CN109280345A - A kind of composite antibacterial polyester master particle and preparation method thereof - Google Patents
A kind of composite antibacterial polyester master particle and preparation method thereof Download PDFInfo
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- CN109280345A CN109280345A CN201811004112.9A CN201811004112A CN109280345A CN 109280345 A CN109280345 A CN 109280345A CN 201811004112 A CN201811004112 A CN 201811004112A CN 109280345 A CN109280345 A CN 109280345A
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- 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
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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
- 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
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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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/098—Metal salts of carboxylic acids
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- 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
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Abstract
The invention discloses a kind of composite antibacterial polyester master particles and preparation method thereof, its main feature is that using with metal ion boil together effect disodium ethylene diamine tetraacetate as chelating agent, using with antibacterial action copper, zinc, calcium ion different factors in precipitation, achieve the purpose that the cladding that gradually boils together, forms the complex antimicrobials with antibacterial action；Composite antibacterial polyester master particle head product is prepared by the method for melt blending again, composite antibacterial polyester master particle is most prepared after liquid phase increasing stick afterwards；The sum of mass fraction of copper and zinc ion content in composite antibacterial polyester master particle with antibacterial action is 10~15%, and the molar ratio of copper ion and zinc ion is 1:1；The mass fraction of complex antimicrobials is 10~20% in composite antibacterial polyester master particle；The inherent viscosity of composite antibacterial polyester master particle is 0.65~0.75dL/g.Composite antibacterial polyester master particle viscosity of the invention is high, and composite antibacterial agent content is big, influences less, to have in terms of the processing of polyester fiber and be widely applied on following process especially high temperature spinning.
Description
Technical field
The present invention relates to functional polyester technical fields, and in particular to a kind of composite antibacterial polyester master particle and preparation method thereof.
Background technique
Polyester staple fiber has excellent soft, wear-resisting, processability, is widely used in clothes, the fields such as home textile,
It is the important source material of high-end clothes, home decoration.And the approval with people to ecological, environmental protective theory, and national one put into effect
Serial macro policy supports the development of circular economy related industry, and Regenerated Polyester Fibres field will further be developed.
The short fibre of recycled polyester refers to that using terylene cloth, waste polyester bottle chip, spinning waste silk, foam material, lumps be raw material, and raw material is through powder
After broken, cleaning, drying, then melt-spinning technology is carried out, then shape after rolled, boundling, drawing-off, curling, relaxation heat setting, cutting
At the polyester staple fiber of different length.But due to being raw material using polyester or terylene waste material in regenerated fiber production process,
There is raw material sources it is complicated, impurity content is high, viscosity is low, fusing point is low the features such as.If direct fabrics are only applicable to regenerate general
The production of logical polyester staple fiber, and final product quality is relatively poor, purposes is greatly limited.Simultaneously differential
Functional regeneration polyester staple fiber production aspect, due to the addition of functional agglomerate, bad dispersibility in recycled polyester melt itself, from
And cause the production of fire-retardant, antibacterial and the regenerative polyester staple fiber of functions such as hydrophilic difficult.Therefore Waste Polyester textile is utilized,
The regeneration short polyester fiber for developing the functions such as the antibacterial of high-quality is needed to the physical index progress with Waste Polyester textile processing
Control, the as small as possible and impurity content of the differences in viscosity opposite sex are few as far as possible, it is ensured that polyester foam material homogenizes energy in preparation process in melt
It is enough stable and continuous.Simultaneously because anti-microbial type inorganic particle is such as: nano zine oxide, silver oxide and cuprous oxide material, tool
There is high surface-active, during melt blending, as catalyst component, causes the regeneration of polyester especially inferior quality poly-
The degradation of ester, it is therefore desirable to introduce the component with high-temperature shielding performance, reduce inorganic antibacterial agent material under the high temperature conditions
The degradation of oxidation catalysis polyester guarantees that polyester has excellent high-quality, stable viscosity, conducive to the spinning process in later period.
Polyester is antibacterial modified at present, and according to the incorporation way of antibacterial agent, the antibacterial modified method of polyester is broadly divided into altogether
The methods of polycondensation, blending, composite spinning, graft copolymerization, final finishing coating.Especially in-situ polymerization is modified, utilizes antibacterial agent
It is introduced into polymerization system in the course of the polymerization process, has good dispersion, antibacterial effect excellent, and opposite anti-microbial property stability is good
The features such as, it is widely used in fields such as plastics, fibers.Current research is concentrated mainly on preparation and the antibacterial agent of antibacterial agent
High efficiency dispersion in the polyester achievees the purpose that high-efficiency antimicrobial.Gao Wei et al. prepares PET/ZnO nanometers again by situ aggregation method
Condensation material is improved between matrix and inorganic particle by being added in polymerization system after being surface modified to inorganic particle
Compatibility, and inquired into and influence of the inorganic nano-particle to PET performance be added.Result of study shows that inorganic nano-particle can be with
Improve the crystal property and thermal stability of PET, the inorganic nano-particle of surface treatment is the heterogeneous nucleation agent of PET crystallization.Liu Wei
When et al. prepare antibacterial matrices by the way that nanometer silver-series antibacterial agent is added in PET is sliced, it is anti-to be prepared for nanometer by melt spinning
Bacterium deodorization PET fiber, and the mechanical property and anti-microbial property of fiber are studied, as a result, it has been found that, when addition antibacterial matrices
When additive amount is 5wt%, the antibiotic property of PET fiber is preferable, and has good mechanical property.Lei Xiaoyun etc. has studied using inorganic
The spinning technique of silver system antibacterial matrices and PET slice blend spinning production antibacterial PET staple fiber.Zhu's equal utilization nano-antibacterial
PET master batch and the silver-colored composite phosphate antibacterial agent of homemade load carry out melt spinning after mixing respectively with common PET slice, and preparation is seen
Nano-antibacterial PET fiber, while having studied bacteriostasis property, infrared spectrum, physical mechanical property and the hot property of modified fibre.Liu
Inorganic antiseptic titanium phosphate salt form is added in PET and carries silver by Mei Na etc., obtains antibacterial polyester fibre by mixing method, and have studied
The physicochemical structure and anti-microbial property of the modified antibacterial PET fiber of nano silver.
A kind of preparation method (CN 201711192688.8) of copper zinc composite antibacterial polyester fiber of Chinese patent application, packet
Include following steps: (1) preparation of copper-zine oxide complex antimicrobials；(2) antibacterial modified polyethylene terephthalate slice
Preparation；(3) preparation of antibacterial modified pet fiber.Copper zinc composite antibacterial polyester made of the invention is fine
Dimension is respectively 91.2% and 93.2% to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, has good antibacterial effect.
By introducing complex antimicrobials in the course of the polymerization process, but it is big inevitably to will lead to subsequent polymerization control difficulty, fiberizing
Difficult problem.
A kind of preparation method (the CN of the anti-radiation copper modified polyester complex fiber of antibacterial of Chinese patent application
201610183872.5) comprising the preparation of polyester composite master batch, melt spinning, the modification of polyester complex fiber, copper are modified poly-
The preparation of ester composite fibre and etc..The invention is added to zinc undecylenate, nanometer titanium dioxide, loess stone etc. in polyester master particle
Raw material, above-mentioned raw materials are mutually compound, not only increase the mechanical property of master batch, also enhance the anti-microbial property of master batch, gather simultaneously
After scientific and reasonable copper modification, the anti-microbial property of polyester fiber greatly improves ester fiber, makes the compound fibre of polyester obtained
Antibacterial is tieed up, sterilization, fungistatic effect is lasting, safe to the human body harmless, safety and environmental protection；It also added in the invention polyester complex fiber
The raw materials such as nm-class boron nitride, barite, the shielding property for substantially increasing polyester complex fiber is good, to various rays have compared with
Good shield effectiveness, shielding rate can reach 80% or more.
A kind of preparation method of antibacterial polyester material (ZL 201310478246.5) of Chinese patent application, specific steps packet
It includes: 1) preparing the dispersion of nano cuprous oxide particle and polyalcohol composition；2) dispersion prepared into step 1)
The polyester compounding flux of the particle containing nano cuprous oxide is made in middle addition polyacid；It 3) will be obtained sub- containing oxidation in step 2
Antibacterial polyester material is made through extrusion, tie rod, water cooling, pelletizing in the polyester compounding flux of copper particle；Antibacterial made from the invention
Polyester material has the advantages that antibacterial effect is good, lasting, stable.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of composite antibacterial polyester master particle and its preparation sides
Method, composite antibacterial agent content is big in the composite antibacterial polyester master particle of main this method preparation, and the big viscosity of molecular weight is high, to subsequent plus
Work especially high temperature spinning influences less, have wide application prospect in terms of the processing of polyester fiber.
The purpose of the present invention is achieved through the following technical solutions:
A kind of composite antibacterial polyester master particle is to utilize the disodium ethylene diamine tetraacetate that there is metal ion to boil together effect to chelate
Agent, by having gradually enduring for the different metal ions of different factors in precipitation to copper ion, zinc ion etc. with antibacterial action
It closes precipitating and obtains complex antimicrobials, that is, realize the load that boils together of the metal ion of antibacterial action, while table is realized to chelating agent
Face passivation protection, then by raw material, complex antimicrobials of polyester oligomer be modifying agent, it is further processed and increasing stick process is real
The effective addition and the growth of molecular weight of polyesters of existing complex antimicrobials obtain composite antibacterial polyester master particle.
In the composite antibacterial polyester master particle the sum of mass fraction of copper ion and zinc ion be 10~15%, and copper from
The molar ratio of son and zinc ion is 1:1；In the composite antibacterial polyester master particle mass fraction of complex antimicrobials be 10~
20%；The inherent viscosity of the composite antibacterial polyester master particle is 0.65~0.75dL/g.
It is specific as follows the present invention also provides the preparation method of the composite antibacterial polyester master particle:
(1) preparation of complex antimicrobials
Under conditions of ultrasound and stirring, calcium nitrate solution is added into disodium ethylene diamine tetra-acetic acid solution, then regulation system
PH is 9~10, and keeping complexation temperature is 5~10 DEG C, and complexation time is that 10~25min carries out first time complexing；Then it adjusts again
System pH is 4~6, and complexation temperature is 10~25 DEG C, and acetic acid zinc solution is added, and carries out second and is complexed, complexation time is 15~
25min；Regulation system pH is 7.5~8.0 again, and 35~45 DEG C of complexation temperature, copper acetate solution is added, carries out third time complexing,
Complexation time is 20~30min；Ethylene glycol is finally added into system, complex compound sediment is precipitated, Precipitation object vacuum is dry
Complex antimicrobials are obtained after dry 48h；
In the step, the molar ratio of the calcium nitrate and disodium ethylene diamine tetraacetate is 1:2~1:3；The zinc acetate with
The molar ratio of calcium nitrate is 1:0.3~1:0.5；The molar ratio of the copper acetate and zinc acetate is 1:1.Further, described
The mass concentration of disodium ethylene diamine tetra-acetic acid solution is 5~10g/L, and the molar concentration of the calcium nitrate solution is 0.5mol/
L, the molar concentration of the acetic acid zinc solution are 0.5mol/L, and the molar concentration of the copper acetate solution is 0.5mol/L；
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, through double screw extruder into
Composite antibacterial polyester master particle head product is prepared in row extruding pelletization；
The weight average molecular weight of the polyester oligomer is 5000~8000；The complex antimicrobials are female in composite antibacterial polyester
Mass fraction in grain head product is 10~20%；The melt blending process conditions are that melting temperature is 200~260 DEG C, spiral shell
Bar shear rate is 103~104s-1；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum liquid phase increasing stick are walked, composite antibacterial polyester master particle is prepared.
The mass ratio of the diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:25~1:30；
The increasing stick temperature of the first step liquid phase increasing stick is 180~195 DEG C, and the increasing stick time is 5~10min；Described is compound
Antibacterial polyester masterbatches head product after first time liquid phase increasing stick inherent viscosity decline 8~10%, and content of carboxyl end group be 35~
55mol/t；
The increasing stick temperature of the second step low vacuum liquid phase increasing stick is 240~250 DEG C, and the increasing stick time is 30~45min；It is described
Inherent viscosity of the composite antibacterial polyester master particle head product after second of low vacuum liquid phase increasing stick be 0.35~0.45dL/g；
In the preparation process of the composite antibacterial polyester master particle, the increasing stick temperature of the third step high temperature high vacuum liquid phase increasing stick
Degree is 260~270 DEG C, and the increasing stick time is 45~60min；The composite antibacterial polyester master particle head product is high through third time high temperature
Inherent viscosity after vacuum liquid phase increasing stick is 0.65~0.75dL/g.
Compared with prior art, the positive effect of the present invention is:
The preparation method of composite antibacterial polyester master particle of the invention, mainly to boil together the ethylenediamine tetraacetic of effect with metal ion
Acetic acid disodium be chelating agent, using with antibacterial action copper, zinc, calcium ion different factors in precipitation, reach the packet that gradually boils together
The purpose covered forms the complex antimicrobials with antibacterial action, avoids that high activity metal ion pair polyester etc. is high molecular to urge
Change degradation；It is acted on, is acted on using the extraction of ethylene glycol, disodium ethylene diamine tetraacetate by multiple liquid phase increasing stick simultaneously
Reaction is extracted, conducive to the growth of polyester molecule segment, so as to avoid since inorganic cupric, zinc isoreactivity antibacterial agent are in high temperature
It is condensed during increasing stick because molecular weight is lower, increasing stick effect is few, leads to the chain rupture of polyester molecule chain and degrades, it is difficult to spin for fiber
Silk；The present invention reaches therefore by carrying out substep with the boil together material of effect of ion and boil together and meets the reduction of antibacterial agent activity,
Conducive to pyrocondensation reaction, while the gradually release action of ethylene glycol and chelating agent under different acid conditions is utilized, reached
To the further release of antibacterial active constituents, to realize the complex antimicrobials in-situ copolymerization of high activity in high-temperature polyester reactant
In system, the degradation of strand during polycondensation of polyester increasing stick is avoided, therefore compound in composite antibacterial polyester master particle of the invention
Antimicrobial levels are big, and the big viscosity of molecular weight is high, influence less on following process, and especially high temperature spinning influences few, can be used for making
The standby regeneration fine-denier with high added value, super fine denier polyester staple fiber have wide in fields such as footgear, clothes and home textiles
Application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope map of complex antimicrobials of the present invention；
Fig. 2 is the scanning electron microscope map in composite antibacterial polyester master particle of the present invention section；
Fig. 3 a is the antibacterial effect of the Escherichia coli of the normal polyester powder as control sample；
Fig. 3 b is the antibacterial effect of the Escherichia coli of composite antibacterial polyester master particle powder of the present invention；
Fig. 4 a is the antibacterial effect of the staphylococcus glucose coccus of the normal polyester powder as control sample；
Fig. 4 b is the antibacterial effect of the staphylococcus glucose coccus of composite antibacterial polyester master particle powder of the present invention.
Specific embodiment
A kind of composite antibacterial polyester master particle, be using with metal ion boil together effect disodium ethylene diamine tetraacetate be chela
Mixture, by the way that there are the different metal ions of different factors in precipitation gradually to copper ion, zinc ion etc. with antibacterial action
The precipitating that boils together obtains complex antimicrobials, then by raw material, complex antimicrobials of polyester oligomer is modifying agent, is prepared compound anti-
Bacterium polyester master particle.The sum of mass fraction of copper ion and zinc ion is 10~15% in the composite antibacterial polyester master particle, and copper
The molar ratio of ion and zinc ion is 1:1；In the composite antibacterial polyester master particle mass fraction of complex antimicrobials be 10~
20%；The inherent viscosity of the composite antibacterial polyester master particle is 0.65~0.75dL/g.
The preparation method of the composite antibacterial polyester master particle, specific as follows:
(1) preparation of complex antimicrobials
Under conditions of ultrasound and high-speed stirred, it is added into the disodium ethylene diamine tetra-acetic acid solution that mass concentration is 5~10g/L
The calcium nitrate solution of 0.5mol/L, then regulation system pH is 9~10, and keeping complexation temperature is 5~10 DEG C, complexation time 10
~25min carries out first time complexing；Then regulation system pH is 4~6 again, and complexation temperature is 10~25 DEG C, and 0.5mol/L is added
Acetic acid zinc solution, carry out second and be complexed, complexation time is 15~25min；Regulation system pH is 7.5~8.0 again, complexing temperature
The copper acetate solution of 0.5mol/L is added in 35~45 DEG C of degree, carries out third time complexing, and complexation time is 20~30min；Finally to
Ethylene glycol is added in system, complex compound sediment is precipitated, obtains complex antimicrobials after Precipitation object vacuum drying 48h；
Wherein, the molar ratio of calcium nitrate and disodium ethylene diamine tetraacetate is 1:2~1:3；The molar ratio of zinc acetate and calcium nitrate is
1:0.3~1:0.5；The molar ratio of copper acetate and zinc acetate is 1:1；
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, through double screw extruder into
Composite antibacterial polyester master particle head product is prepared in row extruding pelletization；
Wherein, the weight average molecular weight of polyester oligomer is 5000~8000；Complex antimicrobials are in composite antibacterial polyester master particle primiparity
Mass fraction in object is 10~20%；Melt blending process conditions are that melting temperature is 200~260 DEG C, and screw rod shearing rate is
103~104s-1；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum liquid phase increasing stick are walked, composite antibacterial polyester master particle is prepared；
Wherein, the mass ratio of diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:25~1:30；
The increasing stick temperature of first step liquid phase increasing stick is 180~195 DEG C, and the increasing stick time is 5~10min；The composite antibacterial is poly-
Inherent viscosity decline 8~10% of the ester master batch head product after first time liquid phase increasing stick, and content of carboxyl end group is 35~55mol/t；
The increasing stick temperature of second step low vacuum liquid phase increasing stick is 240~250 DEG C, and the increasing stick time is 30~45min；Described is compound
Inherent viscosity of the antibacterial polyester masterbatches head product after second of low vacuum liquid phase increasing stick is 0.35~0.45dL/g；
The increasing stick temperature of third step high temperature high vacuum liquid phase increasing stick is 260~270 DEG C, and the increasing stick time is 45~60min；Described
Inherent viscosity of the composite antibacterial polyester master particle head product after third time high temperature high vacuum liquid phase increasing stick is 0.65~0.75dL/g.
The present invention is illustrated in further details below in conjunction with specific embodiment.
Embodiment 1
A kind of the sum of mass fraction of copper and zinc ion content in composite antibacterial polyester master particle with antibacterial action is 10%, and
The molar ratio of copper ion and zinc ion is 1:1.
The preparation method of above-mentioned composite antibacterial polyester master particle, the specific steps are that:
(1) preparation of complex antimicrobials
Under conditions of ultrasound band high-speed stirred, it is added into the disodium ethylene diamine tetra-acetic acid solution that mass concentration is 5g/L
The calcium nitrate solution of 0.5mol/L, then regulation system pH is 9, and keeping complexation temperature is 5 DEG C, and complexation time is 10min progress
It is complexed for the first time；Then regulation system pH is 4 again, and complexation temperature is 10 DEG C, is added the acetic acid zinc solution of 0.5mol/L, carries out the
Secondary complexing, complexation time 15min；Regulation system pH is 7.5 again, and 35 DEG C of complexation temperature, the copper acetate of 0.5mol/L is added
Solution carries out third time complexing, complexation time 20min；Ethylene glycol is finally added into system, complex compound sediment is precipitated,
Precipitation object obtains complex antimicrobials after using vacuum drying 48h；
Wherein, the molar ratio of calcium nitrate and disodium ethylene diamine tetraacetate is 1:2；The molar ratio of zinc acetate and calcium nitrate is 1:0.3；
The molar ratio of copper acetate and zinc acetate is 1:1；
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, are squeezed out through twin-screw
It is granulated, composite antibacterial polyester master particle head product is prepared；
Wherein, the weight average molecular weight of polyester oligomer is 5000；Complex antimicrobials are in composite antibacterial polyester master particle head product
Mass fraction is 10%；The melt blending process conditions are that melting temperature is 200~260 DEG C, and screw rod shearing rate is 103s-1；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum increasing stick technique are walked, composite antibacterial polyester master particle is prepared；
Wherein, the mass ratio of diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:25；
First step liquid phase increasing stick technique: increasing stick temperature is 180 DEG C, and the increasing stick time is 10min；Composite antibacterial polyester master particle head product
Inherent viscosity decline 8% after first time liquid phase increasing stick, and content of carboxyl end group is 35mol/t；
Second step low vacuum liquid phase increasing stick technique: increasing stick temperature is 2400 DEG C, and the increasing stick time is 45min；Composite antibacterial polyester is female
Inherent viscosity of the grain head product after second of liquid phase increasing stick is 0.35dL/g；
Third step high temperature high vacuum increasing stick technique: increasing stick temperature is 260 DEG C, and the increasing stick time is 60min；Composite antibacterial polyester master particle
Inherent viscosity of the head product after third time liquid phase increasing stick is 0.65dL/g.
Embodiment 2
A kind of the sum of mass fraction of copper and zinc ion content in composite antibacterial polyester master particle with antibacterial action is 15%, and
The molar ratio of copper ion and zinc ion is 1:1.
The preparation method of above-mentioned composite antibacterial polyester master particle, the specific steps are that:
(1) preparation of complex antimicrobials
Under conditions of ultrasound band high-speed stirred, it is added into the disodium ethylene diamine tetra-acetic acid solution that mass concentration is 10g/L
The calcium nitrate solution of 0.5mol/L, then regulation system pH be 10, keep complexation temperature be 10 DEG C, complexation time be 25min into
Row is complexed for the first time；Then regulation system pH is 6 again, and complexation temperature is 25 DEG C, and the acetic acid zinc solution of 0.5mol/L is added, and is carried out
Second of complexing, complexation time 25min；Regulation system pH is 8.0 again, and 45 DEG C of complexation temperature, the acetic acid of 0.5mol/L is added
Copper solution, progress third time complexing, complexation time 30min,；Ethylene glycol is finally added into system, analyses complex compound sediment
Out, Precipitation object obtains complex antimicrobials after using vacuum drying 48h；
Wherein, the molar ratio of calcium nitrate and disodium ethylene diamine tetraacetate is 1:3；The molar ratio of zinc acetate and calcium nitrate is 1:0.5；
The molar ratio of copper acetate and zinc acetate is 1:1；
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, are squeezed out through twin-screw
It is granulated, composite antibacterial polyester master particle head product is prepared；
Wherein, the weight average molecular weight of polyester oligomer is 8000；Complex antimicrobials are in composite antibacterial polyester master particle head product
Mass fraction is 20%；The melt blending process conditions are that melting temperature is 260 DEG C, and screw rod shearing rate is 104s-1；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum increasing stick technique are walked, composite antibacterial polyester master particle is prepared；
Wherein, the mass ratio of diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:30；
First step liquid phase increasing stick technique: increasing stick temperature is 195 DEG C, and the increasing stick time is 5min；The composite antibacterial polyester master particle
Inherent viscosity decline 8% of the head product after first time liquid phase increasing stick, and content of carboxyl end group is 55mol/t；
Second step low vacuum liquid phase increasing stick technique: increasing stick temperature is 250 DEG C, and the increasing stick time is 30min；The composite antibacterial is poly-
Inherent viscosity of the ester master batch head product after second of liquid phase increasing stick is 0.45dL/g；
Third step high temperature high vacuum increasing stick technique: increasing stick temperature is 270 DEG C, and the increasing stick time is 45min；The composite antibacterial is poly-
Inherent viscosity of the ester master batch head product after third time liquid phase increasing stick is 0.75dL/g.
Embodiment 3
A kind of the sum of mass fraction of copper and zinc ion content in composite antibacterial polyester master particle with antibacterial action is 12.5%,
And the molar ratio of copper ion and zinc ion is 1:1.
The preparation method of above-mentioned composite antibacterial polyester master particle, the specific steps are that:
(1) preparation of complex antimicrobials
Under conditions of ultrasound band high-speed stirred, it is added into the disodium ethylene diamine tetra-acetic acid solution that mass concentration is 7.5g/L
The calcium nitrate solution of 0.5mol/L, then regulation system pH be 9.5, keep complexation temperature be 5 DEG C, complexation time be 25min into
Row is complexed for the first time；Then adjusting complexing pH again is 6, and complexation temperature is 10 DEG C, and the acetic acid zinc solution of 0.5mol/L is added, and is carried out
Second of complexing, complexation time 25min；Regulation system pH is 7.5 again, and 35 DEG C of complexation temperature, the acetic acid of 0.5mol/L is added
Copper solution carries out third time complexing, complexation time 30min；Ethylene glycol is finally added into system, analyses complex compound sediment
Out, Precipitation object obtains complex antimicrobials after using vacuum drying 48h；
Wherein, the molar ratio of calcium nitrate and disodium ethylene diamine tetraacetate is 1:3；The molar ratio of zinc acetate and calcium nitrate is 1:0.5；
The molar ratio of copper acetate and zinc acetate is 1:1.
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, are squeezed out through twin-screw
It is granulated, composite antibacterial polyester master particle head product is prepared.
Wherein, the weight average molecular weight of polyester oligomer is 6000；Complex antimicrobials are in composite antibacterial polyester master particle head product
In mass fraction be 15.5%；The melt blending process conditions are that melting temperature is 260 DEG C, and screw rod shearing rate is
104s-1；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum increasing stick technique are walked, composite antibacterial polyester master particle is prepared；
Wherein, the mass ratio of diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:30；
First step liquid phase increasing stick technique: increasing stick temperature is 195 DEG C, and the increasing stick time is 8min；The composite antibacterial polyester master particle
Inherent viscosity decline 8% of the head product after first time liquid phase increasing stick, and content of carboxyl end group is 39mol/t；
Second step low vacuum liquid phase increasing stick technique: increasing stick temperature is 250 DEG C, and the increasing stick time is 45min；The composite antibacterial is poly-
Inherent viscosity of the ester master batch head product after second of liquid phase increasing stick is 0.375dL/g；
Third step high temperature high vacuum increasing stick technique: increasing stick temperature is 270 DEG C, and the increasing stick time is 45min；The composite antibacterial is poly-
Inherent viscosity of the ester master batch head product after third time liquid phase increasing stick is 0.75dL/g.
Fig. 1 is the scanning electron microscope map of complex antimicrobials, after the effect that boils together of disodium ethylene diamine tetraacetate, compound
The more body that boils together is formed in antibacterial agent structure, and its particle size dispersion utilizes the structure that boils together to form dendroid in powder, and
And the ion particles that boil together formed on branch cutting-edge structure are tiny.
Fig. 2 be composite antibacterial polyester master particle section scanning electron microscope map, in map by chelating agent boil together and
It polymerize the acid regulation of increasing stick process, antibacterial activity release in structure, and the structure that boils together of disodium ethylene diamine tetraacetate is removed,
Therefore dendritic structure destroys, while the active ion release at tip, forms the complex antimicrobials with antibacterial action, therefore multiple
Antibacterial agent is closed to be uniformly dispersed in polyester master particle.
Fig. 3 a and Fig. 3 b are respectively the antibacterial effect and composite antibacterial for being used as the Escherichia coli of normal polyester powder of control sample
The antibacterial effect of the Escherichia coli of polyester master particle powder；In control sample, after 7 days Bacteria Cultures, in culture agar, it is distributed with
Uniform tiny microbe colony, and in composite antibacterial polyester master particle powder, have no microbe colony, it is seen then that composite antibacterial is poly-
Ester master batch powder is good to the antibacterial effect of Escherichia coli.
Fig. 4 a and Fig. 4 b is corresponding be the polyester powder staphylococcus glucose coccus as control sample antibacterial effect and
The antibacterial effect of the staphylococcus glucose coccus of composite antibacterial polyester master particle powder, in Fig. 4 a, due to no complex antimicrobials, gold
Yellow glucose coccus well-grown, and be distributed from centre to external diffusion, and due to joined containing complex antimicrobials in Fig. 4 b
Composite antibacterial polyester master particle powder, therefore its bacterium in the culture medium close to complex antimicrobials is less, and in whole culture medium
Bacterium is greatly reduced, it is seen then that complex antimicrobials are good to the antibacterial effect of staphylococcus glucose coccus.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (10)
1. a kind of composite antibacterial polyester master particle, it is characterised in that: using disodium ethylene diamine tetraacetate be chelating agent, by including
The precipitating that gradually boils together of different metal ions including copper ion, zinc ion obtains complex antimicrobials, then is with polyester oligomer
Raw material, complex antimicrobials are modifying agent, and composite antibacterial polyester master particle is prepared；In the composite antibacterial polyester master particle copper from
The sum of mass fraction of son and zinc ion is 10~15%, and the molar ratio of copper ion and zinc ion is 1:1；Described is compound anti-
The mass fraction of complex antimicrobials is 10~20% in bacterium polyester master particle.
2. a kind of composite antibacterial polyester master particle according to claim 1, it is characterised in that: the composite antibacterial polyester is female
The inherent viscosity of grain is 0.65~0.75dL/g.
3. a kind of preparation method of composite antibacterial polyester master particle as claimed in claim 1 or 2, it is characterised in that: it include with
Lower step:
(1) preparation of complex antimicrobials
Under conditions of ultrasound and stirring, calcium nitrate solution is added into disodium ethylene diamine tetra-acetic acid solution, then regulation system
PH is 9~10, and keeping complexation temperature is 5~10 DEG C, and complexation time is that 10~25min carries out first time complexing；Then it adjusts again
System pH is 4~6, and complexation temperature is 10~25 DEG C, and acetic acid zinc solution is added, and carries out second and is complexed, complexation time is 15~
25min；Regulation system pH is 7.5~8.0 again, and 35~45 DEG C of complexation temperature, copper acetate solution is added, carries out third time complexing,
Complexation time is 20~30min；Ethylene glycol is finally added into system, complex compound sediment is precipitated, Precipitation object vacuum is dry
Complex antimicrobials are obtained after dry；
(2) preparation of composite antibacterial polyester master particle head product
Using the method for melt blending, using polyester oligomer as raw material, complex antimicrobials are modifying agent, through double screw extruder into
Composite antibacterial polyester master particle head product is prepared in row extruding pelletization；
(3) preparation of composite antibacterial polyester master particle
Using the technique of multistage liquid phase increasing stick, using composite antibacterial polyester master particle head product as raw material, it is with diethylene glycol calcium first
Catalyst and displacer, are first catalyzed through low temperature hydrolysis, and carry out first step liquid phase increasing stick in atmospheric conditions, then again through second
Low vacuum liquid phase increasing stick and third step high temperature high vacuum liquid phase increasing stick are walked, composite antibacterial polyester master particle is prepared.
4. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described is compound
In the preparation process of antibacterial agent, the molar ratio of the calcium nitrate and disodium ethylene diamine tetraacetate is 1:2~1:3；The second
The molar ratio of sour zinc and calcium nitrate is 1:0.3~1:0.5；The molar ratio of the copper acetate and zinc acetate is 1:1.
5. a kind of preparation method of composite antibacterial polyester master particle according to claim 4, it is characterised in that: described is compound
In the preparation process of antibacterial agent, the mass concentration of the disodium ethylene diamine tetra-acetic acid solution is 5~10g/L, the nitric acid
The molar concentration of calcium solution is 0.5mol/L, and the molar concentration of the acetic acid zinc solution is 0.5mol/L, the copper acetate
The molar concentration of solution is 0.5mol/L.
6. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described is compound
In the preparation process of antibacterial polyester masterbatches head product, the weight average molecular weight of the polyester oligomer is 5000~8000；It is described
Mass fraction of the complex antimicrobials in composite antibacterial polyester master particle head product be 10~20%；The melt blending technique
Condition is that melting temperature is 200~260 DEG C, and screw rod shearing rate is 103~104s-1。
7. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described is compound
In the preparation process of antibacterial polyester masterbatches, the mass ratio of the diethylene glycol calcium and composite antibacterial polyester master particle head product is 1:
25~1:30.
8. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described is compound
In the preparation process of antibacterial polyester masterbatches, the increasing stick temperature of the first step liquid phase increasing stick is 180~195 DEG C, the increasing stick time
For 5~10min；The composite antibacterial polyester master particle head product after first time liquid phase increasing stick inherent viscosity decline 8~
10%, and content of carboxyl end group is 35~55mol/t.
9. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described is compound
In the preparation process of antibacterial polyester masterbatches, the increasing stick temperature of the second step low vacuum liquid phase increasing stick is 240~250 DEG C, is increased
The glutinous time is 30~45min；Characteristic of the composite antibacterial polyester master particle head product after second of low vacuum liquid phase increasing stick
Viscosity is 0.35~0.45dL/g.
10. a kind of preparation method of composite antibacterial polyester master particle according to claim 3, it is characterised in that: described answers
In the preparation process for closing antibacterial polyester masterbatches, the increasing stick temperature of the third step high temperature high vacuum liquid phase increasing stick is 260~270
DEG C, the increasing stick time is 45~60min；The composite antibacterial polyester master particle head product is through third time high temperature high vacuum liquid phase increasing stick
Inherent viscosity afterwards is 0.65~0.75dL/g.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| CN110528106A (en) * | 2019-06-03 | 2019-12-03 | 东华大学 | A kind of function industrial yarn and preparation method thereof |
| CN110528106B (en) * | 2019-06-03 | 2020-11-24 | 东华大学 | Functional industrial yarn and preparation method thereof |
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