CN112694423A - Isophthalic acid diethylene glycol ester sulfonate solution and preparation method and application thereof - Google Patents
Isophthalic acid diethylene glycol ester sulfonate solution and preparation method and application thereof Download PDFInfo
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- CN112694423A CN112694423A CN201911009134.9A CN201911009134A CN112694423A CN 112694423 A CN112694423 A CN 112694423A CN 201911009134 A CN201911009134 A CN 201911009134A CN 112694423 A CN112694423 A CN 112694423A
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- Prior art keywords
- diethylene glycol
- isophthalic acid
- sulfonate
- solution
- acid diethylene
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- 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 title claims abstract description 149
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 27
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 152
- 229920000728 polyester Polymers 0.000 claims abstract description 108
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 138
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000908 ammonium hydroxide Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 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 claims description 15
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 100
- 125000002091 cationic group Chemical group 0.000 abstract description 41
- -1 isophthalic acid diethylene glycol ester Chemical class 0.000 abstract description 11
- 238000009987 spinning Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 107
- 230000000704 physical effect Effects 0.000 description 24
- 239000002585 base Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 14
- 238000005886 esterification reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- MWOBKFYERIDQSZ-UHFFFAOYSA-N benzene;sodium Chemical compound [Na].C1=CC=CC=C1 MWOBKFYERIDQSZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 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
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 101000679735 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L16-A Proteins 0.000 description 1
- 101000679737 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L16-B Proteins 0.000 description 1
- 101000751132 Schizosaccharomyces pombe (strain 972 / ATCC 24843) 60S ribosomal protein L19-A Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- DEJILVUPOQKKFM-UHFFFAOYSA-L dilithium;5-sulfobenzene-1,3-dicarboxylate Chemical compound [Li+].[Li+].OS(=O)(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 DEJILVUPOQKKFM-UHFFFAOYSA-L 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
- GIGWNNOCCCHECH-UHFFFAOYSA-L dipotassium;benzene-1,3-dicarboxylate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC(C([O-])=O)=C1 GIGWNNOCCCHECH-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
- C07C309/58—Carboxylic acid groups or esters thereof
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Abstract
The application discloses a substance of a sulfosalt solution of isophthalic acid diethylene glycol ester, a preparation method and application thereof. The mass concentration of the isophthalic acid diethylene glycol ester sulfonate in the solution is 10-90%, and the carboxyl content in the isophthalic acid diethylene glycol ester sulfonate solution is 0.005-0.700 mmol/g. The cationic dyeable polyester prepared from the m-phthalic acid diethylene glycol sulfonate solution has the advantages of less foreign matters, good spinnability, less filter pressure rise in the spinning process, long replacement period of a filter screen and low cost.
Description
Technical Field
The invention relates to a substance of a sulfosalt solution of isophthalic acid diethylene glycol ester, a preparation method and application thereof.
Background
The polyester has excellent physical and mechanical properties, but the polyester has poor dyeing effect because the molecular chain structure of the polyester is compact, the crystallinity and the orientation degree are higher, the polarity is smaller, the hydrophilicity is poor, and gaps which can properly contain dye molecules do not exist among long-chain molecules of the polyester. Among the methods for improving the cationic dyeing effect of polyesters, the copolymerization of a third monomer, diethylene glycol isophthalate-5-sulfonate, in a polyester is most commonly used. For example, chinese patent CN101265218A discloses a method for preparing diethylene glycol isophthalate-5-sulfonate, which mainly uses the isophthalic acid-5-sulfonate as a raw material to prepare the diethylene glycol isophthalate-5-sulfonate, and in order to inhibit the generation of diethylene glycol during the synthesis process, a metal acetate is added, although the addition of acetate can inhibit the generation of diethylene glycol, the addition of acetate can also result in the formation of foreign matters when added into polyester at a later stage, thereby affecting the filtration pressure of polyester spinning at the later stage. For another example, patent GB1311244(a) discloses a method for preparing diethylene glycol isophthalate-5-sulfonate, but self-polymerization of isophthalic acid-5-sulfonate may cause an autopolymer with poor compatibility with polyester, and foreign matter is formed when added to polyester, which affects the filtration pressure of polyester spinning at a later stage.
Disclosure of Invention
The invention aims to provide a diethylene glycol isophthalate sulfonate solution with low foreign matter content and a preparation method thereof. The cationic dyeable polyester prepared from the m-phthalic acid diethylene glycol sulfonate solution has the advantages of less foreign matters, good spinnability, less filter pressure rise in the spinning process, long replacement period of a filter screen and low cost.
The technical solution of the invention is as follows:
the solvent of the isophthalic acid diethylene glycol sulfonate solution is ethylene glycol, the mass concentration of the isophthalic acid diethylene glycol sulfonate is 10-90%, and the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is 0.005-0.700 mmol/g.
The isophthalic acid diethylene glycol sulfonate solution preferably contains quaternary ammonium hydroxide shown as a formula 1,
in the formula 1, R1、R2、R3、R4Preference is given to radicals of the formula 2 or 3,
in the formula 2, n is preferably an integer of 0-17, and m in the formula 3 is preferably an integer of 0-3.
The quaternary ammonium base is preferably tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide.
The content of the quaternary ammonium hydroxide in the isophthalic acid diethylene glycol sulfonate solution is preferably 20ppm to 1000ppm in terms of an N element.
The isophthalic acid diethylene glycol sulfonate is preferably sodium isophthalic acid diethylene glycol sulfonate, potassium isophthalic acid diethylene glycol sulfonate or lithium isophthalic acid diethylene glycol sulfonate.
The invention also provides a preparation method of the isophthalic acid diethylene glycol sulfonate solution, which comprises the step of reacting isophthalic acid-5-sulfonate and ethylene glycol at the temperature of 140-230 ℃ to obtain the isophthalic acid diethylene glycol sulfonate solution, wherein the addition amount molar ratio of the isophthalic acid-5-sulfonate to the ethylene glycol is 1: 3.0 to 40.0, and the mass concentration of the isophthalic acid diethylene glycol sulfonate in the isophthalic acid diethylene glycol sulfonate solution is 10 to 90%.
The addition amount of the isophthalic acid-5-sulfonate and the ethylene glycol is preferably in a molar ratio of 1: 4.0 to 25.0.
In the reaction, quaternary ammonium hydroxide shown in the formula 1 is preferably added, and the addition amount of the quaternary ammonium hydroxide is preferably 70-7500 ppm relative to isophthalic acid-5-sulfonate in terms of N element.
The isophthalic acid diethylene glycol sulfonate solution has less foreign matters, the cationic dye dyeable polyester prepared from the isophthalic acid diethylene glycol sulfonate solution has less foreign matters, the filtration pressure rise in subsequent processing such as spinning is less, the service life of a component is long, and the cost is low.
Detailed Description
The isophthalic acid-diethylene glycol ester sulfonate is generally copolymerized in the polyester to impart dyeability to cationic dyes of the polyester. However, in the preparation process of the isophthalic acid-diethylene glycol sulfonate, an autopolymer with poor compatibility with polyester is easily generated, so that when the isophthalic acid-diethylene glycol sulfonate is applied to polyester, foreign matters in the polyester are generated, the filtration pressure in the subsequent processing process is increased, yarn breakage is easy to occur, and the strength of the prepared yarn is low.
In order to solve the problems, the invention provides a diethylene glycol isophthalate sulfonate solution which is low in foreign matter content and difficult to self-polymerize, wherein the solvent of the diethylene glycol isophthalate sulfonate solution is ethylene glycol, the mass concentration of the diethylene glycol isophthalate sulfonate is 10-90%, and the carboxyl content in the diethylene glycol isophthalate sulfonate solution is 0.005-0.700 mmol/g.
When the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is lower than 0.005mmol/g, the isophthalic acid-5-sulfonate participating in the reaction is more, namely the isophthalic acid-5-sulfonate has high reaction degree, a large amount of self-polymer is generated, and the generated self-polymer can cause the filtration pressure to rise in the polyester preparation process and the subsequent processing process; when the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is higher than 0.700mmol/g, the isophthalic acid-5-sulfonate participating in the reaction is small, the solution contains a large amount of isophthalic acid-5-sulfonate, when the isophthalic acid diethylene glycol sulfonate solution is added to the polyester, excessive carboxyl promotes thermal degradation of the polyester, so that the reaction time is prolonged, terminal carboxyl is increased, and finally the color tone and the heat resistance of the polyester are deteriorated, and meanwhile, excessive carboxyl promotes further generation of diethylene glycol, while a large amount of diethylene glycol deteriorates the thermal oxidation resistance of the polyester, and simultaneously, the regularity of the polyester is deteriorated, so that the irreversible part of creep of the fiber at the later stage is increased. Therefore, when the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is 0.005-0.700 mmol/g, the formation of an autopolymer can be effectively avoided, so that the subsequent spinning filtration pressure of the cation dyeable polyester is improved, and the color tone, the heat resistance, the thermal oxidation resistance and the like of the polyester are not influenced.
The solvent in the isophthalic acid diethylene glycol ester sulfonate solution is ethylene glycol, and the mass concentration of the isophthalic acid diethylene glycol ester sulfonate is 10-90%. When the mass concentration of the isophthalic acid diethylene glycol sulfonate is higher than 90%, when the isophthalic acid diethylene glycol sulfonate solution is added into a polyester reaction, the isophthalic acid diethylene glycol sulfonate is unevenly dispersed in the reaction system, the isophthalic acid diethylene glycol sulfonate is agglomerated, the foreign matter amount is increased, and the filtration pressure in the subsequent processing process is increased; when the mass concentration of the diethylene glycol isophthalate sulfonate is less than 10%, since a large amount of ethylene glycol is contained, when the diethylene glycol isophthalate sulfonate solution is added to the polyester reaction, the generation of diethylene glycol is promoted by the excessive ethylene glycol, and since the mass concentration of the diethylene glycol isophthalate sulfonate is too low, the amount of the diethylene glycol isophthalate sulfonate solution added to the polyester reaction increases, and further the cost increases.
In the preparation of diethylene glycol isophthalate sulfonate, diethylene glycol formation is often accompanied. The effect of reducing the formation of diethylene glycol in the isophthalic acid diethylene glycol sulfonate can generally be achieved by adding an alkaline substance during the preparation process. The alkaline substance used in the prior art is metal acetate, but the introduction of the metal acetate can cause the increase of other foreign matters in the polyester when the metal acetate is added in the polyester at the later stage, and the filtration pressure in the subsequent processing process is increased.
In order to avoid the alkaline substance itself becoming foreign matter in the polyester, the invention selects the alkaline compound as quaternary ammonium base shown in the formula 1,
in the formula 1, R1、R2、R3、R4Preference is given to radicals of the formula 2 or 3,
in the formula 2, n is preferably an integer of 0-17, and m in the formula 3 is preferably an integer of 0-3.
The quaternary ammonium base has strong basicity, can completely dissociate hydroxide radical, can obviously inhibit the generation of diglycol, and simultaneously avoids the formation of self foreign matters. Further, the quaternary ammonium base is preferably tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide.
If the content of quaternary ammonium base in the isophthalic acid diethylene glycol sulfonate solution is too low, the diethylene glycol inhibition effect is not obvious; too high a content of quaternary ammonium base leads to poor color tone of the subsequently formed polyester. In the invention, the content of quaternary ammonium base in the isophthalic acid diethylene glycol sulfonate solution is preferably 20ppm to 1000ppm calculated by N element.
The isophthalic acid diethylene glycol ester sulfonate can be isophthalic acid diethylene glycol ester sodium sulfonate, isophthalic acid diethylene glycol ester potassium sulfonate or isophthalic acid diethylene glycol ester lithium sulfonate.
At present, when preparing the isophthalic acid diethylene glycol ester sulfonate, the isophthalic acid dimethyl ester sulfonate and ethylene glycol are subjected to ester exchange reaction mostly. But the reaction process can produce byproduct methanol, and has the defects of large equipment investment, high methanol recovery cost, environmental protection and the like. The method disclosed by the invention is used for preparing the isophthalic acid diethylene glycol sulfonate solution by taking the isophthalic acid-5-sulfonate and the ethylene glycol as raw materials, so that the defects of the prior art can be effectively overcome.
The invention provides a preparation method of the isophthalic acid diethylene glycol sulfonate solution, which comprises the step of reacting isophthalic acid-5-sulfonate and ethylene glycol at the temperature of 140-230 ℃ to obtain the isophthalic acid diethylene glycol sulfonate solution, wherein the addition amount molar ratio of the isophthalic acid-5-sulfonate to the ethylene glycol is 1: 3-40, wherein the concentration of the isophthalic acid diethylene glycol sulfonate in the isophthalic acid diethylene glycol sulfonate solution is 10-90%.
When the reaction temperature is lower than 140 ℃, the reaction is not completely carried out, a large amount of isophthalic acid-5-sulfonate which does not participate in the reaction is also obtained in the obtained product besides the above-mentioned diethylene glycol isophthalate sulfonate, and when the isophthalic acid-5-sulfonate is added into the polyester, the decomposition of the polyester is promoted, so that the color tone and the heat resistance of the polyester are deteriorated, and the formation of diethylene glycol is promoted; when the reaction temperature is higher than 230 ℃, the formation of an isophthalic acid-5-sulfonate autopolymer is promoted, the autopolymer has low compatibility with the polyester, and when the autopolymer is added into the polyester, foreign matters in the polyester are increased, so that the spinning filtration pressure of the cation dyeable polyester is influenced.
The mol ratio of the addition amount of the 5-sulfoisophthalate to the ethylene glycol is 1: 3.0 to 40.0. When the molar ratio is lower than 1: 40.0, that is, when the amount of ethylene glycol added is too large, a large amount of diethylene glycol is produced; when the molar ratio is higher than 1: 3.0, that is, when the amount of ethylene glycol added is too small, the concentration of the produced diethylene glycol isophthalate sulfonate solution becomes too high, and when the solution is added to a polyester, the dispersion of the diethylene glycol isophthalate sulfonate becomes uneven, causing agglomeration and an increase in the amount of foreign matter, and increasing the filtration pressure in the subsequent processing. The molar ratio of the amount of isophthalic acid-5-sulfonate added to ethylene glycol in the present invention is more preferably 1: 4.0 to 25.0.
Acid (H) present in the reaction System for preparing solution of diethylene glycol isophthalate sulfonate+) The formation of diethylene glycol is promoted to deteriorate the thermal oxidation resistance of the polyester and the regularity of the polyester, resulting in an increase in the irreversible portion of the creep of the fiber at a later stage. In order to inhibit the formation of diethylene glycol, the quaternary ammonium base shown in the formula 1 is preferably added in the preparation process of the diethylene glycol isophthalate sulfonate solution. The quaternary ammonium base shown in formula 1 has strong basicity, can completely dissociate hydroxide radical, and reduces acid (H) in the system+) Thereby suppressing the production of diethylene glycol. The quaternary ammonium base represented by formula 1 is preferably tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide. The form of addition of the quaternary ammonium hydroxide is not particularly limited, and the quaternary ammonium hydroxide may be added alone or in the form of an aqueous solution of the quaternary ammonium hydroxide, and the mass concentration of the aqueous solution of the quaternary ammonium hydroxide may be 10 to 80%. The quaternary ammonium base is added in an amount of N element based on isophthalic acid-5-sulfonic acidThe salt content is 70-7500 ppm. When the amount of quaternary ammonium base added is too small, the effect of diethylene glycol inhibition is weak; when the quaternary ammonium base is added in an amount too large, the formation of diethylene glycol can be suppressed, but when the quaternary ammonium base is added in a later stage to the polyester, the color tone of the polyester is deteriorated.
And when the content of carboxyl in the isophthalic acid diethylene glycol sulfonate solution reaches 0.005-0.700 mmol/g, the reaction is finished.
One of the uses of the diethylene glycol isophthalate sulphonate solution according to the invention is to add it to a polyester, thereby imparting cationic dyeability to the polyester. The polyester may be polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and the like.
The method for synthesizing the cationic-dyeable polyester is not particularly limited, and may be a direct polymerization method or an ester exchange method depending on the raw material, or a batch polymerization method or a continuous polymerization method depending on the polymerization process. According to the conventional polyester preparation method, the reaction temperature, pressure and catalyst can be selected properly in the esterification or ester exchange reaction stage and the polycondensation reaction stage. For example, the catalyst may be an antimony catalyst, a titanium-based catalyst, an alkali metal catalyst, or the like. Depending on the desired function, a heat stabilizer, a delustering agent, a toner, and the like may be added to the polyester.
The addition of the solution of the diethylene glycol isophthalate sulfonate of the present invention may be carried out at the esterification stage of the polyester direct polymerization process, or may be carried out before the completion of the polymerization reaction of the esterification reaction, and is preferably carried out before the completion of the polymerization reaction of the esterification reaction. The addition may be carried out before the completion of the polymerization reaction in the transesterification process, and preferably before the completion of the polymerization reaction in the esterification process. The content of the solution of the isophthalic acid diethylene glycol sulphonate in the polyester may be between 0.05% and 5.00% by weight, calculated as sulphur, relative to the total amount of the final cationically dyeable polyester. In addition to the solution of the isophthalic acid diethylene glycol sulfonate, other additives can be used in combination with the polyester to improve the properties of the polyester, for example, polyethylene glycol is added to further improve the antistatic property of the polyester.
The isophthalic acid diethylene glycol sulfonate solution has the characteristics of less foreign matter and low diethylene glycol content. The cationic dyeable polyester prepared by using the cationic dyeable polyester as the additive not only has the advantages of bright color, firm dyeing degree and the like, but also has the advantages of low foreign matter content, low diethylene glycol content and good spinnability.
The present invention will be described in more detail by way of examples. The physical property parameters in the examples were measured by the following methods.
(1) Dyeing property of cation dyeable polyester
Firstly, cationic dyeable polyester fiber is prepared into a tubular knitting, then, cationic blue dye CB546 (1% owf) of a vendor, a uniform dyeing auxiliary YK91, 1g/L, YL15 auxiliary agent, 1g/L are used for dyeing for 60 minutes under the conditions of bath ratio of 1: 30 and 120 ℃, then, the tubular knitting is treated for 20 minutes under the conditions of 80 ℃, 0.6 g/L of sodium hydroxide and 2 g/L of sodium bisulfite, and then, the tubular knitting is washed with water and dried in the air, the brightness L value of the fabric is measured, and the lower the L value, the better dyeing effect is shown.
(2) Differential filtration pressure Δ Pa
The test was carried out using a small filterability tester for filter pressure test. Under the condition of a certain discharge quantity, enabling the cation-dyeable polyester to pass through a filter screen, wherein the aperture of the filter screen is 5 mu m, the testing temperature is the melting point + 25 ℃ of the polyester, the discharge quantity is 10g/min, the pressure before the filter screen is recorded as initial pressure Pa1 at 30min after the feeding is started, the final pressure Pa2 is recorded after 6hr from the initial pressure, and the filter pressure rise value of 6hr is delta Pa-2-Pa 1. The smaller Δ Pa means that the foreign matter in the polyester is smaller and the spinning is more stable.
(3) Measurement of N element content
Weighing 15-20 mg of sample, placing the sample in oxygen flow for combustion, fully oxidizing organic components of the sample by using an oxidant, quantitatively converting N element into volatile oxides corresponding to the N element, enabling the products to flow through silica gel packed column chromatography, respectively measuring the concentrations of the products by using a thermal conductivity cell detector, and finally determining the content of the N element by using an external standard method.
(4) Heat resistance evaluation method
Weighing 8g of slices, placing the slices into a test tube, carrying out heat treatment on the slices under the condition of heat preservation for 3 hours at 300 ℃ under nitrogen, 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.
(5) Measurement 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 titrator using 0.2 mol/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) Concentration of diethylene glycol isophthalate sulfonate in solution of diethylene glycol isophthalate
100g of solution of isophthalic acid diethylene glycol sulfonate was weighed out and distilled under reduced pressure at 10KPa and 135 ℃ until no effluent was present, and the residual amount was recorded. Isophthalic acid diethylene glycol sulfonate solution the concentration of isophthalic acid diethylene glycol sulfonate is:
concentration (%) × 100% (residual amount/100).
The technical solutions of the present invention are described in more detail below by way of specific embodiments, but the present invention is not limited to these embodiments.
Example 1
Isophthalic acid diethylene glycol sulfonate solution: adding sodium sulfoisophthalate-5 and glycol into an esterification kettle, wherein the molar ratio of the sodium sulfoisophthalate to the glycol is 1: 15.0, while adding tetramethylammonium hydroxide in an amount of 1000ppm as an element N based on sodium 5-sulfoisophthalate. The stirrer was started and the temperature was raised to 140 ℃ for 3hr for 60 minutes at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the isophthalic acid diethylene glycol sulfonate solution. The mass concentration of the isophthalic acid diethylene glycol sulfonate solution was 30%, wherein the carboxyl group content was 0.7mmol/g, and the quaternary ammonium hydroxide content was 280ppm in terms of N element.
Cationic dyeable polyester: uniformly mixing terephthalic acid and ethylene glycol, putting into a reaction kettle, and carrying out esterification reaction at 250 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared isophthalic acid diethylene glycol sulfonate solution, a heat stabilizer trimethyl phosphate and a catalyst antimony trioxide to perform polycondensation reaction at 290 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The amount of copolymerized isophthalic acid diethylene glycol sulfonate solution added (in terms of sulfur) in the cationic dyeable polyester was 0.5wt% of the final cationic dyeable polyester. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 2
Isophthalic acid diethylene glycol sulfonate solution: the reaction temperature was adjusted to 175 ℃ under the same other preparation conditions as in example 1, and the parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate were as shown in Table 1.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Example 3
Isophthalic acid diethylene glycol sulfonate solution: adding sodium sulfoisophthalate-5 and glycol into an esterification kettle, wherein the molar ratio of the sodium sulfoisophthalate to the glycol is 1: 15.0, and simultaneously adding tetraethylammonium hydroxide in an amount of 1000ppm as an element N relative to sodium isophthalate-5 sulfonate. The stirrer was started and the temperature was raised to 180 ℃ for 3hr for 60 minutes at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the isophthalic acid diethylene glycol sulfonate solution. The mass concentration of the isophthalic acid diethylene glycol sulfonate solution was 30%, wherein the carboxyl group content was 0.048mmol/g, and the quaternary ammonium hydroxide content was 280ppm in terms of N element.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Example 4
Isophthalic acid diethylene glycol sulfonate solution: the reaction temperature was adjusted to 210 ℃ under the same other preparation conditions as in example 1, and the parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate were as shown in Table 1. .
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Example 5
Isophthalic acid diethylene glycol sulfonate solution: the reaction temperature was adjusted to 230 ℃ under the same other preparation conditions as in example 1, and the parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate were as shown in Table 1.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Example 6
Isophthalic acid diethylene glycol sulfonate solution: adding potassium isophthalate-5 sulfonate (C) and ethylene glycol into an esterification kettle, wherein the molar ratio of the potassium isophthalate to the ethylene glycol is 1: 15.0, while adding tetramethylammonium hydroxide in an amount of 1000ppm as an element N based on sodium 5-sulfoisophthalate. The stirrer was started and the temperature was raised to 180 ℃ for 3hr for 60 minutes at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the isophthalic acid diethylene glycol sulfonate solution. The mass concentration of the isophthalic acid diethylene glycol sulfonate solution was 30%, wherein the carboxyl group content was 0.048mmol/g, and the quaternary ammonium hydroxide content was 280ppm in terms of N element.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Example 7
Isophthalic acid diethylene glycol sulfonate solution: the same procedure as in example 6 was repeated except that C was adjusted to lithium isophthalate-5 sulfonate (D). The relative parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate are shown in table 1.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 1.
Examples 8 to 14
Isophthalic acid diethylene glycol sulfonate solution: the conditions were the same as in example 3 except that the type of quaternary ammonium base was changed. The parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate are shown in table 2.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 2.
Example 15
Isophthalic acid diethylene glycol sulfonate solution: 5, sodium sulfoisophthalate-5 and ethylene glycol, wherein the molar ratio of the sodium sulfoisophthalate to the ethylene glycol is adjusted to be 1: 40.0, otherwise the same conditions as in example 3, and the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 16
Isophthalic acid diethylene glycol sulfonate solution: 5, sodium sulfoisophthalate-5 and ethylene glycol, wherein the molar ratio of the sodium sulfoisophthalate to the ethylene glycol is adjusted to be 1: 25.0, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 17
Isophthalic acid diethylene glycol sulfonate solution: 5, sodium sulfoisophthalate-5 and ethylene glycol, wherein the molar ratio of the sodium sulfoisophthalate to the ethylene glycol is adjusted to be 1: 20.0, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 18
Isophthalic acid diethylene glycol sulfonate solution: 5, sodium sulfoisophthalate-5 and ethylene glycol, wherein the molar ratio of the sodium sulfoisophthalate to the ethylene glycol is adjusted to be 1: 10.6, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 19
Isophthalic acid diethylene glycol sulfonate solution: 5, sodium sulfoisophthalate-5 and ethylene glycol, wherein the molar ratio of the sodium sulfoisophthalate to the ethylene glycol is adjusted to be 1: 7.0, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 20
Isophthalic acid diethylene glycol sulfonate solution: preparing sodium benzene dicarboxylate-5 sulfonate and ethylene glycol, wherein the molar ratio of the sodium benzene dicarboxylate-5 sulfonate to the ethylene glycol is adjusted to be 1: 4.0, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Example 21
Isophthalic acid diethylene glycol sulfonate solution: preparing sodium benzene dicarboxylate-5 sulfonate and ethylene glycol, wherein the molar ratio of the sodium benzene dicarboxylate-5 sulfonate to the ethylene glycol is adjusted to be 1: 3.0, otherwise the same conditions as in example 3, the relative parameters of the isophthalic acid diethylene glycol sulfonate solution obtained are shown in Table 3.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 3.
Examples 22 to 27
Isophthalic acid diethylene glycol sulfonate solution: the amount of tetraethylammonium hydroxide added (as the element N) was varied during the preparation (relative to sodium isophthalate-5 sulfonate), and the specific amount added was as shown in table 4, except that the conditions were the same as in example 3. The relative parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate are shown in table 4.
Cationic dyeable polyester: the conditions were the same as in example 1. Specific physical properties are shown in table 4.
Example 28
Isophthalic acid diethylene glycol sulfonate solution: adding sodium sulfoisophthalate-5 and glycol into an esterification kettle, wherein the molar ratio of the sodium sulfoisophthalate to the glycol is 1: 15.0, tetrabutylammonium hydroxide was added in an amount of 1000ppm as the element N relative to the amount of sodium isophthalate-5 sulfonate. The stirrer was started and the temperature was raised to 145 ℃ for 3hr over 60 minutes at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the isophthalic acid diethylene glycol sulfonate solution. The mass concentration of the isophthalic acid diethylene glycol sulfonate solution was 30%, wherein the carboxyl group content was 0.5mmol/g, and the quaternary ammonium hydroxide content was 280ppm in terms of N element.
Cationic dyeable polyester: uniformly mixing terephthalic acid and ethylene glycol, putting into a reaction kettle, and carrying out esterification reaction at 250 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared isophthalic acid diethylene glycol sulfonate solution, a heat stabilizer trimethyl phosphate and a catalyst antimony trioxide to perform polycondensation reaction at 290 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The amount of copolymerized isophthalic acid diethylene glycol sulfonate solution added (in terms of sulfur) in the cationic dyeable polyester was 0.5wt% of the final cationic dyeable polyester. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Examples 29 to 32
Isophthalic acid diethylene glycol sulfonate solution: the reaction temperature was changed, and other conditions were the same as in example 28. The relative parameters of the resulting solution of isophthalic acid diethylene glycol sulfonate are shown in table 5.
Cationic dyeable polyester: the conditions were the same as in example 28. Specific physical properties are shown in table 5.
Comparative example 1
Isophthalic acid diethylene glycol sulfonate solution: the preparation was carried out under the same conditions as in example 3 except that 1000ppm of lithium acetate was added in terms of lithium element relative to sodium sulfoisophthalate-5 without adding tetraethylammonium hydroxide, and the parameters of the solution of diethylene glycol sulfonate isophthalate prepared are shown in Table 6.
Cationic dyeable polyester: the conditions were the same as in example 3. Specific physical properties are shown in table 6.
Because lithium acetate is added during the preparation of the isophthalic acid diethylene glycol sulfonate solution, although the generation of diethylene glycol during the preparation process can be inhibited, when the lithium acetate is added into polyester, foreign matters in the polyester are increased due to the introduction of metal salt, and the filtration pressure is increased.
Comparative example 2
Isophthalic acid diethylene glycol sulfonate solution: during preparation, the ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is adjusted to be 1: 2.0, other preparation conditions were the same as in example 3, and the parameters of the isophthalic acid diethylene glycol sulfonate solution prepared are shown in Table 6.
Cationic dyeable polyester: the conditions were the same as in example 3. Specific physical properties are shown in table 6.
When the ratio of sodium 5-sulfoisophthalate to ethylene glycol is too high, that is, the amount of ethylene glycol added is too small, the concentration of the prepared diethylene glycol isophthalate sulfonate solution becomes too high, and when the solution is added to a polyester, the diethylene glycol isophthalate sulfonate is not uniformly dispersed, resulting in agglomeration and an increase in the amount of foreign matter, and the filtration pressure rises. .
Comparative example 3
Isophthalic acid diethylene glycol sulfonate solution: the reaction temperature was adjusted to 280 ℃ during the preparation, the other preparation conditions were the same as in example 3, and the parameters of the solution of isophthalic acid diethylene glycol sulfonate prepared are shown in Table 6.
Cationic dyeable polyester: the conditions were the same as in example 3. Specific physical properties are shown in table 6.
Due to the excessively high reaction temperature, the diethylene glycol content in the produced diethylene glycol isophthalate solution is excessively high, and consequently, the diethylene glycol content in the polyester is excessively high.
Comparative example 4
Isophthalic acid diethylene glycol sulfonate solution: the reaction time was adjusted to 1hr, and other preparation conditions were the same as in example 3, and the carboxyl group content of the obtained isophthalic acid diethylene glycol sulfonate solution was 1.5mmol/g, and other parameters are shown in Table 6.
Cationic dyeable polyester: the conditions were the same as in example 3. Specific physical properties are shown in table 6.
Since the carboxyl group content of the produced isophthalic acid diethylene glycol sulfonate solution is too high, heat resistance of the polyester is deteriorated when it is added to the polyester at a later stage, and the content of diethylene glycol is increased.
Comparative example 5
Isophthalic acid diethylene glycol sulfonate solution: the reaction time was adjusted to 4hr, and the carboxyl group content of the isophthalic acid diethylene glycol sulfonate solution prepared in example 3 was 0.001mmol/g under the same other preparation conditions, and the other parameters are shown in Table 6.
Cationic dyeable polyester: the conditions were the same as in example 3. Specific physical properties are shown in table 6.
When the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is too low, the isophthalic acid-5-sulfonate participating in the reaction is more, that is, the reaction degree of the isophthalic acid-5-sulfonate is high, a large amount of self-polymer is generated, and the generated self-polymer can cause the filtration pressure to rise in the polyester preparation process and the subsequent processing process.
In tables 1 to 6, A represents isophthalic acid 5-sulfonate and B represents ethylene glycol.
Abbreviations for respective substances in tables 1 to 6 represent:
SIPA: the sodium sulfoisophthalic acid-5 has been described,
sulfonate C: the isophthalic acid-5 potassium sulfonate salt is,
sulfonate D: lithium 5-sulfoisophthalate was added to the reaction mixture,
quaternary ammonium base E: as shown in the formula 4,
quaternary ammonium base F: as shown in the formula 5,
quaternary ammonium base G: as shown in the formula 6,
quaternary ammonium base H: as shown in the formula 7,
Claims (9)
1. The isophthalic acid diethylene glycol sulfonate solution is characterized in that: the solvent of the isophthalic acid diethylene glycol sulfonate solution is ethylene glycol, the mass concentration of the isophthalic acid diethylene glycol sulfonate is 10-90%, and the carboxyl content in the isophthalic acid diethylene glycol sulfonate solution is 0.005-0.700 mmol/g.
2. The diethylene glycol isophthalate sulfonate solution of claim 1, wherein: the isophthalic acid diethylene glycol sulfonate solution contains quaternary ammonium hydroxide shown as a formula 1,
in the formula 1, R1、R2、R3、R4Are respectively a group shown in a formula 2 or a formula 3,
in the formula 2, n is an integer of 0-17, and in the formula 3, m is an integer of 0-3.
3. The diethylene glycol isophthalate sulfonate solution according to claim 1 or 2, wherein: the isophthalic acid diethylene glycol ester sulfonate is isophthalic acid diethylene glycol ester sodium sulfonate, isophthalic acid diethylene glycol ester potassium sulfonate or isophthalic acid diethylene glycol ester lithium sulfonate.
4. The diethylene glycol isophthalate sulfonate solution according to claim 1 or 2, wherein: the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide.
5. The diethylene glycol isophthalate sulfonate solution according to claim 1 or 2, wherein: the content of quaternary ammonium hydroxide in the isophthalic acid diethylene glycol sulfonate solution is 20-1000 ppm calculated by N element.
6. The process for preparing a diethylene glycol isophthalate sulfonate solution according to claim 1, wherein: reacting isophthalic acid-5-sulfonate and ethylene glycol at 140-230 ℃ to obtain an isophthalic acid diethylene glycol sulfonate solution, wherein the addition molar ratio of the isophthalic acid-5-sulfonate to the ethylene glycol is 1: 3.0 to 40.0, and the mass concentration of the isophthalic acid diethylene glycol sulfonate in the isophthalic acid diethylene glycol sulfonate solution is 10 to 90%.
7. The process for preparing a solution of diethylene glycol isophthalate sulfonate according to claim 6, wherein: in the reaction, quaternary ammonium hydroxide shown in the formula 1 is also added, and the addition amount of the quaternary ammonium hydroxide is 70-7500 ppm relative to isophthalic acid-5-sulfonate in terms of N element.
8. The process for preparing a solution of diethylene glycol isophthalate sulfonate according to claim 6, wherein: the addition amount of the isophthalic acid-5-sulfonate and the ethylene glycol is in a molar ratio of 1: 4.0 to 25.0.
9. Use of the diethylene glycol isophthalate sulphonate solution of claim 1 in a polyester.
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| JPS49117446A (en) * | 1973-03-20 | 1974-11-09 | ||
| JPS61275422A (en) * | 1985-05-24 | 1986-12-05 | Teijin Ltd | Polyester fiber |
| JPS62238883A (en) * | 1986-04-07 | 1987-10-19 | 帝人株式会社 | Polyester dyed cloth |
| CN101265218A (en) * | 2007-03-12 | 2008-09-17 | 厦门翔鹭化纤股份有限公司 | Method for preparing SIPE from SIPA by direct esterification method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164513A (en) * | 2021-12-27 | 2022-03-11 | 江苏恒科新材料有限公司 | Superfine cationic polyester fiber and preparation method thereof |
| CN114164513B (en) * | 2021-12-27 | 2023-12-22 | 江苏恒科新材料有限公司 | Superfine cationic polyester fiber and preparation method thereof |
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