CN114605678A - Copper antibacterial masterbatch for spinning, preparation method and application thereof - Google Patents
Copper antibacterial masterbatch for spinning, preparation method and application thereof Download PDFInfo
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- CN114605678A CN114605678A CN202210347680.9A CN202210347680A CN114605678A CN 114605678 A CN114605678 A CN 114605678A CN 202210347680 A CN202210347680 A CN 202210347680A CN 114605678 A CN114605678 A CN 114605678A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 63
- 239000010949 copper Substances 0.000 title claims abstract description 63
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 238000009987 spinning Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 238000005469 granulation Methods 0.000 claims abstract description 16
- 230000003179 granulation Effects 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 29
- -1 polybutylene terephthalate Polymers 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000969 carrier Substances 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K5/20—Carboxylic acid amides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a copper antibacterial master batch for spinning, a preparation method and application thereof, relates to a high polymer material technology, and aims to solve the problems that the operation difficulty of the existing copper antibacterial master batch preparation technology is high, the prepared master batch has poor spinnability, fiber color is changeable, and subsequent use is influenced, and the technical scheme main points are as follows: carrying out dry surface modification on the nano copper powder to prepare modified nano copper powder; then premixing PBT powder with an auxiliary agent, and then mixing the PBT powder with the modified nano-copper powder at a high speed to obtain a mixture before granulation, wherein the mass ratio of the modified nano-copper powder to the PBT premix is 10-20: 90-80; and finally, granulating the mixture in a double-screw granulator to obtain the copper antibacterial master batch. The copper antibacterial master batch prepared by the invention can be used for preparing copper antibacterial fibers with copper content of more than 3000ppm and filament number of less than 1.1dpf, the color of the fibers is close to white, and the whiteness (L value) is more than 80.
Description
Technical Field
The invention relates to a high polymer material technology, in particular to a copper antibacterial master batch for spinning and a preparation method thereof.
Background
In the field of antibacterial fiber, silver ion antibacterial fiber is popular initially, but as silver ion antibacterial fiber is considered to have a certain toxicity by the market of europe and america, copper ion antibacterial fiber is gradually opened in europe and america as a substitute for silver ion antibacterial fiber. The production of the copper ion antibacterial fiber necessarily involves the copper antibacterial master batch.
The copper master batch disclosed in Chinese patent with publication number CN107033556B and the preparation method thereof have the technical key points that: the copper master batch comprises the following components in percentage by mass: 75-96% of PET; 4-25% of modified nano copper. The preparation method comprises the following steps: mixing the modified nano-copper with PET to form a mixed solution; so that the nano copper is uniformly distributed in the PET base material; and (4) carrying out vacuum reaction granulation on the mixed solution prepared in the step (S1) to obtain copper master batches, wherein the preparation method of the modified nano copper is to modify the nano copper obtained by nano dispersion and vacuum drying in a negative pressure inert gas environment under a vacuum condition, and the copper master batches are prepared by combining accumulation low-temperature freezing treatment in a vacuum reaction granulation mode during granulation.
According to the scheme, the problems of high pollution, high energy consumption, high purity and unstable pH value of reaction granulation are solved, but in the process of nano-copper modification and subsequent preparation, high-precision equipment such as a vacuum high-speed dispersing agent and a vacuum reaction granulator are required, and when rapid low-temperature freezing treatment is carried out, the temperature of the copper master batch is reduced to-230 ℃, the operation difficulty is high, and the requirement on the equipment is high.
Therefore, a new solution is needed to solve this problem.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a copper antibacterial master batch for spinning, a preparation method and application thereof.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of copper antibacterial master batch for spinning comprises elementary substance nano copper powder, carrier polybutylene terephthalate powder and auxiliary agent, and comprises the following steps:
s1 dry modification, namely, performing dry surface modification on the nano copper powder to prepare the modified nano copper powder, wherein the dry surface modification comprises the following specific steps:
A. pre-mixing, namely adding oleic acid in a corresponding proportion into the nano copper powder, pre-mixing for 5min, then adding zinc stearate powder in an equal proportion, pre-mixing for 5min, then adding titanate powder, and pre-mixing for 5 min;
B. performing dry dispersion, namely performing dry dispersion on the premixed nano copper powder in a fluidized bed jet mill to obtain modified nano copper powder;
s2 mixing carriers, namely adding polypropylene wax and an EBS dispersant into polybutylene terephthalate powder as a carrier, premixing for 5min, adding a titanate coupling agent and a 1010 antioxidant, and premixing for 5min to obtain a PBT premix;
s3, mixing, namely adding the modified nano copper powder into the PBT premix, and mixing for 10min at a high speed to obtain a mixture before granulation, wherein the mass ratio of the modified nano copper powder to the PBT premix is 10-20: 90-80;
and S4, granulating, namely granulating the mixture in a double-screw granulator to obtain the copper antibacterial master batch.
By adopting the technical scheme, the simple substance nano copper is selected as the antibacterial agent, and the simple substance nano copper has wide source and low price, and the prepared fiber has light color, thereby being beneficial to the subsequent dyeing operation of fiber and yarn. In the step of modifying the nano copper powder, the oleic acid, the zinc stearate powder, the titanate powder and other auxiliaries are sequentially added. Oleic acid can be used as a good dispersant to effectively reduce the surface tension of copper powder so as to achieve the purposes of controlling copper powder agglomeration and reducing the oxidation speed of the copper powder. The zinc stearate powder is adopted, so that the nano copper powder can be effectively isolated and dispersed, and a good lubricating effect can be achieved in the subsequent granulation process. The added zinc component can improve the antibacterial property through zinc ions, has a synergistic effect with the copper component, improves the antibacterial capacity of the master batch for preparing fibers, and can effectively fuse the nano copper powder and the PBT premix in the granulation process by taking the titanate powder as a coupling agent, and a gravity-free high-speed mixer is adopted for mixing in the preparation process, and dry dispersion is carried out in a fluidized bed jet mill.
The invention is further configured to: the weight cumulative particle size of the nano copper powder is D50, D90 and D95, wherein D50 is 300-700nm, the particle size of D90 is less than 1.2 microns, and the particle size of D95 is less than 2.0 microns.
By adopting the technical scheme, the powder with D50 between 300-700nm is preferably selected in the aspect of selecting the size of the nanometer copper powder, the smaller size can bring deeper fiber color, the powder is more difficult to disperse, the larger size can cause poor filtering performance of the master batch, the sizes of D90 and D95 are controlled to ensure the concentration ratio of the copper powder, the problem that the excessive large particles influence the filtering performance of the master batch, the larger large particles can cause more broken ends in the master batch spinning process is solved, and the spinnability of the master batch for fiber monofilament spinning is improved by combining D50, D90 and D95.
The invention is further configured to: the viscosity of the carrier polybutylene terephthalate powder is 0.88-1dl/g, and the weight ratios of the polypropylene wax, the EBS dispersant, the titanate coupling agent and the 1010 antioxidant in the master batch are respectively as follows:
polypropylene wax: 0.5-1.5%;
EBS dispersant: 0.5-1.5%;
titanate coupling agent: 0.3-1.2%;
1010 antioxidant: 0.1 to 0.5 percent.
By adopting the technical scheme, the viscosity of the carrier polybutylene terephthalate powder is controlled to be 0.88-1dl/g, the dispersion uniformity of the nano copper powder can be improved according to the weight ratio of the auxiliary agent to the master batch, the 1010 antioxidant is added, and the 1010 antioxidant is used as a phenol antioxidant, so that the nano copper powder has good antioxidant performance, the thermal oxidative degradation of the polymer material in the long-term aging process can be effectively prevented, and the preparation method is beneficial to improving the color change resistance of the master batch under the high-temperature processing condition in the subsequent granulation and spinning processes.
The invention is further configured to: the weight proportions of the oleic acid, the zinc stearate powder and the titanate powder relative to the copper powder are as follows in sequence:
0.5 to 1.5 percent of oleic acid;
0.5 to 1.5 percent of zinc stearate powder;
titanate 0.3-0.8.
By adopting the technical scheme, the polypropylene wax and the EBS dispersant which are 0.5-0.15 percent respectively are added according to the specific gravity of the nano copper powder, and when the nano copper powder and the powdered nano copper powder are mixed, the nano copper powder can be well dispersed by utilizing the mechanical force, so that the aims of improving dispersion and lubrication are fulfilled.
The copper antibacterial master batch for spinning is prepared by applying the preparation method of the copper antibacterial master batch for spinning according to any one of claims 1 to 4.
By adopting the technical scheme, the copper antibacterial master batch prepared by the preparation method is convenient to transport and store, and in the subsequent spinning process, the master batch is only required to be further crystallized and dried, so that the spinning preparation efficiency is improved, the quality of finished silk yarns is improved, and the copper antibacterial master batch has excellent spinnability and antibacterial property and has good whiteness.
The application of the copper antibacterial master batch is characterized in that the antibacterial master batch for spinning is adopted to prepare copper antibacterial fibers with copper content of more than 3000ppm and single filament number of less than 1.1dpf, the copper antibacterial fibers are white, and the whiteness is more than 80.
By adopting the technical scheme, the master batch prepared by the improved preparation method is used for spinning, so that the prepared copper antibacterial fiber with the copper content of more than 3000ppm and the filament number of less than 1.1dpf has a great breakthrough, and the prepared copper antibacterial fiber has good whiteness and is beneficial to subsequent dyeing operation.
In conclusion, the invention has the following beneficial effects:
1) aiming at the surface modification of the nano copper powder, the invention creatively adopts a 2-step method dry method surface modification technology, and has the advantages of uniform dispersion, simple operation, low cost and the like.
2) Aiming at the mixing of the modified nano copper powder and the PBT powder as the carrier, the invention also adopts a 2-step method for orderly mixing and dispersing, and the method obviously improves the mixing uniformity and the dispersibility of the copper powder and the PBT carrier.
3) The prepared copper antibacterial master batch has excellent spinnability and antibacterial property, and the spun fiber has white color
Detailed Description
The present invention will be described in detail with reference to examples.
A preparation method of copper antibacterial master batch for spinning comprises elementary substance nano copper powder, carrier polybutylene terephthalate powder and auxiliary agent, and comprises the following steps:
s1 dry modification, namely, performing dry surface modification on the nano copper powder to prepare the modified nano copper powder, wherein the dry surface modification comprises the following specific steps:
A. pre-mixing, namely selecting elementary nano copper powder with the D50 of 500nm, the D90 of 1.2um and the D95 of 1.8um, quickly pouring the elementary nano copper powder into a gravity-free mixing device after unsealing, adding 0.6% of oleic acid, starting mixing, pre-mixing for 5min to realize uniform mixing of the oleic acid and the nano copper powder, then adding 0.8% of zinc stearate powder, starting mixing, pre-mixing for 5min, uniformly mixing, adding titanate powder, and pre-mixing for 5 min;
B. performing dry dispersion, namely adding the premixed nano copper powder into a fluidized bed jet mill for performing dry dispersion for continuous dispersion for 2 times, wherein the air pressure is 0.8MPa, so as to obtain modified nano copper powder;
s2 mixing carriers, namely adding the polybutylene terephthalate powder serving as the carrier into high-speed mixing equipment, simultaneously adding 1.4% of polypropylene wax and 1.4% of EBS dispersant, premixing for 5min, adding 1.1% of titanate coupling agent and 0.5% of 1010 antioxidant, and premixing for 5min to obtain a PBT premix;
s3, adding the modified nano copper powder into the PBT premix, and performing high-speed mixing for 10min in a high-speed mixing setting to obtain a mixture before granulation, wherein the mass ratio of the modified nano copper powder to the PBT premix is 20: 80;
s4, granulating, namely granulating the mixture in a double-screw granulator to obtain copper antibacterial master batches, and specifically, putting the mixture obtained in the step S3 into the double-screw granulator for granulation, wherein the screw temperature is 180-220 ℃, the head temperature is 220 ℃, the host machine rotating speed is 375 rpm, and the feeding rotating speed is 10 rpm, so as to prepare the copper antibacterial master batches for spinning.
Example two: the preparation method of the copper antibacterial masterbatch for spinning is different from the first embodiment in that: respectively adding 1% of polypropylene wax and 1% of EBS dispersant according to the weight of the master batch, mixing for 5 minutes, adding 0.8% of titanate and 0.4% of antioxidant 1010, mixing for 5 minutes to obtain PBT premix, adding the modified nano copper powder, and mixing for 10 minutes in high-speed mixing equipment to obtain the mixture before granulation. The mass ratio of the modified nanometer copper powder to the PBT premix is 15: 85.
The third embodiment is a method for preparing a copper antibacterial master batch for spinning, which is different from the first embodiment and the second embodiment in that: and respectively adding 1.5 percent of polypropylene wax according to the weight of the master batch, mixing for 5 minutes, adding 0.6 percent of titanate and 0.3 percent of antioxidant 1010, and mixing for 5 minutes to obtain the PBT premix. And adding the modified nano copper powder, and mixing for 10 minutes in high-speed mixing equipment to obtain a mixture before granulation. The mass ratio of the modified nanometer copper powder to the PBT premix is 10: 90.
Comparative example: firstly, adding carrier polybutylene terephthalate powder into high-speed mixing equipment, then respectively adding 1% of polypropylene wax and 1% of EBS dispersant according to the weight of master batch, mixing for 5 minutes, adding 0.8% of titanate and 0.4% of antioxidant 1010, and mixing for 5 minutes to obtain the PBT premix. And then adding unmodified nano copper powder, and mixing for 10 minutes in high-speed mixing equipment to obtain a mixture before granulation, wherein the mass ratio of the nano copper powder to the PBT premix is 15: 85.
And finally, putting the mixture into a double-screw granulator for granulation, wherein the screw temperature is 180-220 ℃, the head temperature is 220 ℃, the main machine rotating speed is 375 rpm, and the feeding rotating speed is 10 rpm, so as to prepare the copper antibacterial master batch for spinning.
Comparative experiment:
the test method comprises the following steps: drying and crystallizing the copper antibacterial master batches prepared in the first to third embodiments and the comparative example, preparing polyester filaments with the same copper content by spinning equipment, wherein the specification is 150D/144f, measuring the spinnability of the master batches by recording the period of a spinning assembly and the number/position of broken ends, and preparing the prepared fibers into fabrics with the same specification density to test the whiteness of the fabrics.
TABLE 1 comparison of spinnability of different copper master batches
Comparative example copper powder, which had not been surface-modified, was poor in spinnability and fiber whiteness. The whiteness of the modified nano copper powder is not greatly different. When the copper content of the master batch is increased, the dispersion between the copper powder and the PBT carrier becomes difficult, so that the spinnability of the master batch is influenced; when the copper content of the master batch is reduced, in order to enable the fibers to reach the same copper content, the addition amount of the master batch is increased, which can cause the increase of melt degradation in the spinning process, thereby influencing the spinning broken ends and the fiber whiteness.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (6)
1. A preparation method of copper antibacterial masterbatch for spinning is characterized by comprising the following steps: the method comprises the following steps of preparing elemental nano copper powder, carrier polybutylene terephthalate powder and auxiliary agent, wherein the method comprises the following steps:
s1 dry modification, namely, performing dry surface modification on the nano copper powder to prepare the modified nano copper powder, wherein the dry surface modification comprises the following specific steps:
A. pre-mixing, namely adding oleic acid in a corresponding proportion into the nano copper powder, pre-mixing for 5min, then adding zinc stearate powder in an equal proportion, pre-mixing for 5min, then adding titanate powder, and pre-mixing for 5 min;
B. performing dry dispersion, namely performing dry dispersion on the premixed nano copper powder in a fluidized bed jet mill to obtain modified nano copper powder;
s2 mixing carriers, namely adding polypropylene wax and an EBS dispersant into polybutylene terephthalate powder as a carrier, premixing for 5min, adding a titanate coupling agent and a 1010 antioxidant, and premixing for 5min to obtain a PBT premix;
s3, mixing, namely adding the modified nano copper powder into the PBT premix, and mixing for 10min at a high speed to obtain a mixture before granulation, wherein the mass ratio of the modified nano copper powder to the PBT premix is 10-20: 90-80;
and S4, granulating, namely granulating the mixture in a double-screw granulator to obtain the copper antibacterial master batch.
2. The preparation method of the copper antibacterial masterbatch for spinning according to claim 1, characterized in that: the weight cumulative particle size of the nano copper powder is D50, D90 and D95, wherein D50 is 300-700nm, the particle size of D90 is less than 1.2 microns, and the particle size of D95 is less than 2.0 microns.
3. The preparation method of the copper antibacterial masterbatch for spinning according to claim 1, characterized in that: the viscosity of the carrier polybutylene terephthalate powder is 0.88-1dl/g, and the weight ratios of the polypropylene wax, the EBS dispersant, the titanate coupling agent and the 1010 antioxidant in the master batch are respectively as follows:
polypropylene wax: 0.5-1.5%;
EBS dispersant: 0.5-1.5%;
titanate coupling agent: 0.3-1.2%;
1010 antioxidant: 0.1 to 0.5 percent.
4. The preparation method of the copper antibacterial masterbatch for spinning according to claim 1, characterized in that: the weight proportions of the oleic acid, the zinc stearate powder and the titanate powder relative to the copper powder are as follows in sequence:
0.5 to 1.5 percent of oleic acid;
0.5 to 1.5 percent of zinc stearate powder;
titanate powder 0.3-0.8.
5. The copper antibacterial master batch for spinning is characterized in that: the copper antibacterial masterbatch prepared by the preparation method of the copper antibacterial masterbatch for spinning according to any one of claims 1 to 4.
6. The application of the copper antibacterial masterbatch is characterized in that: the antibacterial masterbatch for spinning, which is used for preparing the copper antibacterial fiber with the copper content of more than 3000ppm and the single-filament fineness of less than 1.1dpf, according to claim 5, wherein the color of the copper antibacterial fiber is white, and the whiteness is more than 80.
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| CN115262020A (en) * | 2022-07-18 | 2022-11-01 | 湖州草本源新材料有限公司 | Nano copper-zinc composite antibacterial fiber and preparation method thereof |
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