are ethylene/vinyl acetate copolymers.
- In the groups of the formula (I) and in the amines of the formula (III), R1 and R2, independently of one another, are each preferably hydrogen or C1-12-alkyl, particularly preferably hydrogen or C1-4-alkyl, in particular hydrogen. Particularly preferably, ammonia is used as a compound of the formula (III).
- In the structures of the formula (II), R3 is preferably hydrogen or C1-12-alkyl, particularly preferably C1-4-alkyl, in particular methyl. These are therefore in particular vinyl acetate building blocks.
- Particularly preferred compounds which contain the structures of the formula (I) or (II) are polymers having a number average molecular weight of from 100 to 10,000,000, particular preferably from 500 to 100,000.
- The novel reductive amination can be carried out analogously to known processes for the reductive amination of, for example, aldehydes, ketones or esters and alcohols. It is preferably carried out using suitable catalysts. Suitable catalysts are known and are described, for example, in the non-prior-published DE-A-199 10 960 with the earlier priority.
- Catalysts customary for the reductive amination are, for example, those based on Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Al, Si, Ti, Zr, Nb, Mg, Zn or a combination thereof. Typical reaction conditions are temperatures of from 50 to 300° C. and pressures of up to about 600 bar.
- A preferred catalyst contains as catalytically active material, before the reduction with hydrogen,
- from 20 to 85, preferably from 20 to 65, particularly preferably from 25 to 49.7, % by weight of oxygen-containing compounds of zirconium, calculated as ZrO2,
- from 1 to 30, preferably from 5 to 25, particularly preferably from 10 to 25, % by weight of oxygen-containing compounds of copper, calculated as CuO,
- from 14 to 70, preferably from 29.7 to 70, particularly preferably from 40 to 60, % by weight of oxygen-containing compounds of nickel, calculated as NiO,
- from 0 to 5, preferably from 0.3 to 3.5, % by weight of oxygen-containing compounds of molybdenum, calculated as MoO3, and
- from 0 to 10, particularly preferably from 0 to 5, % by weight of oxygen-containing compounds of aluminum, calculated as Al2O3,
- the total amount of which is 100% by weight.
- A particularly preferred catalyst is composed of 51% by weight of NiO, 17% by weight of CuO, 30.5% by weight of ZrO2 and 1.5% by weight of MoO3.
- The catalyst is preferably composed only of catalytically active material and, if required, a molding assistant, such as graphite or stearic acid. The catalyst may be used in any suitable form, for example as pellets, beads, rings or extrudates.
- The catalytically active material can, if required, furthermore contain one or more elements, or inorganic or organic compounds thereof, selected from groups IA to IVA and IB to VIIB and VIII of the Periodic Table of the Elements. Catalysts which, after the final heat treatment and before the reduction with hydrogen, contain less than 20, preferably less than 10, in particular less than 5, very particularly less than 1, % by weight of cobalt, calculated as CoO, are particularly preferred. Very particularly preferably, the catalytically active material contains no catalytically active amounts of cobalt or compounds thereof.
- The catalysts can be prepared by various processes, for example by peptization of pulverulent mixtures of the hydroxides, carbonates, oxides and/or other salts of the components with water and subsequent extrusion and heating of the material thus obtained. In general, however, known precipitation methods are used for preparing the catalysts. In said methods, the individual components can be precipitated individually or together as a coprecipitate.
- The precipitation products are dried in general at from 80 to 200° C., preferably from 100 to 150° C. and then calcined at from 300 to 800° C., preferably from 400 to 600° C., in particular from 450 to 500° C.
- The amines of the formula (III) can be used in stoichiometric amounts, based on the ester groups to be reacted. Preferably, however, an excess of the amines is used, for example more than a 5 molar excess. In particular, ammonia is generally used in a 5- to 250-fold, preferably 10- to 100-fold, in particular 25- to 80-fold, molar excess.
- The novel process can be carried out batchwise or continuously, the catalyst preferably being arranged as a fixed bed in the reactor. The reaction can be carried out in the liquid phase or in the gas phase.
- Usually, the reaction is effected at from 50 to 300° C., preferably from 80 to 250° C., particularly preferably from 80 to 230° C., in particular from 100 to 220° C.
- In general, the reaction is carried out at from 1 to 400, preferably from 10 to 250, in particular from 20 to 200, bar.
- In the reaction, the hydrogen is generally introduced in an amount of from 5 to 400, preferably from 50 to 250, l(S.T.P.) per mol of ester component to be reacted.
- The reaction may be carried out without additional solvent. The reaction involving high molecular weight starting compounds or products which are highly viscous or which are solid at room temperature is advantageously effected in a solvent which is inert under reaction conditions, for example in tetrahydrofuran, dioxane, N-methylpyrrolidone, mihagol, ethylene glycol dimethyl ether, cyclohexane or hexane or generally aliphatic or aromatic solvents.
- The present invention also relates to the copolymers prepared by the novel process, particularly preferably a copolymer containing copolymerized vinylamine building blocks of the formula (I)
- —CH2—CH(NR1R2)— (I)
- where
- R1 and R2, independently of one another, are each hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl or a polyamine radical,
- and, if required, different, polymerized vinyl comonomer building blocks of the formula (IV)
- —CH2CR4R5— (IV)
- where
- R4 is hydrogen or C1-4-alkyl,
- R5 is R6 or
- —O—C(O)—R6,
- —O—R6,
- —C(O)—R6,
- —C(O)—O—R6,
- —CN,
- -halogen,
- —(O—CH2—CHR7)n—O—R6,
- where R7 is hydrogen or C1-4-alkyl and n has a mean value of 1 to 100,
- —C(O)—NHR6,
- where R6 is hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl, which may be unsubstituted or substituted by
- —OR8,
- —NR8R9,
- where R8 and R9, independently of one another, are each hydrogen or C1-4-alkyl.
- Here, R1 and R2 have the preferred meanings stated above. In the structure —O——C(O)—R6, R6 has the preferred meanings stated above for R3.
- In the building blocks of the formula (IV), R4 is preferably hydrogen or methyl, in particular methyl. R5 is preferably R6 or —O—C(O)—R6. If R1 is R6, R6 is preferably hydrogen, C1-12-alkyl, phenyl or C7-10-alkaryl, particularly preferably hydrogen, methyl, ethyl or phenyl.
- In addition to the polymerized vinylamine building blocks of the formula (I), the copolymer particularly preferably contains building blocks of the formula (IVa)
- CH2—CR4(—O—C(O)—R6)— (IVa)
- and/or of the formula (IVb)
- —CH2—CHR5— (IVb)
- where R5 is hydrogen, C1-20-alkyl or C6-18-aryl.
- In particular, the copolymers have the building blocks of the formulae (I), (IVa) and (IVb).
- Such copolymers may also contain up to 20% by weight, based on the total copolymer, of further building blocks; particularly preferably, they are composed essentially or only of the building blocks of the formulae (I), (IVa) and (IVb). Particularly preferably, they are ethylene/vinyl acetate/vinylamine terpolymers. The copolymers or terpolymers preferably have a number average molecular weight of from 100 to 10,000,000, particularly preferably from 500 to 100,000.
- The novel copolymers can be prepared by any desired suitable process. Particularly preferably, the preparation of the copolymers is carried out by free radical copolymerization of vinyl esters of the formula (V)
- H2C═CH(O—C(O)—R3) (V)
- where R3 is hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl or C7-20-aralkyl,
- if required different vinyl comonomers of the formula (VI)
- H2C═CR4R5 (VI)
- where R4 and R5 have the stated meanings, and, if required, further vinylic comonomers to give a copolymer and subsequent reductive amination by the above process.
- The ethylene/vinyl acetate copolymers are prepared, for example, by free radical polymerization by the high-pressure mass polymerization method, alternatively in stirred autoclaves, tubular reactors or segmented tubular reactors. Such processes are described, for example, in DE-A-197 54 039, DE-A-197 19 689 and M. Rätzsch, Erdöl und Kohle-Erdgas-Petrochemie in combination with Brennstoff-Chemie, 42(4) 1989.
- The novel copolymers can be used in a large number of applications. The use as assistants in mineral oils, mineral oil distillates and combustion and power fuels, in chromatography, as ion exchangers, in dispersions, as emulsifiers, in papermaking (Wochenbl. Papierfabr. (1999) 127, 511 to 518), in membranes, in adhesives (WO 00/01783), in the production of cellulose fibers (WO 99/36604), in printing inks and papers for these (EP-A-0 878 323, EP-A-0 911 374, WO 98/42787, for the coating of fibers (U.S. Pat. No. 6,077,794), as fixing compositions (U.S. Pat. No. 6,039,768), as mold release agents, for wastewater treatment (WO 96/38493), in detergent compositions, in particular as dye transfer inhibitors (U.S. Pat. No. 5,863,879), for decolorizing paper mill wastewaters (U.S. Pat. No. 5,476,594), for modifying metal surfaces (U.S. Pat. No. 5,494,535), in films (U.S. Pat. No. 5,492,765), in coating compositions and in other applications is preferred.
- Examples of specific applications are as follows:
- (1) The copolymers are suitable for optimizing the retention and drainage and for fixing anionic substances in papermaking (retention aids, drainage aids, flocculants and fixing compositions). In addition, the polymers improve the dry and wet paper strength (cf. also Wochenbl. Papierfabr. (1999), 127(8), 511-518).
- (2) The copolymers are suitable for colorizing wastewaters from papermaking or for removing dye from said wastewaters (according to U.S. Pat. No. 5,476,594).
- (3) In completely or partly protonated form, the polymers are suitable as water-soluble or water-swellable, cationic polyelectrolytes for aqueous adhesive dispersions for the production of multilayer paper or paper materials (according to DE 198 29 757).
- (4) The copolymers are suitable for modifying cleaned or chemically pretreated metal surfaces, which are then suitable in particular for electrodip coating (according to EP 0 672 467).
- (5) The copolymers are suitable as dye transfer inhibitors for detergents (according to DE 441 3 720).
- (6) The copolymers are suitable as a starting substance for the preparation of polymers containing carbamate units. These polymers are suitable as retention aids, drainage aids and flocculants and as fixing compositions in the production of paper, as protective colloids for the preparation of aqueous alkyldiketene dispersions and as dispersants for the preparation of aqueous filler suspensions (according to WO 98/35999).
- (7) The copolymers are suitable for the treatment and preparation of viscose products with cationic polymers (according to WO 99/36604).
- (8) The copolymers are suitable as water-soluble amine-based polymer components in multilayer membranes for separating acidic gases from gaseous mixtures (according to DE 196 00 954).
- (9) The copolymers are suitable for the preparation of aqueous and organic dispersions, emulsions or solutions of amine-based polymers. The amine-based polymers, dispersions, emulsions or solutions are particularly suitable for coating and imparting water repellency to surfaces (finish surfaces, packaging coating, building material impregnation, particle boards, stone, metal, textiles, plastics, leather, wood, paper), for the treatment of various materials (stone, metal, textiles, plastics, leather, wood, paper), as process chemicals in the textile industry, as additives in printing inks and finishes, and as mold release agents.
- (10) The copolymers are suitable as effective corrosion inhibitors in radiation protection mixtures.
- The copolymers are particularly preferably used as flow improvers, wax-anti-settling-additives and lubricity additives, for reducing fretting, as corrosion inhibitors and/or as internal combustion engine intake system cleaners in mineral oils, mineral oil distillates and combustion and power fuels.
- When used as flow improvers, the novel copolymers are preferably employed in combustion and power fuel compositions, in particular in middle distillates, such as diesel fuels and light heating oils. They can be used together with further conventional additives.
- The novel copolymers can be incorporated into the mineral oils, mineral oil distillates and combustion and power fuels, in particular into a middle distillate, directly but preferably as 20 to 70% strength by weight solutions. Preferably used solvents are hydrocarbon solvents. Suitable solvents are described, for example, in DE-A-196 24 861 and DE-A-43 41 528. The novel copolymers may be dissolved in a large amount in a hydrocarbon solvent; preferably, the solutions contain from 5 to 80, particularly preferably from 20 to 70, particularly from 40 to 60, % by weight of one or more novel copolymers alone or together with other assistants, for example according to the abovementioned applications. The present invention also relates to such concentrates or mixtures.
- The concentrates may be further used, for example, for the preparation of combustion and power fuel compositions (cf DE-A-196 24 861).
- The present invention also relates to combustion and power fuel compositions which contain from 5 to 5000, preferably from 10 to 500, ppm by weight, based on the total weight of the composition, of the copolymer, alone or together with other assistants.
- The Examples which follow illustrate the invention.
- Preparation of the Amination Catalyst:
- An aqueous solution of nickel nitrate, cobalt nitrate and zirconium acetate, which contained 4.48% of NiO, 1.52% of CuO and 2.82% of ZrO2, was precipitated simultaneously in a stirred vessel in a constant stream with a 20% strength aqueous sodium carbonate solution at 70° C. so that the pH of 7.0, measured using a glass electrode, was maintained.
- The suspension obtained was filtered and the filter cake was washed with demineralized water until the electrical conductivity of the filtrate was about 20 mS. 1.5% of MoO3 in the form of an aqueous solution of ammonium heptamolybdate were then stirred in. The filter cake was then dried at 150° C. in a drying oven or in a spray dryer. The basic carbonate mixture obtained in this manner was heated at 500° C. over a period of 4 hours.
- The catalyst thus obtained had the following composition:
- 51% by weight of NiO, 17% by weight of CuO, 30.5% by weight of ZrO2 and 1.5% by weight of MoO3. The catalyst powder was mixed with 3% by weight of graphite and molded to give 6×3 mm pellets.
- Preparation of an Ethylene/vinyl Acetate/vinylamine Terpolymer:
- First, an ethylene/vinyl acetate copolymer which was composed of 70.3% by weight of ethylene and 29.7% by weight of vinyl acetate was prepared. The melt viscosity at 120° C. was 65 mm2/s. The preparation was carried out as described in DE-A-197 54 039.
- 75 g of this copolymer were mixed with 75 g of cyclohexane as a solvent, and 850 g of liquid ammonia were added in an autoclave. They were then heated at 200° C. for 16 hours at a hydrogen pressure of 200 bar in the presence of 50 g of the catalyst described above. Thereafter, cooling was carried out, the pressure was let down and the autoclave content was removed. After the catalyst had been filtered off and the cyclohexane separated off, 80 g of a liquid, colorless product were obtained.
- The content of ethylene, vinyl acetate and vinylamine was determined by NMR spectroscopy. The terpolymer contained 75.6% by weight of ethylene, 14.7% by weight of vinyl acetate and 9.7% by weight of vinylamine. The kinematic melt viscosity, determined using a rotational viscometer at 120° C., was 70 mm2/S.
- Test Oils
- The novel terpolymer described above was used as an additive in various test oils. The test oils had the following characteristic data.
TABLE 1 Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Initial boiling point [° C.] 173 182 168 195 178 5% [° C.] 206 223 186 222 194 10% [° C.] 219 236 192 233 200 50% [° C.] 285 287 233 275 243 95% [° C.] 369 354 353 343 343 Final boiling point [° C.] 380 365 367 354 355 90%-20% [° C.] 115 87 127 80 115 FPB-90% [° C.] 27 25 39 27 30 Cloud point [° C.] 2.8 2 −6.4 −8.9 −7.7 CFPP [° C.] 0 0 −9 −12 −9 Sulfur [ppm] 2000 1800 450 310 45 - The novel terpolymers were introduced into the test oils, and the cold filter plugging point (CFPP) was determined according to EN 116. In addition, the cloud point (CP) was determined according to ISO 3015. The CFPP is shown in Table 2 below.
TABLE 2 Test oil Dose/ppm CFPP [° C.] 1 100 −7 2 250 −2 3 50 −11 3 125 −18 4 25 −15 - Lubricating Effect:
- The lubricating effect of the ethylene/vinyl acetate/vinylamine terpolymer (II) described was determined in test oil 5 according to DIN ISO 121546-1 (HFRR measurement). The results in Table 3 are specified as a wear scar diameter (WS 1.4). A lower wear scar indicates a good lubricating effect. A commercial lubricity additive Kerokorr® LA 99 (K) was used in comparison with the novel ethylene/vinyl acetate/vinylamine terpolymer (T).
TABLE 3 Wear scar diameter/ Additive Dose/ppm μm No additive — 590 T 50 483 T 75 304 K 50 516 K 75 421 K 100 333 - Paraffin Sedimentation:
- The effect on the paraffin sedimentation (wax-anti-settling) in test oil 3 was determined by an ARAL method (cf. Table 4). 500 ml of the diesel fuel were stored at −13° C. for 16 hours. The additives tested were the ethylene/vinyl acetate copolymer (C) described and the novel vinyl acetate/vinylamine terpolymer (T). The quality of the effect on the paraffin sedimentation (wax-anti-settling) is determined by visual assessment:
- Case (A): the sample is uniformly turbid and the paraffins are completely dispersed.
- Case (B): the sample consists of two phases having different turbidities.
- Case (C): the sample consists of two phase, the lower phase being turbid and the upper phase being clear.
- Substances which lead to the results of case (A) and case (B) in the test are efficient wax-anti-settling additives. In addition, the cloud point (CP) and the CFPP are determined for the lower 20%. A positive effect on the low-temperature behavior of the test oil is present when the cloud point of the 20% lower phase is slightly (1-2° C.) above the cloud point before the storage test at −13° C.
Test oil 3 without additive Visual CP: −6.4° C. assessment 20% lower phase CFPP: −9° C. CFPP/° C. Lower phase Upper phase CP/° C. CFPP/° C. 60 ppm of additive (C) −20 42% 58% −0.0 −17 paraffins clear settled out phase 60 ppm of additive (C) −27 28% 72% −5.3 −27 paraffins turbid 75 ppm of additive (T) settled out due to dispersed paraffins - Table 4 shows that the ethylene/vinyl acetate copolymer used for the preparation of the ethylene/vinyl acetate/vinylamine terpolymer has no effect on the paraffin sedimentation. A positive effect on the paraffin sedimentation is achieved by adding the ethylene/vinyl acetate/vinylamine terpolymer to the ethylene/vinyl acetate copolymer.
Claims (10)
1. A process for the preparation of polymers which contain six or more vinylamine building blocks of the formula (I) in the main chain
—CH2—CH(NR1R2)— (I)
where
R1 and R2, independently of one another, are each hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl or a polyamine radical,
by reductive amination of copolymers which consist of C2-12-olefin building blocks and vinyl esters of C1-12-monocarboxylic acids as building blocks,
with amines of the formula (III)
HNR1R2 (III)
and hydrogen.
2. A process as claimed in claim 1 , wherein the copolymers to be aminated are ethylene/vinyl acetate copolymers.
3. A copolymer consisting of polymerized C2-12-olefin building blocks, vinylesters of C1-12-monocarboxylic acids and six or more vinylamine building blocks of the formula (I)
—CH2—CH(NR1R2)— (I)
where
R1 and R2, independently of one another, are each hydrogen, C1-20-alkyl, C6-18-aryl, C7-20-alkaryl, C7-20-aralkyl or a polyamine radical.
4. A copolymer as claimed in claim 3 , consisting of polymerized ethylene, vinyl acetate and vinylamine building blocks.
5. The use of a copolymer as claimed in claim 3 or 4 as an assistant in mineral oils, mineral oil distillates and combustion and power fuels, in chromatography, as an ion exchanger, in dispersions, as an emulsifier, in papermaking, in inks, membranes, adhesives, detergents, mold release agents, in wastewater treatment, for coating and imparting water repellency to surfaces, for the treatment of materials, as a process chemical in the textile industry, and as an additive in printing inks and finishes.
6. The use as claimed in claim 5 , as a flow improver, a wax-anti-settling additive or a lubricity additive, for reducing fretting, as a corrosion inhibitor and/or as an internal combustion engine intake system cleaner in mineral oil distillates.
7. A concentrate containing a mineral oil, a mineral oil distillate or a combustion or power fuel and from 5 to 80% by weight, based on the total amount of the concentrate, of at least one copolymer as claimed in either of claims 3 and 4.
8. A mixture of at least one concentrate as claimed in claim 7 and further assistants which are used according to the applications stated in claim 6 .
9. A combustion or power fuel composition containing a combustion or power fuel and from 5 to 5000 ppm by weight, based on the total amount of the combustion or power fuel composition, of a copolymer as claimed in claim 3 or 4, alone or as a mixture with other mineral oil assistants.
10. A copolymer, obtainable by a process as claimed in claim 1 or 2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10044164.5 | 2000-09-07 | ||
DE10044164A DE10044164A1 (en) | 2000-09-07 | 2000-09-07 | Vinyl amine compounds |
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US20030177690A1 true US20030177690A1 (en) | 2003-09-25 |
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ID=7655349
Family Applications (1)
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US10/363,659 Abandoned US20030177690A1 (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
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US (1) | US20030177690A1 (en) |
EP (1) | EP1373330A1 (en) |
JP (1) | JP2004508436A (en) |
KR (1) | KR20030029927A (en) |
AU (1) | AU2001285917A1 (en) |
CA (1) | CA2421439A1 (en) |
DE (1) | DE10044164A1 (en) |
NO (1) | NO20031040L (en) |
WO (1) | WO2002020627A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040154764A1 (en) * | 2001-08-13 | 2004-08-12 | Thierry Blum | Method for production of coated paper with extreme whiteness |
US20040226620A1 (en) * | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US20060235105A1 (en) * | 2003-06-17 | 2006-10-19 | Gregory Gratson | Directed assembly of three-dimensional structures with micron-scale features |
US20080245266A1 (en) * | 2007-04-09 | 2008-10-09 | Lewis Jennifer A | Sol-gel inks |
US20100084599A1 (en) * | 2008-10-03 | 2010-04-08 | Lewis Jennifer A | Metal nanoparticle inks |
US20100096596A1 (en) * | 2008-10-17 | 2010-04-22 | Lewis Jennifer A | Biphasic inks |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10225944A1 (en) * | 2002-06-11 | 2004-01-08 | Basf Ag | Process for binding particulate, water-absorbent, acid group-containing polymers to a carrier material |
Citations (3)
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US2118713A (en) * | 1934-08-07 | 1938-05-24 | Ig Farbenindustrie Ag | Manufacture of nitrogen containing derivatives of polymerized vinyl esters of halogen fatty acids |
US4070530A (en) * | 1975-10-30 | 1978-01-24 | Monsanto Company | Catalytic amination of polymeric polyols and resulting amino substituted polymers |
US5976202A (en) * | 1994-07-22 | 1999-11-02 | Basf Aktiengesellschaft | Reaction products of polyolefins with vinyl esters and their use as fuel and lubricant additives |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL76601C (en) * | 1948-01-28 | |||
US5349023A (en) * | 1991-12-12 | 1994-09-20 | Kuraray Co., Ltd. | Vinyl alcohol copolymer having terminal amino group |
US5559193A (en) * | 1993-12-20 | 1996-09-24 | Monsanto Company | Controlled functional density polyamines and method for preparation thereof |
-
2000
- 2000-09-07 DE DE10044164A patent/DE10044164A1/en not_active Withdrawn
-
2001
- 2001-08-30 WO PCT/EP2001/010031 patent/WO2002020627A1/en not_active Application Discontinuation
- 2001-08-30 KR KR10-2003-7003309A patent/KR20030029927A/en not_active Application Discontinuation
- 2001-08-30 CA CA002421439A patent/CA2421439A1/en not_active Abandoned
- 2001-08-30 AU AU2001285917A patent/AU2001285917A1/en not_active Abandoned
- 2001-08-30 JP JP2002525246A patent/JP2004508436A/en not_active Withdrawn
- 2001-08-30 EP EP01965237A patent/EP1373330A1/en not_active Withdrawn
- 2001-08-30 US US10/363,659 patent/US20030177690A1/en not_active Abandoned
-
2003
- 2003-03-06 NO NO20031040A patent/NO20031040L/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2118713A (en) * | 1934-08-07 | 1938-05-24 | Ig Farbenindustrie Ag | Manufacture of nitrogen containing derivatives of polymerized vinyl esters of halogen fatty acids |
US4070530A (en) * | 1975-10-30 | 1978-01-24 | Monsanto Company | Catalytic amination of polymeric polyols and resulting amino substituted polymers |
US5976202A (en) * | 1994-07-22 | 1999-11-02 | Basf Aktiengesellschaft | Reaction products of polyolefins with vinyl esters and their use as fuel and lubricant additives |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040154764A1 (en) * | 2001-08-13 | 2004-08-12 | Thierry Blum | Method for production of coated paper with extreme whiteness |
US7641765B2 (en) * | 2001-08-13 | 2010-01-05 | Basf Aktiengesellschaft | Method for production of coated paper with extreme whiteness |
US20070172588A1 (en) * | 2002-09-26 | 2007-07-26 | Daniel Therriault | Microcapillary networks |
US7799251B2 (en) | 2002-09-26 | 2010-09-21 | Board Of Trustees Of University Of Illinois | Microcapillary networks |
US20090000678A1 (en) * | 2002-09-26 | 2009-01-01 | Daniel Therriault | Microcapillary networks |
US20040226620A1 (en) * | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US8101139B2 (en) | 2002-09-26 | 2012-01-24 | Board Of Trustees Of University Of Illinois | Microcapillary networks |
US20060235105A1 (en) * | 2003-06-17 | 2006-10-19 | Gregory Gratson | Directed assembly of three-dimensional structures with micron-scale features |
US20070228335A1 (en) * | 2003-06-17 | 2007-10-04 | Gregory Gratson | Directed assembly of three-dimensional structures with micron-scale features |
US7141617B2 (en) * | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
US20100330220A1 (en) * | 2003-06-17 | 2010-12-30 | Board Of Trustees Of University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
US7790061B2 (en) | 2003-06-17 | 2010-09-07 | Board Of Trustees Of University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
US20080245266A1 (en) * | 2007-04-09 | 2008-10-09 | Lewis Jennifer A | Sol-gel inks |
US7956102B2 (en) | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
US7922939B2 (en) | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
US20100084599A1 (en) * | 2008-10-03 | 2010-04-08 | Lewis Jennifer A | Metal nanoparticle inks |
US20100096596A1 (en) * | 2008-10-17 | 2010-04-22 | Lewis Jennifer A | Biphasic inks |
US8187500B2 (en) | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
Also Published As
Publication number | Publication date |
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DE10044164A1 (en) | 2002-03-21 |
NO20031040L (en) | 2003-05-06 |
CA2421439A1 (en) | 2003-03-06 |
AU2001285917A1 (en) | 2002-03-22 |
WO2002020627A1 (en) | 2002-03-14 |
KR20030029927A (en) | 2003-04-16 |
EP1373330A1 (en) | 2004-01-02 |
NO20031040D0 (en) | 2003-03-06 |
JP2004508436A (en) | 2004-03-18 |
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