CN117512803A - Zxfoom zxfoom Quaternary polymerization ammonium salts antibacterial and stock solution coloring double method for producing functional polyester filaments - Google Patents
Zxfoom zxfoom Quaternary polymerization ammonium salts antibacterial and stock solution coloring double method for producing functional polyester filaments Download PDFInfo
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- CN117512803A CN117512803A CN202311573237.4A CN202311573237A CN117512803A CN 117512803 A CN117512803 A CN 117512803A CN 202311573237 A CN202311573237 A CN 202311573237A CN 117512803 A CN117512803 A CN 117512803A
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- maleic anhydride
- polyester
- antibacterial
- screw
- modified polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 113
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 58
- 238000004040 coloring Methods 0.000 title claims abstract description 22
- 239000011550 stock solution Substances 0.000 title claims abstract description 21
- 150000003863 ammonium salts Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000006116 polymerization reaction Methods 0.000 title 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229920000289 Polyquaternium Polymers 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000002074 melt spinning Methods 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 34
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 25
- 238000009987 spinning Methods 0.000 claims description 25
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004595 color masterbatch Substances 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 12
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000005491 wire drawing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000986 disperse dye Substances 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000985 reactive dye Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000009977 dual effect Effects 0.000 abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- 230000003993 interaction Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F1/06—Dyes
-
- 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
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for preparing polyester filaments with antibacterial and stock solution coloring dual functions through dual modification of maleic anhydride and polyquaternium. The method comprises the steps of screening of a polyquaternium antibacterial material, preparation of maleic anhydride modified polyester chips, preparation of polyester master batches, preparation of maleic anhydride modified polyester master batches and preparation of polyester filaments with the antibacterial function, and finally the maleic anhydride modified polyester chips, the maleic anhydride modified polyester master batches and polyethylene glycol terephthalate chips are injected into a screw mixing mill for ternary blending melt spinning to prepare the polyester filaments with the antibacterial and stock solution coloring dual functions. The polyester filaments prepared through the preparation method have the durable antibacterial effect and the high-fastness stock solution coloring dual functions.
Description
Technical Field
The invention belongs to the technical field of polyester fiber production, and particularly relates to a method for preparing a double-functional polyester filament with antibacterial and stock solution coloring by double modification of maleic anhydride and polyquaternium.
Background
In the aspect of antibacterial textile development, antibacterial materials used in the current market comprise silver series, copper series, zinc series and quaternary ammonium salts, and the processing mode mainly comprises two modes of a blending spinning method for adding antibacterial functional master batches, functional finishing based on antibacterial agents and the like. There has been little research into developing antimicrobial polyester fibers based on Quaternary Ammonium Salts (QAS) and polyquaternary ammonium salts (QAC). In the aspect of preparing the antibacterial textile based on the polyquaternary ammonium salt, the melting point of the antibacterial material of the polyquaternary ammonium salt is relatively low, and the antibacterial material is easy to decompose under the high-temperature condition of melt spinning so as to lose the antibacterial effect; in addition, the polyquaternary ammonium is a cationic antibacterial material, so that chemical bond combination is difficult to be formed with polymer macromolecular groups such as terylene during blending spinning, and the cationic quaternary ammonium group in the QAS structure cannot be fixed or anchored on a polymer macromolecular chain segment, so that the antibacterial function is difficult to be exerted.
In the development of the dope-dyed textile, dope-dyed filaments mainly are prepared by blending masterbatch and polyester chips. However, since the chemical bond between the dye (pigment) molecule and the polymer macromolecule is difficult to form, a strong interaction of the chemical bond between the dye (pigment) molecule and the polymer macromolecule cannot be established, resulting in easy discoloration and unstable color of the dope-dyed fiber during use. Therefore, there is a need to develop a new preparation method to obtain a polyester filament with durable antimicrobial effect and high-fastness stock coloring dual functions.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the technical problems, the invention provides a method for preparing the double-functional polyester filament with antibacterial and stock solution coloring by double modification of maleic anhydride and polyquaternium, which can effectively solve the problems that the melting point of the antibacterial polyester fiber developed based on Quaternary Ammonium Salt (QAS) and polyquaternium (QAC) is lower, and the antibacterial polyester fiber is easy to decompose at high temperature and loses antibacterial effect; the color master batch and the polyester chip blended spinning stock solution colored filament have the defects of easy color change, unstable color and the like in the use process.
The technical scheme is as follows: the method for preparing the antibacterial and stock solution coloring bifunctional polyester filament by double modification of maleic anhydride and polyquaternium comprises the following steps:
s1, screening a polyquaternium antibacterial material: screening a polyquaternary ammonium salt antibacterial high molecular material poly (AAm/DMAEMA-BC/Man) with cationic characteristics, wherein the chain length of an alkyl group on a nitrogen atom in the quaternary ammonium salt is 12-18 carbon atoms;
s2, preparing maleic anhydride modified polyester chips: feeding maleic anhydride and polyethylene terephthalate slices into a double-screw mixer in proportion through a PLC coordinated control double-channel metering pump-screw injection system, blending at a set temperature to generate maleic anhydride melt grafting reaction, and carrying out re-extrusion, wire drawing, cooling and granulating to obtain maleic anhydride modified polyester slices containing polar short side chains, wherein the mass percent of maleic anhydride is 3-10 wt.%, and the mass percent of polyethylene terephthalate slices is 90-97 wt.%;
s3, preparing polyester master batches: carrying out reactive blending and melt extrusion, wire drawing and granulating on the maleic anhydride modified polyester chips obtained in the step S2 and the polyquaternium screened in the step S1 in a double-screw mixer to obtain polyester master batches with high temperature resistance and lasting antibacterial function, wherein the mass percent of the maleic anhydride modified polyester chips is 88-98 wt.%, and the mass percent of the polyquaternium is 2-12 wt.%;
s4, preparing maleic anhydride modified polyester color master batch: carrying out reactive blending and melt extrusion, wire drawing, cooling and granulating on the maleic anhydride modified polyester chips obtained in the step S2 and powdery dye or pigment in a screw to obtain maleic anhydride modified polyester color master batch, wherein the mass percent of the maleic anhydride modified polyester chips is 65-90 wt.%, and the mass percent of the powdery dye or pigment is 10-35 wt.%;
s5, selecting oil-soluble and water-soluble double-soluble polyquaternium to prepare a quaternary ammonium salt modified spinning oil agent, and putting the quaternary ammonium salt modified spinning oil agent into an oiling device of a spinning flow;
s6, preparing a polyester filament with an antibacterial function: injecting the maleic anhydride modified polyester chips obtained in the step S2 into a screw mixer, and coating the quaternary ammonium salt modified spinning oil prepared in the step S5 on the surface of polyester fibers in a bath ratio of 15%, so as to obtain polyester filaments with an antibacterial function;
s7, preparing the antibacterial and stock solution coloring bifunctional polyester filaments: and (3) injecting the maleic anhydride modified polyester chips obtained in the step (S2), the maleic anhydride modified polyester color master batch obtained in the step (S4) and the polyethylene terephthalate chips into a screw mixer for ternary blending melt spinning to obtain the antibacterial and stock solution coloring dual-functional polyester filaments, wherein the mass percentage of the maleic anhydride modified polyester chips is 1.5-15 wt%, the mass percentage of the maleic anhydride modified polyester color master batch is 0.3-1 wt%, and the mass percentage of the polyethylene terephthalate chips is 84-98 wt%.
Preferably, the initiator used in the step S2 is diisopropyl peroxide, the amount of the initiator is 0.2-0.4 wt.%, the amount of the maleic anhydride is 3-5 wt.%, the amount of the polyethylene terephthalate is 94-96 wt.%, the balance is the auxiliary agent, the temperature is set to 175-180 ℃, the screw ejection amount is 600 g/min, and the winding speed is 80-115 m/min.
Preferably, in the step S3, the temperature from the screw to the nozzle at five points of the twin-screw mixer is 120 ℃, 132 ℃, 148 ℃, 171 ℃ and 186 ℃, the screw discharge amount is 600 g/min, and the winding speed is 80-115 m/min.
Preferably, the screw-to-nozzle five-point temperatures of the screw mixer in step S7 are 115 ℃, 125 ℃, 157 ℃, 168 ℃ and 185 ℃, respectively, the screw discharge amount is 132 g/min, and the winding speed is 2800 m/min.
Preferably, the powdery dye or pigment is an organic disperse dye, a reactive dye or an inorganic ore pigment.
The beneficial effects are that: the method of the invention adds maleic anhydride and polyethylene glycol terephthalate for blending and melt grafting, embeds polar short chains in the macromolecular chain of polyester, improves the compatibility and dispersibility of polyester materials and the coupling effect between the polyester materials and other molecules, and improves the bonding fastness between the polyester and other nonpolar materials;
the method comprises the steps of carrying out reactive blending and melt extrusion on a maleic anhydride modified polyester slice and polyquaternary ammonium salt in a screw, enabling the polyester and the quaternary ammonium salt to form strong interaction of chemical bonds based on polar short chains embedded in a polyester molecular chain, fixing or anchoring a cationic quaternary ammonium group in a quaternary ammonium salt structure on a polyester macromolecular chain segment, and improving the durability of the antibacterial function of the quaternary ammonium salt modified polyester;
the method comprises the steps of carrying out reactive blending and melt extrusion-wire drawing-cooling-granulating on maleic anhydride modified polyester chips and dye (or pigment) in a screw, enabling the polyester and the dye (or pigment) to form strong interaction of chemical bonds based on polar short chains embedded in polyester molecular chains, producing a color master batch based on the maleic anhydride modified polyester, and improving color fastness of the color master batch;
the preparation method comprises the steps of selecting oil-soluble and water-soluble double-soluble polyquaternium to prepare a quaternary ammonium salt modified spinning oil agent, putting the quaternary ammonium salt modified spinning oil agent into a spinning oiling device, combining a quaternary ammonium salt antibacterial agent with a polar short chain in a modified polyester macromolecular chain through the modified spinning oil agent to generate a chemical bond, forming an antibacterial layer on the surface of a polyester fiber, and realizing the effect of improving the combination fastness of the quaternary ammonium salt and the modified polyester based on a short process;
based on the double modification of maleic anhydride and polyquaternium, the ternary blending melt spinning of modified polyester master batch, modified color master batch and conventional PET chips is adopted to prepare the bifunctional polyester PET DTY filament with durable antibacterial effect and high-fastness stock solution coloring.
Drawings
FIG. 1 is a schematic illustration of a dual modified dope coloring and antibacterial dual function filament spinning process based on example 1;
fig. 2 is a schematic diagram of a stock solution coloring and antibacterial dual-function filament spinning process based on a modified oiling agent in example 2.
Detailed Description
The invention is described in detail below with reference to the attached drawings and the specific embodiments:
example 1
As shown in fig. 1: based on the double modification of maleic anhydride and quaternary ammonium salt, the dual-functional polyester PET DTY filament with durable antibacterial effect and high-fastness stock solution coloring is prepared by ternary blending melt spinning of modified polyester master batches, modified color master batches and conventional polyethylene terephthalate (PET) slices, and specifically comprises the following steps of:
s1, screening a poly (AAm/DMAEMA-BC/Man) antibacterial polymer material poly (QAC) with cationic characteristics, and penetrating a negative functional group in bacteria through a cationic group carried by the poly (AAm/DMAEMA-BC/Man) antibacterial polymer material poly (AAm/DMAEMA-BC/Man), so as to destroy electrolyte and damage cell membranes, thereby playing a role in sterilization. In order to impart durable antimicrobial properties to the polyquaternium, cationic quaternary ammonium groups in the QAC structure can be immobilized or anchored to the polymer molecular segments and maintain alkyl chain lengths of 12-18 carbon atoms on the nitrogen atoms in the quaternium. The poly-quaternary ammonium salt antibacterial material can achieve the optimal antibacterial effect by meeting the conditions;
s2, based on the requirement of Maleic Anhydride (MAH) melt grafting reaction, feeding MAH and PET slices into a large-length-diameter ratio and small-diameter double-screw mixer accurately in proportion through a PLC coordinated control double-channel metering pump-screw injection system, and generating the maleic anhydride melt grafting reaction through blending at a specific temperature, wherein the reaction process of the MAH and PET melt grafting is accurately regulated and controlled through optimizing factors such as initiator variety and concentration, monomer mass concentration, additive variety and concentration, reaction temperature and reaction time. In general, the grafting yield can be increased by increasing the concentration of the initiator diisophenylpropyl peroxide (DCP), the DCP concentration no longer increasing when a crosslinking reaction is accompanied; the grafting rate can be improved by simply increasing the amount of MAH, and the increase of the amount of MAH can be stopped when the rising trend tends to be stable; when the reaction temperature is selected to be low, the decomposition concentration of DCP is high, but side reaction is easy to generate to consume free radical, so that the free radical is not obviously improved; the melting reaction time (namely the rotating speed of the extruder screw) has great influence on the grafting rate, and when the rotating speed of the screw is too high, the retention time of materials in the charging barrel is shorter, the reaction is insufficient, and the grafting rate is reduced; when the rotating speed of the screw is too low, the shearing force is too small, so that the initiator is unevenly dispersed, and meanwhile, the material residence time is too long, serious crosslinking is caused, and the grafting rate is reduced. Through repeated experiments and optimization of the reaction process of MAH grafted PET, the DCP dosage is 0.4-wt%, the MAH dosage is 4.5-wt%, the PET dosage is 95-wt%, the balance is auxiliary agents (catalyst, dispersing agent and the like), the reaction temperature is 180 ℃, the screw ejection amount is 600 g/min, and the winding speed is 115-m/min;
s3, carrying out reactive blending and melt extrusion-wire drawing-granulating on the maleic anhydride modified polyester chips and the quaternary ammonium salt in a double-screw mixer, forming chemical bond combination of a polar short side chain embedded in a polyester molecular chain and the quaternary ammonium salt molecule based on melt grafting, fixing or anchoring a cationic quaternary ammonium group in a polyquaternary ammonium salt structure on a polyester macromolecular chain segment, and preparing high-temperature-resistant and durable antibacterial polyester master batch based on double modification of maleic anhydride and quaternary ammonium salt; wherein the mass percentages of the maleic anhydride modified polyester chips and the polyquaternium are respectively 96 wt percent and 3 wt percent, the five-point temperatures from the screw to the nozzle are respectively 120 ℃, 132 ℃, 148 ℃, 171 ℃ and 186 ℃, the screw discharge amount is 600 g/min, and the winding speed is 80 m/min;
s4, injecting maleic anhydride modified polyester chips and powdery dye (or pigment) into a screw mixer according to the proportion of 86 wt percent and 14 wt percent respectively through a PLC coordinated control double-channel metering pump-screw injection system, wherein the five-point temperature from a screw to a nozzle is 120 ℃, 132 ℃, 148 ℃, 171 ℃ and 186 ℃, the screw ejection amount is 600 g/min, the winding speed is 90 m/min, and the melt extrusion, wire drawing, cooling and granulating are carried out, so that the polyester and the dye (or dye) form strong interaction of chemical bonds based on polar short chains embedded in the polyester molecular chain, the color master batch based on the maleic anhydride modified polyester is produced, and the color fastness of the color master batch is improved;
s5, injecting maleic anhydride modified polyester chips (5 wt.%) and modified color master batches (0.5 wt%) and conventional PET chips (94.5 wt%) into a screw mixer for ternary blending melt spinning by controlling a three-channel metering pump-screw injection system through a PLC, wherein the five-point temperatures from the screw to the nozzle are 115 ℃, 125 ℃, 157 ℃, 168 ℃ and 185 ℃, the screw discharge amount is 132 g/min, and the winding speed is 2800 m/min. In the POY-DTY stretching and shaping process, the quaternary ammonium salt and the polar short chain in the modified polyester macromolecular chain are combined to generate chemical bonds, and the cationic quaternary ammonium group in the polyquaternary ammonium salt structure is fixed or anchored on the polyester macromolecular chain segment, so that the combination fastness of the quaternary ammonium salt and the modified polyester is improved to realize the durable antibacterial effect, and the polyester filament with high color fastness and durable antibacterial function is prepared.
Example 2
As shown in fig. 2: the preparation method comprises the steps of preparing a quaternary ammonium salt modified spinning oil based on oil-soluble and water-soluble double-soluble polyquaternary ammonium salt, putting the quaternary ammonium salt modified spinning oil into a spinning oiling device, combining a quaternary ammonium salt antibacterial agent with a polar short chain in a modified polyester macromolecular chain to generate a chemical bond, and fixing or anchoring a cationic quaternary ammonium group in a polyquaternary ammonium salt structure on a polyester macromolecular chain segment to form an antibacterial layer, so as to prepare the high-temperature-resistant and durable antibacterial polyester filament, and specifically comprises the following steps of:
s1, preparing a polyquaternium modified spinning oil based on oil-soluble and water-soluble double-soluble polyquaternium, and putting the spinning oil into a spinning oiling device;
s2, selecting a chemical formula asAnd the polar organic compound Maleic Anhydride (MAH) containing various functional groups and having the chemical formula +.>Based on a PLC coordinated control double-channel metering pump-screw injection system, feeding MAH and PET slices into a double-screw mixer with large length-diameter ratio and small caliber according to a proportion, carrying out blending at a set temperature to generate a maleic anhydride melt grafting reaction, and precisely regulating and controlling the reaction process of the MAH and PET melt grafting by optimizing factors such as initiator varieties and concentrations, monomer mass concentrations, additive varieties and concentrations, reaction temperature, reaction time and the like. In general, the grafting rate is increased by increasing the concentration of the initiator DCP, the DCP concentration no longer increasing when a crosslinking reaction is accompanied; the grafting rate can be improved by simply increasing the MAH dosage, and the grafting rate can be stopped when the ascending trend tends to be stableIncreasing the MAH consumption; when the reaction temperature is selected to be low, the decomposition concentration of DCP is high, but the DCP is easy to generate side reaction to consume free radicals, so that the free radicals are not obviously improved; the melting reaction time (namely the rotating speed of the extruder screw) has great influence on the grafting rate, and when the rotating speed of the screw is too high, the retention time of materials in the charging barrel is shorter, the reaction is insufficient, and the grafting rate is reduced; when the rotating speed of the screw is too low, the shearing force is too small, so that the initiator is unevenly dispersed, and meanwhile, the material residence time is too long, serious crosslinking is caused, and the grafting rate is reduced. Through repeated experiments and optimization of the reaction process of MAH grafted PET, the DCP dosage is 0.3 wt percent, the MAH dosage is 3.7 wt percent, the PET dosage is 95.5 wt percent, the rest is auxiliary agent, the reaction temperature is 178 ℃, the screw ejection amount is 600 g/min, and the winding speed is 100 m/min;
s3, injecting maleic anhydride modified polyester chips and powdery dye (or pigment) into a screw mixer by a PLC coordinated control double-channel metering pump-screw injection system according to the dosage of 86 wt percent and 14 wt percent, wherein the five-point temperature from the screw to the nozzle is 120 ℃, 132 ℃, 148 ℃, 171 ℃ and 186 ℃ respectively, the screw ejection amount is 600 g/min, the winding speed is 105 m/min, and the melt extrusion, wire drawing, cooling and granulating are carried out, so that the polyester and the dye (or paint) form strong interaction of chemical bonds based on polar short chains embedded in the polyester molecular chains, the color master batch based on the maleic anhydride modified polyester is produced, and the color fastness of the color master batch is improved;
s4, injecting the maleic anhydride modified polyester chips and modified color master batches into a screw mixer for binary blending melt spinning by controlling a double-channel metering pump-screw injection system through a PLC, wherein the five-point temperatures from the screw to the nozzle are 115 ℃, 125 ℃, 157 ℃, 168 ℃ and 185 ℃, the screw ejection amount is 160 g/min, and the winding speed is 3200 m/min. In the POY spinning process, the quaternary ammonium salt modified spinning oil is coated on the surface of polyester fiber in a bath ratio of 15%, chemical bond combination is generated between the quaternary ammonium salt and polar short chains in modified polyester macromolecular chains in a POY ring blowing and drying device and in the POY-DTY stretching and shaping process, and the cationic quaternary ammonium group in the polyquaternary ammonium salt structure is fixed or anchored on the polyester macromolecular chain segment, so that the combination fastness and durable antibacterial effect of the quaternary ammonium salt and the modified polyester are improved, and the polyester filament with high color fastness and durable antibacterial function is prepared.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The method for preparing the antibacterial and stock solution coloring bifunctional polyester filament by double modification of maleic anhydride and polyquaternium is characterized by comprising the following steps of:
s1, screening a polyquaternium antibacterial material: screening a polyquaternary ammonium salt antibacterial high molecular material poly (AAm/DMAEMA-BC/Man) with cationic characteristics, wherein the chain length of an alkyl group on a nitrogen atom in the quaternary ammonium salt is 12-18 carbon atoms;
s2, preparing maleic anhydride modified polyester chips: feeding maleic anhydride and polyethylene terephthalate slices into a double-screw mixer in proportion through a PLC coordinated control double-channel metering pump-screw injection system, blending at a set temperature to generate maleic anhydride melt grafting reaction, and carrying out re-extrusion, wire drawing, cooling and granulating to obtain maleic anhydride modified polyester slices containing polar short side chains, wherein the mass percent of maleic anhydride is 3-10 wt.%, and the mass percent of polyethylene terephthalate slices is 90-97 wt.%;
s3, preparing polyester master batches: carrying out reactive blending and melt extrusion, wire drawing and granulating on the maleic anhydride modified polyester chips obtained in the step S2 and the polyquaternium screened in the step S1 in a double-screw mixer to obtain polyester master batches with high temperature resistance and lasting antibacterial function, wherein the mass percent of the maleic anhydride modified polyester chips is 88-98 wt.%, and the mass percent of the polyquaternium is 2-12 wt.%;
s4, preparing maleic anhydride modified polyester color master batch: carrying out reactive blending and melt extrusion, wire drawing, cooling and granulating on the maleic anhydride modified polyester chips obtained in the step S2 and powdery dye or pigment in a screw to obtain maleic anhydride modified polyester color master batch, wherein the mass percent of the maleic anhydride modified polyester chips is 65-90 wt.%, and the mass percent of the powdery dye or pigment is 10-35 wt.%;
s5, selecting oil-soluble and water-soluble double-soluble polyquaternium to prepare a quaternary ammonium salt modified spinning oil agent, and putting the quaternary ammonium salt modified spinning oil agent into an oiling device of a spinning flow;
s6, preparing a polyester filament with an antibacterial function: injecting the maleic anhydride modified polyester chips obtained in the step S2 into a screw mixer, and coating the quaternary ammonium salt modified spinning oil prepared in the step S5 on the surface of polyester fibers in a bath ratio of 15%, so as to obtain polyester filaments with an antibacterial function;
s7, preparing the antibacterial and stock solution coloring bifunctional polyester filaments: and (3) injecting the maleic anhydride modified polyester chips obtained in the step (S2), the maleic anhydride modified polyester color master batch obtained in the step (S4) and the polyethylene terephthalate chips into a screw mixer for ternary blending melt spinning to obtain the antibacterial and stock solution coloring dual-functional polyester filaments, wherein the mass percentage of the maleic anhydride modified polyester chips is 1.5-15 wt%, the mass percentage of the maleic anhydride modified polyester color master batch is 0.3-1 wt%, and the mass percentage of the polyethylene terephthalate chips is 84-98 wt%.
2. The method for preparing the polyester filament with the antibacterial and stock solution coloring functions by double modification of maleic anhydride and polyquaternium according to claim 1, which is characterized in that: the initiator used in the step S2 is diisopropyl peroxide, the amount of the initiator is 0.2-0.4 wt%, the amount of the maleic anhydride is 3-5 wt%, the amount of the polyethylene terephthalate is 94-96 wt%, the balance is the auxiliary agent, the temperature is set to 175-180 ℃, the screw ejection amount is 600 g/min, and the winding speed is 80-115 m/min.
3. The method for preparing the polyester filament with the antibacterial and stock solution coloring functions by double modification of maleic anhydride and polyquaternium according to claim 1, which is characterized in that: in the step S3, the temperature from the screw of the twin-screw mixer to the five points of the nozzle is 120 ℃, 132 ℃, 148 ℃, 171 ℃ and 186 ℃, the screw discharge amount is 600 g/min, and the winding speed is 80-115 m/min.
4. The method for preparing the polyester filament with the antibacterial and stock solution coloring functions by double modification of maleic anhydride and polyquaternium according to claim 1, which is characterized in that: in the step S7, the temperatures from the screw to the nozzle at five points of the screw kneader were 115℃and 125℃and 157℃and 168℃and 185℃respectively, the screw discharge amount was 132 g/min, and the winding speed was 2800 m/min.
5. The method for preparing the polyester filament with the antibacterial and stock solution coloring functions by double modification of maleic anhydride and polyquaternium according to claim 1, which is characterized in that: the powdery dye or pigment is an organic disperse dye, a reactive dye or an inorganic ore pigment.
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