Synthesis of PEG-Modified PET Masterbatch: Preparation of Low-Temperature Easy-Dyeing, High-Fastness PET Fibers Based on Phase Domain Size Regulation

Abstract

Polyethylene terephthalate (PET) fibers are the largest category of chemical fibers and are widely used.However, the dyeing of PET fibers requires high temperature and pressure (130 ℃ and 0.2 MPa), and the dyeing process consumes huge amounts of energy.Existing studies have shown that the dyeing ability of PET is directly related to the size of the amorphous region, which determines the external conditions for dyeing.In this research, we synthesized a series of low-temperature easydyeing masterbatches, PET-co-polyethylene glycol (PETEG), using polyethylene glycol (PEG) with different number-average molecular masses Mn and additive amounts.The phase domain size of the amorphous region of PET fibers was regulated via the masterbatch method.The relationship between the phase domain size and dyeing performance was explored from three perspectives: theamount of masterbatch, type of masterbatch, and PEG relative molecular mass.The results indicate that the fiber sample with PEG (Mn = 2 000 g/mol) at a mass fraction of 20% modified masterbatch has a smaller crystalline lamellar thickness (5.59 nm) and a larger interlamellar amorphous layer thickness (6.43 nm).The increase in the long periodand lamellar inclination angle results in a looser structure, allowing small molecule dyes to diffuse into the fibers more easily.The dye-uptake increases from 63.21% to 92.66% at100 ℃ with the addition of the masterbatch.Additionally, the dye-uptake of the modified fibers increases with the relative molecular mass of PEG and the mass fraction of the masterbatch.All modified fibers achieve a staining color fastness of grade 4 or higher.This research demonstrates a simple masterbatch method that enables atmospheric pressure dyeing and provides a practical solution for efficient, low-temperature, and low-energy dyeing of PET fibers.

Keywords

polyethylene terephthalate (PET) fiber / polyethylene glycol (PEG) / low-temperature dyeing / phase domain size / dye-uptake / color fastness

References

[1] DISSANAYAKE L, JAYAKODY L N. Engineering microbes to bio-upcycle polyethylene terephthalate[J]. Frontiers in Bioengineering and Biotechnology, 2021, 9: 656465.

[2] SOUISSI M, KHIARI R, ZAAG M, et al. Ecological and cleaner process for dyeing bicomponent polyester filaments (PET/PTT) using ecological carriers: analysis of dyeing performance[J]. RSC Advances, 2021, 11 (42): 25830-25840.

[3] FU C F, GU L X. Structures and properties of easily dyeable copolyesters and their fibers respectively modified by three kinds of diols[J]. Journal of Applied Polymer Science, 2013, 128 (6): 3964-3973.

[4] HASHIM S, XUE D, BI X Y, et al. Influence of lawsone dye on surface properties of polyethylene terephthalate fabric[J]. Journal of Donghua University (English Edition), 2025, 42 (1): 71-77.

[5] SOUISSI M, KHIARI R, ABDELWAHEB M, et al. Kinetics study of dyeing bicomponent polyester textiles (PET/PTT) using environmentally friendly carriers[J]. RSC Advances, 2022, 12(4): 2361-2374.

[6] SASAKI K, HIROGAKI K, TABATA I, et al. Supercritical fluid dyeing of polyester fabrics using polymeric nanofibers loaded with disperse dye[J]. The Journal of Supercritical Fluids, 2024, 211: 106289.

[7] HSIAO K J, KUO J L, TANG J W, et al. Physics and kinetics of alkaline hydrolysis of cationic dyeable poly (ethylene terephthalate) (CDPET) and polyethylene glycol (PEG)- modified CDPET polymers: effects of dimethyl 5-sulfoisophthalate sodium salt/PEG content and the number-average molecular weight of the PEG[J]. Journal of Applied Polymer Science, 2005, 98(2): 550-556.

[8] MAMUN KABIR S M, RAHMAN M M, HONG I, et al. Comparative characterization and dyeing properties of poly (ethylene terephthalate-copolyethylene glycol) fibers and poly (ethylene terephthalate) fibers[J]. Polymer, 2024, 311: 127488.

[9] GE T J, WANG M Y, HE X F, et al. Synthesis and characterization of poly (butylene glycol adipate-co-terephthalate/diphenylsilanediol adipate-co-terephthalate) copolyester[J]. Polymers, 2024, 16(8): 1122.

[10] HUANG Z, BAO J N, ZHANG X M, et al. New insights in structures, properties, and rheological behaviors of cationic dyeable polyesters[J]. Industrial & Engineering Chemistry Research, 2023, 62 (36): 14648-14656.

[11] ZHOU R, WANG X L, HUANG L Q, et al. Poly (ethylene terephthalate) copolyesters and fibers modified with NPG and SIPE for improved hydrophilicity and dyeability[J]. The Journal of the Textile Institute, 2017, 108 (11): 1949-1956.

[12] ZHANG S M, WU Y H, YANG H B, et al. Preparing cationic dyeable polyamide 6 filaments by combining the masterbatch technique with melt copolymerization[J]. Textile Research Journal, 2022, 92(3/4): 511-524.

[13] RWEI S P, LIN W P, WANG J F. Synthesis and characterization of biodegradable and weatherdurable PET/PEG/NDC copolymers[J]. Colloid and Polymer Science, 2012, 290: 1381-1392.

[14] GAN Z Y, FENG Y B, YANG J J, et al. The copolymerization of flexible poly (ethylene terephthalate)-poly(ethylene oxide terephthalate) poly(ether ester)s and brittle polylactic acid: balanced mechanical properties and potential biodegradability[J]. Reactive and Functional Polymers, 2022, 180: 105392.

[15] LU H, WANG H L, ZHENG A N, et al. Hybrid poly (ethylene terephthalate)/silica nanocomposites prepared by in situ polymerization[J]. Polymer Composites, 2007, 28(1): 42-46.

[16] LI X, LIU R, ZHONG L, et al. Antielectrostatic poly (ether ester) block copolymer of poly (ethylene terephthalate-co-isophthalate)-poly (ethylene glycol)[J]. Journal of Applied Polymer Science, 2003, 89(6): 1696-1701.

[17] GOLMOHAMMADI N, BOLAND-HEMMAT M, BARAHMAND S, et al. Coarse-grained molecular dynamics simulations of poly(ethylene terephthalate)[J]. The Journal of Chemical Physics, 2020, 152(11): 114901.

[18] PENG Y, WANG Y, DAN Y D, et al. Siliconlinked polyethylene glycol-polyethylene terephthalate (PEG-PET) nanostructures loaded with Eu3+ -complexes for hybrid luminescent PET materials[J]. Polymer Composites, 2024, 45 (2): 999-1011.

[19] JI P, LU D P, ZhANG S M, et al. Modification of poly (ethylene 2,5-furandicarboxylate) with poly (ethylene glycol) for biodegradable copolyesters with good mechanical properties and spinnability[J]. Polymers, 2019, 11 (12): 2105.

[20] SUN L N, HUANG L Q, WANG X L, et al. Synthesis and structural characterization of sequential structure and crystallization properties for hydrophilic modified polyester[J]. Polymers, 2020, 12(8): 1733.

[21] GÜNGÖÖR ERTUĞRAL T, ALKAN C. RAL T, ALKAN C.Synthesis of thermally protective PET-PEG multiblock copolymers as food packaging materials[J]. Polymers and Polymer Composites, 2021, 29(Sup.9): S1125-S1133.

[22] KANG C S, YOON H J, HONG C H, et al. Synthesis of hydrophilic copolyesters and the characterization of their moisture-related cooling properties[J]. Fibers and Polymers, 2015, 16 (12): 2513-2518.

[23] SHARMA P R, VARMA A J. Thermal stability of cellulose and their nanoparticles: effect of incremental increases in carboxyl and aldehyde groups[J]. Carbohydrate Polymers, 2014, 114: 339-343.

[24] PAN Z Q, ZHU L Q. Synthesis of a siloxane oligomer containing ether bond for promoting the adhesion between addition-cure silicone rubber and polycarbonate (PC)[J]. Silicon, 2023, 15 (10): 4425-4437.

[25] SUN N, ZOU J X, ZHANG Y, et al. The competition mechanism of orientation and disorientation of PET chains during spinning based on the pre-oriented polyester industrial yarns[J]. Polymer, 2024, 300: 126991.

[26] SHARMA K, BRAUN O, TRITSCH S, et al. 2D Raman, ATR-FTIR, WAXD, SAXS and DSC data of PET mono-and PET/PA6 bicomponent filaments[J]. Data in Brief, 2021, 38: 107416.

[27] PERRET E, HUFENUS R. Fitting of 2D WAXD data: mesophases in polymer fibers[J]. Data in Brief, 2021, 39: 107466.

[28] PERRET E, CHEN K, BRAUN O, et al. Radial gradients in PET monofilaments: a Raman mapping and SAXS tomography study[J]. Polymer, 2022, 238: 124422.

[29] LIU Y T, YIN L X, ZHAO H R, et al. Straininduced structural evolution during drawing of poly (ethylene terephthalate) fiber at different temperatures by in situ synchrotron SAXS and WAXD[J]. Polymer, 2017, 119: 185-194.

[30] STRIBECK N, FAKIROV S, APOSTOLOV A A, et al. Deformation behavior of PET, PBT and PBT-based thermoplastic elastomers as revealed by SAXS from synchrotron[J]. Macromolecular Chemistry and Physics, 2003, 204 (7): 1000-1013.

[31] MA J P, YU L, CHEN S, et al. Structureproperty evolution of poly (ethylene terephthalate) fibers in industrialized process under complex coupling of stress and temperature field[J]. Macromolecules, 2019, 52(2): 565-574.

[32] OMAR A Z, EL-RAHMAN M A, EL-SADANY S K, et al. Synthesis of novel bisazo disperse dyes: spectroscopic characterization, DFT study and dyeing of polyester[J]. Dyes and Pigments, 2021, 196: 109831.

[33] PALUSZKIEWICZ J, GRZELAKOWSKA A, RUTOWICZ J. Diesters of monoimide of perylene-3,4,9,10-tetracarboxylic acid: synthesis, characterization, and application for dyeing polyester fibre, polystyrene, and poly (methyl methacrylate) films[J]. Luminescence, 2024, 39(9): e4890.

Funding

Key R&D Program of the Xinjiang Uygur Autonomous Region, China(2024B01011)