CN115558091B - Black hydrophilic polyester and preparation method thereof - Google Patents
Black hydrophilic polyester and preparation method thereof Download PDFInfo
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- CN115558091B CN115558091B CN202211141522.4A CN202211141522A CN115558091B CN 115558091 B CN115558091 B CN 115558091B CN 202211141522 A CN202211141522 A CN 202211141522A CN 115558091 B CN115558091 B CN 115558091B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 137
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 87
- 238000005886 esterification reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000003381 stabilizer Substances 0.000 claims abstract description 60
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 29
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000002202 Polyethylene glycol Substances 0.000 description 18
- 229920001223 polyethylene glycol Polymers 0.000 description 18
- 229920000180 alkyd Polymers 0.000 description 16
- 230000032050 esterification Effects 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 16
- 229920001634 Copolyester Polymers 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides black hydrophilic polyester and a preparation method thereof, and belongs to the technical field of high polymer materials. The preparation method comprises the following steps: mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, and then carrying out a first esterification reaction, and carrying out a first pre-polycondensation reaction to obtain a black prepolymer melt; mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, performing a second esterification reaction, adding polyether glycol into a reaction system after the second esterification reaction, and performing a second pre-polycondensation reaction to obtain a hydrophilic prepolymer melt; the black prepolymer melt and the hydrophilic prepolymer melt are sequentially subjected to mixing, third pre-polycondensation reaction, final polycondensation reaction and granulating to obtain the black hydrophilic polyester. The black hydrophilic polyester is prepared by the method. The black hydrophilic polyester has good uniformity, is favorable for smooth spinning, and simultaneously, the independent control of the early reaction of the black polyester prepolymer melt and the hydrophilic prepolymer melt is favorable for application, and the polymerization process is stable and reliable.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to black hydrophilic polyester and a preparation method thereof.
Background
The conventional polyester fiber fabric is stiff and smooth and is not easy to deform, ironing is not needed after washing, and the polyester fiber fabric is widely used for clothing, household textiles and industrial textiles. The original liquid coloring polyester and the fiber prepared by the in-situ method have the characteristics of uniform coloring and high color fastness, avoid the discharge of waste water in the dyeing and finishing process, have the advantages of energy conservation and environmental protection, and are increasingly valued by researchers in the large environment of energy conservation and emission reduction. If carbon black color paste and polyether glycol are simultaneously added into a polyester polymerization reaction system to prepare in-situ polymerized black hydrophilic polyester, carbon black is easy to separate out and agglomerate in the mixing process due to lower viscosity, so that a spinneret plate hole is blocked in the subsequent spinning process, and meanwhile, the interaction between the polyether glycol and the surface of the carbon black is easy to generate a foaming phenomenon, so that a gas phase pipeline is blocked by the system in the subsequent polycondensation process.
Disclosure of Invention
In view of the above, the invention provides a black hydrophilic polyester and a preparation method thereof, and when the black hydrophilic polyester is prepared by the preparation method, the process stability is good, and the prepared black hydrophilic polyester has good spinnability, so that the black hydrophilic polyester is more practical.
In order to achieve the first object, the technical scheme of the preparation method of the black hydrophilic polyester provided by the invention is as follows:
the preparation method of the black hydrophilic polyester provided by the invention comprises the following steps:
mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, and then carrying out a first esterification reaction, and carrying out a first pre-polycondensation reaction to obtain a black prepolymer melt, wherein the value range of the mass ratio of the sum of the terephthalic acid and the isophthalic acid to the ethylene glycol is 1: (1.11-1.4); the isophthalic acid is 1% -10% of the amount of terephthalic acid material; the addition amount of the catalyst is 0.03-0.06% of the melt mass of the black prepolymer, the addition amount of the stabilizer is 0.005-0.03% of the melt mass of the black prepolymer, and the addition amount of the carbon black color paste is 1-3% of the melt mass of the black prepolymer;
mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, performing a second esterification reaction, adding polyether glycol into a reaction system after the second esterification reaction, and performing a second pre-polymerization reaction to obtain a hydrophilic prepolymer melt, wherein the value range of the mass ratio of the terephthalic acid to the ethylene glycol is 1: (1.11-1.4); the addition amount of the catalyst is 0.03-0.06% of the melt mass of the hydrophilic prepolymer, and the addition amount of the stabilizer is 0.005-0.03% of the melt mass of the hydrophilic prepolymer; the addition amount of the polyether glycol is 5% -40% of the melt mass of the hydrophilic prepolymer;
the black hydrophilic polyester is obtained by sequentially mixing, third pre-condensing reaction, final polycondensation reaction and granulating the black prepolymer melt and the hydrophilic prepolymer melt, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is (0.25-4): 1.
the preparation method of the black hydrophilic polyester provided by the invention can be further realized by adopting the following technical measures.
Preferably, the limiting viscosity number of the black prepolymer melt is in the range of 0.15dL/g to 0.30dL/g.
Preferably, the hydrophilic prepolymer melt has an inherent viscosity of 0.15 to 0.30dL/g.
Preferably, the value range of the intrinsic viscosity is 0.30-0.45dL/g after the black prepolymer melt and the hydrophilic prepolymer melt are mixed.
Preferably, the catalyst is selected from one or a mixture of more of antimony trioxide, ethylene glycol antimony, tetrabutyl titanate, tetraisopropyl titanate and tetraisooctyl titanate.
Preferably, the stabilizer is selected from one or a mixture of more of triphenyl phosphite, trimethyl phosphate, pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, tri (2, 4-di-tert-butylphenyl) phosphite and 3, 5-di (1, 1-dimethylethyl) -4-hydroxy-phenylpropionate-1, 6-adipoyl.
Preferably, the reaction temperature of the first esterification reaction and the second esterification reaction is 240 ℃ to 265 ℃.
Preferably, the temperature of the first pre-polymerization reaction and the second pre-polymerization reaction is 245 ℃ to 265 ℃, and the reaction pressure of the first pre-polymerization reaction and the second pre-polymerization reaction is 10kPa to 20kPa.
Preferably, the temperature of the third pre-polymerization reaction is 250-275 ℃, and the reaction pressure of the third pre-polymerization reaction is 1-4 kPa; the temperature of the final polycondensation reaction ranges from 270 ℃ to 290 ℃, and the reaction pressure of the final polycondensation reaction ranges from 0.05kPa to 0.5kPa.
In order to achieve the second purpose, the technical scheme of the black hydrophilic polyester provided by the invention is as follows:
the black hydrophilic polyester provided by the invention is prepared by the preparation method of the black hydrophilic polyester according to any one of claims 1 to 9, and the intrinsic viscosity value of the black hydrophilic polyester is 0.65-0.85dL/g.
The invention controls the viscosity matching of the black polyester prepolymer melt and the hydrophilic prepolymer melt, and fully mixes the melt by the dynamic mixing device, thereby effectively reducing the aggregation of carbon black in the polymer melt, ensuring good uniformity of the product and facilitating smooth spinning, and simultaneously, independently controlling the early reaction of the black polyester prepolymer melt and the hydrophilic prepolymer melt, effectively avoiding the situation that the gas phase pipeline is blocked by the system being pumped out in the polycondensation process after polyether glycol is added, ensuring stable and reliable polymerization process and facilitating application.
Detailed Description
In view of the above, the invention provides a black hydrophilic polyester and a preparation method thereof, and when the black hydrophilic polyester is prepared by the preparation method, the process stability is good, and the prepared black hydrophilic polyester has good spinnability, so that the black hydrophilic polyester is more practical.
In order to further describe the technical means and effects adopted by the present invention to achieve the preset purpose, the following description refers to a specific implementation, structure, characteristics and effects of a black hydrophilic polyester and a preparation method thereof according to the present invention in combination with a preferred embodiment. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The term "and/or" is herein merely an association relation describing an associated object, meaning that three relations may exist, e.g. a and/or B, specifically understood as: the composition may contain both a and B, and may contain a alone or B alone, and any of the above three cases may be provided.
Example 1
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity reaching 0.15dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid of the system to glycol alkyd is 1.25; the isophthalic acid is 3% of the amount of terephthalic acid; the addition amount of the carbon black is 3% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.05 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the temperature of the esterification reaction is 250 ℃, after the esterification reaction time is 4 hours, injecting polyethylene glycol melt, continuously performing pre-polycondensation reaction, wherein the pre-polycondensation temperature is 255 ℃, and the reaction pressure is 20kpa, so as to obtain hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.30dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the catalyst is 0.05 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.02 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 1000, and the addition amount is 30% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.40dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 2:1, the second pre-polycondensation reaction temperature is 270 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.70dL/g was obtained.
Example 2
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity reaching 0.15dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid of the system to glycol alkyd is 1.25; the isophthalic acid is 6% of the amount of terephthalic acid; the addition amount of the carbon black is 3% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.05 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the temperature of the esterification reaction is 250 ℃, after the esterification reaction time is 4 hours, injecting polyethylene glycol melt, continuously performing pre-polycondensation reaction, wherein the pre-polycondensation temperature is 255 ℃, and the reaction pressure is 20kpa, so as to obtain hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.30dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the catalyst is 0.05 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.02 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 4000, and the addition amount is 30% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.40dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 2:1, the second pre-polycondensation reaction temperature is 270 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.80dL/g was obtained.
Example 3
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is antimonous oxide, the stabilizer is triphenyl phosphite, the esterification reaction temperature is 240 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 245 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity of 0.15dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid to the ethylene glycol alkyd of the system is 1.4; the isophthalic acid is 1% of the amount of terephthalic acid; the addition amount of the carbon black is 1% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.03 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.005 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is antimony trioxide, the stabilizer is triphenyl phosphite, the esterification reaction temperature is 240 ℃, the esterification reaction time is 4 hours, then, injecting polyethylene glycol melt, and continuously performing pre-polycondensation reaction, wherein the pre-polycondensation temperature is 245 ℃, the reaction pressure is 20kpa, so as to obtain a hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.15dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.4; the addition amount of the catalyst is 0.03 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.005 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 400, and the addition amount is 40% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.30dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 4:1, the second pre-polycondensation reaction temperature is 250 ℃, and the reaction pressure is 4kPa; the final polycondensation reaction temperature was 290℃and the reaction pressure was 0.5kPa, and the intrinsic viscosity of the resulting black polyester was 0.65dL/g.
Example 4
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is trimethyl phosphate, the temperature of the esterification reaction is 265 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 265 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity of 0.30dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid of the system to glycol alkyd is 1.11; the isophthalic acid is 3% of the amount of terephthalic acid; the addition amount of the carbon black is 1% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.06 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.03 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is trimethyl phosphate, the temperature of the esterification reaction is 265 ℃, after the esterification reaction time is 4 hours, the mixture is injected into polyethylene glycol melt to continuously perform pre-polycondensation reaction, the pre-polycondensation temperature is 265 ℃, the reaction pressure is 20kpa, and the hydrophilic prepolymer melt with the prepolymer viscosity of 0.30dL/g is obtained, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.11; the addition amount of the catalyst is 0.06 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.03 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 1000, and the addition amount is 25% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.45dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 4:1, the second pre-polycondensation reaction temperature is 275 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 270℃and the reaction pressure was 0.05kPa, and the intrinsic viscosity of the resulting black polyester was 0.70dL/g.
Example 5
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to carry out esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is tris (2, 4-di-tert-butylphenyl) phosphite and 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionic acid-1, 6-adipoyl ester, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is carried out after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity reaching 0.15dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid to the glycol alkyd of the system is 1.25; the isophthalic acid is 10% of the amount of terephthalic acid; the addition amount of the carbon black is 3% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.05 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is tris (2, 4-di-tert-butylphenyl) phosphite and 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionic acid-1, 6-adipoyl ester, the esterification reaction temperature is 250 ℃, after the esterification reaction time is 4 hours, injecting polyethylene glycol melt, continuously performing pre-polycondensation reaction, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 20kpa, and obtaining hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.20dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the catalyst is 0.05 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.02 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 8000, and the addition amount is 5% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain a mixed prepolymer melt with the intrinsic viscosity of 0.40dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 0.25:1, the second pre-polycondensation reaction temperature is 270 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.85dL/g was obtained.
Example 6
(1) Uniformly mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is tetrabutyl titanate and tetraisopropyl titanate, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity reaching 0.20dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid to the glycol alkyd of the system is 1.25; the isophthalic acid is 10% of the amount of terephthalic acid; the addition amount of the carbon black is 2% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.03 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the temperature of the esterification reaction is 250 ℃, after the esterification reaction time is 4 hours, injecting polyethylene glycol melt, continuously performing pre-polycondensation reaction, wherein the pre-polycondensation temperature is 255 ℃, and the reaction pressure is 20kpa, so as to obtain hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.25dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the catalyst is 0.05 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.02 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 2000, and the addition amount is 20% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.40dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 1:1, the second pre-polycondensation reaction temperature is 270 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.75dL/g was obtained.
Example 7
(1) Uniformly mixing carbon black color paste, terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is tetrabutyl titanate and tetraisooctyl titanate, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 10kpa, and a black prepolymer melt with the prepolymer viscosity reaching 0.20dL/g is obtained, and in the embodiment, the molar ratio of the sum of terephthalic acid and isophthalic acid of the system to the ethylene glycol alkyd is 1.25; the isophthalic acid is 6% of the amount of terephthalic acid; the addition amount of the carbon black is 2% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.03 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer;
(2) Uniformly mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the temperature of the esterification reaction is 250 ℃, after the esterification reaction time is 4 hours, injecting polyethylene glycol melt, continuously performing pre-polycondensation reaction, wherein the pre-polycondensation temperature is 255 ℃, and the reaction pressure is 20kpa, so as to obtain hydrophilic prepolymer melt with the prepolymer viscosity reaching 0.25dL/g, and in the embodiment, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the catalyst is 0.05 percent of the mass percentage of the hydrophilic prepolymer melt; the addition amount of the stabilizer is 0.02 percent of the mass percentage of the hydrophilic prepolymer melt; the molecular weight of the polyethylene glycol is 4000, and the addition amount is 10% of that of the hydrophilic prepolymer melt;
(3) Conveying the black prepolymer melt and the hydrophilic prepolymer melt through a melt conveying pump, mixing for 30min by a dynamic mixing device, introducing the mixture into a second pre-polycondensation kettle for further pre-polycondensation reaction to obtain mixed prepolymer melt with the intrinsic viscosity of 0.40dL/g, and performing polycondensation, cooling and granulating to obtain copolyester chips, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is 1:1, the second pre-polycondensation reaction temperature is 270 ℃, and the reaction pressure is 1kPa; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.75dL/g was obtained.
Comparative example 1
Uniformly mixing carbon black color paste, polyethylene glycol, terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the pre-polycondensation reaction is performed after the esterification reaction time is 4 hours, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 1kpa, a prepolymer melt with the prepolymer viscosity reaching 0.20dL/g is obtained, and the black hydrophilic copolyester slice is obtained after polycondensation, cooling and granulating, wherein in the comparative example 1, the mole ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the carbon black is 2% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.05 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer; the molecular weight of the polyethylene glycol is 1000, and the addition amount is 10% of that of the hydrophilic prepolymer melt; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.70dL/g was obtained.
Comparative example 2
Uniformly mixing carbon black color paste, terephthalic acid, ethylene glycol, a catalyst and a stabilizer, adding the mixture into an esterification reactor to perform esterification reaction, wherein the catalyst is ethylene glycol antimony, the stabilizer is pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, the esterification reaction temperature is 250 ℃, the esterification reaction time is 4 hours, then, polyethylene glycol melt is injected, the pre-polycondensation reaction is continuously performed, the pre-polycondensation temperature is 255 ℃, the reaction pressure is 1kpa, the condition of blocking a vacuum pipeline occurs in the pre-polycondensation process, the pre-polycondensation reaction is continuously performed after dredging, the prepolymer melt with the prepolymer viscosity reaching 0.30dL/g is obtained, and black hydrophilic copolyester slices are obtained after polycondensation, cooling and granulating, and in the comparative example 2, the molar ratio of terephthalic acid to ethylene glycol alkyd of the system is 1.25; the addition amount of the carbon black is 2% of the melt mass of the black prepolymer; the addition amount of the catalyst is 0.05 percent of the melt mass of the black prepolymer, and the addition amount of the stabilizer is 0.02 percent of the melt mass of the black prepolymer; the molecular weight of the polyethylene glycol is 4000, and the addition amount is 10% of that of the hydrophilic prepolymer melt; the final polycondensation reaction temperature was 280℃and the reaction pressure was 0.1kPa, whereby a black polyester having an intrinsic viscosity of 0.80dL/g was obtained.
The above samples were polymerized and spun as follows:
as can be seen from the above table, the polymerization process of example 1-example 7 of the preparation method of the black hydrophilic polyester provided by the implementation of the invention is stable, and the prepared black hydrophilic polyester has good spinnability.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. A process for preparing a black hydrophilic polyester comprising the steps of:
mixing carbon black color paste, terephthalic acid, isophthalic acid, ethylene glycol, a catalyst and a stabilizer, and then carrying out a first esterification reaction, and carrying out a first pre-polycondensation reaction to obtain a black prepolymer melt, wherein the value range of the mass ratio of the sum of the terephthalic acid and the isophthalic acid to the ethylene glycol is 1: (1.11-1.4); the isophthalic acid is 1% -10% of the amount of terephthalic acid material; the addition amount of the catalyst is 0.03-0.06% of the melt mass of the black prepolymer, the addition amount of the stabilizer is 0.005-0.03% of the melt mass of the black prepolymer, and the addition amount of the carbon black color paste is 1-3% of the melt mass of the black prepolymer;
mixing terephthalic acid, ethylene glycol, a catalyst and a stabilizer, performing a second esterification reaction, adding polyether glycol into a reaction system after the second esterification reaction, and performing a second pre-polymerization reaction to obtain a hydrophilic prepolymer melt, wherein the value range of the mass ratio of the terephthalic acid to the ethylene glycol is 1: (1.11-1.4); the addition amount of the catalyst is 0.03-0.06% of the melt mass of the hydrophilic prepolymer, and the addition amount of the stabilizer is 0.005-0.03% of the melt mass of the hydrophilic prepolymer; the addition amount of the polyether glycol is 5% -40% of the melt mass of the hydrophilic prepolymer;
the black hydrophilic polyester is obtained by sequentially mixing, third pre-condensing reaction, final polycondensation reaction and granulating the black prepolymer melt and the hydrophilic prepolymer melt, wherein the mass ratio of the black prepolymer melt to the hydrophilic prepolymer melt is (0.25-4): 1, a step of;
the value range of the intrinsic viscosity of the black prepolymer melt is 0.15-0.30dL/g;
the intrinsic viscosity of the hydrophilic prepolymer melt is 0.15-0.30dL/g;
after the black prepolymer melt and the hydrophilic prepolymer melt are mixed, the value range of the intrinsic viscosity is 0.30-0.45dL/g.
2. The method for preparing a black hydrophilic polyester according to claim 1, wherein the catalyst is one or a mixture of more of antimony trioxide, ethylene glycol antimony, tetrabutyl titanate, tetraisopropyl titanate and tetraisooctyl titanate.
3. The method for preparing a black hydrophilic polyester according to claim 1, wherein the stabilizer is selected from one or a mixture of several of triphenyl phosphite, trimethyl phosphate, pentaerythritol tetrakis (3, 5-di-t-butyl-4-hydroxy) phenylpropionate, tris (2, 4-di-t-butylphenyl) phosphite, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenylpropionate-1, 6-adipoyl ester.
4. The method for producing a black hydrophilic polyester according to claim 1, wherein the reaction temperature of the first esterification reaction and the second esterification reaction is in the range of 240 ℃ to 265 ℃.
5. The method for producing a black hydrophilic polyester according to claim 1, wherein the temperature of the first pre-polymerization reaction and the second pre-polymerization reaction is in the range of 245 ℃ to 265 ℃, and the reaction pressure of the first pre-polymerization reaction and the second pre-polymerization reaction is in the range of 10kPa to 20kPa.
6. The method for producing a black hydrophilic polyester according to claim 1, wherein the temperature of the third pre-polymerization reaction is in the range of 250 ℃ to 275 ℃, and the reaction pressure of the third pre-polymerization reaction is in the range of 1kPa to 4kPa; the temperature of the final polycondensation reaction ranges from 270 ℃ to 290 ℃, and the reaction pressure of the final polycondensation reaction ranges from 0.05kPa to 0.5kPa.
7. A black hydrophilic polyester, wherein the black hydrophilic polyester is prepared by the method for preparing a black hydrophilic polyester according to any one of claims 1 to 6, and the intrinsic viscosity value of the black hydrophilic polyester is 0.65 to 0.85dL/g.
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| US6204319B1 (en) * | 1998-10-30 | 2001-03-20 | E.I. Du Pont De Nemours And Company | Aqueous coating compositions |
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| CN109750385A (en) * | 2018-12-29 | 2019-05-14 | 中国纺织科学研究院有限公司 | A kind of continuous process system and preparation method of functional polyester |
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| US6204319B1 (en) * | 1998-10-30 | 2001-03-20 | E.I. Du Pont De Nemours And Company | Aqueous coating compositions |
| CN101338067A (en) * | 2007-07-04 | 2009-01-07 | 中国纺织科学研究院 | Black polyester chip and method for preparing black polyester chip |
| CN104893429A (en) * | 2015-05-14 | 2015-09-09 | 四川大学 | Prepolymer method used for preparing modified nano carbon black water-based color paste |
| CN105063797A (en) * | 2015-07-16 | 2015-11-18 | 中国纺织科学研究院 | Method for preparing low-melting-point polyester composite fiber by adopting continuous polymerization and melt direct-spinning |
| CN109750385A (en) * | 2018-12-29 | 2019-05-14 | 中国纺织科学研究院有限公司 | A kind of continuous process system and preparation method of functional polyester |
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