CN111253732A - Plant-derived polyamide master batch and preparation method and application thereof - Google Patents
Plant-derived polyamide master batch and preparation method 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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- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
Abstract
The invention relates to a plant-derived polyamide master batch and a fiber, a film or a molded body prepared from the plant-derived polyamide master batch. The polyamide masterbatch and the product thereof can emit fragrance, inhibit bacteria and mildew, improve the problem of poor light resistance, increase the moisture regain of the polyamide fiber obtained by spinning, and improve the wearing comfort by adding the plant extract. However, the plant extract is easy to be carbonized at high temperature, so the carbonization-preventing additives chitin and starch are added into the plant extract powder, and the modified plant extract is obtained after banburying by a mixer, so the carbonization in the high-temperature melting process is reduced, and the effective components of the plant extract are retained to the maximum extent.
Description
Technical Field
The invention relates to the technical field of polymer materials, in particular to a plant-derived polyamide master batch, and a preparation method and application thereof.
Background
Polyamide is commonly known as nylon, is a general name of high polymer containing amide groups in macromolecular main chain repeating units, is originally used as a raw material for manufacturing polyamide fibers, has the advantages of excellent wear resistance, high breaking strength, light and thin texture, good rebound resilience and the like, and is the best choice for clothing materials such as sports wear, swimwear, body building wear, down jackets, mountaineering wear and the like. Later becomes engineering plastic with wide industrial application, and has the advantages of toughness, wear resistance, self lubrication, wide application temperature range and the like. With the rapid development of industries such as clothing and the like and the rapid growth of public demands, market competition is intensified, and the development of functional products by adopting chemical or physical methods and through process improvement becomes a great trend of the polyamide industry.
The plant extract contains glycoside, acid, polyphenol, polysaccharide, terpenes, flavone and alkaloid, and has effects of diminishing inflammation, resisting bacteria, whitening skin, relieving and tranquilizing, treating insomnia and purifying air. Plants have been widely used in the industries of food, traditional Chinese medicine, beauty and the like, are used for preparing clothes or bedding in the fiber field, are added into films for packaging food, medicines, medical instruments, electronic parts and the like, or are used for processing plastics into various products, and can play the roles of fragrance, antibiosis, emotion relief, inflammation elimination and the like of the plants.
Patent No. CN201710334526.7 discloses a mosquito repellent polyamide-6 fiber and a preparation method thereof, wherein, attapulgite and microcapsules prepared from plant mosquito repellent products are prepared into mosquito repellent master batches, and then the mosquito repellent master batches and polyamide-6 fiber are prepared into the mosquito repellent polyamide-6 fiber, and the main preparation method comprises the following steps: taking 40-50 parts of nylon chips, 7-9 parts of the antibacterial agent, 6-9 parts of polyurethane, 4-7 parts of silicon dioxide and 5-7 parts of p-phenylenediamine, uniformly mixing, putting into a double-screw extruder for extrusion granulation, collecting particles, putting into a spinning machine, and then putting into a traction machine to obtain the antibacterial nylon fiber. However, the fiber strength of the nylon fiber prepared by the method cannot be guaranteed, the light resistance, the heat resistance and the wear resistance of the prepared nylon fiber are correspondingly reduced, the service life of the product is short, and the practicability of the fiber is influenced. The application number CN108047531A improves the moisture absorption of the fiber by taking PE as a carrier, chitosan as an antibacterial substance and cellulose extracts of agave and eucalyptus as cellulose adhesives, and the prepared antibacterial master batch has better antibacterial property and dispersibility. The antibacterial master batch has single function and can only play the antibacterial action of chitosan.
Disclosure of Invention
Based on the above, the invention aims to provide the plant-derived polyamide master batch, and the preparation method and the application thereof. The plant source of the invention refers to a plant in nature.
The modified plant extract of the invention is a composition formed by adding anti-carbonization agents chitin and starch into plant extract powder.
Further, the modified plant extract of the invention refers to a composition prepared by mixing 45-75 parts of plant extract powder, 15-35 parts of chitin and 4-8 parts of starch.
Furthermore, the modified plant extract of the invention is only that after 45-75 parts of plant powder, 15-35 parts of chitin and 4-8 parts of starch are mixed, 50-80 parts of deionized water is added, the pH is adjusted, and the mixture is heated to 55-75 ℃ for mixing; shaking the obtained mixture evenly, distilling under reduced pressure, dissolving in 40-60 parts of deionized water, continuously filtering through a semipermeable membrane, and adding 10-30 parts of acrylic acid; banburying the obtained extract in an internal mixer for 1-5h, naturally drying, grinding, and sieving to obtain modified plant extract.
The parts in the invention are parts by weight unless otherwise specified.
Extruding and granulating the plant extract and polyamide slices on a screw extruder to prepare plant-derived polyamide master batches, and then carrying out blended spinning or molding to prepare the polyamide fiber or polyamide film or plastic containing the modified plant extract. The plant-derived polyamide master batch is a component with excellent pre-dispersibility, generally, the product prepared from the plant-derived polyamide master batch has the dispersion degree of the plant extract which is greatly better than that of the product containing the modified plant extract obtained by directly blending the plant extract, so that the function of the plant extract can be improved, and the product quality is more stable. When the polyamide product containing the modified plant extract plays the functions of the plant, the mechanical properties are not reduced much, and the performance of the polyamide product is not influenced. The plant extract is carbonized when melted at high temperature, and the invention modifies the plant extract, adds anti-carbonization agent chitin and starch, and can retain the effective components of the plant extract in the high-temperature process, thereby exerting the effect.
The plant source polyamide master batch is mainly prepared by blending, melting and granulating polyamide slices and modified plant extracts, wherein the addition amount of the modified plant extracts is 1-20 wt%.
Preferably, the modified plant extract is added in an amount of 13-20 wt%.
The modified plant extract is prepared by adding chitin and starch into plant extract powder and then banburying the mixture by an internal mixer.
Preferably, the modified plant extract is one or more of sarcandra glabra, wormwood, isatis root, mint, apocynum venetum and lavender.
The preparation steps of the modified plant extract of the invention are as follows:
A1. mixing 45-75 parts of plant extract powder, 15-35 parts of chitin and 4-8 parts of starch, adding 50-80 parts of deionized water, adjusting the pH, heating to 55-75 ℃, and mixing;
A2. shaking the mixture obtained from A1 uniformly, distilling under reduced pressure, dissolving in 40-60 parts of deionized water, continuously filtering by a semipermeable membrane, and adding 10-30 parts of acrylic acid;
A3. and banburying the obtained product of A2 in an internal mixer for 1-5h, naturally drying, grinding, and sieving to obtain the modified plant extract.
Preferably, in step A1, the pH is adjusted to 7-9. The spinning process needs to be in an alkaline environment, and the modified plant extract can be placed in a weak alkaline environment, so that the spinning is facilitated.
The preparation method of the plant source polyamide master batch comprises the following preparation steps:
B1. adding 4-6.5 wt% of reaction auxiliary agent into the modified plant extract;
B2. melting polyamide slices, continuously stirring, adding a modified plant extract containing a reaction auxiliary agent, a dispersing agent and a cross-linking agent, wherein the addition amount of the cross-linking agent is 0.2-0.7 wt% of the modified plant extract containing the reaction auxiliary agent, and reacting to obtain a product;
B3. and putting the product into a double-screw extruder, melting, extruding, cooling, and granulating by a granulator to obtain the plant source polyamide master batch.
Preferably, in step B1, the reaction assistant is prepared from the following raw materials in parts by weight: 1-3 parts of 3, 4-dimethyl-3, 4-diphenylhexane, 1-3 parts of surface hardening and wear-resisting agent T8011-3 parts, 2-5 parts of adipic acid dihydrazide, 1.5-5 parts of epoxy chloropropane, 2-6 parts of defoaming agent BYK0251-2.5 parts, 2-6 parts of polycarbodiimide and 1-4.5 parts of zinc hydroxide. The addition of the reaction auxiliary agent helps to improve the reaction progress.
In the step B2, the dispersant is composed of 1-3 parts of single-walled carbon nanotube, 4-6 parts of trimeric fatty acid, 1-3 parts of palladium-tin modified nano titanium dioxide, 5-7 parts of isopropanolamine, 0.3-0.9 part of magnesium silicate hydroxide and 2-4 parts of polyethylene oxide, and the adding amount is 6-7 wt% of the polyamide slice, or EBS P200, and the adding amount is 0.1-2 wt% of the modified plant extract.
Preferably, the dispersing agent is EBS P-200, N-ethylene bis stearamide, the two ends of the dispersing agent are non-polar long-chain alkyl, and the middle of the dispersing agent is polar bisamide, so that the symmetrical meso-position polar structure endows EBS with excellent wetting and penetrating abilities, and the plant extract is not easy to agglomerate.
The plant source polyamide master batch and the preparation method thereof can be used for preparing polyamide fibers, polyamide films or plastics containing modified plant extracts. The polyamide fiber or polyamide molded product comprises polyamide slices and plant source polyamide master batches, and the addition amount of the plant extract is 0.1-1 wt%.
The invention has the beneficial effects that: the plant extract is modified after banburying by a mixer, amino and hydroxyl of the chitin have high hygroscopicity, cage-shaped molecules similar to a net structure can be formed by means of hydrogen bonds and ionic bonds, and the starch and the chitin have strong interaction, so that the plant extract can be protected in the net structure by the amino and hydroxyl, the carbonization in the high-temperature melting process is reduced, and the slow release effect is achieved. Chitin itself also has certain antibacterial properties. The prepared plant-derived polyamide master batch and the product have small reduction of mechanical properties, and normal spinning or forming process and finished product quality are not influenced. The dispersing agent is added in the preparation process of the master batch, so that the dispersion of the plant extract is more uniform, and the agglomeration is reduced. The plant extract contains hydrophilic groups such as hydroxyl and acyl, so that the moisture regain is increased, the problem of poor heat resistance and light resistance of the chinlon is solved, and the wearing comfort is improved. Meanwhile, the beneficial components of the plant extract can emit fragrance to make people relaxed and happy, and the plant extract can resist bacteria and prevent mildew, and improve the functionality and added value of the plant-derived polyamide master batch and the fiber.
Detailed Description
Examples
EXAMPLES 1 to 8 preparation of plant-derived Polyamide Master batch
The plant extract powder is commercially available, 99.5% of the plant extract powder is sieved by a 10000-mesh sieve, and the plant extract powder is loose, has no agglomeration and has no visible impurities; the color is uniform and consistent; no bad smell; the water content is less than or equal to 5 percent, the total number of colonies is less than 99cfu/g, and salmonella and escherichia coli can not be detected. The dispersant of the embodiment 1-7 is EBS P-200, and the dispersant of the embodiment 8 is selected from the following components, by weight, 1-3 parts of single-walled carbon nanotubes, 4-6 parts of trimeric fatty acid, 1-3 parts of palladium-tin modified nano titanium dioxide, 5-7 parts of isopropanolamine, 0.3-0.9 part of magnesium silicate hydroxide and 2-4 parts of polyethylene oxide.
EXAMPLE 1 preparation of a Wormwood Polyamide Master batch
Mixing 45 parts of wormwood extract powder, 15 parts of chitin and 4 parts of starch, adding 60 parts of deionized water, adjusting the pH value to 7 by using sodium carbonate, heating to 55-75 ℃, and mixing; shaking the mixture evenly, distilling under reduced pressure for 0.5-1.5h, dissolving in 40 parts of deionized water, continuously filtering by using a semipermeable membrane, and adding 15 parts of acrylic acid into the filtered membrane; banburying the obtained material in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified folium Artemisiae Argyi extract with good compatibility and mesh number of 10000 mesh.
990 parts of polyamide chips are heated to be molten, and then polyvinylpyrrolidone, ultraviolet protective agent, superfine sodium phosphate, high-activity phosphate LYCO-P08, dispersant, lanthanum chloride and stabilizer are sequentially added and stirred at the speed of 750-900 rad/min. And (2) uniformly mixing 10 parts of modified wormwood extract and 0.4 part of reaction auxiliary agent, adding the polyamide slices, 0.01 part of dispersing agent and 0.02 part of cross-linking agent, continuously stirring, putting into a double-screw extruder, melting, extruding, cooling, and granulating by a granulator to obtain wormwood polyamide master batch.
EXAMPLE 2 preparation of Isatis root Polyamide Master batch
Mixing 75 parts of radix isatidis extract powder, 35 parts of chitin and 8 parts of starch, adding 80 parts of deionized water, adjusting the pH value to 9 by using sodium carbonate, heating to 55-75 ℃, and mixing; shaking the mixture evenly, distilling under reduced pressure for 0.5-1.5h, dissolving in 60 parts of deionized water, continuously filtering by using a semipermeable membrane, and adding 30 parts of acrylic acid into the filtered membrane; banburying the obtained extract in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified radix Isatidis extract with good compatibility and mesh number of 10000 mesh.
The masterbatch was prepared as in example 1, except that the parts of the raw materials were changed. Weighing 800 parts of polyamide slices, 200 parts of modified isatis root extract, 13 parts of reaction auxiliary agent, 4 parts of dispersing agent and 1.4 parts of cross-linking agent, uniformly stirring and granulating to obtain isatis root polyamide master batches.
EXAMPLE 3 preparation of a mint Polyamide masterbatch
Mixing 60 parts of mint extract powder, 25 parts of chitin and 6 parts of starch, adding 70 parts of deionized water, adjusting the pH value to 8 by using sodium bicarbonate, heating to 55-75 ℃, and mixing; shaking the mixture, distilling under reduced pressure for 0.5-1.5h, dissolving in 50 parts of deionized water, filtering with semipermeable membrane, and adding 23 parts of acrylic acid into the filtered membrane; banburying the obtained extract in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified herba Menthae extract with good compatibility and mesh number of 10000 mesh.
The masterbatch was prepared as in example 1, except that the parts of the raw materials were changed. Weighing 900 parts of polyamide slices, 100 parts of modified mint extracts, 5 parts of reaction aids, 1 part of dispersing agents and 0.4 part of cross-linking agents, uniformly stirring, and granulating to obtain mint polyamide master batches.
EXAMPLE 4 preparation of Apocynum venetum Polyamide Master batch
Mixing 55 parts of apocynum venetum extract powder, 20 parts of chitin and 6 parts of starch, adding 66 parts of deionized water, adjusting the pH to 8.5 by using sodium carbonate, heating to 55-75 ℃, and mixing; shaking the mixture, distilling under reduced pressure for 0.5-1.5h, dissolving in 52 parts of deionized water, continuously filtering with semipermeable membrane, and adding 20 parts of acrylic acid into the filtered membrane; banburying the obtained product in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified herba Apocyni Veneti extract with good compatibility and mesh number of 10000 meshes.
The masterbatch was prepared as in example 1, except that the parts of the raw materials were changed. 890 parts of polyamide slices, 110 parts of modified apocynum venetum extract, 7 parts of reaction auxiliary agent, 2 parts of dispersing agent and 0.7 part of cross-linking agent are weighed, stirred uniformly and granulated to obtain apocynum venetum polyamide master batch.
Example 5 preparation of Lavender Polyamide Master batch
Mixing 60 parts of lavender extract powder, 29 parts of chitin and 7 parts of starch, adding 66 parts of deionized water, adjusting the pH value to 7.6 by using sodium carbonate, heating to 55-75 ℃, and mixing; shaking the mixture, distilling under reduced pressure for 0.5-1.5h, dissolving in 48 parts of deionized water, continuously filtering with semipermeable membrane, and adding 20 parts of acrylic acid into the filtered membrane; banburying the obtained extract in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified Lavender extract with good compatibility and mesh number of 10000 mesh.
The masterbatch was prepared as in example 1, except that the parts of the raw materials were changed. Weighing 850 parts of polyamide slices, 150 parts of modified lavender extract, 9 parts of reaction auxiliary agent, 0.9 part of dispersing agent and 0.9 part of cross-linking agent, uniformly stirring, and granulating to obtain lavender polyamide master batch.
EXAMPLE 6 preparation of a Mixed Polyamide Master batch of Isatis root and mint
The modified isatis root and mint extracts prepared in examples 2 and 3 were mixed, and 180 parts of the mixed extract was added to 11 parts of the reaction assistant. Weighing 820 parts of polyamide slices, melting, continuously stirring, adding a modified isatis root and mint extract containing a reaction auxiliary agent, 2.7 parts of a dispersing agent and 1 part of a cross-linking agent, continuously stirring, filling into a double-screw extruder, melting, extruding, cooling, and granulating by using a granulator to obtain the isatis root and mint mixed polyamide master batch.
EXAMPLE 7 preparation of a blended Polyamide Master batch of Artemisia princeps, mint, Apocynum venetum and Lavender
The modified wormwood, mint, apocynum venetum and lavender extracts prepared in examples 1, 3 and 5 are mixed, and 130 parts of the mixed extract is added with 6 parts of a reaction auxiliary agent. Weighing 870 parts of polyamide slices, melting, continuously stirring, adding modified wormwood, mint, apocynum venetum and lavender extracts containing reaction aids, 2.6 parts of dispersing agent and 0.3 part of cross-linking agent, continuously stirring, filling into a double-screw extruder, melting, extruding, cooling, and granulating by a granulator to obtain the wormwood, mint, apocynum venetum and lavender mixed polyamide master batch.
Example 8 preparation of a sarcandra glabra polyamide masterbatch
Mixing 65 parts of sarcandra glabra extract powder, 25 parts of chitin and 7 parts of starch, adding 70 parts of deionized water, adjusting the pH to 8 with sodium carbonate, heating to 55-75 ℃, and mixing; shaking the mixture uniformly, distilling under reduced pressure for 0.5-1.5h, dissolving in 50 parts of deionized water, continuously filtering with a semipermeable membrane, and adding 20 parts of acrylic acid into the filtered membrane; banburying the obtained product in an internal mixer for 3-5h, naturally drying, grinding, and sieving to obtain modified sarcandra glabra extract with good compatibility and mesh number of 10000 mesh.
The masterbatch was prepared as in example 1, except that the parts of the raw materials were changed. Weighing 840 parts of polyamide slices, 160 parts of modified sarcandra glabra extract, 8.8 parts of reaction auxiliary agent, 54 parts of dispersing agent and 0.8 part of cross-linking agent, uniformly stirring and granulating to obtain sarcandra glabra polyamide master batch.
Second, example 9-16 preparation of Polyamide fiber by spinning of plant-derived Polyamide Master batch
The plant-derived polyamide master batches prepared in examples 1 to 8 and polyamide chips are mixed according to a certain weight ratio and are processed by the working procedures of spinning, oiling, drafting, elasticizing or cutting, and the like, so that the polyamide fiber (with the specification of 1.1dtex 38mm) containing the modified plant extract is prepared. The specific feed ratio is shown in Table 1. In the preparation process of the fiber, an antioxidant and the like can be added, but other auxiliary agents are not added, and only the plant-derived polyamide master batch and the polyamide chips are used for spinning, so that the natural fiber is closer to the natural fiber, and the pursuit of people for natural green is met. The polyamide chips and the plant-derived polyamide master batches can also be blended and melted to be fed into an extruder to be stretched into a polyamide film or extruded to prepare plastics in a conventional way, and are not listed in detail here.
TABLE 1 preparation of Nylon fibers
Third, comparative example
Comparative example 1 is a general polyamide master batch to which no plant extract was added, and no plant extract was added during extrusion granulation. Comparative example 2 is the isatis root polyamide agglomerate prepared according to the method of example 2, but chitin and starch were not added in the preparation process of the isatis root extract. Comparative example 3 is a mixed polyamide master batch of isatis root and mint prepared according to the method of example 6, but chitin and starch were not added during the preparation of the extract. And (3) weighing the master batches of the comparative examples 1 to 3 according to the parts of the raw materials in the table 2, and spinning to obtain the fiber.
TABLE 2
Fourth, example of experiment
The content of the modified plant extract in the plant source polyamide master batch is screened, when the content of the modified plant extract in the master batch exceeds 20 wt%, chipping occurs on the surface of the master batch, and along with the increase of the content of the modified plant extract, the chipping also increases, the surface is not smooth, and subsequent processing is influenced. It can be seen that the more modified plant extract content is not the better. However, when the content of the modified plant extract in the polyamide master batch is too low and is lower than 1%, the antibacterial performance of the prepared fiber and other products is almost the same as that of the products without the modified plant extract. Therefore, the content of the modified plant extract in the master batch adopted by the invention is 1-20 wt%.
In the present invention, the content of the modified plant extract in the fiber and other products prepared from the plant-derived polyamide masterbatch is selected as shown in table 3. Experimental example 1 and Experimental example 2 were prepared as in example 9 except that the parts ratio of the polyamide chips to the plant-derived polyamide master batch was changed.
TABLE 3
The bacteriostasis rate of the experimental examples 1-2 to escherichia coli is 86.3-86.9%, and the yellowing grade after 3 days of illumination is grade 2. Comparative example 4 has an inhibitory rate of 85.2% against escherichia coli and a yellowing grade of 2 after 3 days of illumination. It can be seen that when the content of the modified plant extract in the fiber is less than 0.1%, the efficacy exerted by the plant is very weak, and there is little difference in efficacy from the non-modified plant extract. Although the function of the fiber and other products is increased along with the increase of the content of the modified plant extract in the fiber and other products, when the content exceeds 1 wt%, the plant extract is easy to agglomerate together, particles are formed on the surface of the fiber and other products, and scraps exist, so that the surface is not soft and smooth. Therefore, the content of the modified plant extract in the fiber, the film or the plastic and other products prepared by the plant-derived polyamide master batch is 0.1-1 wt%.
Fifth, performance test
1. Appearance shape and odor
The polyamide mother particle of comparative example 1 was regular in shape. The plant-derived polyamide master batches of examples 1 to 8 have no obvious difference from the master batch of comparative example 1, are uniform in particle, uniform in shape, smooth in surface, free of continuous particles and fragments, fragrant, good in spinnability, low in winding rate of 0.00007%, and stable in production process. However, the master batches of comparative examples 2 to 3 had rough and uneven surfaces and poor spinnability, and were susceptible to drawability, winding around rolls and breakage.
After the plant-derived polyamide master batch is placed for three months, the fact that when the content of the modified plant extract in the polyamide master batch exceeds 13 percent, the polyamide master batch still emits special plant odor, and the polyamide master batch can make people relaxed and happy when being made into products such as fibers and the like. When the content of the modified plant extract in the polyamide masterbatch is less than 13%, the odor becomes light. Therefore, the content of the modified plant extract in the master batch may preferably be 13 to 20%.
The fiber of comparative example 4 had a dull luster and a non-vivid color. The fibers of comparative examples 5-6 had slightly uneven surfaces with black spots visible to the naked eye. The plant-derived polyamide fibers of examples 9 to 16 had smooth and clean surfaces, no roughness, a faint scent, and few broken ends and filaments.
2. The obtained nylon fiber products (specification 1.1dtex 38mm) were tested, and the main test results are shown in Table 4.
TABLE 4
As can be seen from Table 4, the breaking strength of the polyamide fiber of comparative example 4 without the plant extract was 7.95cN/dtex, and the deviation ratio of the linear density was. + -. 4.5%. After the modified plant extract is added, the breaking strength of the nylon fiber of the examples 9-16 is 6.22-7.91cN/dtex, the deviation rate of the linear density is + -4.6% + -6.1%, the breaking strength after 50 times of washing is 6.00-7.59cN/dtex, the deviation rate of the linear density is + -4.9% + -6.3%, the breaking strength after 100 times of washing is 5.88-7.41cN/dtex, and the deviation rate of the linear density is + -5.2% + -6.8%. After the modified plant extract is added, the physical strength is slightly reduced, but the performance index of the nylon fiber is still a superior product. After washing for 100 times, the performance index is also a superior product. Therefore, the quality of the nylon fiber is not influenced by the addition of the modified plant extract. However, the nylon fibers of comparative examples 5 to 6 had a serious decrease in mechanical strength, which affected performance. Probably because the plant extract charred and agglomerated during the high temperature process. The film or plastic prepared from the plant-derived polyamide master batch has less reduction of mechanical properties and can meet normal use.
3. Moisture regain and yellowing rating
And (3) determining the moisture regain of the nylon fiber by an oven drying method. And respectively placing the nylon fiber in a vacuum drying oven under the irradiation of natural sunlight for 3 days and at 150 ℃ for 3 days to observe the color change, and recording the yellowing grade. The results are shown in Table 5.
TABLE 5 moisture regain and yellowing rating of Polyamide fiber
The moisture regain of the nylon fiber in comparative example 4 was 4.5%, and the moisture regain of comparative examples 5-6 was not different from that of comparative example 4. The moisture regain of the plant-derived nylon fibers of examples 9 to 16 was 6.5% to 13.2%. After the modified plant extract is added, the moisture regain of the nylon fiber can be improved to 1.4-2.9 times, and the nylon fiber is more comfortable when being directly contacted with the skin of a human body. The nylon fibers of comparative examples 4-6 had a yellowing rating of less than 3, representing significant discoloration. After the plant extract is added, the yellowing grade is 4-5, namely, the color of the nylon fiber is basically not changed after the nylon fiber is subjected to sun drying and high-temperature drying. Chinlon has poor light resistance, and the fabric becomes yellow after being dried for a long time, so that the strength is reduced, and the chinlon is not suitable for outdoor fabrics. The modified plant extract can improve the defect of poor light resistance of chinlon.
4. Antibacterial property
The antibacterial rate of the polyamide fiber is detected according to an oscillation method in the antibacterial performance of GB/T20944.3-2008 textiles, the mildew-proof detection standard is GB/T24346-. The results are shown in tables 6 to 7.
TABLE 6
TABLE 7
The bacteriostasis rates of comparative example 4 to escherichia coli, staphylococcus aureus and candida albicans are 85.2%, 83.9% and 86.2% respectively, the bacteriostasis effects of comparative examples 5-6 are superior to that of comparative example 4, but the bacteriostasis effects of examples 9-16 are optimal and are 93.6% -98.7%, 92.5% -98.2% and 94.1% -98.6% respectively. The comparative example was rated at 1 for mildew resistance and examples 9-16 were rated at 0 for mildew resistance. With the increase of the content of the modified plant extract, the antibacterial performance and the mildew-proof grade are improved. After being washed by water for 100 times, the nylon fibers containing the modified plant extracts of the examples 9-16 still can release the effective components of plants, the bacteriostasis rates on escherichia coli, staphylococcus aureus and candida albicans are 91.6-96.9%, 90.5-96.8% and 92.0-96.9%, respectively, and the mildew-proof grade is 0-1. The addition of the modified plant extract can ensure that the nylon fiber has excellent antibacterial performance and mildew-proof grade and can be kept for a long time. Other products of the plant-derived polyamide master batch, such as films or plastics, also have excellent antibacterial and mildew-proof properties.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A plant source polyamide master batch is characterized in that: the plant source polyamide master batch is prepared by blending, melting and granulating polyamide slices and modified plant extracts, wherein the addition amount of the modified plant extracts is 1-20 wt%.
2. The plant-derived polyamide masterbatch according to claim 1, characterized in that: the modified plant extract is prepared by adding chitin and starch into plant extract powder and banburying the mixture by an internal mixer.
3. The plant-derived polyamide masterbatch according to claim 1, characterized in that: the modified plant extract is one or more of herba Pileae Scriptae, folium Artemisiae Argyi, radix Isatidis, herba Menthae, herba Apocyni Veneti and Lavender.
4. A method for preparing the plant-derived polyamide masterbatch according to any one of claims 1 to 3, wherein: the preparation method of the modified extract comprises the following steps:
A1. mixing 45-75 parts of plant extract powder, 15-35 parts of chitin and 4-8 parts of starch, adding 50-80 parts of deionized water, adjusting the pH, heating to 55-75 ℃, and mixing;
A2. shaking the mixture obtained from A1 uniformly, distilling under reduced pressure, dissolving in 40-60 parts of deionized water, continuously filtering by a semipermeable membrane, and adding 10-30 parts of acrylic acid;
A3. and banburying the obtained product of A2 in an internal mixer for 1-5h, naturally drying, grinding, and sieving to obtain the modified plant extract.
5. The method for preparing the plant-derived polyamide masterbatch according to claim 4, wherein the method comprises the steps of: in step A1, the pH is adjusted to 7-9 with sodium carbonate.
6. A method for preparing the plant-derived polyamide masterbatch according to any one of claims 1 to 5, wherein the method comprises the following steps: the preparation steps are as follows:
B1. adding 4-6.5 wt% of reaction auxiliary agent into the modified plant extract;
B2. melting polyamide slices, continuously stirring, adding a modified plant extract containing a reaction auxiliary agent, a dispersing agent and a cross-linking agent, wherein the addition amount of the cross-linking agent is 0.2-0.7 wt% of the modified plant extract containing the reaction auxiliary agent, and reacting to obtain a product;
B3. and putting the product into a double-screw extruder, melting, extruding, cooling, and granulating by a granulator to obtain the plant source polyamide master batch.
7. The method for preparing the plant-derived polyamide masterbatch according to claim 6, wherein the method comprises the steps of: in the step B1, the reaction auxiliary agent is prepared from the following raw materials in parts by weight: 1-3 parts of 3, 4-dimethyl-3, 4-diphenylhexane, 1-3 parts of surface hardening and wear-resisting agent T8011-3 parts, 2-5 parts of adipic acid dihydrazide, 1.5-5 parts of epoxy chloropropane, 2-6 parts of defoaming agent BYK0251-2.5 parts, 2-6 parts of polycarbodiimide and 1-4.5 parts of zinc hydroxide.
8. The method for preparing the plant-derived polyamide masterbatch according to claim 6, wherein the method comprises the steps of: in the step B2, the dispersant is composed of 1-3 parts of single-walled carbon nanotube, 4-6 parts of trimeric fatty acid, 1-3 parts of palladium-tin modified nano titanium dioxide, 5-7 parts of isopropanolamine, 0.3-0.9 part of magnesium silicate hydroxide and 2-4 parts of polyethylene oxide, and the adding amount is 6-7 wt% of the polyamide slice, or EBS P200, and the adding amount is 0.1-2 wt% of the modified plant extract.
9. Use of the plant-derived polyamide masterbatch according to any one of claims 1 to 8 in the preparation of nylon fibers, films or plastics.
10. Use according to claim 9, characterized in that: the nylon fiber, the nylon film or the nylon plastic comprises polyamide slices and plant source polyamide master batches, and the addition amount of the plant extract is 0.1-1 wt%.
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