CN109280345B - Composite antibacterial polyester master batch and preparation method thereof - Google Patents
Composite antibacterial polyester master batch and preparation method thereof Download PDFInfo
- Publication number
- CN109280345B CN109280345B CN201811004112.9A CN201811004112A CN109280345B CN 109280345 B CN109280345 B CN 109280345B CN 201811004112 A CN201811004112 A CN 201811004112A CN 109280345 B CN109280345 B CN 109280345B
- Authority
- CN
- China
- Prior art keywords
- composite antibacterial
- master batch
- antibacterial polyester
- preparation
- polyester master
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (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)
- Processes Of Treating Macromolecular Substances (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a composite antibacterial polyester master batch and a preparation method thereof, which are characterized in that disodium ethylene diamine tetraacetate with metal ion decoction function is used as a decoction agent, different precipitation coefficients of copper ions, zinc ions and calcium ions with antibacterial function are utilized to achieve the purpose of gradual decoction and coating, so as to form a composite antibacterial agent with antibacterial function, a composite antibacterial polyester master batch primary product is prepared by a melt blending method, and finally the composite antibacterial polyester master batch is prepared by liquid phase tackifying, wherein the sum of mass fractions of copper ions and zinc ions with antibacterial function in the composite antibacterial polyester master batch is 10-15%, the molar ratio of the copper ions to the zinc ions is 1:1, the mass fraction of the composite antibacterial agent in the composite antibacterial polyester master batch is 10-20%, and the intrinsic viscosity of the composite antibacterial polyester master batch is 0.65-0.75 d L/g.
Description
Technical Field
The invention relates to the technical field of functional polyester, in particular to a composite antibacterial polyester master batch and a preparation method thereof.
Background
The polyester staple fiber has excellent softness, wear resistance and processability, is widely applied to the fields of clothing, home textiles and the like, and is an important raw material for high-end clothing and home decoration. With the acceptance of people on the ecological environment protection concept and the development of the related industry of the circular economy supported by a series of national emerging macro policies, the field of the regenerated polyester fiber will be further developed. The regenerated polyester staple fiber is produced with polyester fabric, waste polyester bottle flake, waste spinning filament, bubble material and pulp as material, and through crushing, washing, drying, melt spinning, winding, bundling, drafting, curling, loosening, heat setting and cutting. However, in the production process of the regenerated fiber, polyester or terylene waste is adopted as a raw material, so that the regenerated fiber has the characteristics of complex raw material source, high impurity content, low viscosity, low melting point and the like. If the direct spinning is only suitable for the production of regenerated common polyester staple fibers, the quality of the final product is relatively poor, and the application is greatly limited. Meanwhile, in the aspect of production of the differential functional regenerated polyester staple fiber, due to the addition of the functional master batch, the self dispersibility in the regenerated polyester melt is poor, so that the production of the regenerated polyester staple fiber with the functions of flame retardance, antibiosis, hydrophilicity and the like is difficult. Therefore, the waste polyester textiles are utilized to develop the high-quality regenerated short polyester fibers with the antibacterial function and the like, the physical indexes of the waste polyester textiles are required to be controlled, the viscosity difference is as small as possible, the impurity content is as small as possible, and the polyester foam materials can be stably and continuously prepared in the melt homogenization process. Meanwhile, the antibacterial inorganic powder is as follows: the materials such as nano zinc oxide, silver oxide, cuprous oxide and the like have high surface activity, and are used as catalyst components in the melt blending process to cause the degradation of polyester, particularly regenerated polyester with poor quality, so that components with high-temperature shielding performance need to be introduced, the oxidative catalysis of the inorganic antibacterial agent material on the degradation of the polyester under the high-temperature condition is reduced, the polyester is ensured to have excellent high-quality and stable viscosity, and the later spinning process is facilitated.
At present, according to the introduction mode of an antibacterial agent, the antibacterial modification method of polyester is mainly divided into methods such as copolycondensation, blending, composite spinning, graft copolymerization, after-finishing coating and the like. In particular to in-situ polymerization modification, the antibacterial agent is introduced into a polymerization system in the polymerization process, has the characteristics of good dispersibility, excellent antibacterial effect, good relative antibacterial property stability and the like, and is widely applied to the fields of plastics, fibers and the like. The current research mainly focuses on the preparation of the antibacterial agent and the efficient dispersion of the antibacterial agent in the polyester to achieve the purpose of efficient antibacterial. Gao mu et al prepared PET/ZnO nano composite material by in-situ polymerization method, and added into polymerization system after surface modification of inorganic powder, improved compatibility between matrix and inorganic powder, and discussed the influence of adding inorganic nano particles on PET performance. Research results show that the inorganic nanoparticles can improve the crystallization performance and thermal stability of PET, and the surface-treated inorganic nanoparticles are heterogeneous nucleating agents of PET crystallization. Liuwei et al have found that when the addition amount of the antibacterial master batch is 5wt%, the antibacterial property of the PET fiber is good, and the PET fiber has good mechanical properties. And the Lei Xiao Yun and the like research the spinning process for producing the antibacterial PET short fiber by mixing and spinning the inorganic silver antibacterial master batch and the PET slices. The nano-antibacterial PET fiber is prepared by mixing nano-antibacterial PET master batches and a self-made silver-loaded composite phosphate antibacterial agent with common PET slices respectively and then carrying out melt spinning, and the like, and meanwhile, the antibacterial property, infrared spectrogram, physical and mechanical properties and thermal properties of the modified fiber are researched. Liu Mei Na and the like add inorganic antibacterial agent titanium phosphate type silver-carrying into PET, obtain the antibacterial polyester fiber by a mixing method, and research the physical and chemical structure and antibacterial performance of the nano-silver modified antibacterial PET fiber.
The Chinese patent application for a preparation method (CN 201711192688.8) of copper-zinc composite antibacterial polyester fiber comprises the following steps: (1) preparing a copper-zinc oxide composite antibacterial agent; (2) preparing antibacterial modified polyethylene glycol terephthalate slices; (3) preparing the antibacterial modified polyethylene glycol terephthalate fiber. The copper-zinc composite antibacterial polyester fiber prepared by the invention has the bacteriostasis rates of 91.2% and 93.2% to escherichia coli and staphylococcus aureus respectively, and has good antibacterial effect. By introducing the composite antibacterial agent in the polymerization process, the problems of difficult control of subsequent polymerization and difficult fiber forming are inevitably caused.
The Chinese patent application discloses a preparation method (CN 201610183872.5) of an antibacterial and anti-radiation copper-modified polyester composite fiber, which comprises the steps of preparation of a polyester composite master batch, melt spinning, modification of the polyester composite fiber, preparation of the copper-modified polyester composite fiber and the like. According to the invention, the raw materials such as zinc undecylenate, nano titanium dioxide and loess stone are added into the polyester master batch, and the raw materials are compounded with each other, so that the mechanical property of the master batch is improved, the antibacterial property of the master batch is also enhanced, and meanwhile, after the polyester fiber is subjected to scientific and reasonable copper modification treatment, the antibacterial property of the polyester fiber is greatly improved, so that the prepared polyester composite fiber has the advantages of antibiosis, sterilization and lasting antibacterial effect, safety and harmlessness to human bodies, safety and environmental protection; the polyester composite fiber is also added with the raw materials such as nano boron nitride, barite and the like, so that the radiation resistance of the polyester composite fiber is greatly improved, the polyester composite fiber has a good shielding effect on various rays, and the shielding rate can reach over 80 percent.
The Chinese patent application discloses a preparation method (Z L201310478246.5) of an antibacterial polyester material, which comprises the specific steps of 1) preparing a dispersion system composed of nano cuprous oxide particles and polyhydric alcohol, 2) adding polybasic acid into the dispersion system prepared in the step 1) to prepare a polyester composite melt containing the nano cuprous oxide particles, and 3) extruding, bracing, water cooling and granulating the polyester composite melt containing the cuprous oxide particles prepared in the step 2) to prepare the antibacterial polyester material.
Disclosure of Invention
The composite antibacterial polyester master batch prepared by the method mainly has high content of a composite antibacterial agent, high molecular weight and high viscosity, has little influence on subsequent processing, particularly high-temperature spinning, and has wide application prospect in the aspect of processing of polyester fibers.
The purpose of the invention is realized by the following technical scheme:
a composite antibacterial polyester master batch is prepared by using disodium ethylene diamine tetraacetate with metal ion decoction function as chelating agent, obtaining composite antibacterial agent through successive decoction and precipitation of different metal ions with different precipitation coefficients such as copper ions and zinc ions with antibacterial function, realizing the decoction load of the metal ions with antibacterial function, realizing surface passivation protection of the chelating agent, using polyester oligomer as raw material and the composite antibacterial agent as modifier, and realizing effective addition of the composite antibacterial agent and increase of polyester molecular weight through further processing and adhesion increasing processes.
The composite antibacterial polyester masterbatch is characterized in that the sum of the mass fractions of copper ions and zinc ions in the composite antibacterial polyester masterbatch is 10-15%, the molar ratio of the copper ions to the zinc ions is 1:1, the mass fraction of a composite antibacterial agent in the composite antibacterial polyester masterbatch is 10-20%, and the intrinsic viscosity of the composite antibacterial polyester masterbatch is 0.65-0.75 d L/g.
The invention also provides a preparation method of the composite antibacterial polyester master batch, which comprises the following steps:
(1) preparation of composite antibacterial agent
Under the conditions of ultrasound and stirring, adding a calcium nitrate solution into an ethylene diamine tetraacetic acid disodium solution, then adjusting the pH of the system to be 9-10, keeping the complexing temperature to be 5-10 ℃, and performing first complexing for 10-25 min; then adjusting the pH value of the system to 4-6, the complexing temperature to 10-25 ℃, adding a zinc acetate solution, and carrying out secondary complexing for 15-25 min; then adjusting the pH value of the system to 7.5-8.0, the complexing temperature to 35-45 ℃, adding a copper acetate solution, and carrying out complexing for the third time, wherein the complexing time is 20-30 min; finally, adding ethylene glycol into the system to precipitate a complex, and drying the precipitate in vacuum for 48 hours to obtain the composite antibacterial agent;
in the step, the molar ratio of calcium nitrate to disodium ethylene diamine tetraacetate is 1: 2-1: 3, the molar ratio of zinc acetate to calcium nitrate is 1: 0.3-1: 0.5, the molar ratio of copper acetate to zinc acetate is 1:1, furthermore, the mass concentration of the disodium ethylene diamine tetraacetate solution is 5-10 g/L, the molar concentration of the calcium nitrate solution is 0.5 mol/L, the molar concentration of the zinc acetate solution is 0.5 mol/L, and the molar concentration of the copper acetate solution is 0.5 mol/L;
(2) preparation of composite antibacterial polyester master batch primary product
By adopting a melt blending method, polyester oligomer is used as a raw material, a composite antibacterial agent is used as a modifier, and extrusion granulation is carried out by a double-screw extruder to prepare a composite antibacterial polyester master batch primary product;
the weight average molecular weight of the polyester oligomer is 5000-8000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 10-20%; the melt blending process conditions are that the melting temperature is 200-260 ℃, and the screw shear rate is 103～104s-1；
(3) Preparation of composite antibacterial polyester master batch
The preparation method comprises the steps of adopting a multistage liquid phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, firstly using diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid phase tackifying under the normal pressure condition, and then carrying out second-step low-vacuum liquid phase tackifying and third-step high-temperature high-vacuum liquid phase tackifying to prepare the composite antibacterial polyester master batch.
The mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 25-1: 30;
the viscosity increasing temperature of the first step of liquid phase viscosity increasing is 180-195 ℃, and the viscosity increasing time is 5-10 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8-10% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl groups is 35-55 mol/t;
the viscosity increasing temperature of the second-step low vacuum liquid phase viscosity increasing is 240-250 ℃, the viscosity increasing time is 30-45 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the second-step low vacuum liquid phase viscosity increasing is 0.35-0.45 d L/g;
in the preparation process of the composite antibacterial polyester master batch, the third step of high-temperature high-vacuum liquid-phase tackifying has the tackifying temperature of 260-270 ℃ and the tackifying time of 45-60 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the third step of high-temperature high-vacuum liquid-phase tackifying is 0.65-0.75 d L/g.
Compared with the prior art, the invention has the following positive effects:
the preparation method of the composite antibacterial polyester master batch mainly takes the disodium ethylene diamine tetraacetate with metal ion decoction effect as a decoction agent, and achieves the purpose of gradual decoction and coating by utilizing different precipitation coefficients of copper, zinc and calcium ions with antibacterial effect, so as to form the composite antibacterial agent with antibacterial effect and avoid the catalytic degradation effect of high-activity metal ions on macromolecules such as polyester; meanwhile, through multiple liquid-phase tackifying effects and by utilizing the extraction effect of ethylene glycol, the disodium ethylene diamine tetraacetate is extracted by reaction, so that the molecular chain segment of the polyester is increased, and the degradation of the polyester molecular chain due to chain scission of the inorganic active antibacterial agents containing copper, zinc and the like caused by low molecular weight and less tackifying effect in the high-temperature condensation tackifying process is avoided, and the polyester molecular chain is difficult to use for fiber spinning; the invention further releases antibacterial active components by carrying out step-by-step decoction on materials with ion decoction function, so as to realize the in-situ copolymerization of the high-activity composite antibacterial agent in a high-temperature polyester reaction system and avoid the degradation of molecular chains in the polycondensation and tackifying process of polyester, and the composite antibacterial agent has high content of the composite antibacterial agent in the composite antibacterial polyester master batch, high molecular weight and high viscosity, has little influence on subsequent processing, especially has little influence on high-temperature spinning, can be used for preparing regenerated fine denier and superfine denier polyester staple fibers with high added value, and has wide application prospect in the fields of shoes, socks, clothes, home textiles and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a composite antimicrobial agent of the present invention;
FIG. 2 is a scanning electron microscope atlas of the cross section of the composite antibacterial polyester masterbatch of the invention;
FIG. 3a is a graph showing the antibacterial effect of Escherichia coli as a comparative conventional polyester powder;
FIG. 3b shows the antibacterial effect of E.coli of the composite antibacterial polyester master batch powder of the present invention;
FIG. 4a is a graph showing the antibacterial effect of Staphylococcus aureus as a comparative conventional polyester powder;
FIG. 4b shows the antibacterial effect of Staphylococcus aureus from the composite antibacterial polyester masterbatch powder of the present invention.
Detailed Description
A composite antibacterial polyester master batch is prepared by using disodium ethylene diamine tetraacetate with metal ion decoction effect as a chelating agent, performing successive decoction precipitation on copper ions, zinc ions and other different metal ions with different precipitation coefficients with antibacterial effect to obtain a composite antibacterial agent, and using a polyester oligomer as a raw material and the composite antibacterial agent as a modifier, wherein the sum of mass fractions of the copper ions and the zinc ions in the composite antibacterial polyester master batch is 10-15%, the molar ratio of the copper ions to the zinc ions is 1:1, the mass fraction of the composite antibacterial agent in the composite antibacterial polyester master batch is 10-20%, and the intrinsic viscosity of the composite antibacterial polyester master batch is 0.65-0.75 d L/g.
The preparation method of the composite antibacterial polyester master batch comprises the following specific steps:
(1) preparation of composite antibacterial agent
Under the conditions of ultrasonic and high-speed stirring, adding 0.5 mol/L of calcium nitrate solution into an ethylene diamine tetraacetic acid disodium solution with the mass concentration of 5-10 g/L, then adjusting the pH of the system to 9-10, keeping the complexing temperature to 5-10 ℃, and complexing for 10-25 min for first complexing, then adjusting the pH of the system to 4-6, the complexing temperature to 10-25 ℃, adding 0.5 mol/L of zinc acetate solution, performing second complexing, wherein the complexing time is 15-25 min, then adjusting the pH of the system to 7.5-8.0, the complexing temperature to 35-45 ℃, adding 0.5 mol/L of copper acetate solution, performing third complexing, wherein the complexing time is 20-30 min, finally adding ethylene glycol into the system, precipitating a complex, and performing vacuum drying on the precipitated complex for 48h to obtain a composite antibacterial agent;
wherein the molar ratio of the calcium nitrate to the ethylene diamine tetraacetic acid is 1: 2-1: 3; the molar ratio of the zinc acetate to the calcium nitrate is 1: 0.3-1: 0.5; the molar ratio of copper acetate to zinc acetate is 1: 1;
(2) preparation of composite antibacterial polyester master batch primary product
By adopting a melt blending method, polyester oligomer is used as a raw material, a composite antibacterial agent is used as a modifier, and extrusion granulation is carried out by a double-screw extruder to prepare a composite antibacterial polyester master batch primary product;
wherein the weight average molecular weight of the polyester oligomer is 5000-8000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 10-20%; the melt blending process conditions are that the melting temperature is 200-260 ℃, and the screw shear rate is 103～104s-1；
(3) Preparation of composite antibacterial polyester master batch
The preparation method comprises the following steps of (1) adopting a multistage liquid phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, firstly using diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid phase tackifying under a normal pressure condition, and then carrying out second-step low-vacuum liquid phase tackifying and third-step high-temperature high-vacuum liquid phase tackifying to prepare the composite antibacterial polyester master batch;
wherein the mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 25-1: 30;
the first step is that the viscosity increasing temperature of liquid phase viscosity increasing is 180-195 ℃, and the viscosity increasing time is 5-10 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8-10% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl groups is 35-55 mol/t;
the second step of low vacuum liquid phase tackifying, wherein the tackifying temperature is 240-250 ℃, the tackifying time is 30-45 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the second low vacuum liquid phase tackifying is 0.35-0.45 d L/g;
and thirdly, the tackifying temperature of the high-temperature high-vacuum liquid-phase tackifying is 260-270 ℃, the tackifying time is 45-60 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the third high-temperature high-vacuum liquid-phase tackifying is 0.65-0.75 d L/g.
The present invention is further illustrated in detail below with reference to specific examples.
Example 1
The sum of the mass fractions of copper and zinc ions with antibacterial effect in the composite antibacterial polyester master batch is 10%, and the molar ratio of the copper ions to the zinc ions is 1: 1.
The preparation method of the composite antibacterial polyester master batch comprises the following specific steps:
(1) preparation of composite antibacterial agent
Under the condition of ultrasonic high-speed stirring, adding 0.5 mol/L of calcium nitrate solution into an ethylene diamine tetraacetic acid disodium solution with the mass concentration of 5 g/L, then adjusting the pH of the system to be 9, keeping the complexing temperature to be 5 ℃, complexing for 10min for the first time, then adjusting the pH of the system to be 4, adjusting the complexing temperature to be 10 ℃, adding 0.5 mol/L of zinc acetate solution, performing the second complexing for 15min, adjusting the pH of the system to be 7.5, the complexing temperature to be 35 ℃, adding 0.5 mol/L of copper acetate solution, performing the third complexing for 20min, finally adding ethylene glycol into the system, precipitating the complex, and drying the precipitate in vacuum for 48h to obtain the composite antibacterial agent;
wherein the molar ratio of the calcium nitrate to the ethylene diamine tetraacetic acid is 1: 2; the molar ratio of the zinc acetate to the calcium nitrate is 1: 0.3; the molar ratio of copper acetate to zinc acetate is 1: 1;
(2) preparation of composite antibacterial polyester master batch primary product
By adopting a melt blending method, polyester oligomer is used as a raw material, a composite antibacterial agent is used as a modifier, and extrusion granulation is carried out by a double screw to prepare a primary product of the composite antibacterial polyester master batch;
wherein the polyester oligomer has a weight average molecular weight of 5000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 10 percent; the melt blending process conditions are that the melting temperature is 200-260 ℃, and the screw shear rate is 103s-1；
(3) Preparation of composite antibacterial polyester master batch
The preparation method comprises the following steps of (1) preparing a composite antibacterial polyester master batch by adopting a multistage liquid-phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, taking diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid-phase tackifying under a normal pressure condition, and then carrying out second-step low-vacuum liquid-phase tackifying and third-step high-temperature high-vacuum tackifying processes;
wherein the mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 25;
the first step of liquid phase tackifying process: the tackifying temperature is 180 ℃, and the tackifying time is 10 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl is 35 mol/t;
a second step of low vacuum liquid phase tackifying process, wherein the tackifying temperature is 2400 ℃, the tackifying time is 45min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the secondary liquid phase tackifying is 0.35d L/g;
and a third step of high-temperature high-vacuum tackifying, wherein the tackifying temperature is 260 ℃, the tackifying time is 60min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after third liquid phase tackifying is 0.65d L/g.
Example 2
The sum of the mass fractions of copper and zinc ions with antibacterial effect in the composite antibacterial polyester master batch is 15%, and the molar ratio of the copper ions to the zinc ions is 1: 1.
The preparation method of the composite antibacterial polyester master batch comprises the following specific steps:
(1) preparation of composite antibacterial agent
Under the condition of high-speed stirring of an ultrasonic belt, adding 0.5 mol/L of calcium nitrate solution into 10 g/L-mass-concentration disodium ethylene diamine tetraacetate solution, then adjusting the pH of the system to 10, keeping the complexing temperature at 10 ℃ and complexing time at 25min for carrying out first complexing, then adjusting the pH of the system to 6 and the complexing temperature at 25 ℃, adding 0.5 mol/L of zinc acetate solution, carrying out second complexing for 25min, then adjusting the pH of the system to 8.0 and the complexing temperature at 45 ℃, adding 0.5 mol/L of copper acetate solution, carrying out third complexing for 30min, finally adding ethylene glycol into the system to precipitate a complex, and drying the precipitate in vacuum for 48h to obtain a composite antibacterial agent;
wherein the molar ratio of the calcium nitrate to the ethylene diamine tetraacetic acid is 1: 3; the molar ratio of zinc acetate to calcium nitrate is 1: 0.5; the molar ratio of copper acetate to zinc acetate is 1: 1;
(2) preparation of composite antibacterial polyester master batch primary product
By adopting a melt blending method, polyester oligomer is used as a raw material, a composite antibacterial agent is used as a modifier, and extrusion granulation is carried out by a double screw to prepare a primary product of the composite antibacterial polyester master batch;
wherein the polyester oligomer has a weight average molecular weight of 8000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 20 percent; the melt blending process conditions are that the melting temperature is 260 ℃ and the screw shear rate is 104s-1；
(3) Preparation of composite antibacterial polyester master batch
The preparation method comprises the following steps of (1) preparing a composite antibacterial polyester master batch by adopting a multistage liquid-phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, taking diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid-phase tackifying under a normal pressure condition, and then carrying out second-step low-vacuum liquid-phase tackifying and third-step high-temperature high-vacuum tackifying processes;
wherein the mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 30;
the first step of liquid phase tackifying process: the tackifying temperature is 195 ℃ and the tackifying time is 5 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl is 55 mol/t;
the second step of low vacuum liquid phase tackifying process, wherein the tackifying temperature is 250 ℃, the tackifying time is 30min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the secondary liquid phase tackifying is 0.45d L/g;
and a third step of high-temperature high-vacuum tackifying, wherein the tackifying temperature is 270 ℃, the tackifying time is 45min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after third liquid phase tackifying is 0.75d L/g.
Example 3
The sum of the mass fractions of copper and zinc ions with antibacterial effect in the composite antibacterial polyester master batch is 12.5%, and the molar ratio of the copper ions to the zinc ions is 1: 1.
The preparation method of the composite antibacterial polyester master batch comprises the following specific steps:
(1) preparation of composite antibacterial agent
Under the condition of ultrasonic high-speed stirring, adding 0.5 mol/L of calcium nitrate solution into 7.5 g/L mass concentration disodium ethylene diamine tetraacetate solution, then adjusting the pH of the system to 9.5, keeping the complexing temperature to 5 ℃, complexing for 25min for the first time, then adjusting the complexing pH to 6, the complexing temperature to 10 ℃, adding 0.5 mol/L of zinc acetate solution, performing the second complexing for 25min, then adjusting the pH of the system to 7.5, the complexing temperature to 35 ℃, adding 0.5 mol/L of copper acetate solution, performing the third complexing for 30min, finally adding ethylene glycol into the system, precipitating the complex, and drying the precipitate in vacuum for 48h to obtain the composite antibacterial agent;
wherein the molar ratio of the calcium nitrate to the ethylene diamine tetraacetic acid is 1: 3; the molar ratio of zinc acetate to calcium nitrate is 1: 0.5; the molar ratio of copper acetate to zinc acetate was 1: 1.
(2) Preparation of composite antibacterial polyester master batch primary product
The method adopts a melt blending method, takes polyester oligomer as a raw material and a composite antibacterial agent as a modifier, and performs extrusion granulation by a double screw to prepare a primary product of the composite antibacterial polyester master batch.
Wherein the polyester oligomer has a weight average molecular weight of 6000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 15.5 percent; the melt blending process conditions are that the melting temperature is 260 ℃ and the screw shear rate is 104s-1；
(3) Preparation of composite antibacterial polyester master batch
The preparation method comprises the following steps of (1) preparing a composite antibacterial polyester master batch by adopting a multistage liquid-phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, taking diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid-phase tackifying under a normal pressure condition, and then carrying out second-step low-vacuum liquid-phase tackifying and third-step high-temperature high-vacuum tackifying processes;
wherein the mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 30;
the first step of liquid phase tackifying process: the tackifying temperature is 195 ℃ and the tackifying time is 8 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl is 39 mol/t;
the second step of low vacuum liquid phase tackifying process, wherein the tackifying temperature is 250 ℃, the tackifying time is 45min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after the secondary liquid phase tackifying is 0.375d L/g;
and a third step of high-temperature high-vacuum tackifying, wherein the tackifying temperature is 270 ℃, the tackifying time is 45min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch after third liquid phase tackifying is 0.75d L/g.
Fig. 1 is a scanning electron microscope atlas of the composite antibacterial agent, and after the disodium ethylenediamine tetraacetate is decocted, more decocted bodies are formed in the structure of the composite antibacterial agent, the particle size of the composite antibacterial agent is dispersed in powder, the decocted structure is utilized to form a tree shape, and decocted ion particles formed on the tip structure of the tree shape are fine.
Fig. 2 is a scanning electron microscope atlas of the cross section of the composite antibacterial polyester master batch, in the atlas, through the boiling of chelating agent and the acid regulation and control in the polymerization and adhesion process, the antibacterial activity in the structure is released, and the boiling structure of the disodium edetate is removed, so that the dendritic structure is damaged, and meanwhile, the active ions at the tip are released to form the composite antibacterial agent with the antibacterial effect, so that the composite antibacterial agent is uniformly dispersed in the polyester master batch.
FIGS. 3a and 3b are the antibacterial effect of Escherichia coli as a comparative conventional polyester powder and the antibacterial effect of Escherichia coli as a composite antibacterial polyester master powder, respectively; in the control sample, after 7 days of bacterial culture, fine microbial colonies are uniformly distributed in the culture agar, and no microbial colonies exist in the composite antibacterial polyester mother particle powder, so that the composite antibacterial polyester mother particle powder has a good antibacterial effect on escherichia coli.
Fig. 4a and 4b correspond to the antibacterial effect of staphylococcus aureus of polyester powder and the antibacterial effect of composite antibacterial polyester mother particle powder as a control sample, respectively, in fig. 4a, the staphylococcus aureus grows well and is distributed to diffuse from the middle to the outside because of no composite antibacterial agent, and in fig. 4b, the composite antibacterial polyester mother particle powder containing the composite antibacterial agent is added, so that the bacteria in the culture medium close to the composite antibacterial agent are less, the bacteria in the whole culture medium are greatly reduced, and the antibacterial effect of the composite antibacterial agent on staphylococcus aureus is good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (10)
1. A preparation method of composite antibacterial polyester master batch is characterized by comprising the following steps: the preparation method comprises the steps of taking disodium ethylene diamine tetraacetate as a chelating agent, obtaining a composite antibacterial agent by successively decocting and precipitating different metal ions including copper ions and zinc ions, and then taking polyester oligomer as a raw material and the composite antibacterial agent as a modifier to prepare a composite antibacterial polyester master batch; the sum of the mass fractions of copper ions and zinc ions in the composite antibacterial polyester master batch is 10-15%, and the molar ratio of the copper ions to the zinc ions is 1: 1; the mass fraction of the composite antibacterial agent in the composite antibacterial polyester master batch is 10-20%;
the method specifically comprises the following steps:
(1) preparation of composite antibacterial agent
Under the conditions of ultrasound and stirring, adding a calcium nitrate solution into an ethylene diamine tetraacetic acid disodium solution, then adjusting the pH of the system to be 9-10, keeping the complexing temperature to be 5-10 ℃, and performing first complexing for 10-25 min; then adjusting the pH value of the system to 4-6, the complexing temperature to 10-25 ℃, adding a zinc acetate solution, and carrying out secondary complexing for 15-25 min; then adjusting the pH value of the system to 7.5-8.0, the complexing temperature to 35-45 ℃, adding a copper acetate solution, and carrying out complexing for the third time, wherein the complexing time is 20-30 min; finally, adding ethylene glycol into the system to precipitate the complex, and drying the precipitate in vacuum to obtain the composite antibacterial agent;
(2) preparation of composite antibacterial polyester master batch primary product
By adopting a melt blending method, polyester oligomer is used as a raw material, a composite antibacterial agent is used as a modifier, and extrusion granulation is carried out by a double-screw extruder to prepare a composite antibacterial polyester master batch primary product;
(3) preparation of composite antibacterial polyester master batch
The preparation method comprises the steps of adopting a multistage liquid phase tackifying process, taking a primary product of the composite antibacterial polyester master batch as a raw material, firstly using diethylene glycol calcium as a catalyst and a displacer, carrying out low-temperature hydrolysis catalysis, carrying out first-step liquid phase tackifying under the normal pressure condition, and then carrying out second-step low-vacuum liquid phase tackifying and third-step high-temperature high-vacuum liquid phase tackifying to prepare the composite antibacterial polyester master batch.
2. The preparation method of the composite antibacterial polyester master batch according to claim 1, characterized by comprising the following steps: in the preparation process of the composite antibacterial agent, the molar ratio of the calcium nitrate to the disodium ethylene diamine tetraacetate is 1: 2-1: 3; the molar ratio of the zinc acetate to the calcium nitrate is 1: 0.3-1: 0.5; the molar ratio of the copper acetate to the zinc acetate is 1: 1.
3. The preparation method of the composite antibacterial polyester masterbatch according to claim 2, wherein in the preparation process of the composite antibacterial agent, the mass concentration of the disodium ethylene diamine tetraacetate solution is 5-10 g/L, the molar concentration of the calcium nitrate solution is 0.5 mol/L, the molar concentration of the zinc acetate solution is 0.5 mol/L, and the molar concentration of the copper acetate solution is 0.5 mol/L.
4. The preparation method of the composite antibacterial polyester master batch according to claim 1, characterized by comprising the following steps: the preparation process of the composite antibacterial polyester master batch primary productWherein the weight average molecular weight of the polyester oligomer is 5000-8000; the mass fraction of the composite antibacterial agent in the primary product of the composite antibacterial polyester master batch is 10-20%; the melt blending process conditions are that the melting temperature is 200-260 ℃, and the screw shear rate is 103～104s-1。
5. The preparation method of the composite antibacterial polyester master batch according to claim 1, characterized by comprising the following steps: in the preparation process of the composite antibacterial polyester master batch, the mass ratio of the diethylene glycol calcium to the primary product of the composite antibacterial polyester master batch is 1: 25-1: 30.
6. The preparation method of the composite antibacterial polyester master batch according to claim 1, characterized by comprising the following steps: in the preparation process of the composite antibacterial polyester master batch, the viscosity increasing temperature of the liquid phase viscosity increasing in the first step is 180-195 ℃, and the viscosity increasing time is 5-10 min; the intrinsic viscosity of the primary product of the composite antibacterial polyester master batch is reduced by 8-10% after the primary product is subjected to primary liquid phase tackifying, and the content of terminal carboxyl groups is 35-55 mol/t.
7. The preparation method of the composite antibacterial polyester masterbatch according to claim 1, wherein in the preparation process of the composite antibacterial polyester masterbatch, the viscosity increasing temperature of the second-step low-vacuum liquid-phase viscosity increasing is 240-250 ℃, the viscosity increasing time is 30-45 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester masterbatch after the second-step low-vacuum liquid-phase viscosity increasing is 0.35-0.45 d L/g.
8. The preparation method of the composite antibacterial polyester masterbatch according to claim 1, wherein in the preparation process of the composite antibacterial polyester masterbatch, the third high-temperature high-vacuum liquid-phase tackifying temperature is 260-270 ℃, the tackifying time is 45-60 min, and the intrinsic viscosity of the primary product of the composite antibacterial polyester masterbatch after the third high-temperature high-vacuum liquid-phase tackifying is 0.65-0.75 d L/g.
9. The composite antibacterial polyester master batch obtained by the preparation method according to any one of claims 1 to 8.
10. The composite antibacterial polyester masterbatch according to claim 9, wherein the intrinsic viscosity of the composite antibacterial polyester masterbatch is 0.65-0.75 d L/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811004112.9A CN109280345B (en) | 2018-08-30 | 2018-08-30 | Composite antibacterial polyester master batch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811004112.9A CN109280345B (en) | 2018-08-30 | 2018-08-30 | Composite antibacterial polyester master batch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109280345A CN109280345A (en) | 2019-01-29 |
| CN109280345B true CN109280345B (en) | 2020-07-24 |
Family
ID=65183180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811004112.9A Active CN109280345B (en) | 2018-08-30 | 2018-08-30 | Composite antibacterial polyester master batch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109280345B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110528106B (en) * | 2019-06-03 | 2020-11-24 | 东华大学 | Functional industrial yarn and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO130618A0 (en) * | 2014-06-12 | 2015-10-30 | Universitatea Politehnica Din Bucureşti | Process and catalyst for preparing biodiesel fuel |
| CN105671678A (en) * | 2016-03-27 | 2016-06-15 | 吴正锋 | Preparation method of antibacterial anti-radiation copper-modified polyester composite fiber |
| CN107083579A (en) * | 2017-06-07 | 2017-08-22 | 广州市中诚新型材料科技有限公司 | Anion, far infrared, antibiosis anti-acarien composite polyester fiber and its manufacture method |
-
2018
- 2018-08-30 CN CN201811004112.9A patent/CN109280345B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO130618A0 (en) * | 2014-06-12 | 2015-10-30 | Universitatea Politehnica Din Bucureşti | Process and catalyst for preparing biodiesel fuel |
| CN105671678A (en) * | 2016-03-27 | 2016-06-15 | 吴正锋 | Preparation method of antibacterial anti-radiation copper-modified polyester composite fiber |
| CN107083579A (en) * | 2017-06-07 | 2017-08-22 | 广州市中诚新型材料科技有限公司 | Anion, far infrared, antibiosis anti-acarien composite polyester fiber and its manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109280345A (en) | 2019-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109267168B (en) | Composite antibacterial polyester staple fiber and preparation method thereof | |
| CN107287682B (en) | Graphene-containing stone needle composite fiber and preparation method and application thereof | |
| CN100513655C (en) | Antibiotic ultraviolet-resistant composite function health fiber | |
| CN106977751B (en) | A kind of composite antibacterial deodorization functions master batch, the preparation method of fiber | |
| CN111548607B (en) | Preparation method of antibacterial color master batch and stock solution colored PET antibacterial functional fiber | |
| CN102719929B (en) | Method for preparing functional polyamide fiber | |
| CN116288768B (en) | Far infrared anion antibacterial anti-mite health care multifunctional fiber and preparation and application thereof | |
| CN112522802B (en) | Anti-ultraviolet antibacterial polypropylene filament and preparation method thereof | |
| CN109280345B (en) | Composite antibacterial polyester master batch and preparation method thereof | |
| CN111019288A (en) | Preparation method of ABS (acrylonitrile-butadiene-styrene) composite plastic product capable of reducing loss of plant extract | |
| CN112663167A (en) | Flame-retardant polyester fiber and preparation method thereof | |
| CN110358189B (en) | Non-woven fabric soft master batch and preparation method thereof | |
| CN112812521A (en) | PETG (polyethylene terephthalate glycol) antibacterial composite membrane and preparation method thereof | |
| CN110144650B (en) | Multifunctional pearl polylactic acid blended yarn and preparation method thereof | |
| Jin et al. | Preparation of Nano Cu-ZnO/PET fiber for antibacterial application | |
| CN1552765A (en) | Method for preparing uvioresistant polyester by nanometer titania generated in situ | |
| CN111155199A (en) | Preparation method of graphene composite fiber | |
| CN104805521B (en) | Preparation method of polyester fiber with antibacterial function | |
| CN115433410B (en) | Antibacterial polypropylene material and preparation method thereof | |
| CN114921868B (en) | Preparation method of nano biochar modified melt direct-spun superfine denier polyester fiber | |
| CN114276527B (en) | Polyester, antibacterial polyester fiber and preparation method thereof | |
| CN112143025A (en) | Compound antibacterial agent and preparation method and application thereof | |
| CN210048894U (en) | Antibacterial and deodorant polyester fiber | |
| Chung et al. | Preparation of hydroxyapatite/poly (vinyl alcohol) composite fibers by wet spinning and their characterization | |
| KR100836604B1 (en) | Plastic master batch and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |