CN114134594A - Colored polyester fiber and preparation method thereof - Google Patents
Colored polyester fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114134594A CN114134594A CN202111615472.4A CN202111615472A CN114134594A CN 114134594 A CN114134594 A CN 114134594A CN 202111615472 A CN202111615472 A CN 202111615472A CN 114134594 A CN114134594 A CN 114134594A
- Authority
- CN
- China
- Prior art keywords
- polyester fiber
- reaction
- colored polyester
- terephthalic acid
- vanadium pentoxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000728 polyester Polymers 0.000 title claims abstract description 122
- 239000000835 fiber Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 154
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 143
- 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 140
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 80
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 72
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005886 esterification reaction Methods 0.000 claims abstract description 43
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000002829 reductive effect Effects 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 47
- 238000009987 spinning Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 19
- 239000004595 color masterbatch Substances 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 14
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000009998 heat setting Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical group [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 36
- 229910052681 coesite Inorganic materials 0.000 description 30
- 229910052906 cristobalite Inorganic materials 0.000 description 30
- 229910052682 stishovite Inorganic materials 0.000 description 30
- 229910052905 tridymite Inorganic materials 0.000 description 30
- 239000000047 product Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 238000010036 direct spinning Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- -1 p-carboxybenzaldehyde diethylene glycol Chemical compound 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000002431 foraging effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 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
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- FHEPPGUPJKCEBH-UHFFFAOYSA-N [Si](=O)=O.[O-2].[V+5].[O-2].[O-2].[O-2].[O-2].[V+5] Chemical compound [Si](=O)=O.[O-2].[V+5].[O-2].[O-2].[O-2].[O-2].[V+5] FHEPPGUPJKCEBH-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a colored polyester fiber and a preparation method thereof, belonging to the technical field of fiber preparation. When the colored polyester fiber is prepared, the silicon dioxide loaded with vanadium pentoxide is added in the esterification reaction of terephthalic acid and ethylene glycol, and due to the reaction characteristic of the silicon dioxide loaded with vanadium pentoxide, the silicon dioxide and impurity p-carboxybenzaldehyde in the terephthalic acid undergo oxidation reaction, carboxyl in the p-carboxybenzaldehyde is catalytically oxidized into the terephthalic acid, and the generation of a polyolefin compound is reduced. And the silicon dioxide loaded with vanadium pentoxide is used as an oxidant, so that the thermal stability is good, and other side reactions cannot be generated in the esterification reaction. The silicon dioxide loaded with vanadium pentoxide can also be used as a catalyst, O2 ‑And O‑Has certain oxidability, can efficiently oxidize p-carboxybenzaldehyde, reduce the generation amount of insoluble gel, improve the filtering performance, reduce the generation of polyolefin compounds and achieve the aim of improving the thermal stability of polyester.
Description
Technical Field
The invention relates to a colored polyester fiber and a preparation method thereof, belonging to the technical field of fiber preparation.
Background
Since the industrial production of the ethylene terephthalate, abbreviated as PET, has been realized, the ethylene terephthalate has the characteristics of low cost, excellent mechanical property, good thermal stability, chemical corrosion resistance, transparency, good insulativity, low hygroscopicity and the like, and is widely applied to the fields of textiles, films, beverage bottles and the like.
At present, the demand of China on functional fibers is rising day by day, the research and application enthusiasm of China on functional textiles including functional polyester fiber textiles is continuously rising, the industrialization direction mainly focuses on dyeing modified fibers, flame-retardant fibers, antistatic fibers, far infrared fibers and the like, but the production mainly takes chip spinning as main production with small yield and low added value of products. Meanwhile, the development of high-performance decorative and industrial textiles in China is slow. The production and development capabilities of related high-technology, high-performance and high-simulation fibers are quite weak, especially some functional fibers with high technical content are still in scientific research state at home, and many varieties are still blank, so that the competitive capability of chemical fibers in China in domestic and foreign markets is directly influenced.
The functional differential fiber production is carried out on the melt direct spinning line by the online adding technology, so that the advantages of low cost and contribution to developing high-quality fibers of the melt direct spinning technology are fully utilized, and the problems of single product structure and homogeneous competition are effectively solved. Greatly improves the market competitiveness of the product, and obviously improves the technical level of high-capacity direct spinning polyester in China. The popularization of the technology can lead enterprises to develop products according to market requirements and own technical characteristics, especially develop high-quality functional differentiated fibers with high added values, enhance the effective supply capacity of the market, form independent brands in the fields of high-grade fibers and fabrics and accelerate the structure adjustment of the industry. The development of the colored fiber direct spinning technology reduces the subsequent dyeing process, realizes 100 percent recovery of dyeing and finishing water, and is beneficial to energy conservation and emission reduction of the industry.
Firstly, accurately adding color master batch on line, highly and uniformly dispersing the color master batch in polyester, and accurately controlling the cross section shape of the fiber; secondly, the addition of the color master batch causes the increase of the amount of inorganic impurities, so that the difficulty of filtration is higher, and the filtration precision of a filter and a component is improved.
In order to improve the quality of the colored polyester fiber, the filtering precision of the filter and the component is very high, but the replacement period of the related filter and the component is short, and the quality of the colored polyester fiber is also influenced.
Disclosure of Invention
The invention aims to provide a preparation method of colored polyester fibers, and the colored polyester fibers prepared by the method have low content of infusible gel and high thermal stability.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of colored polyester fiber is characterized in that polyester and color master batch are prepared through an FDY process, and the polyester is obtained through esterification reaction of terephthalic acid, ethylene glycol and silicon dioxide loaded with vanadium pentoxide and then polycondensation reaction;
wherein the content of the color master batch pigment is 25-30 wt%, and the addition amount of the color master batch is 3 wt% of the polyester;
the terephthalic acid contains impurity p-carboxybenzaldehyde, and the silicon dioxide loaded with vanadium pentoxide and the p-carboxybenzaldehyde are subjected to oxidation reaction to generate the terephthalic acid;
the adding amount of the silicon dioxide loaded with vanadium pentoxide is 120-150ppm, wherein the weight content of the vanadium pentoxide in the silicon dioxide loaded with vanadium pentoxide is 25-30%.
Further, the preparation method of the polyester comprises the following steps:
s1, taking terephthalic acid, ethylene glycol and silicon dioxide loaded with vanadium pentoxide as raw materials, adding a catalyst and a stabilizer into the raw materials to prepare slurry, and uniformly stirring the slurry and the slurry to perform an esterification reaction to obtain an esterification product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled to be between normal pressure and 0.2MPa, the temperature is controlled to be 250-260 ℃, and the end point of the esterification reaction is that the distillate quantity of the esterification water reaches more than 95 percent of the theoretical value;
s2, after the esterification reaction is finished, starting a polycondensation reaction, wherein the polycondensation reaction comprises a polycondensation low-vacuum stage and a polycondensation high-vacuum stage;
in the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 260-270 ℃, and the reaction time is 30-50 min;
in the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum pumping is continued, so that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃ and 280 ℃, and the reaction time is 50-70 min; preparing polyester;
s3, adopting an FDY process to prepare the colored polyester fiber through metering, extruding, cooling, oiling, stretching, heat setting and winding the polyester;
wherein the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
Further, the preparation method of the vanadium pentoxide-loaded silicon dioxide comprises the following steps:
respectively weighing equimolar NH4VO3And H2C2O4Respectively dissolving the two solutions in distilled water to prepare 1mol/L solution, mixing the two solutions, adjusting the pH value to about 2 with oxalic acid solution to obtain green solution, standing and aging to obtain blue-green aging solution;
preparing the silicon dioxide loaded with the vanadium pentoxide according to a dipping method, adding chromatographic silica gel into the aging solution, stirring, heating in a water bath at 75-80 ℃ for 1-2h, standing and aging for 1-2h, heating and evaporating to dryness, placing in a high-temperature furnace for high-temperature oxidation treatment at 550-600 ℃ for 6-7h to finally obtain a light yellow solid, and crushing and sanding to obtain the silicon dioxide loaded with the vanadium pentoxide.
Further, the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.3-1.5; and because the content of p-carboxybenzaldehyde in the terephthalic acid is extremely low, the molar mass of the terephthalic acid is regarded as the molar mass of a terephthalic acid standard in the present document by default.
The adding amount of the catalyst is 0.010-0.018 wt% of the terephthalic acid, and the catalyst is ethylene glycol antimony;
the addition amount of the stabilizer is 0.01-0.03% of the weight of the terephthalic acid, and the stabilizer is any one of triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
Further, the spinning process parameters of the colored polyester fiber are as follows:
spinning temperature: 283-287 ℃;
cooling temperature: 20-25 ℃;
network pressure: 0.20-0.30 MPa;
a roll speed: 2200-
First roll temperature: 80-85 ℃;
two roll speed: 3900-;
temperature of the two rolls: 135 ℃ and 165 ℃;
speed of winding: 3850 and 4040 m/min.
Further, the average particle size of the vanadium pentoxide-loaded silica is <0.30 μm.
Furthermore, the glossiness of the colored polyester fiber is more than or equal to 60 percent, and the color is any one of black, red, blue or yellow.
Further, the number average molecular weight of the colored polyester fiber is 23000-28000g/mol, and the molecular weight distribution index is 1.8-2.2.
Furthermore, the breaking strength of the colored polyester fiber is more than or equal to 3.2cN/dtex, the elongation at break is 28.0 +/-2.0%, the CV value of the breaking strength is less than or equal to 5.0%, the CV value of the elongation at break is less than or equal to 8.0%, the CV value of the linear density is less than or equal to 0.8%, and the CV (%) of the evenness is less than or equal to 1.2%.
The invention also provides a colored polyester fiber prepared by the preparation method of the colored polyester fiber.
The invention has the beneficial effects that: when the colored polyester fiber is prepared, the silicon dioxide loaded with vanadium pentoxide is added in the esterification reaction of terephthalic acid and ethylene glycol, and due to the reaction characteristic of the silicon dioxide loaded with vanadium pentoxide, the silicon dioxide and p-carboxybenzaldehyde in the terephthalic acid undergo oxidation reaction, carboxyl in the p-carboxybenzaldehyde is catalytically oxidized into the terephthalic acid, and the generation of a polyolefin compound is reduced. And the silicon dioxide loaded with vanadium pentoxide is used as an oxidant, so that the thermal stability is good, and other side reactions cannot be generated in the esterification reaction. The silicon dioxide loaded with vanadium pentoxide can also be used as a catalyst, O2 -And O-Has certain oxidability, can efficiently oxidize p-carboxybenzaldehyde, reduce the generation amount of insoluble gel, improve the filtering performance, reduce the generation of polyolefin compounds and achieve the aim of improving the thermal stability of polyester. The prepared colored polyester fiber has better glossiness, is beneficial to forming independent brands in the fields of high-grade fibers and fabrics, and accelerates the structure adjustment of the industry. The invention can also prepare a colored polyester fiber.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In order to solve the problem that the colored polyester fiber is difficult to filter, the invention firstly analyzes the reason that the prepared colored polyester fiber is difficult to filter and has high requirement.
In the prior art, terephthalic acid (PTA) has a molecular formula of C8H6O4Is an organic compound and is the dicarboxylic acid with the highest yield. Terephthalic Acid (PTA) is an important raw material of polyester fiber, is mainly produced by a Paraxylene (PX) liquid-phase air oxidation method, and can be divided into an oxidation unit and a hydrofining unit in the production process. Oxidizing p-xylene with acetic acid as solvent in the presence of catalyst to obtain crude terephthalic acid, crystallizing, filtering, and drying to obtain crude product; the crude terephthalic acid is hydrogenated to remove impurities, and then is crystallized, centrifugally separated and dried to obtain a PTA finished product. Wherein, the p-carboxybenzaldehyde (4-CBA) is a main byproduct and is also a main impurity and an important quality index in a Purified Terephthalic Acid (PTA) product.
The content of p-carboxybenzaldehyde tends to fluctuate from about 50 to 100ppm, sometimes up to 130 ppm. The formaldehyde in the p-carboxybenzaldehyde can react with ethylene glycol in the polyester polymerization process to generate p-carboxybenzaldehyde diethylene glycol which is an organic molecule with three functional groups (two hydroxyl groups and one carboxyl group), and the three functional groups can respectively react with terephthalic acid and ethylene glycol to form a net structure, so that the quality of fine denier fiber is influenced due to the small net structure, and the infusible gel with large net structure influences the filtering performance of the fine denier fiber. At the same time, the carboxybenzaldehyde can also be subjected to addition reaction with other substances to generate unsaturated double bonds, thereby influencing the thermal property of the polyester. The difficulty of filtration is further increased for colored polyester fibers.
The invention provides a preparation method of colored polyester fibers, and specifically relates to a preparation method of colored polyester fibers, which comprises the steps of adding loaded vanadium pentoxide silicon dioxide in esterification reaction of terephthalic acid and ethylene glycol, carrying out polycondensation reaction to obtain polyester, and then preparing the colored polyester fibers by an FDY (fully drawn yarn) process.
Specifically, the preparation method of the polyester comprises the following steps:
s1, taking terephthalic acid, ethylene glycol and silicon dioxide loaded with vanadium pentoxide as raw materials, adding a catalyst and a stabilizer to prepare slurry, uniformly stirring, and carrying out esterification reaction to obtain an esterification product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled to be between normal pressure and 0.2MPa, the temperature is controlled to be 250-260 ℃, and the end point of the esterification reaction is that the distillate quantity of the esterification water reaches more than 95 percent of the theoretical value;
s2, after the esterification reaction is finished, starting a polycondensation reaction, wherein the polycondensation reaction comprises a polycondensation low-vacuum stage and a polycondensation high-vacuum stage;
in the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 260-270 ℃, and the reaction time is 30-50 min;
in the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum pumping is continued, so that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃ and 280 ℃, and the reaction time is 50-70 min; preparing polyester;
s3, adopting an FDY process to meter, extrude, cool, oil, stretch, heat-set and wind the polyester to obtain the colored polyester fiber.
The terephthalic acid comprises p-carboxybenzaldehyde, and the silicon dioxide loaded with vanadium pentoxide reacts with the p-carboxybenzaldehyde to generate the terephthalic acid.
Vanadium pentoxide-loaded silica (V)2O5/SiO2) The preparation method comprises the following steps:
respectively weighing equimolar NH4VO3And H2C2O4Respectively dissolving in distilled water to obtain 1mol/L solution, mixing the obtained 2 solutions, adjusting pH to about 2 with oxalic acid solution to obtain green solution, standing, aging to obtain blue-green aged solution, which is VO2+Salt solution due to VO in solution2 +And H2C2O4The reaction formula is shown in the following formula.
2VO2 ++H2C2O4+2H+＝2VO2++2CO2+2H2O
According to the immersionPreparation of vanadium pentoxide-loaded silicon dioxide (V) by impregnation method2O5/SiO2) Adding chromatographic silica gel into the aging solution, stirring, heating in a water bath at 75-80 ℃ for 1-2h, standing and aging for 1-2h, heating to dryness, placing in a high-temperature furnace for high-temperature oxidation treatment at 550-600 ℃ for 6-7h to obtain a light yellow solid, and crushing and sanding to obtain the vanadium pentoxide-loaded silicon dioxide. Wherein NH4VO3The weight ratio of the silica gel to the silica gel is 1:2.78-2.83, and the weight of the silica in the chromatography silica gel accounts for 93-97%.
Specifically, vanadium pentoxide (V)2O5) Belongs to an orthorhombic system, is the highest valence oxide of vanadium, has a layered structure, and is generally regarded as V2O5Is a compound having a plane of symmetry D2HLattice, VO5The polyhedron is of a trigonal two-cone type and is a crystal structure with plane connection sharing a vertex. Of the five oxygen atoms in this structure, each has a bond length different from that of the vanadium atom, with the oxygen atom (denoted as O) having the shortest bond length with vanadium being formedI) Is easier to be separated.
These 5 oxygen atoms are classified into 3 groups, O (1), O '(3), O' (1), each vanadium atom having a single terminal oxygen atom with a bond length of 0.154nm, corresponding to a VO double bond; 1 oxygen atom O' is connected with 2 vanadium atoms in a bridge mode, and the bond length is 0.177 nm; the remaining 3 oxygen atoms O' are: each linked to 3 vanadium atoms with a bridging oxygen, 0.188nm (2) and 0.204nm (1), respectively. V2O5Can be imagined as VO4The tetrahedrons are combined into a chain through oxygen bridges, and 2 chains are connected with each other through another oxygen bridge by the 5 th oxygen atom to form a compound chain, thereby forming a corrugated laminated structure. These layered structures are connected by the 6 th oxygen atom to form a bulk V2O5The V-O bond length was 0.281 nm.
V2O5The structure is in addition to the significant twist described above, at V2O5There are many channels in the structure, which help the diffusion of oxygen atoms in the structure from the catalytic point of view. These channels will be V2O5With gas-phase oxygen isotopesWhen exchanging, not only on the surface, but also in bulk phase, oxygen ions in the oxide structure can move from the surface to the inside or from the inside to the surface, so that V2O5Has catalytic ability compared with other oxides.
Silica gel is used as a carrier, and the characteristic of large specific surface area of the silica gel can be utilized to make vanadium oxide adsorbed on the surface of the carrier to prepare loaded V2O5/SiO2Catalyst due to V2O5Highly dispersed in SiO2A two-dimensional transition metal oxide coating is formed on the carrier, and the active component V is increased2O5Thereby increasing the number of active centers and the contact area of the active components and reactants, and further increasing the catalytic activity.
At the same time, in SiO2Upper load V2O5Since the catalyst is at a high temperature during its preparation, V2O5Will be coated with SiO2Reduction to produce a partially irreversible reduction to produce oxygen vacancies, whereby the catalyst can adsorb O at room temperature2Then can generate O at the time of temperature rise2 -And O-Isolattice oxygen, O2 -And O-Has oxidability and hydrophilicity, and can be absorbed by aldehyde group to generate carboxylic acid. In SiO2Upper load V2O5Since the weak oxidizing agent is capable of oxidizing aldehyde to produce carboxylic acid and is stable to PTA and EG, V can be used2O5/SiO24-CBA impurities in the PET polymerization are oxidized, the generation amount of infusible gel is reduced, the filtering performance is improved, and meanwhile, the generation of a polyene compound is reduced, so that the purpose of improving the thermal stability of the polyester is achieved.
In step S1, the amount of vanadium pentoxide-supporting silica added is 120-150ppm, wherein the content of vanadium pentoxide in the vanadium pentoxide-supporting silica is 25-30%. The average particle size of the vanadium pentoxide-loaded silica is <0.30 μm. As the mole number of the generated oxygen in the oxidant in the PTA per unit weight is similar to or the same as that of the CBA, the adding amount of the silicon dioxide loaded with vanadium pentoxide is 150ppm in the specification. In the spinning process, when the vanadium pentoxide-loaded silica is added, attention needs to be paid to the influence of the vanadium pentoxide-loaded silica on the fiber quality, when the added substance is too large, the adverse effect is large, when the added substance is too small, such as less than 0.1 μm, the vanadium pentoxide-loaded silica is easy to agglomerate, and the use effect is not good, so in the application document, the vanadium pentoxide-loaded silica particles with the average particle size of about 0.30 μm are selected, and when the vanadium pentoxide-loaded silica particles are actually used, the average particle size is preferably 0.25-0.30 μm.
In step S1, the molar ratio of terephthalic acid to ethylene glycol is 1: 1.3-1.5; the addition amount of the catalyst is 0.01 to 0.02 percent of the weight of the terephthalic acid; the adding amount of the silicon dioxide loaded with vanadium pentoxide is 120-150ppm of the weight of terephthalic acid; the addition amount of the stabilizer is 0.01-0.03% of the weight of the terephthalic acid.
In step S1, the catalyst is any one of antimony trioxide, ethylene glycol antimony, or antimony acetate; the stabilizer is any one of triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
Wherein, the addition of the catalyst can promote the reaction process of polyester esterification; the addition of the stabilizer can effectively reduce the side reaction in the esterification reaction process of the polyester.
Wherein, in step S1, the esterification reaction is carried out under nitrogen atmosphere under pressure of-0.20 MPa. Namely, the reaction can be completed even in an atmosphere of normal pressure. The nitrogen atmosphere can reduce oxygen participating in the oxidation reaction in the esterification reaction.
After the polyester is finished, preparing the colored polyester fiber according to an FDY process. And dyeing the polyester by using color master batches, wherein the color master batches are added in a branch pipe of the spinning pipeline. In the invention, the content of the color master batch pigment is 25-30 wt%, and the addition amount of the color master batch is 3 wt% of the polyester. The FDY process prepares the colored polyester fiber by adding color master batch into polyester, metering, extruding, cooling, oiling, stretching, heat setting and winding. The FDY process is prior art and will not be described in detail herein.
The spinning process parameters are as follows:
spinning temperature: 283-287 ℃;
cooling temperature: 20-25 ℃;
network pressure: 0.20-0.30 MPa;
a roll speed: 2200-
First roll temperature: 80-85 ℃;
two roll speed: 3900-;
temperature of the two rolls: 135 ℃ and 165 ℃;
speed of winding: 3850-4040 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
During spinning, the spinning assembly is installed, and the pressure at this time is the initial pressure, which is 120bar in the present application. The pressure of the component can be gradually increased along with the continuous spinning production, when the pressure reaches a certain value, the component needs to be replaced, and the larger the pressure increase is, the higher the impurity content of the prepared polyester is, so that the replacement period of the component is shortened. In the prior art, the replacement period of the component is 25-30 days, but the replacement period of the component exceeds 40 days, and the yarns can be sent out according to the replacement period of the component.
In the present embodiment, the finally obtained colored polyester fiber has a glossiness of not less than 60% and a color of any one of black, red, blue or yellow. Gloss is determined by test method ASTM D523.
The number average molecular weight of the prepared colored polyester fiber is 23000-28000g/mol, and the molecular weight distribution index is 1.8-2.2. The breaking strength is more than or equal to 3.2cN/dtex, the elongation at break is 28.0 +/-2.0%, the CV value of the breaking strength is less than or equal to 5.0%, the CV value of the elongation at break is less than or equal to 8.0%, the CV value of the linear density is less than or equal to 0.8%, and the CV (%) of the evenness is less than or equal to 1.2%.
The above-mentioned preparation process is described in detail below with specific examples.
It should be noted that, in the examples, the molar ratio of each substance is not used, and the weight g or kg is not used, because if the weight is used, other problems may be caused during spinning, and the continuous melt direct spinning is used in the application, which is inconvenient to be expressed by weight.
Example one
Step one, preparing V2O5/SiO2
Respectively weighing equimolar NH4VO3And H2C2O4Adding NH to4VO3Dissolving in distilled water to obtain 1mol/L solution, and adding H2C2O4Dissolving in distilled water to obtain 1mol/L solution, mixing the obtained 2 solutions, adjusting pH to about 2 with oxalic acid solution to obtain green solution, standing, and aging to obtain blue-green aging solution. Preparation of Supported form V by the impregnation method2O5/SiO2Adding silica gel into the aging solution, stirring, heating in 75 deg.C water bath for 2 hr, standing for aging for 2 hr, evaporating to dryness, oxidizing at 600 deg.C for 7 hr to obtain light yellow solid, pulverizing, and sanding to obtain load type V2O5/SiO2An oxidizing agent.
Wherein NH4VO3And H2C2O4Molar ratio of 1.0:1.0, NH4VO3The weight ratio to silica gel was 1: 2.78.
Step two, esterification reaction
Preparing terephthalic acid and ethylene glycol into slurry, and adding V2O5/SiO2Uniformly stirring the catalyst and the stabilizer, pressurizing in a nitrogen atmosphere, controlling the pressure at the normal pressure of-0.2 MPa and the temperature at 250 ℃, and taking the esterification reaction end point as the point when the distillate of the esterification water reaches more than 95% of the theoretical value;
the molar ratio of terephthalic acid to ethylene glycol is 1: 1.3; the adding amount of the catalyst is 0.01 percent of the weight of the terephthalic acid; the adding amount of the silicon dioxide loaded with vanadium pentoxide is 120ppm of the weight of terephthalic acid; the amount of triphenyl phosphate as a stabilizer added was 0.01% by weight of terephthalic acid.
Step three, polycondensation reaction
In the low vacuum stage of polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 260 ℃, and the reaction time is 50 min;
a polycondensation reaction high vacuum stage, after a polycondensation reaction low vacuum stage, continuously vacuumizing to reduce the reaction pressure to an absolute pressure of less than 100Pa, controlling the reaction temperature at 280 ℃ and the reaction time for 50 min; to obtain the polyester.
Step four, spinning
The polyester is prepared into the superfine denier polyester fiber by adding color master batch, metering, extruding, cooling, oiling, stretching, heat setting and winding, wherein the spinning process parameters are as follows:
spinning temperature: 283 ℃;
cooling temperature: 20 ℃;
network pressure: 0.20 MPa;
a roll speed: 2200m/min
First roll temperature: 85 ℃;
two roll speed: 3900 m/min;
temperature of the two rolls: 135 deg.C;
speed of winding: 3850 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
During the spinning process, due to V2O5/SiO2The addition of the (B) compound can oxidize the p-carboxybenzaldehyde contained in the terephthalic acid into the terephthalic acid, thereby effectively improving the filtering performance of the polyester melt and the quality of the colored polyester fiber. In addition, the pressure rise of the spinning assembly and the filter is effectively reduced.
The glossiness of the colored polyester fiber obtained by the steps is 63 percent; the color is black. The number average molecular weight of the colored polyester fiber was 23000g/mol, and the molecular weight distribution index was 2.2.
The colored polyester fiber had a breaking strength of 3.37cN/dtex, an elongation at break of 26.0%, a breaking strength CV value of 4.8%, an elongation at break CV value of 7.7%, a linear density CV value of 0.8%, and a yarn levelness CV (%) of 1.2%.
Example two
Step one, preparing V2O5/SiO2
Respectively weighing equimolar NH4VO3And H2C2O4Adding NH to4VO3Dissolving in distilled water to obtain 1mol/L solution, and adding H2C2O4Dissolving in distilled water to obtain 1mol/L solution, mixing the obtained 2 solutions, adjusting pH to about 2 with oxalic acid solution to obtain green solution, standing, and aging to obtain blue-green aging solution. Preparation of Supported form V by the impregnation method2O5/SiO2Adding silica gel into the aging solution, stirring, heating in 80 deg.C water bath for 2 hr, standing for aging for 2 hr, evaporating to dryness, oxidizing at 600 deg.C for 7 hr to obtain light yellow solid, pulverizing, and sanding to obtain load type V2O5/SiO2An oxidizing agent.
Wherein NH4VO3And H2C2O4Molar ratio of 1.0:1.0, NH4VO3The weight ratio of the silica gel to the silica gel was 1: 2.83.
Step two, esterification reaction
Preparing terephthalic acid and ethylene glycol into slurry, and adding V2O5/SiO2Uniformly stirring the catalyst, the flatting agent and the stabilizer, pressurizing in a nitrogen atmosphere, controlling the pressure at the normal pressure of-0.2 MPa and the temperature at 260 ℃, and taking the esterification reaction end point when the distillate of the esterification water reaches more than 95% of the theoretical value;
the molar ratio of terephthalic acid to ethylene glycol is 1: 1.5; the addition amount of the catalyst is 0.02 percent of the weight of the terephthalic acid; the adding amount of the silicon dioxide loaded with vanadium pentoxide is 150ppm of the weight of terephthalic acid; the amount of trimethyl phosphate added as a stabilizer was 0.03% by weight based on the weight of terephthalic acid.
Step three, polycondensation reaction
In the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 270 ℃, and the reaction time is 30 min;
performing polycondensation reaction in a high vacuum stage, and continuing to vacuumize after performing polycondensation reaction in a low vacuum stage to reduce the reaction pressure to an absolute pressure of less than 100Pa, controlling the reaction temperature at 275 ℃ and reacting for 70 min; to obtain the polyester.
Step four, spinning
The polyester is prepared into the superfine denier polyester fiber by adding color master batch, metering, extruding, cooling, oiling, stretching, heat setting and winding, wherein the spinning process parameters are as follows:
spinning temperature: 287 deg.C;
cooling temperature: 25 ℃;
network pressure: 0.30 MPa;
a roll speed: 2600m/min
First roll temperature: 80 ℃;
two roll speed: 4100 m/min;
temperature of the two rolls: 1165 deg.C;
speed of winding: 4040 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
During the spinning process, due to V2O5/SiO2The addition of the (B) compound can oxidize the p-carboxybenzaldehyde contained in the terephthalic acid into the terephthalic acid, thereby effectively improving the filtering performance of the polyester melt and the quality of the colored polyester fiber. In addition, the pressure rise of the spinning assembly and the filter is effectively reduced.
The glossiness of the colored polyester fiber obtained by the steps is 66%; the color is red. The number average molecular weight of the colored polyester fiber was 28000g/mol, and the molecular weight distribution index was 1.8.
The colored polyester fiber had a breaking strength of 3.52cN/dtex, an elongation at break of 28.0%, a breaking strength CV value of 4.8%, an elongation at break CV value of 7.5.0%, a linear density CV value of 0.7%, and a yarn levelness CV (%) of 1.1%.
EXAMPLE III
Step one, preparing V2O5/SiO2
Respectively weighing equimolar NH4VO3And H2C2O4Adding NH to4VO3Dissolving in distilled waterPreparing a solution of 1mol/L, and adding H2C2O4Dissolving in distilled water to obtain 1mol/L solution, mixing the obtained 2 solutions, adjusting pH to about 2 with oxalic acid solution to obtain green solution, standing, and aging to obtain blue-green aging solution. Preparation of Supported form V by the impregnation method2O5/SiO2Adding silica gel into the aging solution, stirring, heating in 77 deg.C water bath for 1.5 hr, standing for aging for 1.5 hr, heating to dry, oxidizing at 600 deg.C for 6.5 hr to obtain light yellow solid, pulverizing, and sanding to obtain load type V2O5/SiO2An oxidizing agent.
Wherein NH4VO3And H2C2O4Molar ratio of 1.0:1.0, NH4VO3The weight ratio of the silica gel to the silica gel was 1: 2.80.
Step two, esterification reaction
Preparing terephthalic acid and ethylene glycol into slurry, and adding V2O5/SiO2Uniformly stirring the catalyst and the stabilizer, pressurizing in a nitrogen atmosphere, controlling the pressure at the normal pressure of-0.2 MPa and the temperature at 250 ℃, and taking the esterification reaction end point as the point when the distillate of the esterification water reaches more than 95% of the theoretical value;
the molar ratio of terephthalic acid to ethylene glycol is 1: 1.4; the adding amount of the catalyst is 0.02 percent of the weight of the terephthalic acid; the adding amount of the silicon dioxide loaded with vanadium pentoxide is 130ppm of the weight of terephthalic acid; the stabilizer trimethyl phosphite was added in an amount of 0.02% by weight based on the weight of terephthalic acid.
Step three, polycondensation reaction
In the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 265 ℃, and the reaction time is 40 min;
a polycondensation reaction high vacuum stage, after a polycondensation reaction low vacuum stage, continuously vacuumizing to reduce the reaction pressure to an absolute pressure of less than 100Pa, controlling the reaction temperature at 277 ℃ and reacting for 60 min; to obtain the polyester.
Step four, spinning
The polyester is prepared into the superfine denier polyester fiber by adding color master batch, metering, extruding, cooling, oiling, stretching, heat setting and winding, wherein the spinning process parameters are as follows:
spinning temperature: 285 ℃;
cooling temperature: 23 ℃;
network pressure: 0.25 MPa;
a roll speed: 2400m/min
First roll temperature: 80-85 ℃;
two roll speed: 4000 m/min;
temperature of the two rolls: 150 ℃;
speed of winding: 3950 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
During the spinning process, due to V2O5/SiO2The addition of the (B) compound can oxidize the p-carboxybenzaldehyde contained in the terephthalic acid into the terephthalic acid, thereby effectively improving the filtering performance of the polyester melt and the quality of the colored polyester fiber. In addition, the pressure rise of the spinning assembly and the filter is effectively reduced.
The glossiness of the colored polyester fiber obtained by the steps is 65 percent; the color is yellow. The number average molecular weight of the colored polyester fiber was 25000g/mol, and the molecular weight distribution index was 2.0.
The colored polyester fiber had a breaking strength of 3.50cN/dtex, an elongation at break of 30.0%, a breaking strength CV value of 4.3%, an elongation at break CV value of 7.6%, a linear density CV value of 0.6%, and a yarn levelness CV (%) of 1.0%.
Comparative example 1
Without addition of V2O5/SiO2
Step one, esterification reaction
Preparing terephthalic acid and ethylene glycol into slurry, adding a catalyst and a stabilizer, uniformly stirring, pressurizing in a nitrogen atmosphere, controlling the pressure at normal pressure of-0.2 MPa and the temperature at 250 ℃, and taking the esterification reaction endpoint when the distillate of esterification water reaches more than 95% of a theoretical value;
the molar ratio of terephthalic acid to ethylene glycol is 1: 1.4; the adding amount of the catalyst is 0.02 percent of the weight of the terephthalic acid; the stabilizer trimethyl phosphite was added in an amount of 0.02% by weight based on the weight of terephthalic acid.
Step two, polycondensation reaction
In the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 265 ℃, and the reaction time is 40 min;
a polycondensation reaction high vacuum stage, after a polycondensation reaction low vacuum stage, continuously vacuumizing to reduce the reaction pressure to an absolute pressure of less than 100Pa, controlling the reaction temperature at 277 ℃ and reacting for 60 min; to obtain the polyester.
Step three, spinning
The polyester is prepared into the superfine denier polyester fiber by adding color master batch, metering, extruding, cooling, oiling, stretching, heat setting and winding, wherein the spinning process parameters are as follows:
spinning temperature: 285 ℃;
cooling temperature: 23 ℃;
network pressure: 0.25 MPa;
a roll speed: 2400m/min
First roll temperature: 80-85 ℃;
two roll speed: 4000 m/min;
temperature of the two rolls: 150 ℃;
speed of winding: 3950 m/min;
the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 1.6 bar/day.
During the spinning process, V is not added2O5/SiO2The formaldehyde in the p-carboxybenzaldehyde can react with ethylene glycol in the polyester polymerization process to generate p-carboxybenzaldehyde diethylene glycol which is an organic molecule with three functional groups (two hydroxyl groups and one carboxyl group), and the three functional groups can respectively react with terephthalic acid and ethylene glycol to form a reticular structure, the reticular structure is small so as to influence the quality of fine denier fibers, and the reticular structure is large so as to become an infusible gel to influence the filtration performance of the infusible gel to cause the formation of a reticular structureThe pressure rises to a greater extent.
The glossiness of the colored polyester fiber obtained by the steps is 57%; the color is yellow. The number average molecular weight of the colored polyester fiber was 25000g/mol, and the molecular weight distribution index was 2.5.
The colored polyester fiber had a breaking strength of 3.23cN/dtex, an elongation at break of 34.0%, a breaking strength CV value of 6.4%, an elongation at break CV value of 10.1%, a linear density CV value of 0.9%, and a yarn levelness CV (%) of 1.6%.
The colored polyester fibers obtained in example three and comparative example one were compared, and comparative example one was prepared without adding V2O5/SiO2And the rest of the process is consistent with the third embodiment. With addition of V2O5/SiO2The gloss of the colored polyester fiber obtained was 65% without the addition of V2O5/SiO2The glossiness of the prepared colored polyester fiber is 57%, and V can be added according to the glossiness2O5/SiO2Can improve the glossiness of the prepared colored polyester fiber and the market competitiveness of the product. The indexes of the prepared colored polyester fiber, such as breaking strength, breaking elongation, breaking strength CV value, breaking elongation CV value, linear density CV value, evenness CV (%) and the like, show that V is added2O5/SiO2The product quality of the prepared colored polyester fiber is higher.
The invention also provides the colored polyester fiber prepared by the preparation method of the colored polyester fiber, and the properties of the obtained colored polyester fiber are described above, and are not described again here.
In conclusion, when the colored polyester fiber is prepared, the silicon dioxide loaded with vanadium pentoxide is added in the esterification reaction of terephthalic acid and ethylene glycol, and due to the reaction characteristic of the silicon dioxide loaded with vanadium pentoxide, the silicon dioxide and p-carboxybenzaldehyde in the terephthalic acid undergo oxidation reaction, carboxyl in the p-carboxybenzaldehyde is catalytically oxidized into the terephthalic acid, and meanwhile, the generation of the polyolefin compound is reduced. And the silicon dioxide loaded with vanadium pentoxide is adopted as an oxidant, so that the thermal stability is good, and other substances cannot be generated in the esterification reactionAnd (4) side reaction. The silicon dioxide loaded with vanadium pentoxide can also be used as a catalyst, O2 -And O-The prepared colored polyester fiber has better glossiness, is beneficial to forming independent brands in the fields of high-grade fibers and fabrics, and accelerates the structure adjustment of the industry. The invention can also prepare a colored polyester fiber.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the colored polyester fiber is characterized in that polyester and color master batch are prepared by an FDY process, and the polyester is obtained by esterification reaction of terephthalic acid, ethylene glycol and silicon dioxide loaded with vanadium pentoxide and then polycondensation reaction;
wherein the content of the color master batch pigment is 25-30 wt%, and the addition amount of the color master batch is 3 wt% of the polyester;
the terephthalic acid contains impurity p-carboxybenzaldehyde, and the silicon dioxide loaded with vanadium pentoxide and the p-carboxybenzaldehyde are subjected to oxidation reaction to generate the terephthalic acid;
the adding amount of the silicon dioxide loaded with vanadium pentoxide is 120-150ppm of the weight of the terephthalic acid, wherein the content of the vanadium pentoxide in the silicon dioxide loaded with vanadium pentoxide is 25-30%.
2. The method of producing colored polyester fibers according to claim 1, wherein the polyester is produced by a method comprising:
s1, taking terephthalic acid, ethylene glycol and silicon dioxide loaded with vanadium pentoxide as raw materials, adding a catalyst and a stabilizer into the raw materials to prepare slurry, and uniformly stirring the slurry and the slurry to perform an esterification reaction to obtain an esterification product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled to be between normal pressure and 0.2MPa, the temperature is controlled to be 250-260 ℃, and the end point of the esterification reaction is that the distillate quantity of the esterification water reaches more than 95 percent of the theoretical value;
s2, after the esterification reaction is finished, starting a polycondensation reaction, wherein the polycondensation reaction comprises a polycondensation low-vacuum stage and a polycondensation high-vacuum stage;
in the low vacuum stage of the polycondensation reaction, the polycondensation is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of below 400Pa, the temperature is controlled at 260-270 ℃, and the reaction time is 30-50 min;
in the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum pumping is continued, so that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃ and 280 ℃, and the reaction time is 50-70 min; preparing polyester;
s3, adopting an FDY process to prepare the colored polyester fiber through metering, extruding, cooling, oiling, stretching, heat setting and winding the polyester;
wherein the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.7 bar/day.
3. The method for preparing colored polyester fibers according to claim 1 or 2, wherein the method for preparing vanadium pentoxide-supporting silica comprises:
respectively weighing equimolar NH4VO3And H2C2O4Respectively dissolved in distilled waterPreparing 1mol/L solution, mixing the two solutions, adjusting the pH value to about 2 with oxalic acid solution to obtain green solution, standing and aging to obtain blue-green aging solution;
preparing the silicon dioxide loaded with the vanadium pentoxide according to a dipping method, adding chromatographic silica gel into the aging solution, stirring, heating in a water bath at 75-80 ℃ for 1-2h, standing and aging for 1-2h, heating and evaporating to dryness, placing in a high-temperature furnace for high-temperature oxidation treatment at 550-600 ℃ for 6-7h to finally obtain a light yellow solid, and crushing and sanding to obtain the silicon dioxide loaded with the vanadium pentoxide.
4. The method for preparing colored polyester fiber according to claim 2, wherein the molar ratio of terephthalic acid to ethylene glycol is 1: 1.3-1.5;
the adding amount of the catalyst is 0.010-0.018 wt% of the terephthalic acid, and the catalyst is ethylene glycol antimony;
the addition amount of the stabilizer is 0.01-0.03% of the weight of the terephthalic acid, and the stabilizer is any one of triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
5. The method for preparing the colored polyester fiber according to any one of claims 2 to 4, wherein the spinning process parameters of the colored polyester fiber are as follows:
spinning temperature: 283-287 ℃;
cooling temperature: 20-25 ℃;
network pressure: 0.20-0.30 MPa;
a roll speed: 2200-2600 m/min;
first roll temperature: 80-85 ℃;
two roll speed: 3900-;
temperature of the two rolls: 135 ℃ and 165 ℃;
speed of winding: 3850 and 4040 m/min.
6. The process for the preparation of colored polyester fibers according to claim 1, wherein the vanadium pentoxide-loaded silica has an average particle size <0.30 μm.
7. The method for preparing the colored polyester fiber according to claim 1, wherein the gloss of the colored polyester fiber is not less than 60%, and the color is any one of black, red, blue or yellow.
8. The method for preparing the colored polyester fiber as claimed in claim 1, wherein the number average molecular weight of the colored polyester fiber is 23000 and 28000g/mol, and the molecular weight distribution index is 1.8-2.2.
9. The method for preparing colored polyester fiber according to claim 1, wherein the colored polyester fiber has a breaking strength of 3.2cN/dtex or more, an elongation at break of 28.0. + -. 2.0%, a CV value of breaking strength of 5.0% or less, a CV value of elongation at break of 8.0% or less, a linear density CV value of 0.8% or less, and a yarn levelness CV (%) -1.2% or less.
10. A colored polyester fiber produced by the method for producing a colored polyester fiber according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153038A (en) * | 2014-05-04 | 2014-11-19 | 常州大学 | Method for preparing vanadium oxide doped nanowires by using electrostatic spinning process |
| CN109735926A (en) * | 2018-12-27 | 2019-05-10 | 江苏恒力化纤股份有限公司 | Easily contaminate porous modified polyester fiber and preparation method thereof |
| CN109853074A (en) * | 2018-12-27 | 2019-06-07 | 江苏恒力化纤股份有限公司 | The siliceous glycol modified polyester fiber and preparation method thereof of main chain |
| WO2020134494A1 (en) * | 2018-12-27 | 2020-07-02 | 江苏恒力化纤股份有限公司 | Semi-matte polyester drawn yarn and preparation method therefor |
| CN112760743A (en) * | 2020-12-31 | 2021-05-07 | 扬州富威尔复合材料有限公司 | Preparation method of colored low-melting-point polyester fiber |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153038A (en) * | 2014-05-04 | 2014-11-19 | 常州大学 | Method for preparing vanadium oxide doped nanowires by using electrostatic spinning process |
| CN109735926A (en) * | 2018-12-27 | 2019-05-10 | 江苏恒力化纤股份有限公司 | Easily contaminate porous modified polyester fiber and preparation method thereof |
| CN109853074A (en) * | 2018-12-27 | 2019-06-07 | 江苏恒力化纤股份有限公司 | The siliceous glycol modified polyester fiber and preparation method thereof of main chain |
| WO2020134494A1 (en) * | 2018-12-27 | 2020-07-02 | 江苏恒力化纤股份有限公司 | Semi-matte polyester drawn yarn and preparation method therefor |
| CN112760743A (en) * | 2020-12-31 | 2021-05-07 | 扬州富威尔复合材料有限公司 | Preparation method of colored low-melting-point polyester fiber |
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