CN118955810A - Polyester type high-molecular chelating dispersant, and preparation method and application thereof - Google Patents
Polyester type high-molecular chelating dispersant, and preparation method and application thereof Download PDFInfo
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- CN118955810A CN118955810A CN202411258719.5A CN202411258719A CN118955810A CN 118955810 A CN118955810 A CN 118955810A CN 202411258719 A CN202411258719 A CN 202411258719A CN 118955810 A CN118955810 A CN 118955810A
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- diisocyanate
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- 229920000728 polyester Polymers 0.000 title claims abstract description 114
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000003999 initiator Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000986 disperse dye Substances 0.000 claims abstract description 46
- 125000003118 aryl group Chemical group 0.000 claims abstract description 42
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 unsaturated hydroxyalkyl ester Chemical class 0.000 claims abstract description 35
- 125000000129 anionic group Chemical group 0.000 claims abstract description 33
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 38
- 238000004043 dyeing Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 33
- 238000010992 reflux Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 22
- 230000005494 condensation Effects 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 17
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001826 dimethylphthalate Drugs 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 230000009920 chelation Effects 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 34
- 239000004744 fabric Substances 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 7
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 14
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 14
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 14
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 description 10
- 229920005610 lignin Polymers 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229920001732 Lignosulfonate Polymers 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000008233 hard water Substances 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- QLCAGXDTDCDEGN-UHFFFAOYSA-N 3-sulfanylcarbonylhexanedioic acid Chemical compound OC(=O)CCC(C(O)=S)CC(O)=O QLCAGXDTDCDEGN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to the technical field of textile, and discloses a polyester type macromolecular chelating dispersant, a preparation method and application thereof. The method comprises the following steps: (1) The raw materials comprise transesterification catalyst, aromatic dimethyl ester, dihydric alcohol, diisocyanate, unsaturated hydroxyalkyl ester, unsaturated anionic monomer, initiator, organic solvent and water; (2) The transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer; (3) Reacting the polyester type macromolecular chelating dispersant prepolymer, diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to obtain a polyester type macromolecular chelating dispersant intermediate; (4) The polyester type macromolecule chelate dispersing agent intermediate, unsaturated anionic monomer, initiator and water are reacted. The polyester type high molecular chelating dispersant has strong affinity to disperse dyes and polyester oligomers, and can realize effective cleaning of fabrics dyed by the disperse dyes without the assistance of reducing agents and alkaline agents.
Description
Technical Field
The invention relates to the technical field of textile, in particular to a polyester type macromolecule chelating dispersant, a preparation method and application thereof.
Background
Currently, in the process of dyeing polyester fibers by using disperse dyes in a high-temperature high-pressure dye bath, in order to inhibit the melting and aggregation of the disperse dyes and the crystal form transformation thereof under the alternating action of cold and hot, and ensure the thermal stability of the dye bath and the stability of the aggregation state of the dyes, a high-temperature leveling agent based on a nonionic surfactant and anionic surfactant composite system or a dispersing agent of lignin, cardanol, polycarboxylic acid and naphthalene sulfonic acid formaldehyde condensate is usually added in the dye bath. Wherein, the naphthalene sulfonic acid formaldehyde condensate dispersant has low heat resistance stability and high raw material cost; the polycarboxylic acid dispersant has the advantages of harsh reaction conditions, complex process and high industrialization cost. In addition, the low hydrophilic polyester oligomer generated in the high temperature and high pressure dyeing process of the polyester fiber can be removed relatively effectively under the high temperature and alkaline conditions with the help of a surfactant (or a dispersing agent). Meanwhile, in order to sufficiently remove the after-dyeing flooding, the water-insoluble disperse dye has to be subjected to reduction soaping under alkaline and reduction conditions. The process technology has the advantages of high energy consumption, complex process, poor environmental protection and unsatisfactory process effect. Theoretically, the above confusion is due to the significant lack of affinity of traditional dispersants, leveling agents, soaping agents for polyester oligomers and disperse dyes, and their hydrophilicity/water solubility is sensitive to hard water and high temperatures, even failing at high temperatures.
Specifically, the dispersing agent and the leveling agent which are commonly related to polyester fibers or disperse dyes mainly comprise the following components:
1. The cardanol disperse dye dispersant and the high temperature leveling agent mainly comprise cardanol sulfonate, cardanol sulfate, cardanol ethoxy, cardanol carboxylate, cardanol quaternary ammonium salt, a gemini surfactant and the like.
As shown in Zhang Shenggang, liuqing and the like, namely the preparation and dyeing performance of a high-dispersion hard water-resistant high-temperature leveling agent (paper and paper making, 37 volume 8 in 2020) and the dispersibility, slow-dyeing property, transfer dyeing property and dyeing effect (color-obtaining effect, dyeing fastness and the like) of a cardanol polyoxyethylene ether TF-n (EOn =3, 5, 7, 9 and 10) and cardanol polyoxyethylene ether ammonium sulfonate when the compound is used for high-temperature high-pressure dyeing of a disperse dye, the slow-dyeing property of the cardanol polyoxyethylene ether TF-n and the dyeing effect (color-obtaining effect, dyeing fastness and the like) of the cardanol polyoxyethylene ether ammonium sulfonate are found to be superior to that of an AB type high-temperature leveling agent formed by compounding glycerol polyoxyethylene ether oleate and styrylphenol polyoxyethylene ether sulfonate, and the dyeing performance difference of the cardanol polyoxyethylene ether sulfonate and the cardanol polyoxyethylene ether sulfonate is more obvious under the hard water condition; meanwhile, the two performances in the transfer dyeing performance are relatively close.
The cardanol polyoxyethylene ether and sulfamic acid sulfonated cardanol polyoxyethylene ether sulfate type high-temperature leveling agent disclosed in synthesis of biomass cardanol series high-temperature leveling agent (6 th phase of 29. Of the university of western Engineers, 2015) of Linan and Wang Shugen has good dispersing ability to disperse dye, good leveling property and transfer dyeing property to disperse dye-dyed polyester fabric, and the leveling property and transfer dyeing property of the disperse dye-dyed polyester fabric are approximately the same as those of commercially available commercial high-temperature leveling agents.
However, although the high-dispersion, hard-water-resistant and high-temperature leveling agent in the literature contains an aromatic ring structure having a good affinity with polyester and disperse dye, the compound surfactant dispersant or the high-temperature leveling agent composed of a "hydrophilic+hydrophobic" and a "nonionic+anionic" structure still has problems such as poor ionization, lack of a common structure with the object to be dispersed (disperse dye, polyester oligomer), lack of an effective chelating structure, and serious deterioration of hydrophilicity at high temperature of polyether chain links having important significance on the dispersing ability, because of lack of an ionic property, poor high-temperature resistance, weak dispersing chelating ability, and the like.
2. The lignin disperse dye dispersing agent and the high-temperature leveling agent mainly comprise lignin sulfonate which is a byproduct of acid pulping and alkali lignin sulfonate which is a byproduct of alkali pulping.
As disclosed in Zhang Zhiming, zhou Mingsong, yang Dongjie et al, preparation and performance of high temperature sulfomethylated alkali lignin dye dispersant (12 th edition of volume 31 in fine chemical engineering 2014), sulfomethylated alkali lignin prepared by sulfomethylation reaction of formaldehyde and sodium bisulphite at high temperature is used as raw material. The sulfomethylated alkali lignin sulfonate has better comprehensive performance when the content of sulfomethylated alkali lignin sulfonate is 1.2-1.4 mmol/g, and particularly has obviously better high-temperature stability than the traditional commercial dye dispersant, but still has certain staining property on fibers.
Lignin is used as raw material, and after carboxymethylation, formaldehyde and sodium bisulphite are subjected to methylolation and sulfonation reaction to prepare the lignin-based dye dispersant, which is disclosed in research on preparation and application of lignin-based dye dispersant (3 rd phase of volume 23 of cellulose science and technology) by Liu Zhipeng and Liu Minghua. The dispersion grade of the disperse dye can reach 5.0 grade, the dispersion performance of the disperse dye can reach the commodity requirement, and the product can keep good dispersion performance at 150 ℃.
However, although the lower the staining rate of Gao Huangsuan base content lignin to polyester fibers, the staining property is higher than that of the traditional commercial dye dispersant; meanwhile, the sulfonation modification of lignin is usually assisted by formaldehyde, so that the product has poor environmental protection. Similarly, due to the lack of a common structure and an effective chelating structure of lignosulfonate and a dispersing object (polyester oligomer and disperse dye), the lignosulfonate still cannot meet the requirement of effective cleaning of the dyed polyester flooding under the support of lack of a reducing and alkaline environment.
3. Polycarboxylic acid dispersants and soaping agents are mainly copolymers of maleic acid and acrylic acid or composites based thereon.
As disclosed in acid soaping of maleic anhydride acrylic acid polymer (acid soaping agent) by Song Qingshuang, zheng Qingkang and Du Gaomin (period 1 of 2013 in knitting industry), the K/S value, color saturation and various color fastness of dyed fabrics are higher after the fabrics are washed by the acid soaping agent; compared with the traditional soaping process based on the surfactant, the K/S value and the color saturation of the fabric after being washed by the acid soaping agent are higher, the dye hydrolysis is less, the color fastness is improved or leveled, and the water-saving effect is obvious.
As disclosed in "development and application of novel acid soaping agent" by Swallow (university of Western-A engineering journal "2011, volume 25, 6 th period), maleic anhydride, acrylic acid and N-vinylpyrrolidone are copolymerized, and then compounded with carboxyethyl thiosuccinic acid and hydroxyethylidene diphosphonic acid to prepare the novel acid soaping agent. The research shows that the color light of the fabric after the novel acid soaping agent is brighter and the color fastness of the fabric is higher than that of the fabric after the ordinary soaping agent is soaped; meanwhile, the acid soap has extremely strong acidity, can be used for replacing acetic acid neutralization, and has simpler soaping process.
However, although the polycarboxylic acid-based acidic soaping agent is excellent in dispersibility, bubble-free and low in production cost, it is not satisfactory in discoloration resistance. Similarly, because the polycarboxylic acid soaping agent lacks a common structure with polyester oligomer and disperse dye, the polycarboxylic acid soaping agent cannot be used for dyeing and soaping the polyester fiber by the disperse dye, and cannot meet the requirement of effectively cleaning the floating color of the dyed polyester under the support of lacking a reducing and alkaline environment.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a polyester type macromolecular chelating dispersant, and a preparation method and application thereof. The polyester type macromolecular chelating dispersant can be used as a high-temperature leveling agent for dyeing disperse dyes and a reduction-free soaping agent, and can also be used for aqueous dispersion of micro powder of polyester materials, surface hydrophilic modification, inhibition of aggregation tendency of water-based disperse dyes and the like. In the invention, the polyester chain links in the molecular structure of the product have better affinity to polyester oligomer and disperse dye; meanwhile, a plurality of ortho-carboxyl and isolated carboxyl groups on the polycarboxylic acid chain units and isolated sulfonic groups on the polyester macromolecules in the molecular structure of the product endow the product with excellent chelating and dispersing forces; in addition, the product is formed by a core-shell structure formed by a polyester core and a polycarboxylic acid shell, so that the product can provide excellent thermodynamic stabilization effect on polyester oligomer and disperse dye, further endow the product with excellent leveling and soaping performances on the disperse dye, and greatly expand the application range of the product.
In order to achieve the above object, the present invention provides a method for preparing a polyester type polymeric chelation dispersant, comprising the steps of:
(1) Raw material preparation: the raw materials comprise a transesterification catalyst, aromatic dimethyl ester, dihydric alcohol, diisocyanate, unsaturated hydroxyalkyl ester, unsaturated anionic monomer, an initiator, water and optional organic solvent;
wherein the transesterification catalyst is zinc acetate;
the aromatic dimethyl ester is dimethyl isophthalate-5-sodium sulfonate, dimethyl terephthalate and dimethyl phthalate;
The dihydric alcohol is selected from one or more than two of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and diethylene glycol;
the diisocyanate is toluene diisocyanate or isophorone diisocyanate;
the unsaturated hydroxyalkyl ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate;
the unsaturated anionic monomer is maleic anhydride and acrylic acid;
the initiator is potassium persulfate or ammonium persulfate;
The organic solvent is propylene glycol methyl ether acetate;
the raw materials comprise the following components in parts by mole: aromatic dimethyl ester 5, dihydric alcohol 6-10, the mole fraction of diisocyanate=2× (mole fraction of dihydric alcohol-mole fraction of aromatic dimethyl ester), the mole fraction of unsaturated hydroxyalkyl ester is 1-1.1 times of the mole fraction of diisocyanate;
the weight of the unsaturated anionic monomer is 0.5 to 1.5 times of the total weight of the aromatic dimethyl ester and the dihydric alcohol;
based on the total molar amount of the aromatic dimethyl ester, the molar ratio of the dimethyl isophthalate-5-sodium sulfonate is 10-30%, the molar ratio of the dimethyl terephthalate is 30-60%, and the molar ratio of the dimethyl phthalate is 30-60%;
the content of the maleic anhydride is 30-70wt% based on the total weight of the unsaturated anionic monomer;
(2) Transesterification: the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(3) And (3) end capping: reacting the polyester type macromolecular chelating dispersant prepolymer, diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to obtain a polyester type macromolecular chelating dispersant intermediate;
(4) Polymerization: the polyester type polymer chelating dispersant is prepared by reacting a polyester type polymer chelating dispersant intermediate, an unsaturated anionic monomer, an initiator and water.
Preferably, the transesterification catalyst is used in an amount of 0.4 to 0.8wt% based on the total weight of the aromatic dimethyl ester and the glycol.
Preferably, the initiator is used in an amount of 0.5 to 1wt% based on the total weight of the unsaturated hydroxyalkyl ester and the unsaturated anionic monomer.
Preferably, the organic solvent is used in an amount of 0 to 1 times the total weight of the aromatic dimethyl ester, the dihydric alcohol, the diisocyanate and the unsaturated hydroxyalkyl ester.
Preferably, the water is used in an amount of 1 to 2 times the total weight of the aromatic dimethyl ester, the diol, the diisocyanate, the unsaturated hydroxyalkyl ester and the unsaturated anionic monomer.
Preferably, the specific process of the step (2) includes:
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 150-200 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring;
(2.2) heating the reaction system in the step (2.1) to 200-250 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring to obtain the polyester polymer chelating dispersant initial polymer.
Preferably, the specific process of the step (3) includes:
(3.1) cooling the reaction system in the step (2) to 150-200 ℃, adding an organic solvent and diisocyanate, and then reacting for 20-40 min under the protection of nitrogen at 150-200 ℃ and under the condition of condensation reflux and stirring;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuing to react for 20-40 min to prepare the intermediate of the polyester type high polymer chelating dispersant.
Preferably, the specific process of the step (4) includes:
(4.1) cooling the reaction system in the step (3) to 80-110 ℃, removing a reflux device, adding unsaturated anionic monomers and 40-60wt% of water in total, shearing and dispersing at 60-80 ℃ to obtain a dispersion liquid, and then taking out 70-90 wt% of the dispersion liquid for later use;
(4.2) adding 35-45wt% of water and 20-40 wt% of initiator to the rest of the dispersion liquid in the step (4.1) under stirring, and maintaining stirring at 70-90 ℃ for 20-60 min; controlling the temperature of the reaction system to be 70-90 ℃ and adding 5-15wt% of water, the rest initiator and 70-90 wt% of the dispersion liquid taken out in the step (4.1) in 40-90 min; then continuously reacting for 30-60 min at 70-90 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, thus obtaining the polyester type polymer chelating dispersant.
In a second aspect, the present invention provides a polyester polymeric chelation dispersant prepared according to the method described hereinbefore.
The third aspect of the invention provides the use of the polyester polymer chelating dispersant in a disperse dye dyeing process.
Compared with the prior art, the invention has the following beneficial effects:
1. In the invention, the polyester chain in the molecular structure of the product has universal affinity (namely, affinity under any process environment) for disperse dye and polyester molecules, and the affinity is simple, direct and clear. The affinity based on the principle of similar compatibility ensures that the disperse dye has excellent dye bath stabilizing effect and leveling effect in a dyeing system of the polyester fiber by the disperse dye, thereby enabling a simple, direct and efficient dyeing and heating process to be possible. Particularly, the polyester type macromolecular chelating dispersant has strong affinity for dispersing dye and polyester oligomer and good chelating and dispersing capacity derived from a polycarboxylic acid network on the polyester type macromolecular chelating dispersant, so that the polyester type macromolecular chelating dispersant can realize effective cleaning of fabrics dyed by the disperse dye without the assistance of a reducing agent and an alkaline agent, and the cleaning process after dyeing is simple and environment-friendly.
2. In the invention, a plurality of ortho-carboxyl and isolated carboxyl groups on the polycarboxylic acid network chain links and isolated sulfonic groups on the polyester macromolecules in the molecular structure of the product endow the product with excellent chelating and dispersing forces, and the two special chemical structures provide excellent complementarity for the chelating and dispersing properties of the product, so that the properties of dispersing, chelating, cleaning and the like are further enhanced.
3. In the present invention, the "core" formed from the polyester segments and the "shell" formed from the polycarboxylic acid network together form the "core-shell" structure of the product. The special physical and chemical structures enable the product of the invention to provide excellent thermodynamic stabilization effect on polyester oligomer and disperse dye, further endow the product with excellent leveling and soaping performances on the disperse dye, greatly strengthen the performance characteristics and expand the application range of the product.
4. The polyester type high molecular chelating dispersant has excellent water dispersibility and hard water chelating/softening capacity, and has good affinity for polyester oligomer and disperse dye. Therefore, the dye can be used as a levelling agent for dyeing polyester fibers in a high-temperature high-pressure dye bath by using disperse dyes, or used as a reduction-free soaping agent in a soaping process after dyeing, so as to simplify the technical process and strengthen the technical effect.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing a polyester type polymeric chelation dispersant, the method comprising the steps of:
(1) Raw material preparation: the raw materials comprise a transesterification catalyst, aromatic dimethyl ester, dihydric alcohol, diisocyanate, unsaturated hydroxyalkyl ester, unsaturated anionic monomer, an initiator, water and optional organic solvent;
wherein the transesterification catalyst is zinc acetate;
the aromatic dimethyl ester is dimethyl isophthalate-5-sodium sulfonate, dimethyl terephthalate and dimethyl phthalate;
The dihydric alcohol is selected from one or more than two of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and diethylene glycol;
the diisocyanate is toluene diisocyanate or isophorone diisocyanate;
the unsaturated hydroxyalkyl ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate;
the unsaturated anionic monomer is maleic anhydride and acrylic acid;
the initiator is potassium persulfate or ammonium persulfate;
The organic solvent is propylene glycol methyl ether acetate;
the raw materials comprise the following components in parts by mole: aromatic dimethyl ester 5, dihydric alcohol 6-10, the mole fraction of diisocyanate=2× (mole fraction of dihydric alcohol-mole fraction of aromatic dimethyl ester), the mole fraction of unsaturated hydroxyalkyl ester is 1-1.1 times of the mole fraction of diisocyanate;
the weight of the unsaturated anionic monomer is 0.5 to 1.5 times of the total weight of the aromatic dimethyl ester and the dihydric alcohol;
based on the total molar amount of the aromatic dimethyl ester, the molar ratio of the dimethyl isophthalate-5-sodium sulfonate is 10-30%, the molar ratio of the dimethyl terephthalate is 30-60%, and the molar ratio of the dimethyl phthalate is 30-60%;
The content of the maleic anhydride is 30-70wt% based on the weight of the unsaturated anionic monomer;
(2) Transesterification: the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(3) And (3) end capping: reacting the polyester type macromolecular chelating dispersant prepolymer, diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to obtain a polyester type macromolecular chelating dispersant intermediate;
(4) Polymerization: the polyester type polymer chelating dispersant is prepared by reacting a polyester type polymer chelating dispersant intermediate, an unsaturated anionic monomer, an initiator and water.
In a preferred embodiment, the transesterification catalyst is used in an amount of 0.4 to 0.8wt% based on the total weight of the aromatic dimethyl ester and the glycol; specifically, it may be 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt% or 0.8wt%.
In a preferred embodiment, the initiator is used in an amount of 0.5 to 1wt% based on the total weight of unsaturated hydroxyalkyl ester and unsaturated anionic monomer; specifically, it may be 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt%.
In a preferred embodiment, the organic solvent is used in an amount of 0 to 1 times the total weight of the aromatic dimethyl ester, the diol, the diisocyanate and the unsaturated hydroxyalkyl ester.
In a preferred embodiment, the water is used in an amount of 1 to 2 times the total weight of the aromatic dimethyl ester, glycol, diisocyanate, unsaturated hydroxyalkyl ester and unsaturated anionic monomer. Further, in the steps (4.1) to (4.2), the water is put into use three times.
Preferably, the water is soft water having a total hardness of no more than 50ppm CaCO 3.
In a preferred embodiment, the specific process of step (2) includes:
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 150-200 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring;
(2.2) heating the reaction system in the step (2.1) to 200-250 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring to obtain the polyester polymer chelating dispersant initial polymer.
In the process according to the invention, in step (2.1), the distilled by-products may be separated during the warming and incubation; in step (2.2), the distilled by-products may be separated during the warming and incubation.
In a preferred embodiment, the specific process of step (3) includes:
(3.1) cooling the reaction system in the step (2) to 150-200 ℃, adding an organic solvent and diisocyanate, and then reacting for 20-40 min under the protection of nitrogen, condensation reflux and stirring at 150-200 ℃;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuing to react for 20-40 min to prepare the intermediate of the polyester type high polymer chelating dispersant.
In the process according to the invention, in step (3.2), the reaction conditions (temperature, nitrogen protection, condensation reflux and stirring) in the continuation of the reaction are kept identical to those in step (3.1).
In a preferred embodiment, the specific process of step (4) includes:
(4.1) cooling the reaction system in the step (3) to 80-110 ℃, removing a reflux device, adding unsaturated anionic monomers and 40-60wt% of water in total, shearing and dispersing at 60-80 ℃ to obtain a dispersion liquid, and then taking out 70-90 wt% of the dispersion liquid for later use;
(4.2) adding 35-45wt% of water and 20-40 wt% of initiator to the rest of the dispersion liquid in the step (4.1) under stirring, and maintaining stirring at 70-90 ℃ for 20-60 min; controlling the temperature of the reaction system to be 70-90 ℃, adding 5-15wt% of water, the rest initiator and 70-90 wt% of dispersion liquid taken out in the step (4.1) in the total amount within 40-90 min, and controlling the reaction temperature to be 70-90 ℃; then continuously reacting for 30-60 min at 70-90 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, thus obtaining the polyester type polymer chelating dispersant.
In the process according to the invention, in step (4.1), a portion is taken out of the dispersion obtained for further use, the remainder remaining in the reactor; the resulting dispersion is divided into two parts, wherein the removal part accounts for 70-90 wt% and the rest part accounts for 10-30 wt%.
In the method according to the present invention, in step (4.2), when water in an amount of 35 to 45% by weight in total and an initiator in an amount of 20 to 40% by weight in total are added to the remaining dispersion in step (4.1), the initiator and water may be mixed to prepare an aqueous initiator solution, and then the aqueous initiator solution is added to the dispersion.
In the method of the present invention, in the step (4.2), when water in an amount of 5 to 15wt% in total, the remaining initiator and the dispersion in an amount of 70 to 90wt% taken out in the step (4.1) are added within 40 to 90 minutes, water and the initiator may be first mixed to prepare an aqueous initiator solution, and then the aqueous initiator solution and the dispersion may be simultaneously added dropwise to the reaction system. Specifically, two dropping devices may be used to hold the aqueous initiator solution and the dispersion liquid, respectively, and then simultaneously drop-added to the reaction system.
In a second aspect, the present invention provides a polyester polymeric chelation dispersant prepared according to the method described hereinbefore.
The polyester polymer chelating dispersant prepared by the method can be used as a high-temperature leveling agent for dyeing disperse dyes and a reduction-free soaping agent, and can also be used for aqueous dispersion of micro powder of polyester materials, surface hydrophilic modification, inhibition of aggregation tendency of water-based disperse dyes and the like. In the invention, the polyester type macromolecular chelating dispersant has excellent affinity and excellent chelating and dispersing force on disperse dye and polyester oligomer, can provide obvious positive and beneficial thermodynamic stabilization effect on disperse dye bath, further endows the disperse dye with excellent level dyeing and soaping performance, and has obvious positive significance on simplifying the dyeing process of the disperse dye.
The finished product of the polyester polymer chelating dispersant of the invention is required to be stored in a sealed way at a cool and dry place.
The third aspect of the invention provides the use of the polyester polymer chelating dispersant in a disperse dye dyeing process.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
TABLE 1
Example 1
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) A transesterification step, wherein a transesterification catalyst, aromatic dimethyl ester and dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 175+/-1 ℃ within 22min, and carrying out heat preservation reaction for 75min under the protection of nitrogen, condensation reflux and stirring, wherein distilled byproducts are separated during the heating and heat preservation;
(2.2) heating the reaction system in the step (2.1) to 235+/-1 ℃ within 25min, and carrying out heat preservation reaction for 75min under the protection of nitrogen, condensation reflux and stirring, wherein distilled byproducts are separated during heating and heat preservation, so as to prepare a polyester polymer chelating dispersant initial polymer;
(3) A capping step, wherein the polyester polymer chelating dispersant precursor reacts with diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to prepare a polyester polymer chelating dispersant intermediate;
(3.1) the reaction system in the step (2.2) is reduced to 175+/-1 ℃, an organic solvent and diisocyanate are added, and the reaction is carried out for 35min under the conditions of 175+/-1 ℃ and nitrogen protection, condensation reflux and stirring;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuing to react for 35min under the protection of nitrogen at 175+/-1 ℃ and under the condition of condensation reflux and stirring to obtain a polyester type high polymer chelating dispersant intermediate;
(4) And initiating polymerization, namely reacting the intermediate of the polyester type macromolecular chelating dispersant with an unsaturated anionic monomer, an initiator and water to obtain the polyester type macromolecular chelating dispersant.
(4.1) The reaction system in the step (3.2) is reduced to 95+/-1 ℃, a reflux device is removed, unsaturated anionic monomers and 50wt% of water are added, and the mixture is fully sheared and dispersed at 75+/-1 ℃ to obtain a dispersion liquid, and 80wt% of the dispersion liquid is taken out for standby;
(4.2) adding 40wt% of total water and 40wt% of total initiator to the rest of the dispersion liquid in the step (4.1) under stirring (the water and the initiator are mixed in advance to prepare an aqueous initiator solution), and maintaining stirring and reacting for 50min at 80+/-1 ℃; controlling the temperature of the reaction system to 80+/-1 ℃ and uniformly dripping an aqueous solution of an initiator (prepared by using 10 weight percent of water and the rest of the initiator) and the dispersion liquid taken out in the step (4.1) in 85 min; then continuously reacting for 50min at 80+/-1 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, and thus obtaining the polyester type high polymer chelating dispersant.
Example 2
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) A transesterification step, wherein a transesterification catalyst, aromatic dimethyl ester and dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 180+/-1 ℃ within 18min, stirring and reacting for 85min under the protection of nitrogen and under the condition of condensation reflux, and separating distilled byproducts during heating and heat preservation;
(2.2) heating the reaction system in the step (2.1) to 235+/-1 ℃ in 18min, and carrying out heat preservation reaction for 85min under the protection of nitrogen, condensation reflux and stirring, and separating distilled byproducts during heating and heat preservation to prepare a polyester polymer chelating dispersant initial polymer;
(3) A capping step, wherein the polyester polymer chelating dispersant precursor reacts with diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to prepare a polyester polymer chelating dispersant intermediate;
(3.1) the reaction system in the step (2.2) is reduced to 165+/-1 ℃, an organic solvent and diisocyanate are added, and then the reaction is carried out for 30min under the conditions of 165+/-1 ℃ and nitrogen protection, condensation reflux and stirring;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuously reacting for 30min under the conditions of 165+/-1 ℃ and nitrogen protection, condensation reflux and stirring to obtain a polyester type high polymer chelating dispersant intermediate;
(4) And initiating polymerization, namely reacting the intermediate of the polyester type macromolecular chelating dispersant with an unsaturated anionic monomer, an initiator and water to obtain the polyester type macromolecular chelating dispersant.
(4.1) The reaction system in the step (3.2) is reduced to 88+/-1 ℃, a reflux device is removed, unsaturated anionic monomers and 50wt% of water are added, and the mixture is fully sheared and dispersed at 67+/-1 ℃ to obtain a dispersion liquid, and 85wt% of the dispersion liquid is taken out for standby;
(4.2) adding 40wt% of water and 30wt% of initiator (water and initiator are mixed in advance to prepare an aqueous initiator solution) to the rest of the dispersion in the step (4.1) with stirring, and stirring and reacting for 35min at 84+ -1deg.C; controlling the temperature of the reaction system to be 84+/-1 ℃ and uniformly dripping an initiator solution (obtained by mixing 10 weight percent of water and the rest initiator) and the dispersion liquid taken out in the step (4.1) within 75 minutes, and controlling the reaction temperature to be 84+/-1 ℃; then continuously reacting for 45min at 84+/-1 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, and thus obtaining the polyester type high polymer chelating dispersant.
Example 3
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) A transesterification step, wherein a transesterification catalyst, aromatic dimethyl ester and dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 155+/-1 ℃ within 17min, and carrying out heat preservation reaction for 60min under the protection of nitrogen, condensation reflux and stirring, wherein distilled byproducts are separated during the heating and heat preservation;
(2.2) heating the reaction system in the step (2.1) to 215+/-1 ℃ within 15min, and carrying out heat preservation reaction for 75min under the protection of nitrogen, condensation reflux and stirring, wherein distilled byproducts are separated during heating and heat preservation, so as to prepare a polyester polymer chelating dispersant initial polymer;
(3) A capping step, wherein the polyester polymer chelating dispersant precursor reacts with diisocyanate, unsaturated hydroxyalkyl ester and organic solvent to prepare a polyester polymer chelating dispersant intermediate;
(3.1) the reaction system in the step (3.2) is reduced to 155+/-1 ℃, an organic solvent and diisocyanate are added, and the reaction is carried out for 35min under the conditions of 155+/-1 ℃ and nitrogen protection, condensation reflux and stirring;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuing to react for 35min under the protection of nitrogen at 155+/-1 ℃ and under the condition of condensation reflux and stirring to prepare a polyester type high polymer chelating dispersant intermediate;
(4) And initiating polymerization, namely reacting the intermediate of the polyester type macromolecular chelating dispersant with an unsaturated anionic monomer, an initiator and water to obtain the polyester type macromolecular chelating dispersant.
(4.1) The reaction system in the step (3.2) is reduced to 85+/-1 ℃, a reflux device is removed, unsaturated anionic monomers and 50wt% of water are added, and the mixture is fully sheared and dispersed at 65+/-1 ℃ to obtain a dispersion liquid, and 90wt% of the dispersion liquid is taken out for standby;
(4.2) adding 40wt% of water and 20wt% of initiator (the water and the initiator are mixed in advance to prepare an aqueous initiator solution) to the rest of the dispersion liquid in the step (4.1) under stirring, and stirring and reacting for 45min at 80+/-1 ℃; controlling the temperature of the reaction system to be 80+/-1 ℃ and uniformly dripping an initiator solution (obtained by mixing 10 weight percent of water and the rest initiator) and the dispersion liquid taken out in the step (4.1) in 65 min; then, the reaction is continued for 40min at 80+/-1 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, and thus obtaining the polyester type high polymer chelating dispersant.
The polyester type macromolecular chelating dispersant prepared by the embodiment of the invention can be used for a reduction-free washing process for dyeing disperse dyes. Namely, after the polyester fiber is dyed by the disperse dye, the residual disperse dye 'flooding' on the fiber does not need to be washed out under the action of sodium hydrosulfite and alkaline agent like the traditional process (process: sodium hydrosulfite 4-8g/L, sodium carbonate 3-6g/L and 75 ℃ water washing for 10 min) to obtain good dyeing fastness, and the residual disperse dye 'flooding' on the fiber after the disperse dye dyeing is only needed to be washed out by the polyester type macromolecular chelating dispersant of the invention (process: polyester type macromolecular chelating dispersant 3-6g/L and 75 ℃ water washing for 10 min), thus the dyeing fastness (various wet treatment fastness 4-5 grade) same as the traditional post-dyeing washing process can be obtained. The polyester type macromolecular chelating dispersant disclosed by the invention is used for a cleaning process after dyeing of disperse dyes without the assistance of alkaline agents and sodium hydrosulfite, so that the polyester type macromolecular chelating dispersant has good environmental friendliness and convenience in implementation of a production process.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The method for preparing the polyester type macromolecular chelating dispersant is characterized by comprising the following steps of:
(1) Raw material preparation: the raw materials comprise a transesterification catalyst, aromatic dimethyl ester, dihydric alcohol, diisocyanate, unsaturated hydroxyalkyl ester, unsaturated anionic monomer, an initiator, water and optional organic solvent;
wherein the transesterification catalyst is zinc acetate;
the aromatic dimethyl ester is dimethyl isophthalate-5-sodium sulfonate, dimethyl terephthalate and dimethyl phthalate;
The dihydric alcohol is selected from one or more than two of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and diethylene glycol;
the diisocyanate is toluene diisocyanate or isophorone diisocyanate;
the unsaturated hydroxyalkyl ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate;
the unsaturated anionic monomer is maleic anhydride and acrylic acid;
the initiator is potassium persulfate or ammonium persulfate;
The organic solvent is propylene glycol methyl ether acetate;
the raw materials comprise the following components in parts by mole: aromatic dimethyl ester 5, dihydric alcohol 6-10, the mole fraction of diisocyanate=2× (mole fraction of dihydric alcohol-mole fraction of aromatic dimethyl ester), the mole fraction of unsaturated hydroxyalkyl ester is 1-1.1 times of the mole fraction of diisocyanate;
the weight of the unsaturated anionic monomer is 0.5 to 1.5 times of the total weight of the aromatic dimethyl ester and the dihydric alcohol;
based on the total molar amount of the aromatic dimethyl ester, the molar ratio of the dimethyl isophthalate-5-sodium sulfonate is 10-30%, the molar ratio of the dimethyl terephthalate is 30-60%, and the molar ratio of the dimethyl phthalate is 30-60%;
the content of the maleic anhydride is 30-70wt% based on the total weight of the unsaturated anionic monomer;
(2) Transesterification: the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol are reacted to prepare a polyester type macromolecular chelating dispersant initial polymer;
(3) And (3) end capping: reacting the polyester type macromolecular chelating dispersant prepolymer, diisocyanate, unsaturated hydroxyalkyl ester and optional organic solvent to obtain a polyester type macromolecular chelating dispersant intermediate;
(4) Polymerization: the polyester type polymer chelating dispersant is prepared by reacting a polyester type polymer chelating dispersant intermediate, an unsaturated anionic monomer, an initiator and water.
2. The method according to claim 1, wherein the transesterification catalyst is used in an amount of 0.4 to 0.8wt% based on the total weight of the aromatic dimethyl ester and the glycol.
3. The process according to claim 1 or 2, characterized in that the initiator is used in an amount of 0.5 to 1% by weight based on the total weight of unsaturated hydroxyalkyl ester and unsaturated anionic monomer.
4. The method according to claim 1 or 2, wherein the organic solvent is used in an amount of 0 to 1 times the total weight of the aromatic dimethyl ester, the diol, the diisocyanate and the unsaturated hydroxyalkyl ester.
5. The method according to claim 1 or 2, wherein the amount of water is1 to 2 times the total weight of the aromatic dimethyl ester, the diol, the diisocyanate, the unsaturated hydroxyalkyl ester and the unsaturated anionic monomer.
6. The method according to claim 1, wherein the specific process of step (2) comprises:
(2.1) putting the transesterification catalyst, the aromatic dimethyl ester and the dihydric alcohol into a reactor, heating the reaction system to 150-200 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring;
(2.2) heating the reaction system in the step (2.1) to 200-250 ℃ within 10-30 min, and carrying out heat preservation reaction for 50-100 min under the protection of nitrogen, condensation reflux and stirring to obtain the polyester polymer chelating dispersant initial polymer.
7. The method according to claim 1 or 6, wherein the specific process of step (3) comprises:
(3.1) cooling the reaction system in the step (2) to 150-200 ℃, adding an organic solvent and diisocyanate, and then reacting for 20-40 min under the protection of nitrogen at 150-200 ℃ and under the condition of condensation reflux and stirring;
(3.2) adding unsaturated hydroxyalkyl ester into the reaction system in the step (3.1), and continuing to react for 20-40 min to prepare the intermediate of the polyester type high polymer chelating dispersant.
8. The method of claim 1, wherein the specific process of step (4) comprises:
(4.1) cooling the reaction system in the step (3) to 80-110 ℃, removing a reflux device, adding unsaturated anionic monomers and 40-60wt% of water in total, shearing and dispersing at 60-80 ℃ to obtain a dispersion liquid, and taking out 70-90 wt% of the dispersion liquid for later use;
(4.2) adding 35-45wt% of water and 20-40 wt% of initiator to the rest of the dispersion liquid in the step (4.1) under stirring, and maintaining stirring at 70-90 ℃ for 20-60 min; controlling the temperature of the reaction system to be 70-90 ℃ and adding 5-15wt% of water, the rest initiator and 70-90 wt% of the dispersion liquid taken out in the step (4.1) in 40-90 min; then continuously reacting for 30-60 min at 70-90 ℃;
(4.3) cooling the reaction system in the step (4.2) to below 50 ℃ under stirring, thus obtaining the polyester type polymer chelating dispersant.
9. A polyester polymer chelating dispersant prepared by the method of any one of claims 1 to 8.
10. The use of the polyester type polymeric chelation dispersant of claim 9 in a disperse dye dyeing process.
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| Publication Number | Publication Date |
|---|---|
| CN118955810A true CN118955810A (en) | 2024-11-15 |
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