CN114957907A - Degradable TPE hollow fiber tube for filling pillow inner and preparation method thereof - Google Patents
Degradable TPE hollow fiber tube for filling pillow inner and preparation method thereof Download PDFInfo
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- CN114957907A CN114957907A CN202210918924.4A CN202210918924A CN114957907A CN 114957907 A CN114957907 A CN 114957907A CN 202210918924 A CN202210918924 A CN 202210918924A CN 114957907 A CN114957907 A CN 114957907A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention provides a degradable TPE hollow fiber tube for filling a pillow inner and a preparation method thereof, belonging to the field of polymer compositions. The degradable TPE hollow fiber tube for filling the pillow core is prepared from the following raw materials: SEBS, white oil, rosin oil, linear low-density polyethylene, high-density polyethylene, TPE anaerobic degradation master batch, modified carbon fiber, a modified antibacterial agent, sodium carboxymethylcellulose, an antioxidant 1010, a coupling agent KH550, diisooctyl sebacate and citric acid betaine. The tensile strength of the degradable TPE hollow fiber tube is 13.1-13.7MPa, and the elongation at break is 540-; the bacteriostasis rate to staphylococcus aureus can reach 99.8-99.9%, and the bacteriostasis rate to colibacillus can reach 98.5-98.8%.
Description
Technical Field
The invention relates to the field of polymer compositions, in particular to a degradable TPE hollow fiber tube for filling a pillow inner and a preparation method thereof.
Background
TPE, also known as thermoplastic high-elasticity plastic or thermoplastic elastomer, is an elastic material with high elasticity, high strength, high resilience, aging resistance and injection-moldable processing characteristics, can be produced by injection molding, extrusion, blow molding and other processing modes, and can be generally used as a raw material of articles such as toys, sports equipment and the like.
The TPE material is environment-friendly, nontoxic and safe, has excellent colorability, fatigue resistance and temperature resistance, is soft in touch, excellent in processing performance and free from vulcanization. Since the first preparation of Thermoplastic Polyurethane (TPU) by Bayer corporation in 1958, TPE has been rapidly developed, and particularly, since the introduction of styrenic thermoplastic elastomer in 1963, the theory of thermoplastic elastomer preparation has been gradually improved, and the application field has been further expanded. Currently, the TPEs industrially produced in the prior art are: styrenes (SBS, SIS, SEBS, SEPS), olefins (TP0, TPV), dienes (TPB, TPI), vinyl chlorides (TPVC, TCPE), urethanes (TPU), esters (TPEE), amides (TPAE), organofluorine (TPF), silicones, and vinyls, and the like, and cover almost all fields of synthetic rubbers and synthetic resins at present. Meanwhile, the TPE material can be formed independently, and can also be coated and bonded with PP, PE, PC, PS, ABS and other matrix materials. The TPE material can injection moulding for the TPE material can recycle reduce cost.
In recent years, as the TPE hose has the characteristics of softness, air permeability, no need of vulcanization, recyclability and the like, the technical scheme that the antibacterial TPE hose is used as the pillow core for filling is disclosed in the prior art, and the antibacterial TPE hose has the characteristics of light weight, good air flowability, high antibacterial rate, capability of dispersing head pressure and the like, so that the sleep health is effectively ensured. Meanwhile, the TPE hose is used as the pillow inner filler, so that the pillow inner filler has the characteristics of being washable and easy to dry after washing, can be washed by a washing machine, and is high in use convenience.
However, the inventor researches and discovers that the TPE hose is adopted as the pillow inner filler, after the TPE hose bears pressure for a long time, the TPE hose can collapse and deform, the original supporting performance cannot be provided, the head pressure cannot be effectively dispersed, and the TPE hose not only can easily cause neck ache, but also can cause adverse effects on the cervical vertebra of a human body after long-term use. Meanwhile, the inventor also finds that functional substances (such as an antibacterial agent and the like) in the existing TPE hose are easy to run off, and the phenomenon of running off of the functional substances exists in the daily washing for multiple times or the daily frequent use and friction processes, so that ideal long-term performance cannot be realized.
Further, with the continuous improvement of the requirement of green environmental protection, the requirement of rubber products on environmental protection is also continuously improved. Therefore, the degradable TPE hollow fiber tube for filling the pillow inner is also significant for environmental protection.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the degradable TPE hollow fiber tube for filling the pillow inner and the preparation method thereof, which can solve the problems of collapse, deformation and the like caused by long-term pressure bearing when the existing TPE hose is used as the pillow inner filler to be filled into the pillow, can keep good bearing performance for a long time, and can effectively disperse the pressure of the head; meanwhile, functional substances in the TPE hollow fiber tube are not easy to run off, and the functional substances are low in running-off rate in the daily multiple-washing or daily frequent-use rubbing process, so that ideal long-term performance can be maintained; and, the TPE hollow fiber tube can realize ideal degradable effect.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a degradable TPE hollow fiber tube for filling a pillow inner is prepared from the following raw materials in parts by weight: 70-80 parts of SEBS, 10-15 parts of white oil, 5-10 parts of rosin oil, 8-14 parts of linear low-density polyethylene, 25-30 parts of high-density polyethylene, 1-2 parts of TPE anaerobic degradation master batch, 7-10 parts of modified carbon fiber, 10-15 parts of modified antibacterial agent, 5-8 parts of sodium carboxymethyl cellulose, 10100.1-0.2 part of antioxidant, KH 5500.5-1.5 parts of coupling agent, 0.1-0.15 part of diisooctyl sebacate and 0.3-0.5 part of citric acid betaine.
Further, the preparation method comprises the steps of putting the raw materials into a screw extruder, and carrying out extrusion forming to obtain a hollow fiber tube; after the hollow fiber tube is shaped by a mould, cooled, pulled and cut, the degradable TPE hollow fiber tube for filling the pillow inner is prepared;
in the extrusion forming process, the screw rotating speed of the screw extruder is 200-230 rpm; the screw extruder is divided into five zones, the temperature of the first zone is controlled to be 150 ℃ plus the temperature of the second zone is controlled to be 150 ℃ plus the temperature of the first zone, the temperature of the third zone is controlled to be 190 ℃ plus the temperature of the first zone, the temperature of the fourth zone is controlled to be 150 ℃ plus the temperature of the fourth zone, and the temperature of the fifth zone is controlled to be 120 ℃ plus the temperature of the fifth zone.
Preferably, the SEBS is linear SEBS, and the styrene content is 33-40%; the viscosity in the toluene solution is 1200-1500cps at 25 ℃ and 10 wt%;
the high-density polyethylene has the crystallinity of 85-90 percent and the weight-average molecular weight of 10-20 ten thousand;
the TPE anaerobic degradation master batch is a low-pressure TPE anaerobic microorganism degradation master batch produced by Shandong Huali environmental protection engineering limited company, and the product model is TPE 6000.
The modified carbon fiber is prepared by the following steps: pretreating carbon fibers, preparing powder, carbonizing and post-treating;
the carbon fiber pretreatment method comprises the steps of putting carbon fibers into deionized water, uniformly stirring at 20-100rpm, putting the mixture into a closed environment, boosting the pressure to 19-21MPa at a boosting rate of 0.5-1.5MPa/min, and keeping the pressure stable; then heating to 368-; naturally cooling, and when the temperature is reduced to 100 ℃, releasing pressure and separating out solids to prepare the pretreated carbon fiber;
the weight part ratio of the carbon fiber to the deionized water is 1: 1-1.5;
the diameter of the carbon fiber is 5-8 μm;
the preparation method of the powder comprises the steps of putting micro silicon powder, alumina powder, titanium powder, light magnesium oxide, potassium feldspar powder and phenolic resin into a ball mill, controlling the ball-material ratio to be 8-10:1 during ball milling, the rotating speed to be 400-600rpm and the ball milling time to be 20-30min, and preparing ball grinding materials after the ball milling is finished; placing the ball-milled material on a conductive supporting plate for corona treatment for 10-20min to obtain powder;
the weight ratio of the micro silicon powder, the alumina powder, the titanium powder, the light magnesium oxide, the potassium feldspar powder and the phenolic resin is 40-50:10-15:20-30:5-10:5-10: 5-10;
in the corona treatment process, the distance between the needle electrode and the conductive supporting plate is controlled to be 5-8cm, and the corona intensity is controlled to be 20-30 kV;
the carbonization method comprises the steps of embedding the pretreated carbon fibers into 7-10 parts by volume of powder, and standing for 10-30min in an environment with a vacuum degree of 0.07-0.09 MPa; then heating to 1000-1200 ℃ at the heating rate of 4-7 ℃/min, and preserving the heat for 1-2 h; then cooling to 800-900 ℃ at the cooling rate of 0.5-1 ℃/min, and preserving the heat for 30-50 min; then naturally cooling to room temperature to prepare carbide;
the post-treatment method comprises the steps of putting the carbide into 5-8 times of hydrochloric acid solution by volume, stirring for 1-2 hours at the rotating speed of 30-150rpm, and filtering out solids; then leaching the solid with deionized water until the pH value is 5.5-6.5 to prepare modified carbon fiber;
in the hydrochloric acid solution, the mass fraction of the hydrochloric acid is 10-12 wt%.
The preparation method of the modified antibacterial agent comprises the steps of putting the diatomite and the perlite into a ball mill according to the weight ratio of 3-5:1, controlling the ball-material ratio to be 6-8:1, ball milling at the ball milling rotation speed of 500-; putting the ball mill into a load solution with the volume 2-3 times that of the ball mill, stirring at 30-80rpm for 3-5 hours, and filtering out solids; putting the solid into an environment with the vacuum degree of 0.04-0.07MPa, and drying at 75-85 ℃ until the moisture content is 0.5-1wt% to obtain a load;
the preparation method of the negative carrier liquid comprises the steps of putting tea polyphenol, chitosan, sodium chloride and acetic acid in a preset part into deionized water, and stirring at the temperature of 25-35 ℃ and 200rpm for 6-10h at 100-35 ℃ to prepare a treatment liquid;
wherein the weight ratio of the tea polyphenol, the chitosan, the sodium chloride, the acetic acid and the deionized water is 10-12:4-5:0.2-0.3:6-8: 250-300;
the particle size of the diatomite is 200-250 meshes;
the particle size of the perlite is 150-200 meshes;
the chitosan has a deacetylation degree of 80-90% and a relative molecular weight of 1500-.
The degradable TPE hollow fiber tube for filling the pillow core is prepared by the preparation method, the wall thickness is 0.1-0.3mm, the inner diameter is 5-10mm, and the length-diameter ratio is 1: 0.5-1.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the degradable TPE hollow fiber tube for filling the pillow inner, the raw material components are selected, and the carbon fiber pretreatment step, the powder preparation step and the carbonization step are arranged, so that the dispersing and enhancing effects of the modified carbon fibers in the degradable TPE hollow fiber tube are realized, the bearing performance of the degradable TPE hollow fiber tube for filling the pillow inner is improved, and the problems of collapse and deformation of the pillow due to long-term pressure bearing are solved; meanwhile, tea polyphenol and chitosan are loaded in a specific carrier (diatomite and perlite), so that the bearing performance of the degradable TPE hollow fiber tube is improved, the antibacterial function is effectively and durably exerted, and the antibacterial function is effectively prevented from being reduced in the daily multiple-time washing or daily frequent use friction process.
(2) The degradable TPE hollow fiber tube for filling the pillow inner has good mechanical property, the tensile strength is 13.1-13.7MPa, and the elongation at break is 540-; meanwhile, the pillow inner is used as the pillow inner filler to be filled into the pillow, the pillow inner is not easy to deform under the condition of bearing pressure for a long time, and the problems of collapse, deformation and the like do not exist, and the pressure is 0.1kg/cm 2 After the pressure is borne for 300 hours under the condition, the deformation rate of the TPE hose is only 0.2-0.3%, the TPE hose can keep good bearing performance for a long time, and the head pressure can be effectively dispersed.
(3) According to the degradable TPE hollow fiber tube for filling the pillow inner, the bacteriostasis rate of staphylococcus aureus can reach 99.8-99.9%, the bacteriostasis rate of escherichia coli can reach 98.5-98.8%, and bacteria breeding in the daily use process after the degradable TPE hollow fiber tube is filled into the pillow can be effectively prevented; meanwhile, functional substances in the TPE hollow fiber tube are not easy to lose, the bacteriostasis rate to staphylococcus aureus can still reach 94.4-95.4 percent after repeated washing for 50 times, the bacteriostasis rate to escherichia coli can reach 93.3-94.1 percent, and the antibacterial performance attenuation rate is lower than 5.5 percent; after stirring for 1000 hours at 60rpm, the bacteriostasis rate of the mixture on staphylococcus aureus can still reach 92.5-93.6 percent, the bacteriostasis rate on escherichia coli can reach 91.6-92.4 percent, and the attenuation rate of the antibacterial performance is lower than 7.2 percent; the problem of loss of functional substances in the daily repeated washing or daily frequent use friction process is effectively prevented, and ideal long-term performance can be effectively maintained;
(4) the degradable TPE hollow fiber tube for filling the pillow inner can be effectively degraded by microorganisms in an anaerobic environment, the degradation rate of the TPE hose is 99.02-99.17%, and the degradable TPE hollow fiber tube effectively realizes greenness, environmental protection, no pollution and outstanding environmental protection benefits.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of a degradable TPE hollow fiber tube for filling a pillow inner comprises the following raw materials in parts by weight: 70 parts of SEBS, 10 parts of white oil, 5 parts of rosin oil, 8 parts of linear low-density polyethylene, 25 parts of high-density polyethylene, 1 part of TPE anaerobic degradation master batch, 7 parts of modified carbon fiber, 10 parts of modified antibacterial agent, 5 parts of sodium carboxymethylcellulose, 10100.1 parts of antioxidant, KH 5500.5 parts of coupling agent, 0.1 part of diisooctyl sebacate and 0.3 part of citric acid betaine, putting into a screw extruder, and extruding and molding to obtain a hollow fiber tube; and after the hollow fiber tube is shaped by a mould, cooled, pulled and cut, the degradable TPE hollow fiber tube for filling the pillow inner is prepared.
The degradable TPE hollow fiber tube for filling the pillow inner has the wall thickness of 0.1mm, the inner diameter of 5mm and the length-diameter ratio of 1: 0.5.
In the extrusion forming process, the screw rotating speed of the screw extruder is 200 rpm; the screw extruder is divided into five zones, the temperature of the first zone is controlled to be 130 ℃, the temperature of the second zone is controlled to be 150 ℃, the temperature of the third zone is controlled to be 190 ℃, the temperature of the fourth zone is controlled to be 150 ℃, and the temperature of the fifth zone is controlled to be 120 ℃.
The SEBS is linear SEBS, the styrene content is 33%, and the viscosity of a toluene solution (25 ℃, 10 wt%) is 1200 cps.
The high-density polyethylene has a crystallinity of 85% and a weight-average molecular weight of 10 ten thousand.
The TPE anaerobic degradation master batch is a low-pressure TPE anaerobic microorganism degradation master batch produced by Shandong Huali environmental protection engineering limited company, and the product model is TPE 6000.
The modified carbon fiber is prepared by the following steps:
1) carbon fiber pretreatment
Putting carbon fibers into deionized water, uniformly stirring at 20rpm, putting into a closed environment, boosting to 19MPa at a boosting rate of 0.5MPa/min, and keeping the pressure stable; then heating to 368 ℃ at the heating rate of 2 ℃/min, and keeping the temperature and the pressure for 10 min; naturally cooling, and when the temperature is reduced to 100 ℃, releasing pressure and separating out solids to obtain the pretreated carbon fiber.
Wherein the weight part ratio of the carbon fiber to the deionized water is 1:1.
The diameter of the carbon fiber is 5 μm.
2) Preparation of powder
Putting silica fume, alumina powder, titanium powder, light magnesium oxide, potassium feldspar powder and phenolic resin into a ball mill, controlling the ball-to-material ratio to be 8:1 during ball milling, the rotating speed to be 400rpm, and the ball milling time to be 20min, and preparing a ball grinding material after the ball milling is finished; and placing the ball-milled material on a conductive supporting plate for corona treatment for 10min to obtain powder.
Wherein the weight ratio of the micro silicon powder, the alumina powder, the titanium powder, the light magnesium oxide, the potassium feldspar powder and the phenolic resin is 40:10:20:5:5: 5.
In the corona treatment process, the distance between the control needle electrode and the conductive supporting plate is 5cm, and the corona intensity is 20 kV.
3) Carbonizing
Embedding the pretreated carbon fibers into 7 parts by volume of powder, and then standing for 10min in an environment with a vacuum degree of 0.07 MPa; then heating to 1000 ℃ at the heating rate of 4 ℃/min, and preserving heat for 1 h; then cooling to 800 ℃ at a cooling rate of 0.5 ℃/min, and preserving heat for 30 min; then naturally cooling to room temperature to prepare carbide.
4) Post-treatment
Adding the carbide into 5-time volume part of hydrochloric acid solution, stirring for 1h at the rotating speed of 30rpm, and filtering out solid; and then leaching the solid with deionized water until the pH value is 5.5 to prepare the modified carbon fiber.
In the hydrochloric acid solution, the mass fraction of hydrochloric acid is 10 wt%.
The modified antibacterial agent is prepared by the following steps: putting the diatomite and the perlite into a ball mill according to the weight ratio of 3:1, controlling the ball-to-material ratio to be 6:1, ball-milling at the rotating speed of 500rpm for 40min, and preparing a ball-milled material; putting the ball mill into 2 times of load liquid, stirring at 30rpm for 3h, and filtering out solids; and (3) putting the solid into an environment with the vacuum degree of 0.04MPa, and drying at 75 ℃ until the moisture content is 0.5wt% to obtain the load.
The particle size of the diatomite is 200 meshes.
The particle size of the perlite is 150 meshes.
The preparation method of the negative carrier liquid comprises the steps of putting tea polyphenol, chitosan, sodium chloride and acetic acid in a preset part into deionized water, and stirring for 6 hours at 100rpm under the condition of 25 ℃ to prepare the treatment liquid.
Wherein the ratio of the tea polyphenol to the chitosan to the sodium chloride to the acetic acid to the deionized water is 10:4:0.2:6: 250.
The chitosan has a deacetylation degree of 80% and a relative molecular weight of 1500.
Example 2
A preparation method of a degradable TPE hollow fiber tube for filling a pillow inner comprises the following raw materials in parts by weight: 75 parts of SEBS, 12 parts of white oil, 8 parts of rosin oil, 10 parts of linear low-density polyethylene, 28 parts of high-density polyethylene, 1.5 parts of TPE anaerobic degradation master batch, 8 parts of modified carbon fiber, 12 parts of modified antibacterial agent, 7 parts of sodium carboxymethylcellulose, 10100.15 parts of antioxidant, KH 5501 parts of coupling agent, 0.12 part of diisooctyl sebacate and 0.4 part of citric acid betaine, putting into a screw extruder, and extruding and forming to obtain a hollow fiber tube; and after the hollow fiber tube is shaped by a mould, cooled, pulled and cut, the degradable TPE hollow fiber tube for filling the pillow inner is prepared.
The degradable TPE hollow fiber tube for filling the pillow inner has the wall thickness of 0.2mm, the inner diameter of 8mm and the length-diameter ratio of 1: 0.8.
In the extrusion forming process, the rotating speed of a screw of the screw extruder is 220 rpm; the screw extruder is divided into five zones, the temperature of the first zone is controlled to be 140 ℃, the temperature of the second zone is controlled to be 160 ℃, the temperature of the third zone is controlled to be 200 ℃, the temperature of the fourth zone is controlled to be 160 ℃, and the temperature of the fifth zone is controlled to be 130 ℃.
The SEBS was a linear SEBS having a styrene content of 38% and a toluene solution (25 ℃ C., 10 wt%) viscosity of 1400 cps.
The high-density polyethylene has the crystallinity of 88 percent and the weight-average molecular weight of 15 ten thousand.
The TPE anaerobic degradation master batch is a low-pressure TPE anaerobic microorganism degradation master batch produced by Shandong Huali environmental protection engineering limited company, and the product model is TPE 6000.
The modified carbon fiber is prepared by the following steps:
1) carbon fiber pretreatment
Putting carbon fibers into deionized water, uniformly stirring at 80rpm, putting into a closed environment, boosting to 20MPa at a boosting rate of 1MPa/min, and keeping the pressure stable; then heating to 370 ℃ at the heating rate of 4 ℃/min, and keeping the temperature and the pressure for 15 min; naturally cooling, and when the temperature is reduced to 100 ℃, releasing pressure and separating out solids to obtain the pretreated carbon fiber.
Wherein the weight part ratio of the carbon fiber to the deionized water is 1: 1.2.
The diameter of the carbon fiber is 7 μm.
2) Preparation of the powder
Putting silica fume, alumina powder, titanium powder, light magnesium oxide, potassium feldspar powder and phenolic resin into a ball mill, controlling the ball-to-material ratio of 9:1 during ball milling, the rotating speed of 500rpm and the ball milling time of 25min, and preparing a ball grinding material after the ball milling is finished; and placing the ball-milled material on a conductive supporting plate for corona treatment for 15min to obtain powder.
Wherein the weight ratio of the micro silicon powder, the alumina powder, the titanium powder, the light magnesium oxide, the potassium feldspar powder and the phenolic resin is 45:12:25:8:7: 7.
In the corona treatment process, the distance between the control needle electrode and the conductive supporting plate is 6cm, and the corona intensity is 25 kV.
3) Carbonizing
Embedding the pretreated carbon fibers into 8 parts by volume of powder, and then standing for 20min in an environment with a vacuum degree of 0.08 MPa; then heating to 1100 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1.5 h; then cooling to 850 ℃ at a cooling rate of 0.8 ℃/min, and preserving heat for 40 min; then naturally cooling to room temperature to prepare carbide.
4) Post-treatment
Putting the carbide into 6-time volume part of hydrochloric acid solution, stirring for 1.5h at the rotating speed of 100rpm, and filtering out solids; and then leaching the solid with deionized water until the pH value is 6.0 to obtain the modified carbon fiber.
In the hydrochloric acid solution, the mass fraction of hydrochloric acid is 11 wt%.
The modified antibacterial agent is prepared by the following steps: putting the diatomite and the perlite into a ball mill according to the weight ratio of 4:1, controlling the ball-material ratio to be 7:1, ball-milling at the rotating speed of 600rpm for 50min, and preparing a ball-milled material; putting the ball mill into 2.5 times of load liquid, stirring at 60rpm for 4h, and filtering out solids; and (3) putting the solid into an environment with the vacuum degree of 0.05MPa, and drying at 80 ℃ until the moisture content is 0.7wt% to obtain the load.
The particle size of the diatomite is 220 meshes.
The particle size of the perlite is 180 meshes.
The preparation method of the negative carrier liquid comprises the steps of putting tea polyphenol, chitosan, sodium chloride and acetic acid in a preset part into deionized water, and stirring at the temperature of 30 ℃ and at the speed of 150rpm for 8 hours to prepare the treatment liquid.
Wherein the ratio of the tea polyphenol to the chitosan to the weight parts of the sodium chloride to the acetic acid to the deionized water is 11:4.5:0.25:7: 280.
The chitosan has a deacetylation degree of 85% and a relative molecular weight of 1550.
Example 3
A preparation method of a degradable TPE hollow fiber tube for filling a pillow inner comprises the following raw materials in parts by weight: 80 parts of SEBS, 15 parts of white oil, 10 parts of rosin oil, 14 parts of linear low-density polyethylene, 30 parts of high-density polyethylene, 2 parts of TPE anaerobic degradation master batch, 10 parts of modified carbon fiber, 15 parts of modified antibacterial agent, 8 parts of sodium carboxymethylcellulose, 10100.2 parts of antioxidant, KH 5501.5 parts of coupling agent, 0.15 part of diisooctyl sebacate and 0.5 part of citric acid betaine, putting into a screw extruder, and extruding and molding to obtain a hollow fiber tube; and after the hollow fiber tube is shaped by a mould, cooled, pulled and cut, the degradable TPE hollow fiber tube for filling the pillow inner is prepared.
The degradable TPE hollow fiber tube for filling the pillow inner has the wall thickness of 0.3mm, the inner diameter of 10mm and the length-diameter ratio of 1:1.
In the extrusion forming process, the rotating speed of a screw of the screw extruder is 230 rpm; the screw extruder is divided into five zones, the temperature of the first zone is controlled to be 150 ℃, the temperature of the second zone is controlled to be 170 ℃, the temperature of the third zone is controlled to be 210 ℃, the temperature of the fourth zone is controlled to be 170 ℃, and the temperature of the fifth zone is controlled to be 140 ℃.
The SEBS is linear SEBS, the styrene content is 40%, and the viscosity of a toluene solution (25 ℃, 10 wt%) is 1500 cps.
The high-density polyethylene has the crystallinity of 90 percent and the weight-average molecular weight of 20 ten thousand.
The TPE anaerobic degradation master batch is a low-pressure TPE anaerobic microorganism degradation master batch produced by Shandong Huali environmental protection engineering Limited company, and the product model is TPE 6000.
The modified carbon fiber is prepared by the following steps:
1) carbon fiber pretreatment
Putting carbon fibers into deionized water, uniformly stirring at 100rpm, placing in a closed environment, boosting to 21MPa at a boosting rate of 1.5MPa/min, and keeping the pressure stable; then heating to 372 ℃ at the heating rate of 5 ℃/min, and keeping the temperature and the pressure for 20 min; naturally cooling, and when the temperature is reduced to 100 ℃, releasing pressure and separating out solids to obtain the pretreated carbon fiber.
Wherein the weight part ratio of the carbon fiber to the deionized water is 1: 1.5.
The diameter of the carbon fiber is 8 μm.
2) Preparation of powder
Putting silica fume, alumina powder, titanium powder, light magnesium oxide, potassium feldspar powder and phenolic resin into a ball mill, controlling the ball-to-material ratio of 10:1 during ball milling, the rotating speed of 600rpm and the ball milling time of 30min, and preparing a ball grinding material after the ball milling is finished; and placing the ball-milled material on a conductive supporting plate for corona treatment for 20min to obtain powder.
Wherein the weight ratio of the micro silicon powder, the alumina powder, the titanium powder, the light magnesium oxide, the potassium feldspar powder and the phenolic resin is 50:15:30:10:10: 10.
In the corona treatment process, the distance between the control needle electrode and the conductive supporting plate is 8cm, and the corona intensity is 30 kV.
3) Carbonizing
Embedding the pretreated carbon fibers into 10 parts by volume of powder, and then standing for 30min in an environment with a vacuum degree of 0.09 MPa; then heating to 1200 ℃ at the heating rate of 7 ℃/min, and preserving heat for 2 h; then cooling to 900 ℃ at a cooling rate of 1 ℃/min, and keeping the temperature for 50 min; then naturally cooling to room temperature to prepare carbide.
4) Post-treatment
Putting the carbide into 8 times of hydrochloric acid solution by volume, stirring for 2 hours at the rotating speed of 150rpm, and filtering out solids; and then leaching the solid with deionized water until the pH value is 6.5 to obtain the modified carbon fiber.
In the hydrochloric acid solution, the mass fraction of hydrochloric acid is 12 wt%.
The modified antibacterial agent is prepared by the following steps: putting the diatomite and the perlite into a ball mill according to the weight ratio of 5:1, controlling the ball-material ratio to be 8:1, ball-milling at the rotating speed of 700rpm for 60min, and preparing a ball-milled material; putting the ball mill into a load solution with the volume 3 times that of the ball mill, stirring at 80rpm for 5 hours, and filtering out solids; and (3) putting the solid into an environment with the vacuum degree of 0.07MPa, and drying at 85 ℃ until the moisture content is 1wt% to obtain the load.
The particle size of the diatomite is 250 meshes.
The particle size of the perlite is 200 meshes.
The preparation method of the negative carrier liquid comprises the steps of putting tea polyphenol, chitosan, sodium chloride and acetic acid in a preset part into deionized water, and stirring at 200rpm for 10 hours at the temperature of 35 ℃ to prepare the treatment liquid.
Wherein the ratio of the tea polyphenol to the chitosan to the weight parts of the sodium chloride to the acetic acid to the deionized water is 12:5:0.3:8: 300.
The chitosan has deacetylation degree of 80-90% and relative molecular weight of 1600.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) the carbon fiber pretreatment step in the preparation of the modified carbon fiber and the corona treatment in the powder preparation step are omitted; 2) chitosan and tea polyphenol are used as antibacterial agents to replace modified antibacterial agents; wherein the weight ratio of chitosan to tea polyphenol is 1: 2.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) replacing modified carbon fibers with carbon fibers of the same specification; 2) omitting the tea polyphenols used in the preparation of the modified antibacterial agent, and supplementing the omitted tea polyphenols with chitosan; namely, the weight part ratio of the chitosan, the sodium chloride and the acetic acid in the loading liquid is 15.5:0.25:7: 280.
Test example 1
By adopting the technical schemes of the embodiments 1-3 and the comparative examples 1-2, the wall thickness of the degradable TPE hollow fiber tube for filling the pillow inner prepared by the technical schemes is adjusted to be 0.2mm, the inner diameter is 8mm, and the length-diameter ratio is 1:0.8, and the degradable TPE hollow fiber tube is used as a test sample. The tensile strength and the elongation at break of each test sample are detected, the specific detection method refers to JIS K6251-2017, and the specific test results are as follows:
furthermore, each test sample is used as a filler and is respectively filled into a pillow case with the size of 40cm multiplied by 60cm multiplied by 10cm, and the quantity of the filled degradable TPE hollow fiber tubes in each pillow case is ensured to be the same.
Respectively applying pressure to the pillow filled with each test sample for 300h, and keeping the pressure applied to the pillow at 0.1kg/cm during the pressure application 2 And standing and rebounding for 30min after the pressure is applied, and counting the probability of deformation of the degradable TPE hollow fiber tube serving as the filler in each pillow filled with the test sample.
Wherein, the probability (namely the deformation rate) that the hollow fiber pipe of the degradable TPE is deformed, and the calculation method comprises the following steps: (the number of deformed degradable TPE hollow fiber tubes/the total number of the degradable TPE hollow fiber tubes filled in the pillow) x 100%.
The specific test results are as follows:
further, antibacterial performance detection of staphylococcus aureus, escherichia coli and candida albicans is respectively carried out on each test sample, the specific antibacterial performance detection method refers to the related content of GB/T31402-. The specific test results are as follows:
further, the test samples of examples 1 to 3 were respectively put into 10 times of volume of deionized water, and stirred and washed at a stirring speed of 30RPM for 30min, which is a primary water washing step; and after 50 times of water washing, performing antibacterial performance detection on staphylococcus aureus and escherichia coli on each test sample. The specific test results are as follows:
further, the test samples of examples 1 to 3 were put into a 30L stirred tank in an amount of 50% of the volume of the stirred tank, and stirred at a stirring speed of 60RPM, the test samples were rubbed against each other, and after stirring for 1000 hours, the test samples were subjected to the antimicrobial property test of staphylococcus aureus and escherichia coli. The specific test results are as follows:
further, the test samples of examples 1 to 3 were placed in an inoculum containing a methanogenic anaerobic microorganism (from an anaerobic digester), and anaerobic microorganism degradation tests were performed under dark conditions until five consecutive days without gas production, and the degradation rate of each test sample was measured. Specific test methods refer to ASTM D5511. The specific test results are as follows:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: 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 (4)
1. A preparation method of a degradable TPE hollow fiber tube for filling a pillow core is characterized by comprising the following raw materials in parts by weight: 70-80 parts of SEBS, 10-15 parts of white oil, 5-10 parts of rosin oil, 8-14 parts of linear low-density polyethylene, 25-30 parts of high-density polyethylene, 1-2 parts of TPE anaerobic degradation master batch, 7-10 parts of modified carbon fiber, 10-15 parts of modified antibacterial agent, 5-8 parts of sodium carboxymethyl cellulose, 10100.1-0.2 part of antioxidant, KH 5500.5-1.5 parts of coupling agent, 0.1-0.15 part of diisooctyl sebacate and 0.3-0.5 part of citric acid betaine;
the modified carbon fiber is prepared by the following steps: carbon fiber pretreatment, powder preparation, carbonization and aftertreatment;
the carbon fiber pretreatment method comprises the steps of putting carbon fibers into deionized water, uniformly stirring at 20-100rpm, putting the mixture into a closed environment, boosting the pressure to 19-21MPa at a boosting rate of 0.5-1.5MPa/min, and keeping the pressure stable; then heating to 368-; naturally cooling, and when the temperature is reduced to 100 ℃, releasing pressure and separating out solids to prepare the pretreated carbon fiber;
the weight part ratio of the carbon fiber to the deionized water is 1: 1-1.5;
the diameter of the carbon fiber is 5-8 μm;
the preparation method of the powder comprises the steps of putting micro silicon powder, alumina powder, titanium powder, light magnesium oxide, potassium feldspar powder and phenolic resin into a ball mill, controlling the ball-material ratio to be 8-10:1 during ball milling, the rotating speed to be 400-600rpm and the ball milling time to be 20-30min, and preparing ball grinding materials after the ball milling is finished; placing the ball-milled material on a conductive supporting plate for corona treatment for 10-20min to obtain powder;
the weight ratio of the micro silicon powder, the alumina powder, the titanium powder, the light magnesium oxide, the potassium feldspar powder and the phenolic resin is 40-50:10-15:20-30:5-10:5-10: 5-10;
in the corona treatment process, the distance between the needle electrode and the conductive supporting plate is controlled to be 5-8cm, and the corona intensity is controlled to be 20-30 kV;
the carbonization method comprises the steps of embedding the pretreated carbon fibers into 7-10 parts by volume of powder, and standing for 10-30min in an environment with a vacuum degree of 0.07-0.09 MPa; then heating to 1000-1200 ℃ at the heating rate of 4-7 ℃/min, and preserving the heat for 1-2 h; then cooling to 800-900 ℃ at the cooling rate of 0.5-1 ℃/min, and preserving the heat for 30-50 min; then naturally cooling to room temperature to prepare carbide;
the post-treatment method comprises the steps of putting the carbide into 5-8 times of hydrochloric acid solution by volume, stirring for 1-2 hours at the rotating speed of 30-150rpm, and filtering out solids; then leaching the solid with deionized water until the pH value is 5.5-6.5 to prepare modified carbon fiber;
in the hydrochloric acid solution, the mass fraction of the hydrochloric acid is 10-12 wt%;
the preparation method of the modified antibacterial agent comprises the steps of putting the diatomite and the perlite into a ball mill according to the weight ratio of 3-5:1, controlling the ball-material ratio to be 6-8:1, ball milling at the ball milling rotation speed of 500-; putting the ball mill into a load solution with the volume 2-3 times that of the ball mill, stirring at 30-80rpm for 3-5 hours, and filtering out solids; putting the solid into an environment with the vacuum degree of 0.04-0.07MPa, and drying at 75-85 ℃ until the moisture content is 0.5-1wt% to obtain a load;
the preparation method of the negative carrier liquid comprises the steps of putting tea polyphenol, chitosan, sodium chloride and acetic acid in a preset part into deionized water, and stirring at the temperature of 25-35 ℃ and 200rpm for 6-10h at 100-35 ℃ to prepare a treatment liquid;
wherein the weight ratio of the tea polyphenol, the chitosan, the sodium chloride, the acetic acid and the deionized water is 10-12:4-5:0.2-0.3:6-8: 250-300;
the particle size of the diatomite is 200-250 meshes;
the particle size of the perlite is 150-200 meshes;
the chitosan has a deacetylation degree of 80-90% and a relative molecular weight of 1500-.
2. The method for preparing the degradable TPE hollow fiber tube for pillow inner filling according to claim 1 is characterized in that the method comprises the steps of putting raw materials into a screw extruder, and extruding and forming to obtain the hollow fiber tube; after the hollow fiber tube is shaped by a mould, cooled, pulled and cut, the degradable TPE hollow fiber tube for filling the pillow inner is prepared;
in the extrusion forming process, the screw rotating speed of the screw extruder is 200-230 rpm; the screw extruder is divided into five zones, the temperature of the first zone is controlled to be 150-.
3. The method for preparing the degradable TPE hollow fiber tube for filling the pillow inner according to claim 1, wherein the SEBS is linear SEBS, and the content of styrene is 33-40%; under the conditions of 25 ℃ and 10wt%, the viscosity in the toluene solution is 1200-1500 cps;
the high-density polyethylene has the crystallinity of 85-90 percent and the weight-average molecular weight of 10-20 ten thousand;
the TPE anaerobic degradation master batch is a low-pressure TPE anaerobic microorganism degradation master batch produced by Shandong Huali environmental protection engineering Limited company, and the product model is TPE 6000.
4. The degradable TPE hollow fiber tube for filling the pillow inner is characterized by being prepared by the preparation method of any one of claims 1 to 3, and the wall thickness of the degradable TPE hollow fiber tube for filling the pillow inner is 0.1-0.3mm, the inner diameter is 5-10mm, and the length-diameter ratio is 1: 0.5-1.
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| CN118256058A (en) * | 2024-05-31 | 2024-06-28 | 山东立卓睡眠科技有限公司 | Degradable TPE hollow tubular filler and preparation method thereof |
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