CN111234208B - A kind of polyester/polyamide type copolymer and its preparation method and application - Google Patents
A kind of polyester/polyamide type copolymer and its preparation method and application Download PDFInfo
- Publication number
- CN111234208B CN111234208B CN202010250537.9A CN202010250537A CN111234208B CN 111234208 B CN111234208 B CN 111234208B CN 202010250537 A CN202010250537 A CN 202010250537A CN 111234208 B CN111234208 B CN 111234208B
- Authority
- CN
- China
- Prior art keywords
- acid
- polyester
- benzoic acid
- polyamide
- carboxyl
- 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.)
- Active
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 52
- 229920002647 polyamide Polymers 0.000 title claims abstract description 52
- 229920001577 copolymer Polymers 0.000 title claims abstract description 26
- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 38
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000005711 Benzoic acid Substances 0.000 claims description 15
- -1 alkyl benzoic acid Chemical compound 0.000 claims description 15
- 235000010233 benzoic acid Nutrition 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 claims description 2
- UABHETFCVNRGNL-UHFFFAOYSA-N 2-butoxybenzoic acid Chemical compound CCCCOC1=CC=CC=C1C(O)=O UABHETFCVNRGNL-UHFFFAOYSA-N 0.000 claims description 2
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical compound CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 claims description 2
- LXRMKRFJCWLAIX-UHFFFAOYSA-N 2-decoxybenzoic acid Chemical compound CCCCCCCCCCOC1=CC=CC=C1C(O)=O LXRMKRFJCWLAIX-UHFFFAOYSA-N 0.000 claims description 2
- RGRRXKZHELYJHJ-UHFFFAOYSA-N 2-decylbenzoic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1C(O)=O RGRRXKZHELYJHJ-UHFFFAOYSA-N 0.000 claims description 2
- GTRHHOMIEMLBPC-UHFFFAOYSA-N 2-dodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C(O)=O GTRHHOMIEMLBPC-UHFFFAOYSA-N 0.000 claims description 2
- WLPQHPARWSMVFW-UHFFFAOYSA-N 2-dodecylbenzoic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(O)=O WLPQHPARWSMVFW-UHFFFAOYSA-N 0.000 claims description 2
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 claims description 2
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 claims description 2
- ZSTXTALVALLOGG-UHFFFAOYSA-N 2-hexadecoxybenzoic acid Chemical compound CCCCCCCCCCCCCCCCOC1=CC=CC=C1C(O)=O ZSTXTALVALLOGG-UHFFFAOYSA-N 0.000 claims description 2
- BVLVGYXYGXOSOG-UHFFFAOYSA-N 2-hexoxybenzoic acid Chemical compound CCCCCCOC1=CC=CC=C1C(O)=O BVLVGYXYGXOSOG-UHFFFAOYSA-N 0.000 claims description 2
- YQIASAUDDDCAKU-UHFFFAOYSA-N 2-hexylbenzoic acid Chemical compound CCCCCCC1=CC=CC=C1C(O)=O YQIASAUDDDCAKU-UHFFFAOYSA-N 0.000 claims description 2
- YDZIJQXINJLRLL-UHFFFAOYSA-N 2-hydroxydodecanoic acid Chemical compound CCCCCCCCCCC(O)C(O)=O YDZIJQXINJLRLL-UHFFFAOYSA-N 0.000 claims description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims description 2
- OBYWYNKFFLAQBD-UHFFFAOYSA-N 2-octadecoxybenzoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC1=CC=CC=C1C(O)=O OBYWYNKFFLAQBD-UHFFFAOYSA-N 0.000 claims description 2
- GPWWXKMSPDGDBQ-UHFFFAOYSA-N 2-octadecylbenzoic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1C(O)=O GPWWXKMSPDGDBQ-UHFFFAOYSA-N 0.000 claims description 2
- QXFADXLALKKHIZ-UHFFFAOYSA-N 2-octylbenzoic acid Chemical compound CCCCCCCCC1=CC=CC=C1C(O)=O QXFADXLALKKHIZ-UHFFFAOYSA-N 0.000 claims description 2
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 claims description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 2
- RAMRROOXFMYSNA-UHFFFAOYSA-N hexadecyl benzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1 RAMRROOXFMYSNA-UHFFFAOYSA-N 0.000 claims description 2
- LMHJFKYQYDSOQO-UHFFFAOYSA-N hydroxydecanoic acid Natural products CCCCCC(O)CCCC(O)=O LMHJFKYQYDSOQO-UHFFFAOYSA-N 0.000 claims description 2
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011044 succinic acid Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 22
- 238000000227 grinding Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 8
- 238000004873 anchoring Methods 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 125000003368 amide group Chemical group 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- KQGAHNAFXMVSGY-UHFFFAOYSA-N 11-hydroxylauric acid Chemical compound CC(O)CCCCCCCCCC(O)=O KQGAHNAFXMVSGY-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 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 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 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
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyamides (AREA)
Abstract
本发明公开了一种聚酯/聚酰胺型共聚物及其制备方法和应用。该共聚物由如下重量份的物质制备而成：含羧基聚酯83～92份，端氨基聚酰胺5～12份，环氧基硅烷偶联剂3～5份；所述含羧基聚酯的分子量为1800～4000。该共聚物可以作为陶瓷喷墨、数码釉等无机粉体溶剂体系的分散剂，共聚物的酰胺基团对无机粉体具有良好锚固作用，聚酰胺链段上接枝的硅氧烷与无机粉体反应形成牢固的化学键，有利于提高分散稳定性和研磨效率；带有苯环的聚酯为溶剂化链，赋予分散剂立体阻碍效应，起到更优异的防团聚和防沉效果，有利于减少分散剂用量。该分散剂应用于无机粉体溶剂体系，表现出优异的分散稳定性，所制备的陶瓷喷墨和数码釉打印性能优异，无排釉现象。The invention discloses a polyester/polyamide type copolymer and its preparation method and application. The copolymer is prepared from the following parts by weight: 83-92 parts of carboxyl-containing polyester, 5-12 parts of amino-terminated polyamide, and 3-5 parts of epoxy silane coupling agent; The molecular weight is 1800-4000. The copolymer can be used as a dispersant for inorganic powder solvent systems such as ceramic inkjet, digital glaze, etc. The amide group of the copolymer has a good anchoring effect on the inorganic powder. The reaction forms a firm chemical bond, which is conducive to improving dispersion stability and grinding efficiency; polyester with a benzene ring is a solvated chain, giving the dispersant a steric hindrance effect, which has better anti-agglomeration and anti-settling effects, which is conducive to reducing Dispersant dosage. The dispersant is applied to an inorganic powder solvent system and exhibits excellent dispersion stability, and the prepared ceramic inkjet and digital glaze printing performances are excellent, and there is no glaze removal phenomenon.
Description
Technical Field
The invention belongs to the technical field of dispersing agents, and particularly relates to a polyester/polyamide copolymer, and a preparation method and application thereof.
Background
The ceramic ink-jet printing and digital glaze technology grinds inorganic ceramic pigment or inorganic glaze to nano level to prepare ink, and then prints the ink on the surface of the ceramic tile by an ink-jet printer to achieve the aim of decoration. In order to avoid blocking the nozzle during the jet printing process, the D90 ink is generally required to have a particle size of less than 0.9 μm, a narrow particle size distribution and no hard agglomeration. Ceramic pigments and glazes are mostly metal oxides, such as zirconia, titania, alumina, silica and the like, the surface polarity of the ceramic pigments and glazes is high, a large number of hydroxyl groups are easily formed, agglomeration is caused among particles through van der Waals force, hydrogen bonds or chemical bond action, and inorganic powder has high density, is easy to settle and agglomerate and is difficult to deagglomerate.
The hyper-dispersant has an anchoring group which is adsorbed with functional groups on the surface of the inorganic nano powder, and a solvation chain which has good compatibility with a solvent and can provide steric hindrance, plays roles of dispersing powder and preventing agglomeration, is widely applied to ceramic slurry and ceramic glaze formulations, and has great influence on slurry quality and product quality. WO2017140538 reports that a hyperdispersant is prepared by reacting polyethyleneimine with carboxyl-terminated polyester, and the polyester solvation chain of the hyperdispersant plays a role in steric hindrance, so that an oily pigment dispersant with good performance is obtained. However, when the polyester segment is short, the anti-settling effect is not good although the grinding efficiency is high; when the polyester chain segment is longer, the chain segment is easy to fold and coat the anchoring group, so that the grinding efficiency is reduced, and the anchoring chain segment is relatively reduced due to the increase of the polyester solvation chain, so that the dispersant is easy to desorb; in addition, when the molecular weight of the dispersant is large or the dosage is large, the viscosity of an ink system is increased, and the penetration and drying are slow, so that the phenomena of ink discharge, glaze discharge and the like occur in the printing process. The prior dispersing agent is difficult to simultaneously meet the grinding efficiency, the anti-settling effect and the printing performance of ceramic slurry and glaze.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a polyester/polyamide type copolymer. The copolymer can be used as an inorganic powder solvent system dispersant, and simultaneously meets the requirements of grinding efficiency, anti-settling effect and printing performance of ceramic slurry and glaze.
Another object of the present invention is to provide a process for the preparation of said polyester/polyamide type copolymers.
Another object of the present invention is to provide the use of said polyester/polyamide type copolymers.
The above object of the present invention is achieved by the following technical solutions:
the polyester/polyamide copolymer is prepared by the following raw materials in parts by weight: 83-92 parts of carboxyl-containing polyester, 5-12 parts of amino-terminated polyamide and 3-5 parts of epoxy silane coupling agent;
the carboxyl-containing polyester is prepared from mono-hydroxy acid and benzoic acid or benzoic acid derivatives; the amino-terminated polyamide is prepared from a polyethylene polyamine monomer and a dibasic acid, and both ends of the amino-terminated polyamide contain primary amino;
the benzoic acid derivative is alkylbenzoic acid or alkoxy benzoic acid;
the molecular weight of the carboxyl-containing polyester is 1800-4000;
the ratio of the total moles of carboxyl groups of the carboxyl-containing polyester to the total moles of primary amino groups of the amino-terminated polyamide is 0.95 to 1.05.
Compared with carboxyl-containing polyester prepared by fatty acid, the carboxyl-containing polyester prepared by adopting benzoic acid or benzoic acid derivatives can provide larger steric hindrance effect due to the existence of benzene rings, so that the copolymer can be more favorable for preventing inorganic powder from mutually agglomerating, settling and caking under the same molecular chain length, and a better anti-settling effect is obtained; and because of the rigid structure of the benzene ring, the chain segment is not easy to fold, the coating on the anchoring group can be reduced, and the reduction of the grinding efficiency can not be caused.
The amide group of the polyamide chain segment in the copolymer has strong hydrogen bond interaction with the inorganic powder, thereby being beneficial to accelerating the adsorption of the polyamide chain segment on the surface of the inorganic powder and improving the grinding efficiency.
The epoxy silane coupling agent used in the invention is grafted on the polyamide chain segment through the reaction of the epoxy group and the secondary amino group in the polyethylene polyamine monomer, and the siloxane group can be hydrolyzed to perform coupling reaction with the inorganic powder and is tightly combined on the surface of the inorganic powder, thereby effectively preventing desorption.
Preferably, the mono-hydroxy acid is a mixture of one or more of lactic acid, hydroxycaproic acid, hydroxydecanoic acid, hydroxydodecanoic acid, and hydroxystearic acid.
Preferably, the alkyl benzoic acid is one or more of methyl benzoic acid, ethyl benzoic acid, n-butyl benzoic acid, tert-butyl benzoic acid, hexyl benzoic acid, octyl benzoic acid, decyl benzoic acid, dodecyl benzoic acid, hexadecyl benzoic acid and octadecyl benzoic acid.
Preferably, the alkoxy benzoic acid is one or more of methoxy benzoic acid, ethoxy benzoic acid, butoxy benzoic acid, hexyloxy benzoic acid, octyloxy benzoic acid, decyloxy benzoic acid, dodecyloxy benzoic acid, hexadecyloxy benzoic acid and octadecyloxy benzoic acid.
The polyethylene polyamine monomer generally contains two primary amino groups and at least one secondary amino group, and preferably, the polyethylene polyamine monomer is one or a mixture of two or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
Preferably, the dibasic acid is one or more of oxalic acid, succinic acid and adipic acid.
Preferably, the epoxy silane coupling agent is one or a mixture of two of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and gamma- (2, 3-epoxypropoxy) propyl triethoxy silane.
The preparation method of the polyester/polyamide copolymer comprises the following steps:
the method comprises the following steps:
s1, dissolving a polyethylene polyamine monomer in water, dropwise adding a dibasic acid aqueous solution under stirring in an inert atmosphere, heating to 130-140 ℃ after dropwise adding, carrying out heat preservation reaction, and evaporating water; then heating to 170-190 ℃ to enable the system to continue to react in a molten state to obtain amino-terminated polyamide;
s2, adding a mono-hydroxy acid, benzoic acid or a benzoic acid derivative into a reaction kettle, heating to 80-100 ℃ under an inert atmosphere, adding a catalyst when the materials are molten, heating to 160-180 ℃, and reacting to a theoretical acid value to obtain carboxyl-containing polyester;
s3, heating the carboxyl-containing polyester in the step S2 to 58-63 ℃ in an inert atmosphere, and adding the amino-terminated polyamide in the step S1 for reaction; heating to 110-125 ℃, and preserving heat for 2-3 h; then adding epoxy silane coupling agent into the reaction system to react to obtain the polyester/polyamide dispersing agent.
In the step S2, the catalyst is a common catalyst in the polyester synthesis process, and is preferably one or a mixture of more of tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, p-toluenesulfonic acid and antimony acetate.
The invention adopts polyethylene polyamine monomer to react with dibasic acid to generate polyamide with amino at two ends, then the polyamide reacts with polyester with carboxyl at one end to generate polyester-polyamide-polyester triblock copolymer, and siloxane groups are grafted on the polyamide chain segment. Compared with polyester-polyethyleneimine diblock copolymer dispersing agents, the amide group of the copolymer has stronger hydrogen bond interaction with inorganic powder than an ethyleneimine group, so that the absorption of chain segments on the surface of the inorganic powder is accelerated, the grinding efficiency is improved, the introduced siloxane group can react with the inorganic powder to generate firm chemical bonds, the desorption is effectively prevented, and the dispersion stability is more excellent. The triblock structure of polyester-polyamide-polyester is beneficial to reducing the length of a polyester chain segment and reducing chain segment folding, and the introduced benzene ring structure can provide more excellent steric stabilization effect.
The invention also discloses application of the polyester/polyamide copolymer as an inorganic powder solvent system dispersing agent.
The inorganic powder solvent system comprises toner or glaze, a non-aqueous solvent and the like. Common inorganic powder solvent systems include ceramic inkjet, digital glaze, and the like.
An inorganic powder solvent system containing 4.3 to 6 mass% of the polyester/polyamide type copolymer.
Compared with the prior art, the invention has the following beneficial effects:
the novel polyester/polyamide copolymer provided by the invention comprises a polyamide chain segment and a polyester chain segment with a benzene ring, wherein an amide group of the polyamide chain segment has a good anchoring effect on inorganic powder, and a grafted siloxane group reacts with the inorganic powder to form a firm chemical bond, so that the dispersion stability and the grinding efficiency are improved; the polyester chain segment is used as a solvating chain, has a steric hindrance effect, can further increase the steric hindrance by introducing a benzene ring, has more excellent agglomeration prevention and sedimentation prevention effects, and can be used as a dispersing agent of an inorganic powder solvent system. When the dispersant is applied to an inorganic powder solvent system, the dispersant has excellent dispersion stability, can improve the printing performance of ceramic ink jet and glaze spraying, and avoids the phenomenon of glaze discharging.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are intended to be included in the scope of the present invention. Unless otherwise indicated, the reagents and methods referred to in the examples are those commonly used in the art.
Preparation of polyester/polyamide type copolymer
The formulations of the carboxyl group-containing polyester and the amino group-terminated polyamide used in the examples and comparative examples are shown in tables 1 to 2, respectively. Table 3 shows the amounts of the raw materials used in the examples and comparative examples.
The polyester/polyamide type copolymers in the examples and comparative examples were prepared according to the following method:
s1, dissolving a polyethylene polyamine monomer in water, introducing nitrogen, slowly dropwise adding a dibasic acid aqueous solution under stirring, after dropwise adding, heating to 130-140 ℃, carrying out heat preservation reaction, and gradually evaporating water in a system; then heating to 170-190 ℃, continuously reacting the system in a molten state, and vacuumizing to remove water at the later stage of the reaction to obtain amino-terminated polyamide; the addition amount of the polyethylene polyamine monomer and the dibasic acid is preferably 2:1 in molar ratio;
s2, adding hydroxy acid, benzoic acid or a benzoic acid derivative into a reaction kettle, introducing nitrogen, heating to 80-100 ℃, adding a catalyst when the materials are molten, heating to 160-180 ℃, reacting to a theoretical acid value, and vacuumizing to remove water at the later stage of the reaction to obtain carboxyl-containing polyester;
s3, heating the carboxyl-containing polyester in the step S2 to 58-63 ℃ under nitrogen, adding the amino-terminated polyamide in the step S1, reacting for 0.5h, heating to 110-125 ℃, and preserving heat for 2-3 h; and then slowly adding an epoxy silane coupling agent into the reaction system to react for 1-1.5 h to obtain the polyester/polyamide dispersing agent.
TABLE 1 formulation of carboxyl group-containing polyesters in examples and comparative examples (unit: g)
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Lactic acid | — | 93.12 | — | — | — | — |
| 5-Hydroxyhexanoic acid | — | — | — | 96.10 | — | 96.60 |
| 11-Hydroxydodecanoic acid | — | — | 85.70 | — | — | — |
| 12-Hydroxystearic acid | 88.10 | — | — | — | 87.28 | — |
| Benzoic acid | 6.00 | — | — | — | 6.78 | — |
| 4-Hexanoic acid | — | 8.55 | — | — | — | — |
| 4-dodecyl benzoic acid | — | — | 8.42 | — | — | — |
| 4-Octadecyloxybenzoic acid | — | — | — | 8.98 | — | 8.54 |
| Tetrabutyl titanate | 0.3 | 0.3 | 0.3 | 0.4 | 0.3 | 0.4 |
| Theoretical molecular weight of carboxyl group-containing polyester | 1800 | 2000 | 3000 | 4000 | 1600 | 4200 |
TABLE 2 formulation (unit: g) of amino-terminated polyamides in the examples and comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Diethylenetriamine | 5.17 | — | — | 3.70 | 5.35 | 3.67 |
| Triethylene tetramine | — | — | 6.57 | — | — | — |
| Tetraethylenepentamine | — | 9.00 | — | — | — | — |
| Oxalic acid | — | — | — | 2.19 | — | 2.22 |
| Succinic acid | — | — | 3.59 | — | — | — |
| Adipic acid | 3.73 | 3.91 | — | — | 3.52 | — |
TABLE 3 example and comparative example formulation (unit: g) of polyester/polyamide type copolymer
In addition, a copolymer of comparative example 3 was prepared in the same manner as in example 4 using 92g of the carboxyl group-containing polyester of example 4 and 5g of the amino-terminated polyamide of example 4, without adding an epoxy silane coupling agent.
Performance testing
According to the raw materials and the proportion of the formula 1 in the table 4, the ceramic ink-jet is prepared by using brown red toner, and the ceramic ink-jet is ground for 8 hours by a sand mill. Determination of ink-jet D Using Mastersizer 2000 laser particle size Analyzer90And (4) the particle size. Preparing digital glaze according to the raw materials and the proportion of the formula 2 in the table 4, and measuring the digital glaze D90Grinding time for particle size less than 0.9 μm.
The specific assay methods for the other test items listed in table 5 are as follows: viscosity: measuring the viscosity of the dispersion at 40 ℃ by using a rotary viscometer; centrifugal precipitation rate: centrifuging for 5min under the condition of 3000r/min, and measuring the mass ratio of the precipitate; hard precipitation rate: packaging 100g of the dispersion system in a 100ml bottle, placing the bottle in an oven at 60 ℃ for a week, shaking the bottle up and down for 10 minutes, pouring out the content, and reversing the bottle for 3min to determine the mass ratio of the residual substances in the bottle; and (3) glaze discharging: and sequentially spraying ceramic ink jet and digital glaze prepared according to the formula in the table 4 on the ceramic blank coated with the ground glaze, and observing the spreading condition of the digital glaze on the surface of the ceramic ink jet.
TABLE 4 application formulation
TABLE 5 ceramic inkjet and digital glaze Performance test results
As can be seen from Table 5, the dispersants of examples 1 to 4, the components of the carboxyl group-containing polyester segmentThe molecular weight is 1800-4000, and the prepared ceramic ink-jet D90The grain sizes are all less than 0.9 mu m, the centrifugal precipitation rate is less than 2.6 percent, the hard precipitation rate is less than 0.9 percent, and the anti-precipitation effect is good; prepared digital glaze D90The grinding time is less than 10h when the particle size is less than 0.9 mu m, the centrifugal precipitation rate is less than 3.1 percent, the hard precipitation rate is less than 1.6 percent, the grinding efficiency is high, and the dispersion stability is good. The digital glaze is spread evenly on the ceramic ink-jet surface without glaze discharging phenomenon.
As can be seen from comparative example 1 and example 1, when the molecular weight of the carboxyl-containing polyester segment in the dispersant is less than 1800, the centrifugal precipitation rate and the hard precipitation rate of the inkjet and digital glaze are significantly increased, and the anti-settling property is deteriorated; as can be seen from comparative example 2 and example 4, when the molecular weight of the carboxyl group-containing polyester segment in the dispersant is more than 4000, the inkjet particle diameter becomes large and D is large although the centrifugal precipitation rate and the hard precipitation rate of the inkjet and digital glaze are reduced90The grain diameter is more than 0.9 μm, the grinding time is longer, the grinding efficiency is poor, and the glaze discharging phenomenon occurs when the digital glaze is jet-printed on the ceramic ink-jet surface because the dispersant has larger molecular weight and the drying speed is slower. Therefore, the molecular weight of the carboxyl-containing polyester segment is in a proper range, so that the anti-settling effect of the ink-jet and digital glaze is good, and the grinding efficiency is high.
As can be seen from comparative example 3 and example 4, the hard precipitation rate of inkjet and digital glazes was significantly increased when siloxane groups were not introduced into the dispersant, indicating that the dispersant was easily desorbed during aging without chemical bonds formed by siloxane coupling to cause the toner or glaze to settle.
The applicant declares that the above detailed description is a preferred embodiment described for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, i.e. it does not mean that the present invention must be implemented by means of the above embodiment. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010250537.9A CN111234208B (en) | 2020-04-01 | 2020-04-01 | A kind of polyester/polyamide type copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010250537.9A CN111234208B (en) | 2020-04-01 | 2020-04-01 | A kind of polyester/polyamide type copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111234208A CN111234208A (en) | 2020-06-05 |
| CN111234208B true CN111234208B (en) | 2021-07-16 |
Family
ID=70862380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010250537.9A Active CN111234208B (en) | 2020-04-01 | 2020-04-01 | A kind of polyester/polyamide type copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111234208B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322249B (en) * | 2020-11-11 | 2022-04-01 | 温州华特热熔胶股份有限公司 | Polyesteramide silane enhanced hot melt adhesive and preparation method thereof |
| CN118725641A (en) * | 2024-06-03 | 2024-10-01 | 苏州科斯伍德色彩科技有限公司 | Antibacterial printing coating and preparation method, antibacterial coating structure and preparation method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68926129T2 (en) * | 1988-03-07 | 1996-08-14 | Kanebo Ltd | Molded polyamide articles and process for their manufacture |
| CN1119368C (en) * | 2000-11-14 | 2003-08-27 | 中国石化集团巴陵石油化工有限责任公司 | Process for preparing polyamide resin used for alcohol-soluble ink |
| US8772435B2 (en) * | 2005-04-13 | 2014-07-08 | Lubrizol Advanced Materials, Inc. | Dispersants |
| US20080223519A1 (en) * | 2006-12-06 | 2008-09-18 | Locko George A | Polyamide polyols and polyurethanes, methods for making and using, and products made therefrom |
| US20100249322A1 (en) * | 2009-03-30 | 2010-09-30 | Xerox Corporation | Fluorinated sulfonic acid polymer grafted polyaniline containing intermediate transfer members |
| EP2272893B1 (en) * | 2009-06-19 | 2014-11-05 | Agfa Graphics N.V. | Polymeric dispersants and non-aqueous dispersions |
| JP6507103B2 (en) * | 2013-02-13 | 2019-04-24 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Aqueous polyamide-urea dispersion |
| CN106633045A (en) * | 2016-12-29 | 2017-05-10 | 威海晨源分子新材料有限公司 | Modified hyperbranched poly(ester-amide), and preparation method and application thereof |
-
2020
- 2020-04-01 CN CN202010250537.9A patent/CN111234208B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111234208A (en) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5934833B2 (en) | Oxidized carbon black treated with polyetheramine and coating composition containing the same | |
| CN111234208B (en) | A kind of polyester/polyamide type copolymer and its preparation method and application | |
| CN108410254B (en) | A kind of water-based binder and food-contact water-based ink prepared by using the same | |
| CN1942518A (en) | Compositions for producing universal pigment preparations | |
| CN104789045A (en) | Colored resin particle dispersion and inkjet ink | |
| CN105504981A (en) | Water-based ink for intaglio printing process of aluminum foil and preparation method of water-based ink | |
| JP2022003151A (en) | Modified polyacrylate dispersants for decorative ceramic market | |
| CN106752121A (en) | The preparation method of silicon dioxide coating type aluminium pigment | |
| WO2010001965A1 (en) | Coating composition | |
| CN111534148B (en) | Water-based ink, preparation method thereof, and packaging material and product with water-based ink | |
| CN113136009B (en) | Phosphate-group-containing aqueous dispersant, and preparation method and application thereof | |
| CN103102736B (en) | Non-aqua-system pigment ink for ink jet | |
| CN101885928A (en) | A kind of nano iron oxide red water-based printing ink and preparation method thereof | |
| CN114574001B (en) | Method for preparing hydrophilic carbon black through biomimetic modification of phenolic amine and hydrophilic carbon black | |
| CN116004085A (en) | Long-acting corrosion-resistant aqueous epoxy zinc powder primer and preparation method thereof | |
| JP2008094939A (en) | Dispersing resin and pigment ink for inkjet | |
| JP2008094938A (en) | Dispersing resin and pigment ink for inkjet | |
| JP2001311018A (en) | Silica powder and method for producing the same | |
| JP2002256169A (en) | Silica powder and method for producing the same | |
| CN110760239A (en) | Composite nano material reinforced water-based epoxy primer and preparation method thereof | |
| JP2013133344A (en) | Aqueous ink composition | |
| JP4891025B2 (en) | Dispersing resin, dispersion, and ink-jet pigment ink | |
| CN119613739A (en) | A dispersant for solvent-based ceramic inkjet ink and preparation method thereof | |
| CN117699807A (en) | Preparation method of solvent type silicon dioxide sol | |
| JP2010235782A (en) | Polymer-treated pigment and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510275 No. 135 West Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee after: SUN YAT-SEN University Country or region after: China Patentee after: Guangdong Elite High Tech Materials Co.,Ltd. Address before: 510275 No. 135 West Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee before: SUN YAT-SEN University Country or region before: China Patentee before: Guangdong elite inorganic materials Co.,Ltd. |
|
| CP03 | Change of name, title or address |