CN101298493B - Atmospheric cationic dye dyeable copolyester polymer, manufacturing method thereof, and atmospheric cationic dye dyeable copolyester fiber using the same - Google Patents
Atmospheric cationic dye dyeable copolyester polymer, manufacturing method thereof, and atmospheric cationic dye dyeable copolyester fiber using the same Download PDFInfo
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- CN101298493B CN101298493B CN2008100938365A CN200810093836A CN101298493B CN 101298493 B CN101298493 B CN 101298493B CN 2008100938365 A CN2008100938365 A CN 2008100938365A CN 200810093836 A CN200810093836 A CN 200810093836A CN 101298493 B CN101298493 B CN 101298493B
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- -1 hydroxyl ethyl Chemical group 0.000 claims abstract description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 42
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 31
- 238000004043 dyeing Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 150000002632 lipids Chemical class 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 150000007520 diprotic acids Chemical class 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 14
- 235000014347 soups Nutrition 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 229920004935 Trevira® Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G63/88—Post-polymerisation treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
-
- 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
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Coloring (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses atmospheric cationic dye dyeable copolyester polymer, a manufacturing method thereof and atmospheric cationic dye dyeable copolyester fibers using the same, particularly the invention provides atmospheric cationic dye dyeable copolyester polymer, a manufacturing method thereof and atmospheric cationic dye dyeable copolyester fibers using the same, wherein copolyester polymer includes dyadic fatty acid of 1-2 mol% accounting for diprotic acid and m-phthalic acid bis hydroxyl ethyl ester with metal sulfonate of 1.0-2.0 mol% accounting for diprotic acid.
Description
Technical field
The present invention relates to a kind of can be under barometric point with copolyester polymer, its preparation method of cationic dyeing and use that this copolyester polymer makes can be under barometric point with the copolyester fiber of cationic dyeing.Through utilizing cheap terephthalic acid (TPA) to carry out polymerization technology; Can make can barometric point and under 100 ℃ or lower temperature with the copolyester polymer and the copolyester fiber of cationic dyeing, this copolyester polymer and copolyester fiber have uniform quality and production cost low.
Background technology
Be below some known can barometric point and under 100 ℃ or lower temperature with the copolyester polymer and the copolyester fiber of cationic dyeing.The open No.2002-284863 of Japanese Patent disclose a kind of can be under barometric point with the continuous polymerization method of the polyester polymers of cationic dyeing.Particularly; Said polyester comprises: account for the metal sulfonate of 2.0 moles of % to 3.0 mole of % of the total acidic component in the polymkeric substance, the molecular weight that accounts for 4.0 weight % to 6.0 weight % of polymer weight and be 400 to 1000 polyalkylene glycol, account for the Diethylene Glycol of 4.5 moles of % to 6.0 mole of % of polymer weight; Wherein end carboxy concentration be 20 equivalent/tons to 30 equivalent/tons, and the limiting viscosity of said polyester changes little.
But, can under barometric point, keep there is deficiency aspect the fibrous texture by the trevira with cationic dyeing by this invention is prepared, this be because of: metal sulfamate salts contg height causes in the decrement step, and the decrement of said trevira is very fast.In addition, high-load Diethylene Glycol also can make the thermotolerance of prepared polymkeric substance and fiber reduce.
The open No.2001-55626 of Japanese Patent disclosed a kind of can be with the trevira of cationic dyeing under barometric point, this trevira comprises the metal sulfonate of 0.1 mole of % to 10 mole of % and the chemical formula of 0.1 weight % to 10 weight % is HO (CH
2CH
2O)
l(RO)
m(CH
2CH
2O)
nThe compound of H (wherein R is that carbonatoms is 3 to 25 aliphatic group, and l and n are identical or different integer, and satisfies the condition of 1≤l+n≤40, and m is 2 to 50 integer) is to improve its thermotolerance.Yet preparation can use the required this chemical formula of the trevira of cationic dyeing to be HO (CH under barometric point
2CH
2O)
l(RO)
m(CH
2CH
2O)
nThe compound of H costs an arm and a leg.As this invent shown, in the situation of utilizing the DMT. Dimethyl p-benzenedicarboxylate polymerization technique, manufacturing cost can further increase.In addition, in disclosed those copolymerization components with cation stain site of this invention, employed isophthalic acid derivatives costs an arm and a leg, and industry is gone up available methyl esters and is difficult to directly apply in the terephthalic acid polymerization technique process.
The flat 5-331719 of the open No. of Japanese Patent disclosed through phosphonium sulfonates salt and polyoxyalkylene glycol are carried out copolymerization prepare can be under barometric point painted fiber.But the phosphonium sulfonates salt is very expensive, is difficult to industrial applications.
The open No.2006-63215 of Japanese Patent has disclosed use magnesium or aluminum compound as the copolymerization catalyzer, and the metal sulfonate that makes 0.5 mole of % to the 8.0 mole of % that accounts for the total acidic component and the carbonatoms that accounts for 0.5 mole of % to 8.0 mole of % of total acidic component are 5 to 10 binary lipid acid generation copolymerization.But this copolymerization catalyzer is very expensive, thereby can not be used for industrial production.
Therefore; People need a kind of can prepare can be under barometric point with the preparation method of the copolyester polymer of cationic dyeing and the fiber that uses this copolyester polymer manufacturing, wherein said copolyester polymer and fiber have good quality and production cost low.
Summary of the invention
Therefore; The objective of the invention is through the TPA polymerization technology that the production cost that can make polyester reduces provide a kind of in order to preparation can barometric point and under 100 ℃ or lower temperature with the polymkeric substance of the copolyester fiber of cationic dyeing, the present invention also provides a kind of preparation method of said polymkeric substance.
Another object of the present invention is to utilize said preparation method that a kind of copolyester fiber is provided, and this copolyester fiber can be used cationic dyeing under barometric point, and its second-order transition temperature is low, but and has an outstanding dyeability.
Above-mentioned purpose of the present invention can be through being achieved to describing in detail below of the present invention with other purpose and advantage of the present invention.
On the one hand; The present invention provide a kind of can be under barometric point with the copolyester polymer of cationic dyeing, the two hydroxyl ethyl esters of the m-phthalic acid with metal sulfonate that this copolyester polymer comprises the binary lipid acid of 1 mole of % to the 20 mole of % that accounts for the total dicarboxylic acid component and accounts for 1.0 moles of % to 2.0 mole of % of total dicarboxylic acid component.
On the other hand, the present invention provide a kind of can be under barometric point with the preparation method of the copolyester polymer of cationic dyeing, this method may further comprise the steps:
(a) terephthalic acid is mixed with terepthaloyl moietie,, and binary lipid acid joined in the soup compound of gained with the preparation soup compound;
(b) this soup compound is fed in first retort, and carries out esterification;
(c) product with step (b) is transferred in second retort, the two hydroxyl ethyl esters of the m-phthalic acid shown in the Chemical formula 1 is fed in this second retort, and mixes;
(d) product with step (c) is transferred in the polycondensation jar, makes fire-retardant polyester carry out polycondensation; And
(e) product of step (d) is discharged through tablets press, and the polymkeric substance of gained is broken.
On the one hand, the present invention provides a kind of copolyester fiber again, and this copolyester fiber can be made by the copolyester polymer with cationic dyeing under barometric point by said.
Brief Description Of Drawings
To above-mentioned characteristic of the present invention and other characteristic be described in detail with reference to by some exemplary of the present invention shown in the accompanying drawing now, the accompanying drawing of back only is exemplary, therefore do not limit the invention, wherein:
Fig. 1 is the synoptic diagram that the exemplary three still formula TPA polymerization reactors that are used to prepare polymkeric substance of the present invention are shown.
Embodiment
Describe the present invention referring now to the preferred embodiments of the invention, example wherein of the present invention is shown in the drawings.
The objective of the invention is to reduce the second-order transition temperature of polymkeric substance, thereby reduce dyeing temperature.When second-order transition temperature was low, because the dye molecule chain moves freely at low temperatures more easily, so dye molecule was like a cork in the infiltrated fiber.At this on the one hand, binary lipid acid has more advantage as copolymerization monomer than polyoxyalkylene glycol.Though polyoxyalkylene glycol can reduce the second-order transition temperature of polymkeric substance effectively, its not effect of overall flexibility to improving molecular chain.The content of preferably said binary lipid acid is 1 mole of % to 20 mole of % of total dicarboxylic acid component.When the content of said binary lipid acid was lower than 1 mole of % of total dicarboxylic acid component, its effect that reduces second-order transition temperature can reduce.And when the content of said binary lipid acid surpassed 20 moles of %, because crystallinity of polymer significantly reduces, so its spinning property or other processing characteristics may deteriorations.In process, add said binary lipid acid by TPA and EG (terepthaloyl moietie) preparation soup compound.Because said binary lipid acid dissolves among the EG, and has more reactivity than TPA, therefore in this soup compound, add binary lipid acid and help improving reactivity.
As in order to the metal sulfonate of cation-dyeable look property to be provided, use the two hydroxyl ethyl esters (DES) of the m-phthalic acid with chemical formula 1:
Chemical formula 1
Wherein M is a basic metal.
In Chemical formula 1, said basic metal can be (for example) Na, Li, K etc., but is not limited to these.
When using commercially available m-phthalic acid dialkyl to replace the two hydroxyl ethyl ester (DES) of m-phthalic acid with metal sulfonate; This commercially available m-phthalic acid dialkyl does not react behind the TPA polymerization technology yet; Thereby cause component pressure increase in the spinning process, perhaps cause the processing characteristics deterioration.
For the generation of the side reaction (for example forming gel) that prevents to be caused, use three still formula polymerization reactors as shown in Figure 1 to carry out polyreaction by the DES cracking.When using two still formula polymerization reactors (constituting), be difficult to determine when the adding additive by esterification reaction tank and polycondensation jar.In addition, when needs added multiple additives, two still formula polymerization reactors were inappropriate, and this is because the quality of basic oligopolymer (base oligomer) in this case may change.DES is joined among jar DE-2, so that its delay in reactor drum is reduced to minimum.
For polycondensation catalyst, can use the antimony compounds that is generally used for preparing polyester, this antimony compounds has outstanding property with low cost and physical properties.
Make a more detailed description below with reference to Fig. 1.
(a) in preparation jar 1, reactant terephthalic acid and terepthaloyl moietie are processed soup compound.In this step, add binary lipid acid, with the preparation soup compound.The mol ratio of binary lipid acid and terephthalic acid is 20: 80 to 1: 99.
(b) soup compound with preparation in the step (a) is stored in the storage tank 2.
(c) through the soup compound in the storage tank 2 is fed in first retort (DE-1) 3 continuously, carry out esterification with semi-batch technology, wherein in first retort (DE-1) 3, basic oligopolymer remains under the steady temperature (being generally 250 ℃ to 260 ℃).Confirm the end of esterification according to the ratio of the amount of the water of discharging and the oligopolymer that reacted by retort.The basic oligopolymer of initial amount is stayed in the DE-1 retort, and, remaining basic oligopolymer is transferred in second retort (DE-2) 5 through strainer through nitrogen pressure.
(d) through transport pipe strainer (basket filter) 4 oligopolymer after the esterification is transferred to the DE-2 retort by the DE-1 retort, and after further reaction, adds the DES shown in the Chemical formula 1.
(e) through transport pipe strainer (basket filter) 6 resulting flame retardant resistance oligopolymer is transferred to polycondensation jar 7 by the DE-2 retort, and reacts to obtain fire-retardant polyester.Subsequently, the fire-retardant polyester with gained carries out polycondensation.
(f) polymkeric substance that makes in the retort 7 is discharged through tablets press 8, and with its fragmentation.
In the TPA polymerization process, generate Diethylene Glycol (DEG) as by product by acid constituents TPA.In the present invention, DEG content is 1.5 weight % to 3.5 weight % of total polymer weight in the polymkeric substance.In polymerization process of the present invention, DEG content can not be lower than 1.5 weight %.When DEG content is 1.5 weight % or when higher, can obtain to reduce the effect of polymer glass invert point.But, when DEG content surpasses 3.5 weight %, because the poor heat stability of polymkeric substance, so its spinning property generation deterioration.
The terminal carboxyl(group) of unreacted TPA and by the concentration of the terminal carboxyl(group) that cracking caused remain on account for total polymer weight 30 equivalent/tons to 50 equivalent/tons.When end carboxy concentration is lower than 30 equivalents/ton hour; Can make the temperature of reaction reduction or EG content is increased, still, in above-mentioned any one situation; The capital increases the reaction times, thereby causes the content of polymer degradation or by product DEG to increase so unfavorable result.And surpass 50 equivalents/ton hour when end carboxy concentration, and the degraded of polymkeric substance may initiated gelization or other problem, and this is because most terminal carboxyl(group) all is to be caused by cracking.
The content of unreacted TPA remains on and is no more than 20ppm in the polymkeric substance.Because unreacted TPA neither fusion can not be dissolved in the solvent well, therefore when its content surpasses 20ppm, may make the spinning property generation deterioration of polymkeric substance.
Preferably, the melt temperature of polymkeric substance is 215 ℃ to 240 ℃.When this melt temperature was lower than 215 ℃, because thermotolerance is low, deterioration can take place in the spinning property of polymkeric substance, and the fiber poor heat resistance of gained.When polyethylene terephthalate fully copolyreaction took place, fusing point can reduce, and therefore, was difficult to obtain the polymkeric substance that melt temperature is higher than 240 ℃.In addition, when melt temperature was higher than 240 ℃, unreacted comonomer can remain in the polymkeric substance, thereby made polymkeric substance and quality of fiber generation deterioration.
Example
Indefiniteness example through following further describes the present invention.
In embodiment and comparative example, physical properties is analyzed as follows:
1: the degree of esterification of terephthalic acid: the carboxylic acid concentration who confirms the oligopolymer after the esterification through titration.
2. limiting viscosity (IV): with polymer dissolution in being in the solution of forming at 6: 4 according to weight ratio by phenol and sym.-tetrachloroethane.Use Ubbelohde viscometer in 30 ℃ thermostatic bath, to measure IV.
3. melt temperature and second-order transition temperature: use DSC-7 DSC (production of Perkin Elmer company), measure with the rate of heating of 10 ℃/min.
4. the content of diprotic acid and DES: analyze through 400MHz NMR.
5.DEG content: polymer dissolution in thanomin, and is analyzed through vapor-phase chromatography.
Embodiment 1
Hexanodioic acid (AA) is used as binary lipid acid.TPA, AA and EG are mixed (TPA: AA: EG=600: 315: 50, according to volume ratio), with the preparation soup compound.The soup compound of gained is fed to (referring to Fig. 1) in the DE-1 retort continuously, wherein contain 1.3 tons of fused basis oligopolymer (it contains the hexanodioic acid of 8.7 moles of % that account for total dicarboxylic acid) in the DE-1 retort, and this retort remains on 255 ℃.Infeed soup compound and reach 1.5 tons and carried out esterification 30 minutes, use volume pump that 1.5 tons oligopolymer is transferred in the DE-2 retort then until the amount of polymkeric substance.In this oligopolymer, add the DES (its molecular weight is 356, is dissolved among the EG, and concentration is 35 weight %) shown in the Chemical formula 1 of 1.3 moles of % accounting for total dicarboxylic acid (TPA, AA and DES), wherein the M in the Chemical formula 1 is Na.Fully stir and mixture is transferred to (referring to Fig. 1) in the polycondensation jar; (Antimony Trioxide: 99.5Min concentration is 250ppm to add 2% Antimony Trioxide: 99.5Min EG solution then; Weight based on polymkeric substance), and under the temperature of 1 holder or lower pressure and 285 ℃ react.The physical properties of resulting polymers is listed in the table 1.
According to preparing polymkeric substance with embodiment 1 identical mode, difference is to replace AA with the nonane diacid (AZA) of 8.5 moles of % that account for total dicarboxylic acid.The physical properties of resulting polymers is listed in the table 1.
According to preparing polymkeric substance with embodiment 1 identical mode, difference is to add the DES that M is Li.The physical properties of resulting polymers is listed in the table 1.
Comparative example 1
According to preparing polymkeric substance with embodiment 1 identical mode, difference is not add AA.The physical properties of resulting polymers is listed in the table 1.
Comparative example 2
According to preparing polymkeric substance with embodiment 1 identical mode, difference is not add DES.The physical properties of resulting polymers is listed in the table 1.
Table 1
| Embodiment 1 | |
|
Comparative example 1 | Comparative example 2 | |
| Binary fatty acid content (mole %) | 8.32 | 8.23 | 8.35 | 0 | 8.2 |
| Basic metal (M) | Na | Na | Li | Na | - |
| DES content (mole %) | 1.31 | 1.24 | 1.32 | 1.35 | 0 |
| DEG content (mole %) | 2.19 | 2.40 | 2.32 | 1.56 | 1.21 |
| CEG (equivalent/ton) | 35 | 33 | 36 | 31 | 27 |
| Melt temperature (℃) | 232 | 231 | 234 | 243 | 241 |
| Second-order transition temperature (℃) | 65 | 63 | 66 | 76 | 64 |
Embodiment 4
The polymkeric substance of preparation among the embodiment 1 is dry down in 140 ℃ in vacuum drier (moisture content is 15ppm); And 295 ℃ of following spinning, spinning condition is: be 1,750 meter/minute 80 ℃ of lower roll speed at first; It is 3,700 meters/minute 120 ℃ of lower roll speed subsequently.With the fiber of gained weave and with Kayacryl dyestuff (production of Nippon Kayaku company) in 95 ℃ of dyeing down.Obtain outstanding dyeability.
Comparative example 3
According to carrying out drying, spinning and dyeing with embodiment 4 identical modes, difference is to use the polymkeric substance of preparation in the comparative example 1.The dyeability of gained is poor.
According to the present invention, can with low cost preparation can be under barometric point with the copolyester fiber of cationic dyeing, wherein when under 100 ℃ or lower temperature, this copolyester fiber being dyeed, but outstanding dyeability can be provided with cationic dyestuff.Preparing method of the present invention is favourable in the replacing and the polymerization technique characteristic aspect of oligopolymer strainer, therefore can reduce production costs.
This paper has described exemplary of the present invention, although used particular term, these terms use with the letter as the one of which and can only it be construed to has literal expressed general sense, is not to be used to limit the invention.Therefore, it should be appreciated by those skilled in the art, under the condition that does not break away from the spirit and scope of the present invention that claims limited that this specification sheets encloses, can do the change on various forms and the details the present invention.
Claims (3)
- One kind can be under barometric point with the copolyester polymer of cationic dyeing; This polymkeric substance prepares through the terephthalic acid polymerization technique; The two hydroxyl ethyl esters of the m-phthalic acid with metal sulfonate that it comprises the binary lipid acid of 1 mole of % to the 20 mole of % that accounts for the total dicarboxylic acid component and accounts for 1.0 moles of % to 2.0 mole of % of total dicarboxylic acid component, the two hydroxyl ethyl esters of wherein said m-phthalic acid have Chemical formula 1 as follows:
Chemical formula 1Wherein M is a basic metal; AndIt comprises the Diethylene Glycol of 1.5 weight % to the 3.5 weight % that account for this total polymer weight, and this polymkeric substance contains the unreacted terephthalic acid that is lower than 20ppm, and its end carboxy concentration is that 30 equivalent/tons are to 50 equivalent/tons. - 2. the described polymkeric substance of claim 1, the melt temperature of this polymkeric substance is 215 ℃ to 240 ℃.
- One kind can be with the copolyester fiber of cationic dyeing under barometric point, wherein said copolyester fiber is through using claim 1 or 2 described can under barometric point, preparations by the copolyester polymer with cationic dyeing.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020070042569A KR100841175B1 (en) | 2007-05-02 | 2007-05-02 | Atmospheric cationic dye dyeable copolyester polymer, manufacturing method thereof, and atmospheric cationic dye dyeable copolyester fiber using the same |
| KR10-2007-0042569 | 2007-05-02 |
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| CN101298493B true CN101298493B (en) | 2012-02-15 |
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| JP (1) | JP2008274277A (en) |
| KR (1) | KR100841175B1 (en) |
| CN (1) | CN101298493B (en) |
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| US9334608B2 (en) | 2009-10-20 | 2016-05-10 | Teijin Frontier Co., Ltd. | Polyester fiber, method for producing the same, cloth, textile product, and polyester formed article |
| CN102061533B (en) * | 2009-11-18 | 2014-06-25 | 东丽纤维研究所（中国）有限公司 | Easy cation-dyeable polyester (ECDP) fibers and production method thereof |
| WO2012027885A1 (en) * | 2010-08-31 | 2012-03-08 | 东华大学 | Preparation methods for copolyester and its fiber modified by aliphatic diol with side chains and isophthalic acid binary ester 5-sodium or potassium sulfonate |
| CN111019105B (en) * | 2018-10-10 | 2021-08-24 | 中国石油化工股份有限公司 | Modified polyester and preparation method thereof |
| CN113166387B (en) * | 2019-03-20 | 2023-04-18 | 东丽纤维研究所（中国）有限公司 | Cationic dyeable polyester composition and process for producing the same |
| KR102331733B1 (en) | 2019-09-06 | 2021-11-25 | 도레이첨단소재 주식회사 | Polyester resion for preparing cation dye-PET fiber, Composite resin containing the same, Cation dye-PET fiber using the same, and Manufacturing method thereof |
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| JPS57117530A (en) | 1981-01-13 | 1982-07-22 | Toray Ind Inc | Preparation of modified polyester |
| JPS58138731A (en) | 1982-02-15 | 1983-08-17 | Toray Ind Inc | Preparation of modified polyester |
| JPH08850B2 (en) * | 1986-06-26 | 1996-01-10 | 帝人株式会社 | Method for producing modified polyester |
| JP3294385B2 (en) * | 1993-07-06 | 2002-06-24 | 帝人株式会社 | Method for producing modified polyester |
| JP3690768B2 (en) * | 1997-03-10 | 2005-08-31 | 日本エステル株式会社 | Continuous production method of polyester |
| JP2004217939A (en) * | 1999-03-05 | 2004-08-05 | Kanebo Ltd | Polyester resin and its manufacturing process |
| TW550274B (en) * | 2000-03-24 | 2003-09-01 | Kanebo Ltd | Modified polyester and continuous process for manufacturing the same |
| KR20030024191A (en) * | 2001-09-17 | 2003-03-26 | 주식회사 효성 | Alkali soluble copolyester for composite fibre and its manufacturing method |
| JP2003096177A (en) * | 2001-09-21 | 2003-04-03 | Toyobo Co Ltd | Process for producing polyester and polyester |
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| TR200802647A2 (en) | 2008-12-22 |
| CN101298493A (en) | 2008-11-05 |
| TW200906899A (en) | 2009-02-16 |
| TWI378949B (en) | 2012-12-11 |
| JP2008274277A (en) | 2008-11-13 |
| KR100841175B1 (en) | 2008-06-24 |
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