CN115362210A - Cationic dyeable polyester composition, preparation method and application thereof - Google Patents
Cationic dyeable polyester composition, preparation method and application thereof Download PDFInfo
- Publication number
- CN115362210A CN115362210A CN202180028470.7A CN202180028470A CN115362210A CN 115362210 A CN115362210 A CN 115362210A CN 202180028470 A CN202180028470 A CN 202180028470A CN 115362210 A CN115362210 A CN 115362210A
- Authority
- CN
- China
- Prior art keywords
- polyester composition
- formula
- esterification
- cationic dyeable
- sulfonate
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005886 esterification reaction Methods 0.000 claims abstract description 49
- 230000032050 esterification Effects 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 20
- -1 sulfonate compound Chemical class 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 61
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 230000003606 oligomerizing effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 13
- 238000009987 spinning Methods 0.000 abstract description 12
- 230000000704 physical effect Effects 0.000 description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- 208000012886 Vertigo Diseases 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KQHKITXZJDOIOD-UHFFFAOYSA-M sodium;3-sulfobenzoate Chemical compound [Na+].OS(=O)(=O)C1=CC=CC(C([O-])=O)=C1 KQHKITXZJDOIOD-UHFFFAOYSA-M 0.000 description 2
- 150000008054 sulfonate salts Chemical class 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- KFGCQOLKVDHXJP-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)C1=CC=CC(C(O)=O)=C1 KFGCQOLKVDHXJP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- OVPXRLUTUWRYEY-UHFFFAOYSA-N dimethyl naphthalene-1,8-dicarboxylate Chemical compound C1=CC(C(=O)OC)=C2C(C(=O)OC)=CC=CC2=C1 OVPXRLUTUWRYEY-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AAQZFYWLAZKKMP-UHFFFAOYSA-M lithium;3-carboxybenzenesulfonate Chemical compound [Li+].OC(=O)C1=CC=CC(S([O-])(=O)=O)=C1 AAQZFYWLAZKKMP-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- JMCGARBKIAJZLC-UHFFFAOYSA-M potassium;2-sulfobenzoate Chemical compound [K+].OC(=O)C1=CC=CC=C1S([O-])(=O)=O JMCGARBKIAJZLC-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- HFPGULMERUXXDW-UHFFFAOYSA-M sodium;2-carboxybenzenesulfonate Chemical compound [Na+].OS(=O)(=O)C1=CC=CC=C1C([O-])=O HFPGULMERUXXDW-UHFFFAOYSA-M 0.000 description 1
- NUERUBQHXIQIOB-UHFFFAOYSA-M sodium;4-sulfobenzoate Chemical compound [Na+].OS(=O)(=O)C1=CC=C(C([O-])=O)C=C1 NUERUBQHXIQIOB-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The application discloses a cationic dyeable polyester composition and a preparation method thereof. The cationic dyeable polyester composition is mainly composed of aromatic dicarboxylic acid units and ethylene glycol units. During the reaction of the polyester composition, an esterification solution obtained by reacting a sulfonate compound with ethylene glycol and an alkali metal compound are added, and the esterification reaction rate of the esterification solution is over 95 percent. The obtained polyester composition has low content of insoluble compounds, less foreign matters, good spinnability, less filtration pressure rise in the spinning process, long replacement period of a filter screen and low cost.
Description
The invention relates to a cationic dyeable polyester composition, a preparation method and application thereof. More specifically, it relates to a cationic dyeable polyester composition which contains less insoluble compounds and diethylene glycol and has a small filtration pressure rise during spinning.
Polyester resins are widely used in industrial fields such as clothing, industrial fibers, magnetic tapes, surface coating films, and tire meridian and mesh lines because of their excellent mechanical and chemical properties.
When the polyester is used as clothing fibers, in order to improve the dyeability of the polyester, an isophthalic acid component containing a sulfonate group, represented by isophthalic acid-5-sodium sulfonate, is used as a comonomer to prepare a copolymerization modified cation dyeable polyester, or the isophthalic acid component containing the sulfonate group is used together with polyethylene glycol and the like for copolymerization modification, but the sulfonate group is easy to physically crosslink in the polyester, so that the melt viscosity of the polyester is obviously increased under the condition of low Inherent Viscosity (IV), and the finally obtained yarn strength is low; limiting its application in some areas where strength is a high requirement.
In addition, when the copolyester modified with the isophthalic acid component containing a sulfonate group is melt-spun, the filtration pressure rises rapidly, and it is difficult to perform stable production.
In order to improve the thickening phenomenon and the filter pressure problem caused by sulfonate groups, japanese patent laid-open No. 5-25708 discloses a modified polyester fiber, wherein the polyester modification is carried out by using a component with blocked cation at the tail end, polyether and diol, the cation groups in the obtained modified polyester are mainly connected at the tail end of a molecular chain, no physical crosslinking group is arranged in the middle of the molecular chain, the viscosity of the polyester is greatly reduced, and the strength of the obtained cationic polyester fiber is greatly improved compared with the strength of the existing sulfonate group modified polyester with isophthalic acid. However, the terminal blocking cation component used in this patent has a carboxylic acid group, and the problem of high DEG due to direct addition exists.
Disclosure of Invention
The invention aims to provide a polyester composition with excellent cationic dyeability and high strength and a preparation method thereof, which can inhibit the filter pressure rise during polyester spinning by inhibiting the amount of insoluble compounds in a polymer.
The technical solution of the invention is as follows:
the cationic dyeable polyester composition mainly comprises an aromatic dicarboxylic acid structural unit and an ethylene glycol structural unit. The polyester composition contains a sulfonate group shown as a formula 1, and the content of the sulfonate group shown as the formula 1 accounts for 1000-5000 ppm, preferably 1000-3500 ppm of the total amount of the polyester composition in terms of sulfur element; the content of the compound represented by the formula 2 is 10.0mol% or less, preferably 5.0mol% or less, of the total amount of sulfonate groups represented by the formula 1 in terms of sulfur element; the content of diethylene glycol in the polyester composition is 0.8 to 5.0wt% relative to the total weight of the polyester composition;
in the formulas 1 and 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z and M are Li ion, na ion or K ion respectively.
The invention also discloses a preparation method of the cationic dyeable polyester composition, which comprises the steps of firstly carrying out esterification or ester exchange reaction on aromatic dicarboxylic acid or esterified derivatives thereof and ethylene glycol to obtain an oligomer, and then carrying out polymerization reaction on the oligomer to obtain the polyester composition. Adding an esterification solution obtained by reacting a sulfonate compound shown as a formula 3 with ethylene glycol and an alkali metal compound at any stage before obtaining the polyester composition, wherein the esterification reaction rate of the esterification solution is more than 95%,
in the formula 3, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, na ion or K ion.
The addition amount of the esterification liquid is preferably 1000-3500 ppm of the total amount of the polyester composition calculated by sulfur element in the esterification liquid.
The alkali metal compound is preferably one or more of lithium acetate, potassium hydroxide or sodium hydroxide, and the addition amount of the alkali metal compound is preferably 10-1000 ppm relative to the total amount of the polyester composition in terms of alkali metal element.
The esterification liquid obtained by reacting the sulfonate compound represented by the formula 3 with ethylene glycol is preferably added after the polymerization reaction is started.
The polymer of the present invention has excellent cationic dyeability and strength, and contains a small amount of diethylene glycol and insoluble compounds, and can suppress an increase in filtration pressure during spinning.
In the prior art, cationic dyeability is generally imparted to polyesters by copolymerizing in the polyester a cationic dyeable ingredient containing a sulfonate group, such as isophthalic acid-5-sulfonate or the like. However, since the sulfonate group is distributed in the middle of the molecular chain of the polyester, the sulfonate group is likely to physically crosslink in the polyester, resulting in an increase in the viscosity and a decrease in the strength of the polyester. At the same time, the hydrolysis resistance of the polyester is also deteriorated.
In order to overcome the above problems, the cationic dyeable ingredient used in the present invention is a sulfonate compound represented by formula 3,
in the formula 3, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, na ion or K ion.
The sulfonate compound shown in the formula 3 only contains one hydroxyl reaction group, the sulfonate compound is mainly connected to the tail end of a molecular chain in the polyester, and no interactive physical crosslinking group exists in the middle of the molecular chain, so that the obtained polyester composition has higher molecular weight and better strength.
Specific examples of the sulfonate compound represented by the formula 3 include sodium 2-carboxybenzenesulfonate, potassium 2-carboxybenzenesulfonate, sodium 3-carboxybenzenesulfonate, lithium 3-carboxybenzenesulfonate, sodium 4-carboxybenzenesulfonate, methyl 2-sulfonate, methyl 3-sulfonate, methyl 4-sulfonate, ethyl 2-sulfonate, potassium 2-sulfonate, ethyl 3-sulfonate, ethyl 4-sulfonate, and lithium 3-sulfonate, and sodium 3-sulfonate is preferably used.
The polyester composition added with the cationic dyeable component of the sulfonate compound shown as the formula 3 contains a sulfonate group shown as the formula 1,
in the formula 1, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, na ion or K ion.
The content of the sulfonate group shown in the formula 1 in the polyester composition accounts for 1000-5000 ppm of the polyester composition in terms of sulfur element. When the content of the sulfonate group represented by formula 1 in the polyester composition is less than 1000ppm, the obtained product is difficult to achieve a satisfactory color concentration in a subsequent dyeing process; when the content of the sulfonate group represented by the formula 1 in the polyester composition is more than 5000ppm, the growth of the polyester molecular chain is suppressed, and the polymerization is terminated without reaching the target viscosity, so that a polyester composition having good physical properties cannot be obtained. The content of the sulfonate group represented by the formula 1 is preferably 1000 to 3500ppm in terms of sulfur element in the polyester composition, from the viewpoint of both dyeability and physical properties of the polyester composition.
Although the use of the monocarboxylate compound shown in formula 3 can increase the molecular weight and strength of the polyester composition, it also tends to increase the diethylene glycol content and deteriorate the thermal oxidation resistance of the polyester composition. In order to inhibit the increase of diethylene glycol, the polyester composition of the present invention is added with a basic compound, and the alkali metal compound may be potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hexametaphosphate, etc., and among them, lithium acetate, potassium hydroxide, and sodium hydroxide are preferable. The alkali metal compound may be added alone or in combination.
When the content of the diethylene glycol in the polyester composition exceeds 5.0wt%, the thermal oxidation resistance of the polyester composition is deteriorated, the regularity of the polyester composition is deteriorated, and the creep irreversible part of the fiber is increased in the later period; if the content of diethylene glycol in the polyester composition is less than 0.8wt%, the structure of the polyester composition may become compact, which affects the binding of the dye and dyeable sites, further affecting the uniformity and stability of dyeing.
Therefore, in order to ensure that the content of diethylene glycol in the polyester composition of the invention is within a suitable range, the amount of the alkali metal compound added is preferably 10 to 1000ppm in terms of the alkali metal element therein relative to the total amount of the polyester composition. When the amount of the alkali metal compound added is too large, the hue of the polyester composition may be deteriorated by the excessive alkali metal compound; when the amount of the metal base compound added is too low, the formation of diethylene glycol cannot be effectively suppressed.
However, the alkali metal compound reacts with the sulfonate compound represented by formula 3 to produce a compound represented by formula 2,
in the formula 2, M and Z are respectively Li ion, na ion or K ion, and Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms.
The compound shown in the formula 2 is insoluble in a polyester composition and can become a foreign matter in a melt spinning stage, so that the filtration pressure in the melt spinning process is increased, the filter screen replacement period in the spinning engineering is shortened, and the spinning cost is increased. Therefore, in order to achieve good spinnability and reduce spinning cost of the polyester composition, the sulfonate compound shown in the formula 3 is added in the form of an esterification solution of ethylene glycol and the sulfonate compound, and the reaction rate is increased to reduce the terminal carboxyl value, so that the reaction probability of the alkali metal compound and the sulfonate compound shown in the formula 3 is reduced, and the content of the compound shown in the formula 2 in the polyester composition is less than 10.0mol%, preferably less than 5.0mol% of the total amount of the sulfonate group shown in the formula 1 in terms of sulfur.
Specifically, the esterified compound formed by the sulfonate compound shown in the formula 3 and ethylene glycol is shown in the formula 4,
in the formula 4, Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group or an alkylbenzene, and Z is a Li ion, a Na ion or a K ion.
The addition amount of the esterification solution is 1000-5000 ppm relative to the total amount of the polyester composition in terms of sulfur element in the esterification solution. When the addition amount of the esterification liquid is less than 1000ppm, the obtained product is difficult to achieve satisfactory color concentration in the subsequent dyeing process; when the addition amount of the esterification liquid is more than 5000ppm, the increase of the molecular chain of the polyester is suppressed, and the phenomenon of polymerization head beating is caused, and the obtained polyester composition has a small molecular weight and poor physical properties. The amount of the esterification liquid added is preferably 1000 to 3500ppm in terms of sulfur in the esterification liquid based on the total amount of the polyester composition in view of both dyeing properties and physical properties of the polyester composition.
The preparation method of the cationic dyeable polyester composition comprises the steps of firstly carrying out esterification or ester exchange reaction on aromatic dicarboxylic acid or esterified derivatives thereof and ethylene glycol to obtain an oligomer, and then carrying out polymerization reaction on the obtained oligomer to obtain the polyester composition. Adding an esterification solution obtained by reacting a sulfonate compound shown as a formula 3 with ethylene glycol and an alkali metal compound at any stage before obtaining the polyester composition, wherein the esterification reaction rate of the esterification solution is more than 95%,
in the formula 3, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, na ion or K ion.
The esterification rate of the esterification liquid is more than 95%, if the esterification rate of the esterification liquid is less than 95%, a large amount of compounds shown as a formula 2 can be generated, the filtration pressure during melt spinning is increased, the filter screen replacement period in the spinning engineering is shortened, and the cost is greatly increased.
The esterification liquid obtained by reacting the sulfonate compound represented by the formula 3 with ethylene glycol can be added at any stage before the polyester composition is obtained, such as an esterification or ester exchange reaction stage, a polymerization reaction process and the like. In order to obtain a higher degree of polymerization and to suppress the generation of easily extractable sulfonate oligomer, the esterification liquid obtained by reacting the sulfonate compound represented by the formula 3 with ethylene glycol is preferably added after the polymerization reaction is started.
The aromatic dicarboxylic acid or esterified derivative thereof of the present invention may be terephthalic acid, isophthalic acid, naphthoic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, dimethyl phthalate, etc., and among them, terephthalic acid or dimethyl terephthalate is preferable.
The esterification reaction may be carried out by continuously adding a slurry of ethylene glycol and an aromatic dicarboxylic acid in a molar ratio of 1.05 to 1.50 to an esterification reaction tank in which an oligomer is preliminarily present; in the esterification reaction tank in which the oligomer is present in advance, ethylene glycol and the aromatic dicarboxylic acid may be added to the reaction mixture before the esterification reaction is started, and then the esterification reaction may be carried out.
The ester exchange reaction can be controlled at a proper ester exchange reaction speed by adjusting the molar ratio of the ethylene glycol to the aromatic dicarboxylic acid esterified derivative to be in the range of 1.50-2.50.
The transesterification catalyst may be any of various known catalysts, for example, oxides of metals such as cobalt, magnesium, manganese and titanium, or acetates thereof, and may be used in combination or singly.
The polymerization catalyst used in the method for preparing the cationic dyeable polyester composition may be any of various polymerization catalysts known in the art. Such as antimony compounds, germanium compounds, titanium compounds, and the like. These catalysts may be used in combination or individually.
In the polyester composition of the present invention, in addition to the aromatic dicarboxylic acid, the aliphatic diol, and the sulfonate group represented by formula 1, other copolymerized substances, such as polyether or aliphatic dicarboxylic acid, may be added. Because the compound shown as the formula 2 has certain solubility in polyether or aliphatic dibasic acid, the precipitation amount of the compound shown as the formula 2 in the polyester composition can be effectively reduced by copolymerizing the polyether or the aliphatic dibasic acid in the polyester composition, so that the polymerization filter pressure is further improved. In addition, the polyester composition can be endowed with low-temperature dyeing performance by adding polyether or aliphatic dibasic acid. The polyether may be polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., and the aliphatic dibasic acid may be cyclohexanedicarboxylic acid, isophthalic acid, succinic acid, adipic acid, glutaric acid, etc. Among them, polyethylene glycol or cyclohexanedicarboxylic acid is preferable. The molecular weight of the polyethylene glycol is preferably 600-6000 g/mol, and more preferably 600-3000 g/mol. The amount of the polyether or the aliphatic dibasic acid added is preferably 0.5 to 10.0wt%, more preferably 0.5 to 5.0wt%, based on the total amount of the polyester composition.
The esterification and polymerization reaction apparatus for producing the cationic dyeable polyester composition of the present invention may be any of various commonly used reaction apparatuses.
In order to further improve the heat resistance and strength of the cationic-dyeable polyester composition of the present invention, it is preferable to carry out solid-phase polymerization after the polymerization reaction is completed in the production process of the cationic-dyeable polyester composition.
The conditions for the solid-phase polymerization are not particularly limited, and any reaction conditions in the art are acceptable. Specifically, the polyester product obtained by the polymerization reaction is subjected to a pre-crystallization treatment, and then solid-phase polymerization is carried out under the conditions of a reaction temperature of 200 to 240 ℃, a reaction pressure of 1000Pa or less, and a reaction time of 100 hours or less to obtain the final polyester composition.
The cationic dyeable polyester composition has good physical property, excellent dyeing property and good dyeing stability. And the content of insoluble foreign matters in the polyester composition is low, the foreign matters in polyester melt spinning are less, the filtration pressure rise in the spinning process is less, the replacement period of the filter screen is long, and the cost is low by controlling the amount of the terminal carboxyl of the cationic dye dyeable component esterification solution.
The measuring method and the evaluating method of each index of the invention are as follows:
(1) Intrinsic Viscosity (IV)
0.8g of the polyester composition chip was dissolved in 10ml of an o-chlorophenol solution, and the intrinsic viscosity was measured at a water bath temperature of 25. + -. 0.2 ℃ by using a Ubbelohde viscometer.
(2) Sulfur content in insoluble compounds
2g of the sample was weighed, dissolved in 30ml of hexafluoroisopropanol, and the solution was filtered through a 4 μm filter paper, and the content of sulfur on the filter paper was quantitatively analyzed by SEM-EDX.
(3) Analysis of Sulfur element content in polyester composition
And (3) carrying out quantitative analysis on the content of sulfur element in the polymer by using an SEM-EDX element analyzer.
(4) Evaluation of dyeing stability
The polyester composition was spun to obtain drawn yarn, and the obtained drawn fiber was doubled to 2 filaments, to obtain a leg of a stocking under 22 gauge conditions, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, bath ratio of 1. The stained sample was superposed in a non-transparent state, and then subjected to color measurement with a spectrophotometer (Datacolor 650 manufactured by Datacolor Asia Pacific (h.k.) ltd.) under the conditions of a CEI standard light source D65 at an angle of 10 ° to obtain L.
(5) Calculation of reaction Rate of esterification solution (test of carboxyl content)
0.5g of a sample was weighed out and dissolved in 10ml of o-cresol, and the amount of carboxyl groups was measured by a potentiometric titration apparatus using 0.2mol/l of sodium hydroxide.
(6) Diethylene glycol test
Diethylene glycol in isophthalic acid diethylene glycol sulfonate solution: a0.5 g sample was weighed into 10ml of adipic acid, determined by LC and the diethylene glycol content determined by the internal standard method.
Diethylene glycol in polyester: a0.5 g sample was weighed, added to ethanolamine, dissolved by heating, and 10ml of adipic acid was added, measured by LC, and the diethylene glycol content was determined by the internal standard method.
(7) Heat resistance evaluation method
Weighing 8g of slices, placing the slices into a test tube, carrying out heat treatment on the slices under nitrogen at 300 ℃ for 3 hours, and respectively testing the carboxyl content of the slices before and after the heat treatment. A large value of the carboxyl group content Δ COOH before and after the heat treatment (COOH before the heat treatment-COOH after the heat treatment) means that the heat resistance of the polyester is relatively poor.
(8) Differential filtration pressure Δ Pa
The test was carried out using a small filterability tester for filter pressure test. Under a certain discharge rate condition, enabling the cation-dyeable polyester to pass through a filter screen, wherein the aperture of the filter screen is 5 microns, the test temperature is the melting point of the polyester +25 ℃, the discharge rate is 10g/min, the pressure before the filter screen at 30min after the start of feeding is recorded as initial pressure Pa1, the pressure Pa2 after 1 hour from the initial pressure is recorded as final pressure Pa2, and the filter pressure rise value at 1 hour is delta Pa = Pa2-Pa1. A smaller Δ Pa indicates less foreign matter in the polyester and more stable spinning.
(9) Elongation product of fiber
Strength and elongation measurements were made according to JIS L1013:2010 (method of testing long fibers in chemical fiber) 8.8.1. The strength and elongation were measured by ORIENTEC Co., RTC-1225A tensile elongation tester, tensile elongation product = strength x (elongation) 0.5 。
The advantages of the present invention will be described in detail below with reference to the examples and comparative examples. The present invention is not limited to the following examples.
Example 1
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240-260 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding an esterification solution with the esterification rate of 99%, then adding a lithium acetate solution, then adding a catalyst antimony trioxide and a heat stabilizer trimethyl phosphate, and carrying out polymerization reaction at 260-290 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required polyester composition. The intrinsic viscosity IV of the polyester composition is 0.64dl/g, the pressure difference of filtration of the polyester is 0.20MPa/h, and the DEG value is 2.5%.
And carrying out melt spinning on the slices at 290 ℃ to obtain the cation dyeable polyester yarn. The sulfur content in the fiber is 2450ppm, and the sulfur content in the dissolved water solution after hot water treatment is 4.7ppm, which accounts for 0.19 percent of the total sulfur content of the polyester composition. The fiber elongation product was 24, the blue dye concentration was 3.0% o.w.f., and the L value after dyeing was 25.
Example 2
The cationic-dyeable polyester composition was prepared in the same manner as in example 1 except that the kind of the aromatic dicarboxylic acid or the esterified derivative thereof was changed. The physical properties are shown in Table 1.
Examples 3 to 6
The cationic dyeable polyester composition was prepared in the same manner as in example 1 except that the amount of the sulfonate salt shown in the formula 3 was changed. The physical properties are shown in Table 1.
Example 7
The cationic dyeable polyester composition was prepared by changing the reaction rate of the sulfonate esterified liquid as shown in the formula 3, that is, changing the terminal carboxyl value of the sulfonate esterified liquid under the same conditions as in example 1. The physical properties are shown in Table 1.
Examples 8 to 12
A cationic-dyeable polyester composition was obtained in the same manner as in example 1 except that the amount of the alkali metal compound lithium acetate added was changed. Specific physical properties are shown in tables 1 and 2.
Examples 13 to 14
The cationic-dyeable polyester composition was obtained in the same manner as in example 1 except that the kind of the alkali metal compound was changed. The physical properties are shown in Table 2.
Examples 15 to 16
The kind of the sulfonate shown in the formula 3 was changed, and other conditions were the same as those in example 1 to obtain a cationic-dyeable polyester composition. The physical properties are shown in Table 2.
Example 17
After the polymerization reaction, the solid phase polymerization was carried out at a reaction temperature of 230 ℃ under a reaction pressure of 50Pa for a reaction time of 80 hours or less, and the cationic-dyeable polyester composition was obtained in the same manner as in example 1 under the other conditions, and the specific physical properties are shown in Table 2.
Comparative example 1
The cationic dyeable polyester is prepared by directly adding sulfonate 3-carboxyl sodium benzenesulfonate and carrying out the same preparation process as in example 1 under the same conditions. The physical properties are shown in Table 3.
In comparative example 1, the amount of the insoluble compound represented by the formula 2 in the polyester composition was too large due to the direct addition of the unesterified sodium 3-carboxybenzenesulfonate, and finally the polyester melt filtration pressure test showed a large amount of foreign matter, and the filtration pressure difference Δ Pa was large and the spinning was unstable.
Comparative example 2
The non-esterified 3-carboxyl sodium benzenesulfonate monomer is directly added, the alkali metal compound is not added, and the cationic dyeable polyester is prepared under the same conditions as in example 1. The physical properties are shown in Table 3.
As the unesterified 3-carboxyl sodium benzenesulfonate monomer is directly added, the terminal carboxyl is more, the whole polymer system is in an acidic condition, under the condition of not adding the DEG inhibitor alkali metal compound, excessive diethylene glycol is easily generated, the diethylene glycol can cause the heat resistance of the polymer to be poor, and the polymer is easily headed, so that the final IV of the polyester is low.
Comparative example 3
The cationic dyeable polyester was prepared in the same manner as in example 1 except that the sulfonate esterified liquid having a reaction rate of 99% was added without adding the alkali metal compound. The physical properties are shown in Table 3.
Although the esterification solution having a reaction rate of 99% has a small amount of free acidic ions, too much EG is excessive, and thus diethylene glycol is easily produced without adding an alkali metal compound of a DEG inhibitor, and the heat resistance of the polymer is deteriorated by diethylene glycol, resulting in deterioration of the physical properties of the final polyester.
Comparative examples 4 to 6
The cationic dyeable polyester composition was prepared in the same manner as in example 1 except that the reaction rate of the sulfonate esterification solution was changed. The physical properties are shown in Table 3.
Although 3-carboxyl sodium benzenesulfonate is esterified, the amount of insoluble compounds in the polyester composition as shown in formula 2 is too much due to low reaction rate and large amount of terminal carboxyl, so that the final polyester has more foreign matters in a melt filtration pressure test, a large filtration pressure difference delta Pa and unstable spinning.
Comparative examples 7 to 8
The cationic-dyeable polyester composition was obtained by changing the amount of the sulfonate salt represented by the formula 3 and other conditions in the same manner as in example 1. The physical properties are shown in Table 3.
The addition amount of the sulfonate is too low, resulting in poor dyeability and failure to dye a desired color tone. Too high an amount of the sulfonate to be added results in a polyester composition having a small molecular weight, poor physical properties and a yarn having too low a strength.
Claims (9)
- The cationic dyeable polyester composition is mainly composed of an aromatic dicarboxylic acid structural unit and an aliphatic diol structural unit, and is characterized in that: the polyester composition contains a sulfonate group shown as a formula 1, and the content of the sulfonate group shown as the formula 1 accounts for 1000-5000 ppm of the total amount of the polyester composition in terms of sulfur; the content of the compound shown in the formula 2 is less than 10.0mol percent of the total amount of sulfonate groups shown in the formula 1 calculated by sulfur element; the content of diethylene glycol in the polyester composition is 0.8 to 5.0wt% relative to the total weight of the polyester composition;
in the formulas 1 and 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z and M are Li ion, na ion or K ion respectively. - The cationic dyeable polyester composition of claim 1, wherein: the content of the sulfonate group shown in the formula 1 accounts for 1000-3500 ppm of the total amount of the polyester composition in terms of sulfur element.
- The cationic dyeable polyester composition of claim 1 or 2, characterized by: the content of the compound represented by the formula 2 is 5.0mol% or less of the total amount of sulfonate groups represented by the formula 1 in terms of sulfur.
- The process for preparing the cationic dyeable polyester composition according to claim 1, comprising the steps of subjecting an aromatic dicarboxylic acid or an esterified derivative thereof and an aliphatic diol to esterification or transesterification to obtain an oligomer, and polymerizing the oligomer to obtain a polyester composition, wherein: adding an esterification solution obtained by reacting a sulfonate compound shown as a formula 3 with ethylene glycol and an alkali metal compound at any stage before obtaining the polyester composition, wherein the esterification reaction rate of the esterification solution is more than 95%,
in the formula 3, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, na ion or K ion. - The process for preparing a cationic dyeable polyester composition according to claim 4, wherein: the addition amount of the esterification liquid accounts for 1000-3500 ppm of the total amount of the polyester composition in terms of sulfur in the esterification liquid.
- The process for the preparation of the cationic dyeable polyester composition according to claim 4 or 5, characterized in that: the alkali metal compound is one or more of lithium acetate, potassium hydroxide or sodium hydroxide.
- The process for the preparation of the cationic dyeable polyester composition according to claim 4 or 5, characterized in that: the alkali metal compound is added in an amount of 10 to 1000ppm in terms of the alkali metal element therein relative to the total amount of the polyester composition.
- The process for the preparation of the cationic dyeable polyester composition according to claim 4 or 5, characterized in that: the esterification liquid obtained by the reaction of the sulfonate compound shown in the formula 3 and ethylene glycol is added after the polymerization reaction starts.
- Use of the cationic dyeable polyester of claim 1 in fibers.
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