WO2007110333A1 - Polyethylene imine based pigment dispersants - Google Patents
Polyethylene imine based pigment dispersants Download PDFInfo
- Publication number
- WO2007110333A1 WO2007110333A1 PCT/EP2007/052552 EP2007052552W WO2007110333A1 WO 2007110333 A1 WO2007110333 A1 WO 2007110333A1 EP 2007052552 W EP2007052552 W EP 2007052552W WO 2007110333 A1 WO2007110333 A1 WO 2007110333A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pei
- acid
- residue
- polyethyleneimine
- based pigment
- Prior art date
Links
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 48
- 239000000049 pigment Substances 0.000 title claims abstract description 40
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 4
- 229920000570 polyether Polymers 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 125000005314 unsaturated fatty acid group Chemical group 0.000 claims abstract 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 22
- 150000002596 lactones Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 9
- 238000005580 one pot reaction Methods 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000013459 approach Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 27
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000009472 formulation Methods 0.000 description 22
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 11
- 230000002860 competitive effect Effects 0.000 description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- -1 alkylene imine Chemical class 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002320 enamel (paints) Substances 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- IFYYFLINQYPWGJ-UHFFFAOYSA-N gamma-decalactone Chemical compound CCCCCCC1CCC(=O)O1 IFYYFLINQYPWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical group 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- YSEQNZOXHCKLOG-UHFFFAOYSA-N 2-methyl-octanoic acid Chemical compound CCCCCCC(C)C(O)=O YSEQNZOXHCKLOG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- GHBSPIPJMLAMEP-UHFFFAOYSA-N 6-pentyloxan-2-one Chemical compound CCCCCC1CCCC(=O)O1 GHBSPIPJMLAMEP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 229920003264 Maprenal® Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- QTDSLDJPJJBBLE-PFONDFGASA-N octyl (z)-octadec-9-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC QTDSLDJPJJBBLE-PFONDFGASA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Definitions
- This invention refers to a novel process for the synthesis of polyethylene imine (PEI)-based pigment dispersants characterized by a "grafting from” approach, allowing the manufacture of solvent based dispersant systems.
- PEI polyethylene imine
- the European Patent Publication EPO 208 041 B1 describes a dispersant comprising a poly(C 2 - 4 -alkyleneimine) carrying at least two mono- or poly-(carbonyl-Cr 7 -alkyleneoxy) groups prepared according to the so called "grafting to" process.
- the backbone is poly- ethylene imine of various molecular weights (1000-1 OO'OOOg/mol)
- the grafting chain is a polyester, particularly a polylactone, which is obtained by carboxylic acid initiated ring- opening polymerization of lactones (e.g. caprolactone).
- polyester chains are reacted with polyethylene imine through both quaternization (forming salt bonds) and amidification (forming amide bonds) reactions between acid and amine groups.
- the salt bond is easily splitted to obtain free NH 2 groups resulting in yellowing of the final resin.
- the key competitive grades are yellowish crystalline solids with low solubility in non-aromatic solvents, and only limited solubility in aromatic solvents.
- JP07 025993 discloses a poly(lower alkylene imine) modified lactone graft polymer, obtained by ring-opening polymerisation of a lactone with a poly(lower alkylene imine) with an alkylene chain of 1-6 carbon atoms.
- the polymer obtained by this process has a backbone of poly(lower alkylene imine) with pending ester groups X1 and X2 linked by amide linkages.
- JP07 025993 discloses the grafting copolymerization of caprolactone and PEI, but no further transesterification step. Compared to JP07 025993 the "grafting from” copolymerization and the transesterification occurs in the present case in sequence (the two-step method) or in- situ (the one-pot method). The structure and the property of the products obtained is different to that obtained in JP 07 025993.
- US6787600 (Lubrizol) discloses a dispersant made by either reacting the PAI/PEI with hydroxycarboxylic acids or lactones thereof in a stepwise manner or by reacting PAI/PEI with performed polyester chain. Compared to US6787600 the present dispersant is made by reacting PAI with carboxylic compounds and lactones, either by a 'two-step" method or by a "one-pot” method.
- One aspect of the invention is to provide a dispersant having improved storage stability and improved compatibility in medium polar or non-polar systems. Furthermore the dispersant should show less-yellowing in white pigment formulations and less viscosity of pigment concentrates.
- grafting from means PEI is used as macroinitiator to initiate the ring-opening polymerization of lactones.
- the products are hydroxy-functionalized grafting copolymers which are further modified.
- the modified copolymers have at least two types of side chains which are linked to the PEI via an amide bond.
- One side chain is OH-terminated, more polar and hydrophilic and derived from the lactone. This chain can be presented as
- the other side chain is the modified one.
- This chain is apolar or medium polar and hydrophobic and can be presented as
- the invention relates to a polyethylene imine (PEI)-based pigment dispersant of the formula I
- T is a residue -CO-A-O- wherein A is C 2 -C 12 alkylene optionally substituted with d-
- X is a modifier or terminator residue R-CO- wherein R-CO- is a linear or branched, saturated or unsaturated alkanecarboxylic acid residue having from 1 to 22 carbon atoms or an unsaturated fatty acid residue or a hydroxycarboxylic residue or a polyester residue obtained from polycondensation of hydroxycarboxylic acids, or a residue of an acid terminated polyether; n, m independently are a number from 1 to 100.
- Amide bond can be a) with primary N-atom; b, with secondary N-atom or salt bonds
- the polyethylene imine (PEI) may be branched or straight chain having an average molecular weight in the range from 200 to 100'000g/mol. Preferred is PEI with a molecular weight in the range of 1000g/mol to 50,000g/mol. Water-free versions are preferred.
- the group (T) n or (T) m are poly(carboxyalkylene oxy) chains (-CO-A-O- )n, m which can be polyesters obtained by ring-opening polymerization of lactones e.g. from epsilon-capro- lactone, gamma-caprolactone, propiolactone, beta-butyrolactone, gamma-butyrolactone, gamma-valerolactone, delta valerolactone, gamma-decanolactone, delta-decanolactone and the like or from alkyl substituted lactones.
- lactones e.g. from epsilon-capro- lactone, gamma-caprolactone, propiolactone, beta-butyrolactone, gamma-butyrolactone, gamma-valerolactone, delta valerolactone, gamma-decanolactone, delta-decano
- Preferred lactones are epsilon-caprolactone or delta-valerolactone or mixtures thereof.
- A is therefore preferably C 4 -C 5 alkylene.
- the modifier or terminator residue X is derived from carboxylic acid and/or carboxylic acid ester derivatives, which are reacted with the terminal OH-functionality of the grafted chains (T) by esterification (condensation process, water liberated) or transesterification (condensation, alcohol molecule liberated).
- caproic acid hexanoic acid (CH 3 -(CH 2 ) 4 COOH, heptanoic acid, octanoic acid, methyloctanoic acid, nonanoic acid, 3,3,5-isononanoic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric
- unsaturated fatty acids are oleic acid, linolenic acid, palmitoleic acid, myristoleic acid, arachidonic acid, or tall oil fatty acid and the like.
- acid esters are methyloleate, butyloleate, octyloleate, methylstearate and similar CrCe alkyl esters of saturated and unsaturated linear or branched carboxylic acids as mentioned above.
- hydroxycarboxylic acid refers to monomers having at least one carboxylic acid group and at least one hydroxy group but which may also include other substituents which do not interfere with the polymerization of the monomer.
- suitable substituents on the hydroxycarboxylic acid include e.g. linear, branched or cyclic, saturated or unsaturated alkyl, linear, branched or cyclic, saturated or unsaturated alkoxy, halo, and the like.
- Hydroxy- carboxylic acids are well known in the art of polyester production, and are capable of producing polyester polymers via self-polycondensation polymerization reactions. Examples of suitable hydroxycarboxylic acids include e.g.
- the chain length of the polyester is 1 to 100, preferably 1 to 10, more preferably 1 to 5.
- Preferred is polyhydroxystearic acid (PHSA), with acid numbers of PHSA preferably between 10 and 200 mg KOH/g.
- acid terminated polyether refers e.g. to succinic anhydride modified (methoxy)- polyalkyl glycol, molecular weights are 200 to 5000 g/mol, preferably 200 to 2,000 g/mol.
- the PEI-based pigment dispersant of the formula I is prepared based on the "grafting from” approach through either a two step or one pot method.
- the process is characterized by a) using PEI as macroinitiator to initiate the ring-opening polymerisation of lactones by the primary amines and the secondary amines of PEI to obtain
- step a) is followed by step b.
- reaction system is more complex. "Grafting from” copolymerization and (trans)esterification are operated in one pot. The products are obtained in one step.
- the product obtained has at least two types of grafted side chains.
- These compounds carry at least a side chain attached to the PEI by amid bond which side chain further comprises an ester bond in the chain obtained by the transesterification process.
- the chain length of the grafted side chain is determined by the relative molar ratio of used lactone to reactive amine group of PEI.
- the weight ratio of PEI to lactone monomers ranges from 1 :1 to 1 :50, therefore the designed MW of polylactones approximately ranges from 100 to 10'0OO g/mol.
- Preferably the weight ratio of PEI to lactone monomers ranges from 1.1 to 1.20, therefore the designed chain length of polylactones approximately ranges from 500 g/mol to 5000 g/mol.
- Reaction temperatures range from 60 °C to 200 °C under N 2 atmosphere for the "grafting from" copolymerization and from 100 °C to 200 °C under N 2 atmosphere during (trans)esterification.
- the (trans)esterification catalyst may be any catalyst suitable in this field.
- Examples are Tin (II) salts e.g. Tin (II) octoate, dibutyltin dilaurate, dibutyltin dichloride, or Tin (IV) compound SnCI 4 , or titanium complexes e.g. tetrabutyltitanate, tetraisopropyltitanate, or aluminum complexes e.g. tris(acetylacetonato)aluminum, (porphinato)aluminum.
- reaction temperatures range from 150 °C to 180 °C under N 2 atmosphere.
- the pigment dispersants of the formula I preferably have acid numbers of 0 - 50 mg KOH/g, preferably from 0 - 30 mg KOH/g,
- the grafting ratio defined as total reactive amine groups divided by grafted polymer chains (T), is determined according to the contents of the primary and secondary amino groups in the PEI molecule.
- Grafting efficiency defined as polymer grafted divided by total amount of polymer, is up to 100%.
- the grafting density is preferably >30%.
- the preferred products have lower acid number, generally less than 20 mg KOH/g, preferably less than 5 mg KOH/g, which indicates that the linkage of PAI and polyester chain is mainly via amide bonding.
- the pigment dispersant of the formula I is amphiphilic because the grafted polyester chain is a mixture of hydrophilic (HO-terminated) and hydrophobic (alkyl terminated) polymer chains.
- (trans)esterification With (trans)esterification, the polarity and therefore the compatibility of the graft copolymer can be adjusted by using various carboxylic acids or hydroxycarboxylic acids. This method enables an enormous flexibility of adjusting the same OH-functional prepolymer to the situation or condition, by choosing the right carboxylic acid or mixture of carboxylic acid derivatives at the end of the process.
- the amine-initiated ring-opening polymerisation kinetics is very much faster than the acid initiated polymerisation as presented in the state of the art.
- the (hydroxy)carboxylic acid materials in the one-pot process also can act as co-catalyst to accelerate the polymerization. Products with good performance can be obtained in a shorter reaction time with less amount of catalyst, which indicates that the manufacturing costs of one-pot 'grafting from' approach are lower.
- the products obtained by this invention generally show good compatibility in a wide range of let-down resin systems, e.g. alcohol alkyd, CAB etc.
- the viscosity of pigment concentrates is lower, indicating the possibility of higher pigment loading; draw-downs and pour-outs of different pigment preparations show high gloss, less flocculation and no seeding.
- the storage stability of the product is improved, it appears compatible with most paint systems and shows lower viscosity of pigment concentrates, high gloss and less yellowing of white formulations.
- the dispersant is used to stabilise pigment dispersions.
- the moieties being 'grafted from' are polyester side chains, which interact with the resin phase and are necessary to build up a steric environment to stabilize the pigment dispersion.
- the polyethylene imine part of the polymer has affinity for the pigment surface (anchoring group) and therefore provides a strong physical binding of the dispersant to the solid pigment particle.
- the dispersant may be use to stabilize dispersions of pigments and/or fillers for application in coatings, plastics, adhesives, inks and toners, especially ink jet inks, electronic materials like color filter formulations, construction materials like casting resins, formulations for cosmetics and personal care like nail coatings.
- the dispersant may also be used to disperse functional particles like particles to enhance electric or thermal conductivity, e.g. metal particles, graphite, organic and inorganic nano- particles, carbon nanotubes, or magnetic particles, or to disperse charged electrophoretic particles for display applications.
- functional particles like particles to enhance electric or thermal conductivity, e.g. metal particles, graphite, organic and inorganic nano- particles, carbon nanotubes, or magnetic particles, or to disperse charged electrophoretic particles for display applications.
- the dispersant may also be used to disperse effect pigments like aluminium flake pigments, mica.
- the dispersant may also be used for surface modification of pigments, e.g. to improve easy redispersibility of dry pigment powders.
- Step 1 Preparation of HO-functionalized graft copolymers by "Grafting from” approach.
- Examples 2 - 5 were prepared according to the following process: Epomin SP-018 32.25 g (1 part, trade name, from Nippon Shokubai, MW 1800), ⁇ -caprolactone 250.0 g (7.75 parts), and dibutyltin dilaurate (5.0 * 10 "4 w/w) were stirred under nitrogen and heated in a range of 80 - 200 °C for 1.0 - 30 h until solid contents reached 98%. Table 1 lists the results.
- Examples 6-1 1 were prepared according to the flowing process: Epomin SP-018 12.5 g (1 part), ⁇ -caprolactone 250.0 g (20.0 parts), and dibutyltin dilaurate (5.0 * 10- 4 w/w) were stirred under nitrogen and heated in a range of 80-200 °C for 1.0 - 3O h until solid contents reached 98%.
- Table 2 lists the results.
- Examples 12 - 17 were prepared according to the following process: Lupasol PR 8515 (trade name, from BASF, MW 2000), ⁇ -caprolactone 100.0 g, and dibutyltin dilaurate (5.0 * 10 "4 w/w) were stirred under nitrogen and heated at 100-200 °C until solid contents reached 98%. Table 3 lists the results. Table 3.
- Examples 18 - 25 (CL : Epomin SP-200 with various weight ratios) Examples 18-25 were prepared according to the following process: Epomin SP-200 (trade name, from Nippon Shokubai, MW 10,000), ⁇ -caprolactone 100.0 g, and dibutyltin dilaurate (5.0 * 10 "4 w/w) were stirred under nitrogen and heated to 100 - 200 °C until solid contents reached 98%. Table 4 lists the results.
- Polyethyleneimine 5.0 g (1 part, Epomin SP 018, Nippon Shokubai, approx. MW 1800), ⁇ - caprolactone 35.0 g (7.0 parts), ⁇ -valerolactone 35.0 g (VL, 7.0 parts) and dibutyltin dilaurate 0.05 g were stirred under nitrogen and heated to 150 °C for 5.0 h. After cooling, the product was obtained as a yellow clear liquid with a solid content above 98%.
- the amine number is 50 mg KOH/g.
- Polyethyleneimine 5.0 g (1 part, Epomin SP 200, Nippon Shokubai, approx. MW 10,000), ⁇ - caprolactone 35.0 g (7.0 parts), ⁇ -valerolactone 35.0 g (7.0 parts) and dibutyltin dilaurate 0.05 g were stirred under nitrogen and heated to 150 °C for 5.0 h. After cooling, the product was obtained as a yellow clear liquid with a solid content above 98%.
- Example 24 (Table 4) was used as precursor (50.0 g) and stirred with carboxylic acid (1.5:1 in mol ratio of polylactone chain : acid) in a temperature range of 100 - 200 °C for 1.0 - 40.0 h under a nitrogen atmosphere.
- the acid number of product was measures by titration.
- Table 5 lists the results. Table 5. Esterification with different carboxylic acids.
- the graft copolymer obtained in Step 1 was used as precursor and stirred with lauric acid
- Table 6 lists the reaction conditions and the results.
- Example 25 (210 g, Table 4) was stirred with 12-hydroxystrearic acid (24.0 g) at 170 °C for 1.0 - 30.0 h under a nitrogen atmosphere. The acid numbers of products were measured by titration. Table 7 lists the results. Table 7. Modification with HSA.
- 12-Hydroxystearic acid (200.0 g) and dibutyltin dilaurate (0.20 g) were added in a four-neck reactor equipped with a condensation water separator and stirred at 180 °C for 1.0 - 60.0 h under a nitrogen atmosphere.
- the by-product water was removed by refluxing with benzene.
- Example 25 (Table 4) was used as precursor and stirred with the obtained PHSA (1.5:1 in mol ratio of polylactone : hydroxystearic acid) at a temperature of 160 °C for 1.0 - 20.0 h under a nitrogen atmosphere.
- the acid numbers of the products were measured by titration.
- Table 8 lists the reaction conditions and the results.
- Example 24 (Table 4) was used as precursor (50.0 g) and stirred with carboxylic acid esters
- Lupasol PR 8515 (6.45 g), epsilon-caprolactone caprolactone (50.0 g), 12-hydroxystearic acid (15.0 g) and dibutyltin dilaurate (0.12 g) were stirred at 180 °C for 18.0 h.
- the obtained product is a golden liquid at R T with an acid number of 2 mg KOH/g.
- Epomin SP-018 (6.45 g), epsilon-caprolactone (100.0 g), 12-hydroxystearic acid (15.0 g) and dibutyltin dilaurate (0.12 g) were stirred at 180 °C for 11.0 h.
- the obtained product is a yellowish solid with an acid number of 7.5 mg KOH/g.
- Epomin SP-018 (6.45 g), epsilon-caprolactone (85.0 g), delta-valerolactone (15.0 g), 12- hydroxystearic acid (15.0 g) and dibutyltin dilaurate (0.12 g) were stirred at 180 °C for 12.0 h.
- the obtained product is brownish liquid with an acid number of 15 mg KOH/g.
- Epomin SP-018 (6.45 g), epsilon-caprolactone (50.0 g), 12-hydroxystearic acid (30.0 g) and dibutyltin dilaurate (0.08 g) were stirred at 180 °C for 6.0 h.
- the obtained product is golden liquid with an acid number of 26 mg KOH/g.
- Epomin SP-020 (6.45 g), epsilon-caprolactone (100.0 g), 12-hydroxystearic acid (15.0 g) and dibutyltin dilaurate (0.12 g) were stirred at 180 °C for 12.0 h.
- the obtained product is a browish solid with an acid number of 9 mg KOH/g.
- Epomin SP-020 (6.45 g), epsilon-caprolactone (100.0 g), PHSA-4 (Table 8, 80.0 g) and dibutyltin dilaurate (0.20 g) were stirred at 180 °C for 12.0 h.
- the obtained product is a brown solid with an acid number of 6 mg KOH/g.
- Epomin SP-020 (6.45 g), caprolactone (100.0 g), 12-hydroxylstearic acid (15.0 g) and dibutyltin dilauric (0.12) g were stirred at 180°C for 15.0 h. Product is yellowish solid with acid number of 5 mg KOH/g.
- Epomin SP-020 (6.45 g), caprolactone (100.0 g), ethyl laurate (12.0 g) and dibutyltin dilauric
- Epomin SP-020 (6.45 g), caprolactone (100.0 g), methyl stearate (15.5 g) and dibutyltin dilauric (0.12 g) were stirred at 170°C for 6.0 h. Product is yellowish solid with acid number less than 3 mg KOH/g.
- Example 74
- Epomin SP-020 (6.45 g), caprolactone (60.0 g), valerolactone (40.Og), 12-hydroxylstearic acid (15.0 g) and dibutyltin dilauric (0.12 g) were stirred at 170°C for 18.0 h.
- Product is amber liquid with acid number 12 mg KOH/g.
- Epomin SP-020 (6.45 g), caprolactone (60.0 g), valerolactone (40.Og), methyl stearate (15.5 g) and dibutyltin dilauric (0.12 g) were stirred at 170°C for 15.0 h.
- Product is amber liquid with acid number 3 mg KOH/g.
- Epomin SP-018 (6.45 g), caprolactone (60.0 g), valerolactone (40.Og), 12-hydroxystearic acid (15.0 g) and dibutyltin dilauric (0.12 g) were stirred at 170°C for 15.0 h.
- Product is amber liquid with acid number 2.9 mg KOH/g.
- Epoin SP-20 (3.25 g), Epomin SP-018 (3.25 g), caprolactone (60.0 g), valerolactone (40.Og), methyl stearate (15.5 g) and dibutyltin dilauric (0.12 g) were stirred at 170°C for 15.0 h.
- Product is amber wax with acid number less than 3 mg KOH/g.
- Table 10 shows the melting temperature of the invention products are lower than that of the competitive product.
- Resin Free Pigment Concentrates were prepared according to the Formulation 1.
- the mill base was dispersed in Scandex Shaker for 1.5 h with the help of glass beads. Afterwards the mill base was filtered and stored at ambient temperature overnight.
- Let-downs (Formulation 2) for testing were based on a stoving enamel, a CAB base coat and a coil coating resin.
- Formulation 3 shows the paint formulations for the stoving enamel and CAB paints.
- the paint preparation was mixed under high speed stirring for 5 minutes at 2000 rpm, and applied on polyester film with a 35 - 75 ⁇ m wet film thickness.
- Formulation 4 represents a coil coating, which was applied on steel panel with a black strip, and after a rub-out test, baked for 7 seconds at 320 °C.
- Maprenal MF 650 melamine resin, Degussa
- Ciba® EFKA® 3030 is a modified polysiloxane solution slip and leveling agent CAB-531 cellulose acetate butyrate material commercially available from Eastman Chemical Uracron CR 226 XB.
- DSM Coating Resins Uracron CR, OH acrylic Uramex MF 821 DSM Coating Resins Uramex (amino) Cymel 303 melamine resin, Cytec Nacure 1323 amine-blocked sulfonic acid catalyst
- Examples 28 - 70 are acid-modified dispersants and their performance was tested according to Formulations 1 , 2, 3 and 4. It was observed, that the pigment concentrates flow well and their viscosities were lower than the competitive grade.
- the rheological behavior of the pigment concentrates was measured with a Thermo-Haake RheoStress 600 equipment under the CR mode.
- the initial viscosities ( ⁇ o) and dynamic viscosities ( ⁇ t ) of the pigment concentrates are listed in Table 11. According to the viscosity curves, the Pigment White concentrates (PW 21 ) have a Newtonian flow, while the Pigment Black concentrates (Special Black-100) exhibit a pseudoplastic flow.
- Pigment Blue concentrates (PB 15:2) have plastic flows and thixotropic properties, but could easily flow under a low shear stress (T, in Table 11 ).
- Pigment Black 7 (Black FW 200) was dispersed very well by the products of this invention, but no dispersion was observed by competitive grade.
- the performance of the dispersants was generally very good with satisfactory results, e.g. high gloss (on average, above 80 at 20°), no seeding, no rub-out, good color strength, and less yellowing of the white pigment (Table 12).
- the samples were dissolved first, and the results were observed after keeping the samples at ambient temperature.
- the solutions kept stable after 3 months.
- Competitor B is prepared according to Ex. 48 of US6197877
- Zirconium isopropoxide (0.45 parts) was added and temperature raised to 170°C. The reactants were stirred under nitrogen at this temperature for a further 6 hours.
- Ep-Acrylic Ebecry 606; Ur.-Acrylic: Ebecry 210/265; PE/Acrylic: Ebecry 812; TPGDA: Tripropylene glycol diacrylate, SR 306; HDDA: Hexane diol diacryltae; TMPEOTA: trimethyol propane ethoxylate triacrylate, SR 454; TMPTA: trimethylolpropane triacryltate, SR 351. In general, all the liquid leads have better compatibility with UV resins/monomers.
- Step 1 prepare the mill base (set 1 :1 Pigment : Solid Addition): Pigment: 10.0
- Step 3 Final Ink Formulation 25 g Millbase 75 g Letdown Varnish
- PY 110 PE Foil, Gloss 60° N/A 107.0 105.7 106.8
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07727030A EP1999185B1 (en) | 2006-03-29 | 2007-03-19 | Polyethylene imine based pigment dispersants |
AT07727030T ATE547452T1 (en) | 2006-03-29 | 2007-03-19 | POLYETHYLENEIMINE-BASED PIGMENT DISPERSANT |
CN2007800113582A CN101410436B (en) | 2006-03-29 | 2007-03-19 | Polyethylene imine based pigment dispersants |
US12/225,642 US8268957B2 (en) | 2006-03-29 | 2007-03-19 | Polyethylene imine based pigment dispersants |
KR1020087026560A KR101416252B1 (en) | 2006-03-29 | 2007-03-19 | Polyethylene imine based pigment dispersants |
JP2009502012A JP5443971B2 (en) | 2006-03-29 | 2007-03-19 | Pigment dispersants based on polyethyleneimine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06111887 | 2006-03-29 | ||
EP06111887.3 | 2006-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007110333A1 true WO2007110333A1 (en) | 2007-10-04 |
Family
ID=36778083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/052552 WO2007110333A1 (en) | 2006-03-29 | 2007-03-19 | Polyethylene imine based pigment dispersants |
Country Status (7)
Country | Link |
---|---|
US (1) | US8268957B2 (en) |
EP (1) | EP1999185B1 (en) |
JP (1) | JP5443971B2 (en) |
KR (1) | KR101416252B1 (en) |
CN (1) | CN101410436B (en) |
AT (1) | ATE547452T1 (en) |
WO (1) | WO2007110333A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009203462A (en) * | 2008-01-31 | 2009-09-10 | Fujifilm Corp | Resin, pigment dispersion, colored curable composition, color filter using it and its production method |
WO2010149962A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
WO2010149955A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
WO2010149957A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
EP2366456A1 (en) | 2010-03-19 | 2011-09-21 | Omya Development AG | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
CN101637708B (en) * | 2009-09-01 | 2011-12-07 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
WO2017140538A1 (en) | 2016-02-16 | 2017-08-24 | Basf Se | Polyalkylene imine based polymers having polyester groups |
WO2018203035A1 (en) * | 2017-05-05 | 2018-11-08 | Lankem Ltd. | Compositions and methods |
CN109715699A (en) * | 2016-09-16 | 2019-05-03 | 毕克化学有限公司 | The amino adducts of polyester modification |
US10399051B2 (en) | 2016-03-24 | 2019-09-03 | Evonik Degussa Gmbh | Dispersants |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101415019B1 (en) * | 2006-09-27 | 2014-07-16 | 시바 홀딩 인크 | Polyethylene imine based dendritic dispersant |
WO2008107326A1 (en) * | 2007-03-05 | 2008-09-12 | Basf Se | Polyamine-polyacrylate dispersant |
JP5588638B2 (en) | 2009-08-19 | 2014-09-10 | 理想科学工業株式会社 | Non-aqueous pigment ink |
CN104588643B (en) * | 2009-09-30 | 2017-08-29 | 大日本印刷株式会社 | Metal particle dispersion, the manufacture method of conductive board and conductive board |
JP5761191B2 (en) * | 2010-07-15 | 2015-08-12 | 味の素株式会社 | Modified polyamine |
IT1404805B1 (en) * | 2011-02-10 | 2013-11-29 | Lamberti Spa | Dispersing |
CN103159957A (en) * | 2011-12-09 | 2013-06-19 | 叶磊 | Dispersing agent and preparation method thereof |
FR2995901B1 (en) * | 2012-09-21 | 2015-08-14 | Inst Corps Gras Etudes Et Rech S Tech Iterg | NOVEL BIOSOURCES PRE-POLYMERS AND THEIR USES FOR THE PREPARATION OF USEFUL POLYMERS AS ADDITIVES IN A POLY (LACTIC ACID) MATRIX |
US10640611B2 (en) | 2013-11-29 | 2020-05-05 | Byk-Chemie, Gmbh | Polyamine addition compounds |
TWI674301B (en) * | 2014-04-08 | 2019-10-11 | 美商盧伯利索先進材料有限公司 | Ink jet ink compositions and process for milling inorganic particulates |
US9434852B2 (en) | 2014-10-15 | 2016-09-06 | Eastman Kodak Company | Photocurable compositions with dispersed carbon-coated metal particles |
US9359517B2 (en) | 2014-10-15 | 2016-06-07 | Eastman Kodak Company | Non-aqueous compositions of dispersed carbon-coated metal particles |
US9447501B2 (en) | 2014-10-15 | 2016-09-20 | Eastman Kodak Company | Forming articles and devices with carbon-coated metal particles |
US9650533B2 (en) | 2014-10-15 | 2017-05-16 | Eastman Kodak Company | Articles containing carbon-coated metal particles |
EP3252113B1 (en) * | 2015-01-27 | 2020-11-25 | Sumitomo Metal Mining Co., Ltd. | Near-infrared ray absorbing microparticle dispersion solution, production method thereof, counterfeit-preventing ink composition using said near-infrared ray absorbing microparticle dispersion solution, and anti-counterfeit printed matter using said near-infrared ray absorbing microparticles |
JP6508225B2 (en) * | 2015-01-27 | 2019-05-08 | 住友金属鉱山株式会社 | Near infrared ray absorbing fine particle dispersion and method for producing the same |
CN105028398A (en) * | 2015-07-09 | 2015-11-11 | 江苏擎宇化工科技有限公司 | Application and preparation method for polyhydroxyalkanoate grafted organic polyamine dispersant |
JP2017171711A (en) * | 2016-03-18 | 2017-09-28 | 味の素株式会社 | Polyallylamine derivative and polyethyleneimine derivative |
IT201600109323A1 (en) | 2016-10-28 | 2018-04-28 | Giovanni Broggi | UNIVERSAL PIGMENTARY PREPARATIONS FOR COLORING AND REINFORCING PLASTIC MATERIALS |
EP3428216B1 (en) * | 2017-07-11 | 2022-11-02 | Henkel AG & Co. KGaA | Method for producing functionalized polyesters |
ES2925507T3 (en) | 2017-09-19 | 2022-10-18 | Lubrizol Advanced Mat Inc | Multiamine polyester dispersant manufactured through an intermediate anhydride |
CN113795535A (en) * | 2019-03-14 | 2021-12-14 | 路博润先进材料公司 | Polyamine polyester dispersants prepared via anhydride intermediates |
WO2021052999A1 (en) | 2019-09-20 | 2021-03-25 | Basf Se | Polyalkyleneimine-based polymer as dispersants |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0725993A (en) * | 1993-07-12 | 1995-01-27 | Daicel Chem Ind Ltd | Production of poly(lower alkylene imine)-modified lactone graft polymer |
US6787600B1 (en) * | 1999-09-18 | 2004-09-07 | The Lubrizol Corporation | Polyester dispersants |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3778287A (en) * | 1970-12-22 | 1973-12-11 | Ici Ltd | Pigment dispersions |
US3728143A (en) * | 1971-03-31 | 1973-04-17 | Plastic Molders Supply Co | Pigment dispersion |
GB8531635D0 (en) * | 1985-01-22 | 1986-02-05 | Ici Plc | Composition |
US4963275A (en) * | 1986-10-07 | 1990-10-16 | Exxon Chemical Patents Inc. | Dispersant additives derived from lactone modified amido-amine adducts |
CA2178663A1 (en) * | 1995-07-06 | 1997-01-07 | Richard E. Cherpeck | Polylactone aminocarbamates and fuel compositions containing the same |
GB0009798D0 (en) * | 2000-04-20 | 2000-06-07 | Avecia Ltd | Dispersants |
-
2007
- 2007-03-19 KR KR1020087026560A patent/KR101416252B1/en active IP Right Grant
- 2007-03-19 CN CN2007800113582A patent/CN101410436B/en active Active
- 2007-03-19 US US12/225,642 patent/US8268957B2/en active Active - Reinstated
- 2007-03-19 JP JP2009502012A patent/JP5443971B2/en active Active
- 2007-03-19 WO PCT/EP2007/052552 patent/WO2007110333A1/en active Application Filing
- 2007-03-19 AT AT07727030T patent/ATE547452T1/en active
- 2007-03-19 EP EP07727030A patent/EP1999185B1/en not_active Revoked
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0725993A (en) * | 1993-07-12 | 1995-01-27 | Daicel Chem Ind Ltd | Production of poly(lower alkylene imine)-modified lactone graft polymer |
US6787600B1 (en) * | 1999-09-18 | 2004-09-07 | The Lubrizol Corporation | Polyester dispersants |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 04 31 May 1995 (1995-05-31) * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009203462A (en) * | 2008-01-31 | 2009-09-10 | Fujifilm Corp | Resin, pigment dispersion, colored curable composition, color filter using it and its production method |
WO2010149962A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
WO2010149955A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
WO2010149957A1 (en) | 2009-06-22 | 2010-12-29 | Unilever Plc | Branched polymer dispersants |
CN101637708B (en) * | 2009-09-01 | 2011-12-07 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
WO2011113866A1 (en) | 2010-03-19 | 2011-09-22 | Omya Development Ag | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
EP2366456A1 (en) | 2010-03-19 | 2011-09-21 | Omya Development AG | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
US8662311B2 (en) | 2010-03-19 | 2014-03-04 | Omya International Ag | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
WO2017140538A1 (en) | 2016-02-16 | 2017-08-24 | Basf Se | Polyalkylene imine based polymers having polyester groups |
US10808078B2 (en) | 2016-02-16 | 2020-10-20 | Basf Se | Polyalkylene imine based polymers having polyester groups |
US10399051B2 (en) | 2016-03-24 | 2019-09-03 | Evonik Degussa Gmbh | Dispersants |
CN109715699A (en) * | 2016-09-16 | 2019-05-03 | 毕克化学有限公司 | The amino adducts of polyester modification |
CN109715699B (en) * | 2016-09-16 | 2021-05-18 | 毕克化学有限公司 | Polyester-modified amino adducts |
WO2018203035A1 (en) * | 2017-05-05 | 2018-11-08 | Lankem Ltd. | Compositions and methods |
Also Published As
Publication number | Publication date |
---|---|
EP1999185B1 (en) | 2012-02-29 |
KR101416252B1 (en) | 2014-07-07 |
EP1999185A1 (en) | 2008-12-10 |
JP5443971B2 (en) | 2014-03-19 |
KR20080108584A (en) | 2008-12-15 |
JP2009531490A (en) | 2009-09-03 |
US20100174046A1 (en) | 2010-07-08 |
US8268957B2 (en) | 2012-09-18 |
CN101410436B (en) | 2013-10-16 |
CN101410436A (en) | 2009-04-15 |
ATE547452T1 (en) | 2012-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8268957B2 (en) | Polyethylene imine based pigment dispersants | |
CA2268117C (en) | Dispersants | |
US9752067B2 (en) | Amine adducts preparable by Michael addition | |
JP5415768B2 (en) | Novel dispersant and composition thereof | |
EP2066434B1 (en) | Polyethylene imine based dendritic dispersant | |
JP2009518182A5 (en) | ||
US20160215160A1 (en) | Multi-acid multi-base graft copolymer dispersants | |
US20030027873A1 (en) | Dispersants | |
EP3574053A1 (en) | Polymeric dispersants containing one or two quaternary amine anchoring groups with improved chemical and thermal stability | |
KR20160079859A (en) | Dispersants with multiple aromatic imide anchor groups | |
CN112867751A (en) | Dispersants for coating systems | |
US8703850B2 (en) | Dispersant composition | |
CN112654419A (en) | Polyamine polyester dispersants and process for making | |
JP5615460B2 (en) | Polyester quaternary salt and composition thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07727030 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007727030 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12225642 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200780011358.2 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009502012 Country of ref document: JP Ref document number: 5202/CHENP/2008 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020087026560 Country of ref document: KR |