CN117209735A - Cationic dyeable bio-based furan dicarboxylic acid polyester and preparation method of fibers - Google Patents
Cationic dyeable bio-based furan dicarboxylic acid polyester and preparation method of fibers Download PDFInfo
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- CN117209735A CN117209735A CN202310868298.7A CN202310868298A CN117209735A CN 117209735 A CN117209735 A CN 117209735A CN 202310868298 A CN202310868298 A CN 202310868298A CN 117209735 A CN117209735 A CN 117209735A
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- dicarboxylic acid
- furan dicarboxylic
- acid polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 92
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 70
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000004804 winding Methods 0.000 claims abstract description 18
- 238000004043 dyeing Methods 0.000 claims abstract description 12
- 238000002074 melt spinning Methods 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 36
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 32
- 238000005886 esterification reaction Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- -1 dihydroxyethyl Chemical group 0.000 claims description 15
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Polyesters Or Polycarbonates (AREA)
Abstract
The application discloses a cationic dyeable bio-based furan dicarboxylic acid polyester and a preparation method of the fiber, wherein cationic dyeable bio-based furan dicarboxylic acid polyester chips are dried to enable the water content to be lower than 30ppm, then the chips are put into a screw extruder to be melted by adopting a melt spinning method, and the cationic dyeable bio-based furan dicarboxylic acid polyester fiber is prepared by metering, cooling, bundling, hot drawing and winding after the screw extrusion. The cation dyeable bio-based polyester fiber prepared by the method has good spinnability when being used for melt spinning, and the prepared fiber has high breaking strength and excellent dyeing property.
Description
Technical Field
The application relates to the technical field of bio-based polyester synthesis and fiber manufacturing, in particular to a cationic dyeable bio-based furan dicarboxylic acid polyester and a preparation method of fibers.
Background
In recent years, with the emphasis placed on renewable bio-based material development in the country, bio-based polyethylene 2, 5-furandicarboxylate (PEF) has received extensive attention and research. PEF has a structure similar to petroleum-based PET, wherein the polymerized monomer 2, 5-furandicarboxylic acid (FDCA) of PEF is obtained by organic oxidation of 5-hydroxymethyl 2-furancarbaldehyde (HMF), whereas HMF can be obtained by chemical conversion or biological fermentation of biomass raw materials such as corn, beet and straw, and has the advantage of renewable resources compared with PET obtained by petroleum refining-polymerization, and is a novel polyester material most likely to replace PET in the future.
Since bio-based furan dicarboxylic acid polyesters possess some potential advantages in terms of application properties, such as excellent thermodynamic properties, gas barrier properties, and the like, the polyester substrates are currently being studied for use in engineering plastics, films, adhesives, foams, and the like. For example, chinese patent publication No. CN108049492a discloses a poly (ethylene 2, 5-furandicarboxylate) nucleating agent and a rapidly crystallized plastic thereof, publication No. CN107118521a discloses a poly (ethylene 2, 5-furandicarboxylate) resin composition, and publication No. CN108840995A discloses a method for preparing high melt viscosity poly (ethylene 2, 5-furandicarboxylate), which improves the extensibility, ductility or foamability of original PEF by adding functional monomers to poly (ethylene 2, 5-furandicarboxylate) for mixing, and improves the applicability in plastics, films, foams, and the like.
In the field of fiber preparation and application, related application patents related to PEF fiber preparation methods at home and abroad, such as the international patent PCJ/JP2016/004086 method and the international patent PCJ/JP2016/004082 method, disclose a preparation method of PEF fiber with high storage modulus, the fiber can be used in the field of tire production, such as Chinese patent CN115246924A, a biodegradable furan group-containing copolyester and a preparation and spinning method thereof are disclosed, and the prepared fiber has the advantage of environmental protection and degradability, but the application does not relate to and solve the problem of difficult dyeing of PEF fiber. In terms of dyeing, PEF fibers still belong to polyester fibers, and disperse dyes are still required to be used in dyeing, so that some bright colors are difficult to obtain, for example: in Chinese patent CN112760740A, a method for preparing copolyester by adding terephthalic acid and a C12-C20 glycol ether composition for copolymerization in the polymerization process of 2,5 furan dicarboxylic acid and ethylene glycol is disclosed, and the method improves the dyeing rate and normal-pressure dyeability of PEF fibers, but still needs to dye with disperse dye, and the dyeability and the dyeing rate of bio-based polyester are not high, the color spectrum is not complete enough and the color and luster are not bright enough, and meanwhile, the side reaction is more, the quality is not stable, and the prepared fibers are easy to break.
Disclosure of Invention
In order to solve certain or some technical problems in the prior art, one of the purposes of the application is to provide a cationic dyeable bio-based furan dicarboxylic acid polyester, which has less side reaction and stable quality.
The second object of the application is to provide a preparation method of the cationic dyeable bio-based furan dicarboxylic acid polyester fiber, and the cationic dyeable bio-based polyester fiber prepared by the method has good spinnability when being used for melt spinning, and the prepared fiber has high breaking strength and excellent dyeing property.
In order to solve the above existing technical problems, one of the purposes of the present application is achieved by adopting the following technical scheme:
the cationic dyeable bio-based furan dicarboxylic acid polyester is prepared by taking 2, 5-furan dicarboxylic acid, dihydroxyethyl isophthalate-5-sodium sulfonate and ethylene glycol as raw materials through polycondensation under the action of a catalyst, and has the structural formula:
preferably, the polycondensation preparation method comprises the steps of:
s1, esterification: adding bio-based 2, 5-furandicarboxylic acid and ethylene glycol into a polymerization reaction kettle according to a certain proportion, charging nitrogen for protection, heating to 180-200 ℃, and reacting for 2-3 hours under the pressure of 0.1-0.3 MPa until the esterification rate reaches 90%;
s2, pre-condensing: after the esterification reaction is finished, the pressure is removed, a catalyst and the dihydroxyethyl isophthalate-5-sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out to 1000-2000Pa, the temperature is slowly increased to 200-220 ℃, and the reaction is carried out for 30-60min;
s3, final polymerization: after the pre-polycondensation reaction is finished and the internal temperature of the reaction kettle reaches 220-240 ℃, continuously vacuumizing to 100-300Pa, and reacting for 2-4 hours until the power of the stirring motor reaches a certain value;
s4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
Preferably, in the step S1, the molar ratio of the furandicarboxylic acid to the ethylene glycol is 1:1.3-2.0.
Preferably, in the step (2), the catalyst is one or a mixture of more of antimony acetate, ethylene glycol antimony, antimony trioxide, stannous oxide and the like, and the addition amount of the catalyst is 100-500 ppm of the mass of the 2, 5-furandicarboxylic acid.
Preferably, in the step S2, the dihydroxyethyl isophthalate-5-sulfonate is potassium or sodium dihydroxyethyl isophthalate-5-sulfonate, and more preferably dimethyl isophthalate-5-sulfonate, and the addition amount of the dihydroxyethyl isophthalate-5-sulfonate is 2.0 to 5.0% of the total mole number of 2, 5-furandicarboxylic acid.
Preferably, in the polyester molecular chain links in the structural formula, x is y=2:98-5:95.
Preferably, the cationic dyeable bio-based furan dicarboxylic acid polyester has a chip intrinsic viscosity of 0.67 to 0.75dl/g (refer to GB/T14190-2017 method); the vitrification temperature is 70-80 ℃ and the melting point is 170-195 ℃.
The second purpose of the application is realized by adopting the following technical scheme:
the preparation method of the cationic dyeable bio-based furan dicarboxylic acid polyester fiber comprises the steps of drying a cationic dyeable bio-based furan dicarboxylic acid polyester chip to enable the water content to be lower than 30ppm, then feeding the chip into a screw extruder for melting by adopting a melt spinning method, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through metering, cooling, bundling, hot drawing and winding after the screw extrusion.
Preferably, the drying temperature of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is 100-150 ℃ and the drying time is 12-24 hours; the melting point of the cationic dyeable bio-based furan dicarboxylic acid polyester chip after drying and crystallization is 180-200 ℃.
Preferably, the drying temperature of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is 130 ℃; the drying time was 20h.
Preferably, the temperature of the spinning melt when the screw extruder melts is 200-230 ℃; the temperature of the first hot roller is 100-120 ℃, and the temperature of the second hot roller is 120-140 ℃; the draft ratio is 2.0-3.5; the winding speed is 3800-4200 m/min.
Preferably, the breaking strength of the cationic dyeable bio-based furan dicarboxylic acid polyester fiber is more than 3.0cN/dtex, the breaking elongation is less than 20%, the boiling water thermal shrinkage is 10-25%, and the dyeing dye uptake of the cationic dye is more than 80%.
Compared with the prior art, the application has the beneficial effects that:
the main component used by the cationic dyeable bio-based furan dicarboxylic acid polyester chip is biomass raw material, the raw material is mainly derived from corn, beet, straw and other crops with large yield and economy, does not depend on petroleum resources, and has the great advantages of environmental protection and sustainable regeneration. By introducing a cationic dyeable group into a PEF molecular chain, a cationic dyeable bio-based polyester which has good dyeability, high dye-uptake, complete color and luster and is significant for expanding modification research of bio-based materials and promoting market application of the bio-based polyester is developed.
The fiber prepared by the cationic dyeable bio-based furan dicarboxylic acid polyester chip has the advantages of lower required dyeing temperature, high dye-uptake, complete color spectrum, gorgeous color and the like. The cationic dyeable bio-based furan dicarboxylic acid polyester fiber monofilament dpf can reach 0.5-10.0 dtex, the breaking strength is more than or equal to 3.0cN/dtex, the elongation at break is less than or equal to 20.0%, the boiling water heat shrinkage is 10-25%, and the dyeing dye uptake of the cationic dye is more than 80%.
Detailed Description
The present application will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
The terms "first," "second," and the like in this specification are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged where appropriate so that embodiments of the application may be practiced in sequences other than those described herein, and that the objects identified by "first," "second," etc. are generally of a type and are not limited to the number of objects, e.g., the first object may be one or more. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.
Example 1
Preparation of cationic dyeable biobased furan dicarboxylic acid polyester chip
S1, esterification: 624.6g of bio-based 2, 5-furandicarboxylic acid and 322.4g of ethylene glycol are added into a polymerization reaction kettle, nitrogen is filled for protection, the mixture is heated to 180 ℃, and the mixture is reacted for 3 hours under the pressure of 0.25MPa until the esterification rate reaches 90%;
s2, pre-condensing: after the esterification reaction is finished, the pressure is removed, 0.063g of antimonous oxide and 28.5g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1700Pa, the temperature is slowly increased to 220 ℃, and the reaction is carried out for 30min.
S3, final polymerization: and after the temperature reaches 220 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 2 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
The structural formula of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is as follows:
in the structural formula, x and y are respectively 2:98-5:95.
The method for preparing the cationic dyeable bio-based furan dicarboxylic acid polyester fiber by adopting the slice comprises the following steps of
Drying the slices at 130 ℃ for 20 hours to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 200 ℃; heat roller temperature: the first hot roller is at 100 ℃, and the second hot roller is at 120 ℃; a draft ratio of 2.6; the winding speed was 3800m/min.
Example 2
Preparation of cationic dyeable biobased furan dicarboxylic acid polyester chip
S1, esterification: 624.6g of biobased 2, 5-furandicarboxylic acid and 372.0g of ethylene glycol are added into a polymerization reactor, nitrogen is filled for protection, the reaction is carried out for 3 hours under the pressure of 0.25MPa until the esterification rate reaches 90 percent, and the temperature is heated to 200 ℃.
S2, pre-condensing: after the esterification reaction is finished, the pressure is removed, 0.125g of antimonous oxide and 42.8g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1500Pa, the temperature is slowly increased to 230 ℃, and the reaction is carried out for 40min.
S3, final polymerization: and after the temperature reaches 230 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 3 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
The structural formula of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is shown in example 1.
The method for preparing the cationic dyeable bio-based furan dicarboxylic acid polyester fiber by adopting the slice comprises the following steps of
Drying the slices at 130 ℃ for 20 hours to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 210 ℃; heat roller temperature: the first hot roller is 110 ℃, and the second hot roller is 130 ℃; a draft ratio of 2.4; the winding speed was 4200m/min.
Example 3
S1, esterification: 624.6g of biobased 2, 5-furandicarboxylic acid and 372.0g of ethylene glycol are added into a polymerization reactor, nitrogen is filled for protection, the reaction is carried out for 3 hours under the pressure of 0.25MPa until the esterification rate reaches 90 percent, and the temperature is heated to 200 ℃.
S2, pre-condensing: after the esterification reaction is finished, the pressure is removed, 0.125g of ethylene glycol antimony and 57.0g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1500Pa, the temperature is slowly increased to 230 ℃, and the reaction is carried out for 50min.
S3, final polymerization: and after the temperature reaches 230 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 3 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
The structural formula of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is shown in example 1.
The method for preparing the cationic dyeable bio-based furan dicarboxylic acid polyester fiber by adopting the slice comprises the following steps of
Drying the slices at 130 ℃ for 20 hours to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 220 ℃; heat roller temperature: the first hot roller is 120 ℃, and the second hot roller is 140 ℃; a draft ratio of 3.0; the winding speed was 4000m/min.
Example 4
S1, esterification: 624.6g of biobased 2, 5-furandicarboxylic acid and 446.4g of ethylene glycol are added into a polymerization reactor, nitrogen is filled for protection, the reaction is carried out for 3 hours under the pressure of 0.3MPa until the esterification rate reaches 90 percent.
S2, pre-condensing: after the esterification reaction is finished, the pressure is removed, 0.25g of ethylene glycol antimony and 76.0g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1000Pa, the temperature is slowly increased to 240 ℃, and the reaction is carried out for 60min.
S3, final polymerization: and after the temperature reaches 240 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 4 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
The structural formula of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is shown in example 1.
The method for preparing the cationic dyeable bio-based furan dicarboxylic acid polyester fiber by adopting the slice comprises the following steps of
Drying the slices at 130 ℃ for 20 hours to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 200 ℃; heat roller temperature: the first hot roller is at 100 ℃, and the second hot roller is at 120 ℃; a draft ratio of 2.6; the winding speed was 4000m/min.
Example 5
Preparation of cationic dyeable biobased furan dicarboxylic acid polyester chip
S1, esterification: 624.6g of biobased 2, 5-furandicarboxylic acid and 446.4g of ethylene glycol are added into a polymerization reaction kettle, nitrogen is filled for protection, the reaction is carried out for 3 hours under the pressure of 0.2MPa until the esterification rate reaches 90 percent.
S2, pre-condensing: after the esterification reaction is finished, the pressure is removed, 0.25g of antimonous oxide and 28.5g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1700Pa, the temperature is slowly increased to 240 ℃, and the reaction is carried out for 30min.
S3, final polymerization: and after the temperature reaches 240 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 3 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
The structural formula of the cationic dyeable bio-based furan dicarboxylic acid polyester chip is shown in example 1.
The method for preparing the cationic dyeable bio-based furan dicarboxylic acid polyester fiber by adopting the slice comprises the following steps of
Drying the slices at 130 ℃ for 20 hours to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 210 ℃; heat roller temperature: the first hot roller is 120 ℃, and the second hot roller is 140 ℃; a draft ratio of 2.5; the winding speed was 4000m/min.
Comparative example 1
Preparation of biobased furan dicarboxylic acid polyester chip
S1 esterification: 624.6g of biobased 2, 5-furandicarboxylic acid and 372.0g of ethylene glycol are added into a polymerization reactor, nitrogen is filled for protection, the reaction is carried out for 3 hours under the pressure of 0.25MPa until the esterification rate reaches 90 percent, and the temperature is heated to 200 ℃.
S2 pre-polycondensation: after the esterification reaction is finished, the pressure is removed, 0.063g of antimonous oxide is added into the reaction kettle, stirring is continued, vacuum pumping is carried out until about 2000Pa, the temperature is slowly increased to 240 ℃ and the reaction is carried out for 30min.
S3, final polymerization: and after the temperature reaches 240 ℃, continuously vacuumizing to the vacuum degree of 200Pa, and reacting for 2 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
Preparation of biobased furan dicarboxylic acid polyester fiber
Drying the bio-based furan dicarboxylic acid polyester chip for 20 hours at 130 ℃ to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the bio-based furan dicarboxylic acid polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 230 ℃; heat roller temperature: the first hot roller is 120 ℃, and the second hot roller is 140 ℃; a draft ratio of 2.5; the winding speed was 4200m/min.
Comparative example 2
Preparation of cationic dyeable bio-based polyester chips
S1 esterification: 664.5g of terephthalic acid and 347.2g of ethylene glycol are added into a polymerization reaction kettle, nitrogen is filled for protection, the temperature is heated to 260 ℃, and the reaction is carried out for 5 hours under the pressure of 0.25MPa until the esterification rate reaches 90 percent.
S2 pre-polycondensation: after the esterification reaction is finished, the pressure is removed, 0.2g of antimonous oxide and 28.5g of dihydroxyethyl isophthalate-5-sodium sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out until about 1700Pa, the temperature is slowly increased to 270 ℃, and the reaction is carried out for 50min.
S3, final polymerization: and after the temperature reaches 270 ℃, continuously vacuumizing to 100Pa, and reacting for 6 hours until the power of the stirring motor reaches a certain value.
S4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable polyester chip after water cooling, granulating and drying.
Preparation of cationic dyeable polyester fibers
Drying the cationic dyeable polyester chip for 20 hours at 130 ℃ to ensure that the water content is lower than 30ppm, and then adopting a melt spinning method to prepare the cationic dyeable polyester fiber through screw extrusion, metering, cooling, bundling, hot drawing and winding.
The fiber forming process comprises the following steps: the spinning temperature (melt temperature) was 270 ℃; heat roller temperature: the first hot roller is at 80 ℃, and the second hot roller is at 150 ℃; a draft ratio of 3.0; the winding speed was 3900m/min.
The cationic dyeable biobased furan dicarboxylic acid polyester chips and cationic dyeable biobased furan dicarboxylic acid polyester fibers obtained in examples 1 to 5 described above, and the biobased furan dicarboxylic acid polyester chips and fibers obtained in comparative example 1, and the cationic dyeable polyester chips and cationic dyeable polyester fibers obtained in comparative example 2 were as shown in Table 1.
Table 1 is the relevant performance data for the cut sheets and fibers:
TABLE 1
As can be seen from Table 1, the dye uptake of the bio-based furan dicarboxylic acid polyester fiber which has not been modified by cations (comparative example 1) is significantly lower than that of the cationic dyeable bio-based furan dicarboxylic acid polyester fiber, and the reference GB/T3921-2008 "fastness to washing for textile color fastness test" is also lower than level 3, and the dye fastness is not as high as the administration requirement. In addition, the cationic dyeable polyester fiber prepared by the conventional method (comparative example 1) is compared in the test, and the cationic dyeable bio-based furan dicarboxylic acid polyester fiber prepared by the application can be found to have the same dyeing effect as that of the cationic dye.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. A cationic dyeable bio-based furan dicarboxylic acid polyester, characterized in that: the cationic dyeable bio-based furan dicarboxylic acid polyester is prepared by polycondensation of 2, 5-furan dicarboxylic acid, dihydroxyethyl isophthalate-5-sodium sulfonate and ethylene glycol serving as raw materials under the action of a catalyst, and has the structural formula:
2. a cationic dyeable biobased furandicarboxylic acid polyester according to claim 1, wherein the polycondensation preparation process comprises the steps of:
s1, esterification: adding bio-based 2, 5-furandicarboxylic acid and ethylene glycol into a polymerization reaction kettle according to a certain proportion, charging nitrogen for protection, heating to 180-200 ℃, and reacting for 2-3 hours under the pressure of 0.1-0.3 MPa until the esterification rate reaches 90%;
s2, pre-condensing: after the esterification reaction is finished, the pressure is removed, a catalyst and the dihydroxyethyl isophthalate-5-sulfonate are added into a reaction kettle, stirring is continued, vacuum pumping is carried out to 1000-2000Pa, the temperature is slowly increased to 200-220 ℃, and the reaction is carried out for 30-60min;
s3, final polymerization: after the pre-polycondensation reaction is finished and the internal temperature of the reaction kettle reaches 220-240 ℃, continuously vacuumizing to 100-300Pa, and reacting for 2-4 hours until the power of the stirring motor reaches a certain value;
s4, slicing: extruding the final polymer melt from the reaction kettle, and obtaining the cationic dyeable bio-based furan dicarboxylic acid polyester chip after water cooling, granulating and drying.
3. The cationic-dyeable bio-based furan dicarboxylic acid polyester according to claim 2, wherein in the step S1, the molar ratio of the furan dicarboxylic acid to the ethylene glycol is 1:1.3-2.0.
4. The cationic dyeable bio-based furan dicarboxylic acid polyester according to claim 2, wherein in the step (2), the catalyst is one or a mixture of more of antimony acetate, ethylene glycol antimony, antimony trioxide and stannous oxide, and the catalyst is added in an amount of 100-500 ppm based on the mass of 2, 5-furan dicarboxylic acid.
5. The cationic-dyeable bio-based furan dicarboxylic acid polyester according to claim 2, wherein in the step S2, the dihydroxyethyl isophthalate-5-sulfonate is potassium or sodium dihydroxyethyl isophthalate-5-sulfonate, and the amount of dihydroxyethyl isophthalate-5-sulfonate added is 2.0 to 5.0% of the total mole number of 2, 5-furandicarboxylic acid.
6. A cationic dyeable biobased furandicarboxylic acid polyester according to claim 1, wherein the polyester molecular segments in the formula are x:y = 2:98 to 5:95.
7. The cationic-dyeable bio-based furandicarboxylic acid polyester of claim 1, wherein the cationic-dyeable bio-based furandicarboxylic acid polyester has a chip intrinsic viscosity of 0.67 to 0.75dl/g, a glass transition temperature of 70 to 80 ℃ and a melting point of 170 to 195 ℃.
8. A method for preparing cationic-dyeable bio-based furan dicarboxylic acid polyester fiber, which is characterized in that the cationic-dyeable bio-based furan dicarboxylic acid polyester chip according to any one of claims 1 to 7 is dried to have a water content of less than 30ppm, and then the dried cationic-dyeable bio-based furan dicarboxylic acid polyester chip is put into a screw extruder to be melted by adopting a melt spinning method, and is measured, cooled, clustered, thermally drawn and wound after the screw extrusion to prepare the cationic-dyeable bio-based furan dicarboxylic acid polyester fiber.
9. The method for preparing cationic dyeable bio-based furan dicarboxylic acid polyester fiber according to claim 8, wherein the spinning melt temperature is 200-230 ℃ when the screw extruder is melted; the temperature of the first hot roller is 100-120 ℃, and the temperature of the second hot roller is 120-140 ℃; the draft ratio is 2.0-3.5; the winding speed is 3800-4200 m/min.
10. The method for preparing cationic-dyeable bio-based furan dicarboxylic acid polyester fiber according to claim 8, wherein the cationic-dyeable bio-based furan dicarboxylic acid polyester fiber has a breaking strength of > 3.0cN/dtex, an elongation at break of < 20%, a boiling water heat shrinkage of 10-25% and a cationic dye dyeing uptake of > 80%.
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| CN113550022A (en) * | 2021-09-22 | 2021-10-26 | 苏州宝丽迪材料科技股份有限公司 | Preparation method of cation-dyeable regenerated polyester fiber and product thereof |
| CN116377611A (en) * | 2023-04-04 | 2023-07-04 | 中科国生(杭州)科技有限公司 | Bio-based furan polyester bulked continuous filament and application thereof |
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| CN107541803A (en) * | 2017-09-07 | 2018-01-05 | 江苏恒科新材料有限公司 | A kind of preparation method of normal pressure cation dyeable polyester fiber |
| CN107604463A (en) * | 2017-09-07 | 2018-01-19 | 江苏恒科新材料有限公司 | A kind of preparation method of cationic dyeable polyester fiber |
| CN112760740A (en) * | 2021-01-18 | 2021-05-07 | 中国科学院宁波材料技术与工程研究所 | Bio-based 2, 5-furandicarboxylic acid based copolyester fiber and preparation method and application thereof |
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