CN110591306A - Preparation method of copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch, product and application thereof - Google Patents
Preparation method of copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch, product and application thereof Download PDFInfo
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- 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
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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
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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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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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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Abstract
The invention discloses a copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch as well as a preparation method and application thereof, wherein carbonate and ammonia water are added into a cupric salt solution to form a precipitate, and the precipitate is filtered, washed and subjected to microwave radiation treatment under certain power to obtain copper oxide particles; adding the copper oxide, terephthalic acid (PTA), ethylene glycol, a stabilizer and a catalyst into a polyester reactor in proportion, preparing copper oxide/polyester-based composite antibacterial master batch by in-situ polymerization, and blending the copper oxide/polyester-based composite antibacterial master batch and a matrix polymer according to a certain mass ratio at 180-280 ℃ for melt spinning to obtain the copper-based antibacterial PET fiber. The method has the advantages of simple operation, high production efficiency, durable antibacterial effect and wide application prospect.
Description
Technical Field
The invention relates to the technical field of polymer composite materials. In particular to a preparation method of copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch, a product and application thereof.
Background
The functional fiber means that the traditional cotton fiber and chemical fiber have various special functions such as ultraviolet resistance, far infrared resistance, extinction, cool silk and the like through processing and material modification, and as people pay more attention to the health, the antibacterial fiber and fabric are greatly developed. The antibacterial fiber generally refers to that antibacterial materials are added into the fiber, so that the fiber has a long-term antibacterial effect and protects the body of people in daily life.
Among various antibacterial agents, inorganic antibacterial agents are the first choice of high polymer material antibacterial additives due to the characteristics of no toxicity, no harm, high temperature resistance and good stability. Among inorganic antibacterial agents, silver, copper and zinc are mainly used, and since silver is easily discolored and expensive, zinc has an antibacterial effect inferior to that of copper, and copper can increase skin elasticity, the development of copper-based antibacterial fibers is favored by fiber-related research institutes and manufacturers.
At present, the preparation method of the copper-based antibacterial fiber mainly comprises a melt blending method and an in-situ polymerization method, and the composite material prepared by the melt blending method has the defect of poor dispersibility of the antibacterial agent. As is known to all, the antibacterial agent can exert stable and lasting antibacterial effect only if uniformly distributed in the fiber, so the copper-based polyester master batch is prepared by adopting an in-situ polymerization method. Microwave radiation is rapidly applied in material science due to unique reaction characteristics such as an increase in heat capacity, resulting in an increase in reaction rate. Compared with the traditional method, the microwave radiation method has the characteristics of short reaction time, capability of preparing substances with small particle size, narrow particle size distribution and high purity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of copper-based antibacterial PET wire-drawing master batch.
Yet another object of the present invention is to: provides a copper series antibacterial PET wire-drawing master batch product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batches is characterized in that copper oxide with uniform particle size is quickly and efficiently prepared by a microwave radiation method, so that the quality of the copper oxide is improved; then, preparing the copper oxide/polyester master batch by adopting an in-situ polymerization method, which comprises the following specific steps:
the first step is as follows: preparation of copper oxide
a. Adding 0.01 ~ 0.3.3 mol/L carbonate solution into 0.1mol/L cupric salt solution, simultaneously dropwise adding ammonia water to make the pH value of the solution reach 8 ~ 9, wherein the volume ratio of the cupric salt solution to the carbonate solution is 1:10 ~ 5:2, and filtering and washing the precipitate;
b. treating the washed precipitate at 200 deg.C with microwave radiation power of 200 ~ 1000w for 1 ~ 5min to obtain black copper oxide particles;
the second step is that: preparation of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch
Adding copper oxide particles, terephthalic acid (PTA), ethylene glycol, a stabilizer and a catalyst into a polyester reactor, and preparing the copper oxide/polyester-based composite antibacterial master batch by in-situ polymerization, wherein the copper oxide accounts for 1 ~ 15wt% of the mass of the master batch, the terephthalic acid accounts for 50 ~ 80wt% of the mass of the master batch, and the ethylene glycol accounts for 10 ~ 30wt% of the mass of the master batch.
The cupric salt is one or more of cupric nitrate, cupric sulfate and cupric chloride.
The carbonate is one or more of sodium carbonate, potassium carbonate and amine carbonate.
The stabilizer is one or more of organic tin, lead salt, trimethylolpropane and rare earth stabilizer, and the using amount of the stabilizer is 0.01 ~ 0.2.2 wt% of the mass of the master batch.
The catalyst is one or more of antimony sulfide, antimony oxide, antimony nitrate, antimony chloride and antimony acetate, and the using amount of the catalyst is 2 ~ 8wt% of the mass of the master batch.
The process conditions of the in-situ polymerization are as follows: the polymerization temperature is 230-290 ℃, and the pressure change in the reaction process is-0.2-0.5 MPa.
The invention provides a copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch, which is prepared by any one of the methods.
The invention provides an application of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch in functional fibers.
The master batch can be spun purely or blended with natural fibers and chemical fibers, can cover the fields of bedding, home textiles, decorative fabrics, clothing and socks and the like, and can also be widely applied to various sanitary clothing accessories in hospitals, special clothing in food industry, shoe materials, gloves and various underclothes.
Adding carbonate and ammonia water into a cupric salt solution to form a precipitate, filtering and washing the precipitate, and performing microwave radiation treatment under certain power to obtain copper oxide particles; adding the copper oxide, terephthalic acid (PTA), ethylene glycol, a stabilizer and a catalyst into a polyester reactor in proportion, preparing copper oxide/polyester-based composite antibacterial master batch by in-situ polymerization, and blending the copper oxide/polyester-based composite antibacterial master batch and a matrix polymer according to a certain mass ratio at 180-280 ℃ for melt spinning to obtain the copper-based antibacterial PET fiber. The method has the advantages of simple operation, high production efficiency, durable antibacterial effect and wide application prospect.
The copper-based antibacterial PET wire-drawing master batch has the beneficial effects that:
1. the copper-based antibacterial PET wiredrawing master batch can be applied to the fields of bedding, home textiles, decorative textiles, clothing and socks, various sanitary clothing accessories in hospitals, special clothing in the food industry, shoe materials, gloves, various underwear and the like.
2. The copper-based antibacterial PET wire-drawing master batch has the characteristics of simple production process, high production efficiency, no environmental pollution, continuous large-scale industrial production and the like.
3. The copper oxide prepared by the method has uniform particle size, high purity and good dispersibility in polyester, and the obtained copper fiber has excellent performances of antibiosis, long-acting and rapidness.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batch is prepared by quickly and efficiently preparing copper oxide with uniform particle size by using a microwave radiation method, then preparing copper oxide/polyester master batch by using an in-situ polymerization method, and preparing the copper oxide/polyester master batch by the following steps:
the first step is as follows: preparation of copper oxide
a. Adding 0.1mol/L carbonate solution with the volume ratio of 1:2 into 0.1mol/L copper nitrate solution, simultaneously dropwise adding ammonia water to enable the pH value of the solution to reach 8.5, generating precipitate after the reaction is finished, and filtering and washing the precipitate;
b. treating the washed precipitate at 200 deg.C with microwave radiation power of 500w for 2min to obtain black copper oxide particles;
the second step is that: preparation of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch
Adding copper oxide particles accounting for 5wt% of the mass of the master batch, terephthalic acid (PTA) accounting for 70wt% of the mass of the master batch, ethylene glycol accounting for 20wt% of the mass of the master batch, organic tin salt serving as a stabilizer and antimony sulfide catalyst accounting for 5wt% of the mass of the master batch into a polyester reactor, preparing copper oxide/polyester-based composite antibacterial master batch by adopting in-situ polymerization, keeping the temperature at 240 ℃ and the initial pressure at 0.5MPa, vacuumizing to-0.2 MPa along with the reaction, discharging after maintaining the pressure for a period of time, and blending and melt spinning the copper oxide/polyester-based composite antibacterial master batch and a matrix polymer at 180-280 ℃ according to a certain mass ratio to obtain the copper-based antibacterial PET fiber. And cutting into granules.
The copper oxide particles and the antibacterial fibers prepared in this example were respectively tested for particle size and antibacterial performance, and the results are shown in tables 1 and 2 below:
the particle size D10 was 10.5 nm, D50 was 13.5nm, and D90 was 18.3 nm.
The antibacterial rate to colibacillus reaches 96.5 percent, and the antibacterial rate to candida albicans reaches 93.5 percent.
Example 2
A copper-based antibacterial PET wire-drawing master batch similar to that in example 1, which is prepared by the following steps:
the first step is as follows: preparation of copper oxide
a. Adding 0.2mol/L carbonate solution with the volume ratio of 3:2 into 0.1mol/L copper chloride solution, simultaneously dropwise adding ammonia water to enable the pH value of the solution to reach 8.8, enabling the volume ratio of the copper salt solution to the carbonate solution to be 1:10 ~ 5:2, generating precipitate after the reaction is finished, and filtering and washing the precipitate;
b. placing the washed precipitate in a microwave radiation device, and treating for 1min at 200 deg.C under the microwave radiation power of 800w to obtain black copper oxide particles;
the second step is that: preparation of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch
Adding copper oxide particles accounting for 10wt% of the mass of the master batch, terephthalic acid (PTA) accounting for 60wt% of the mass of the master batch, ethylene glycol accounting for 25wt% of the mass of the master batch, an organic lead salt stabilizer accounting for 0.15wt% of the mass of the master batch and an antimony nitrate catalyst accounting for 4wt% of the mass of the master batch into a polyester reactor, preparing copper oxide/polyester-based composite antibacterial master batch by adopting in-situ polymerization, wherein the polymerization temperature is 250 ℃, the initial pressure is 0.5MPa, the initial pressure is reduced to-0.2 MPa along with the reaction, and discharging and granulating after maintaining the pressure for a period of time.
And blending the copper oxide/polyester-based composite antibacterial master batch and the matrix polymer according to a certain mass ratio at 180-280 ℃ for melt spinning to obtain the copper-based antibacterial PET fiber.
The copper oxide particles and the antibacterial fibers prepared in this example were respectively tested for particle size and antibacterial performance, and the results are shown in tables 1 and 2 below:
the particle size D10 was 15.6nm, D50 was 18.3nm, and D90 was 22.7 nm.
The antibacterial rate to colibacillus reaches 97.2 percent, and the antibacterial rate to candida albicans reaches 94.4 percent.
Example 3
A copper-based antibacterial PET wire-drawing master batch similar to that in example 1, which is prepared by the following steps:
the first step is as follows: preparation of copper oxide
a. Adding 0.15mol/L carbonate solution with the volume ratio of 2:1 into 0.1mol/L copper sulfate solution, simultaneously dropwise adding ammonia water to enable the pH value of the solution to reach 9, generating precipitate after the reaction is finished, and filtering and washing the precipitate;
b. placing the washed precipitate in a microwave radiation device, and performing heat treatment at 200 ℃ and microwave radiation power of 350w for 5min to obtain black copper oxide particles;
the second step is that: preparation of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch
Adding copper oxide particles accounting for 12wt% of the mass of the master batch, terephthalic acid (PTA) accounting for 58wt% of the mass of the master batch, ethylene glycol accounting for 26wt% of the mass of the master batch, trimethylolpropane stabilizer accounting for 0.15wt% of the mass of the master batch and antimony acetate catalyst accounting for 3wt% of the mass of the master batch into a polyester reactor, preparing copper oxide/polyester-based composite antibacterial master batch by adopting in-situ polymerization, wherein the polymerization temperature is kept at 280 ℃ and the initial pressure is 0.5MPa, vacuumizing to-0.2 MPa along with the reaction, and discharging and dicing after maintaining the pressure for a period of time.
And blending the copper oxide/polyester-based composite antibacterial master batch and the matrix polymer according to a certain mass ratio at 180-280 ℃ for melt spinning to obtain the copper-based antibacterial PET fiber.
The copper oxide particles and the antibacterial fibers prepared in this example were respectively tested for particle size and antibacterial performance, and the results are shown in tables 1 and 2 below:
the particle size D10 was 18.1nm, D50 was 20.8nm, and D90 was 25.1 nm.
The antibacterial rate to colibacillus reaches 97.9 percent, and the antibacterial rate to candida albicans reaches 95.2 percent.
The particle size and antimicrobial performance results for each example were tested and are shown in the following table:
table 1 shows the particle size of the copper oxide prepared in examples 1, 2 and 3:
table 2 shows the antibacterial properties of the antibacterial fibers prepared in examples 1, 2 and 3 against Escherichia coli and Candida albicans. Detecting according to a QB/T2591-2003 detection method and a standard:
。
Claims (7)
1. a preparation method of copper-based antibacterial PET (polyethylene terephthalate) wire-drawing master batches is characterized in that copper oxide with uniform particle size is quickly and efficiently prepared by a microwave radiation method; then, preparing the copper oxide/polyester master batch by adopting an in-situ polymerization method, comprising the following steps:
the first step is as follows: preparation of copper oxide
a. Adding 0.01 ~ 0.3.3 mol/L carbonate solution into 0.1mol/L cupric salt solution, simultaneously dropwise adding ammonia water to ensure that the pH value of the solution reaches 8 ~ 9, the volume ratio of the cupric salt solution to the carbonate solution is 1:10 ~ 5:2, generating precipitate after the reaction is finished, and filtering and washing the precipitate;
b. treating the washed precipitate at 200 deg.C with microwave radiation power of 200 ~ 1000w for 1 ~ 5min to obtain black copper oxide particles;
the second step is that: preparation of copper-based antibacterial PET (polyethylene terephthalate) drawing master batch
Adding copper oxide particles, terephthalic acid (PTA), ethylene glycol, a stabilizer and a catalyst into a polyester reactor, preparing copper oxide/polyester-based composite antibacterial master batch by in-situ polymerization at the polymerization temperature of 230-290 ℃ and the pressure change of-0.2-0.5 MPa in the reaction process, wherein the copper oxide accounts for 1 ~ 15wt% of the mass of the master batch, the terephthalic acid accounts for 50 ~ 80wt% of the mass of the master batch, and the ethylene glycol accounts for 10 ~ 30wt% of the mass of the master batch.
2. The preparation method of the copper-based antibacterial PET drawing masterbatch according to claim 1, characterized by comprising the following steps: the cupric salt is one or more of cupric nitrate, cupric sulfate and cupric chloride.
3. The preparation method of the copper-based antibacterial PET drawing masterbatch according to claim 1, characterized by comprising the following steps: the carbonate is one or more of sodium carbonate, potassium carbonate and amine carbonate.
4. The preparation method of the copper-based antibacterial PET wiredrawing master batch according to claim 1, wherein the stabilizer is one or more of organic tin, lead salt, trimethylolpropane and rare earth stabilizer, and the using amount of the stabilizer is 0.01 ~ 0.2.2 wt% of the mass of the master batch.
5. The preparation method of the copper-based antibacterial PET wiredrawing master batch according to claim 1, wherein the catalyst is one or more of antimony sulfide, antimony oxide, antimony nitrate, antimony chloride and antimony acetate, and the usage amount of the catalyst is 2 ~ 8wt% of the mass of the master batch.
6. A copper-based antibacterial PET drawing master batch, which is characterized by being prepared by the method of any one of claims 1 to 5.
7. The use of the copper-based antibacterial PET drawing masterbatch according to claim 6 in functional fibers.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318614A (en) * | 2021-12-24 | 2022-04-12 | 江苏微笑新材料科技有限公司 | Preparation method of copper-containing antibacterial polyester yarn, fabric and garment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130245578A1 (en) * | 2000-09-15 | 2013-09-19 | Bruder Healthcare Company | Wound and therapy compress and dressing |
| CN104628026A (en) * | 2014-12-10 | 2015-05-20 | 程如铁 | Method for preparing nano copper oxide |
| CN109023588A (en) * | 2018-08-14 | 2018-12-18 | 安徽和邦纺织科技有限公司 | A kind of preparation method of porous flexible polyester fiber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130245578A1 (en) * | 2000-09-15 | 2013-09-19 | Bruder Healthcare Company | Wound and therapy compress and dressing |
| CN104628026A (en) * | 2014-12-10 | 2015-05-20 | 程如铁 | Method for preparing nano copper oxide |
| CN109023588A (en) * | 2018-08-14 | 2018-12-18 | 安徽和邦纺织科技有限公司 | A kind of preparation method of porous flexible polyester fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318614A (en) * | 2021-12-24 | 2022-04-12 | 江苏微笑新材料科技有限公司 | Preparation method of copper-containing antibacterial polyester yarn, fabric and garment |
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