CN118344723A - TPU film with moisture permeability and processing technology thereof - Google Patents
TPU film with moisture permeability and processing technology thereof Download PDFInfo
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- CN118344723A CN118344723A CN202410595892.8A CN202410595892A CN118344723A CN 118344723 A CN118344723 A CN 118344723A CN 202410595892 A CN202410595892 A CN 202410595892A CN 118344723 A CN118344723 A CN 118344723A
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- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application relates to the field of TPU films, and particularly discloses a TPU film with moisture permeability and a processing technology thereof. The TPU film with the moisture permeability comprises the following components in parts by weight: comprises the following components in parts by mass: 100 parts of thermoplastic polyurethane elastomer, 10-20 parts of modified sepiolite fiber, 4-10 parts of toughening agent, 1-4 parts of antioxidant and 8-12 parts of anti-sticking agent; the modified sepiolite fiber is lignin modified sepiolite fiber; the preparation method comprises the following steps: mixing the raw materials according to the proportion to form a mixture; extruding, cooling and granulating the mixture to obtain premixed particles; and extruding, tape casting and forming the premixed particles to obtain the TPU film with the moisture permeability. The TPU film with the moisture permeability has the advantages of good moisture permeability and strong stretching performance.
Description
Technical Field
The application relates to the field of TPU films, in particular to a TPU film with moisture permeability and a processing technology thereof.
Background
The thermoplastic polyurethane elastomer TPU is a high polymer prepared from the main raw materials of oligomer polyol, polyisocyanate and chain extender, and has excellent comprehensive properties such as high strength, high toughness, wear resistance, oil resistance and the like and good processability. The TPU film is a film prepared from TPU master batches through processes such as calendaring, casting, film blowing or coating, has the characteristics of high elongation, high strength, high wear resistance, low temperature resistance and the like, and has unique application in medical treatment, electronics, chemical industry, construction, national defense and spinning.
TPU films have relatively high water resistance, but generally have relatively poor permeability to small molecular substances such as oxygen, water vapor, and the like. In the related art, the moisture permeability of the TPU film is often improved by increasing the hydrophilicity of the TPU high polymer material and preparing a non-porous hydrophilic film, and the non-porous hydrophilic film can prevent macromolecule water drops from passing through due to the non-porous structure of the non-porous hydrophilic film, and meanwhile, due to the fact that more hydrophilic groups exist in a high polymer chain segment, the non-porous hydrophilic film can interact with water molecules by means of hydrogen bonds and other intermolecular forces, adsorb the water molecules on the high humidity side and then transmit the water molecules to the low humidity side for desorption, so that the moisture permeability effect is achieved.
However, the mechanical properties such as tensile strength of the conventional hydrophilic TPU film are not good enough, and the application range is limited, so that the improvement is needed.
Disclosure of Invention
In order to improve the stretching performance of the moisture permeability TPU film, the application provides a TPU film with excellent moisture permeability and stretching performance and a processing technology thereof.
In a first aspect, the application provides a TPU film with moisture permeability, which adopts the following technical scheme:
the TPU film with the moisture permeability comprises the following components in parts by mass:
100 parts of thermoplastic polyurethane elastomer,
10-20 Parts of modified sepiolite fiber,
4-10 Parts of toughening agent,
1-4 Parts of antioxidant,
8-12 Parts of an anti-sticking agent;
the modified sepiolite fiber is lignin modified sepiolite fiber.
By adopting the technical scheme, the modified sepiolite fiber has rich water channels and pore structures, and the surface of the modified sepiolite fiber has rich hydrophilic groups, so that the moisture permeability of the TPU film can be improved, after the TPU film adsorbs water molecules on the high-humidity side by means of the hydrophilic groups, the water molecules can be transferred from the water channel structure of the modified sepiolite fiber to the low-humidity side, and the moisture permeability effect and efficiency of the TPU film are improved;
The modified sepiolite fiber has better wear resistance, corrosion resistance, elasticity and the like, and the modified sepiolite fiber can form a network-shaped inorganic framework structure after being dispersed in a TPU system, so that the mechanical property of the TPU film is improved, and the tensile strength of the TPU film is enhanced; the lignin loaded on the surface of the modified sepiolite fiber can be cross-linked with a thermoplastic polyurethane elastomer, a toughening agent and the like to form an organic network structure, so that the dispersion uniformity of the modified sepiolite fiber in a TPU system is improved, the organic system is connected with an inorganic sepiolite fiber skeleton system, the improvement of the tensile strength of the TPU film is further promoted, meanwhile, sepiolite can be stably dispersed in the TPU system, the hygroscopicity is further improved, the use effect of the TPU film is enhanced, and the application range is enlarged.
Preferably, the preparation method of the modified sepiolite fiber comprises the following steps:
adding lignin and a macromolecular surfactant into a solvent, uniformly mixing, and performing ultrasonic treatment at 30-50 ℃ for 5-20min to obtain a modified solution;
Immersing sepiolite fiber into the modified solution, uniformly mixing, adjusting the pH value to 4.5-6, performing ultrasonic treatment at 60-90 ℃ for 60-120min, performing suction filtration, and drying to obtain lignin modified sepiolite fiber.
Preferably, in the modified solution, the mass fraction of lignin is 5-15%, and the mass fraction of the macromolecular surfactant is 10-25%; the mass of the sepiolite fiber is 15-30% of that of the modifying solution.
Through the technical scheme, the lignin molecule is provided with the phenylpropane network skeleton structure, the molecular side chain contains rich active hydrophilic groups, the lignin molecule interacts with the macromolecular surfactant, the phenylpropane skeleton of the lignin molecule is wrapped by the hydrophobic section of the macromolecular surfactant, and interaction forces such as hydrogen bonds and the like are formed between the hydrophilic end and the active group of the lignin molecule, so that a lignin coating is formed; the lignin coating interacts with the sepiolite fiber, the hydroxyl group of the high molecular surfactant, the active group of lignin and the active silicon hydroxyl group on the surface of the sepiolite fiber react with each other, and the lignin coating is grafted to the sepiolite fiber to obtain lignin modified sepiolite fiber; the hydrophobic skeleton of lignin is wrapped by more flexible polymer surfactant chain segments, which is favorable for improving the tensile property, and active groups rich in lignin can improve the water absorbability of sepiolite fibers, interact with TPU, toughening agents and other organic molecules in the TPU film to form a crosslinked structure, improve the compatibility of the sepiolite fibers and an organic system, promote the uniform dispersion of the sepiolite fibers and be favorable for improving the moisture permeability and the tensile strength of the TPU film.
Preferably, the macromolecular surfactant is carboxymethyl chitosan derivative, and the preparation method comprises the following steps:
Dissolving carboxymethyl chitosan in water, regulating pH to 10-11, adding dodecyl glycidyl ether, mixing, reacting at 60-80 deg.c for 6-8 hr, regulating pH to 4-5, precipitating with acetone, washing the product, filtering, and vacuum drying to obtain carboxymethyl chitosan derivative.
Preferably, the dosage ratio of the carboxymethyl chitosan to the dodecyl glycidyl ether is 1 (0.8-1.2) g/mL.
By adopting the technical scheme, the carboxymethyl chitosan has good hydrophilicity, the carboxymethyl chitosan and the dodecyl glycidyl ether are subjected to condensation reaction, a hydrophobic side chain is introduced into the generated carboxymethyl chitosan derivative, the phenylpropane skeleton of lignin is wrapped by the hydrophobic section of the carboxymethyl chitosan derivative, the hydrophilic end has higher reactivity with the active silicon hydroxyl on the surface of the sepiolite fiber, and the loading efficiency and effect of the lignin on the surface of the sepiolite fiber are improved.
Preferably, the lignin is methylolated lignin.
Preferably, the preparation method of the methylolated lignin comprises the following steps:
Dissolving alkali lignin in sodium hydroxide solution, dispersing uniformly, regulating pH value to 10.5-12, adding formaldehyde solution into the solution, uniformly mixing, reacting for 90-150min at 75-90 ℃, regulating pH value of reaction solution to 3-4, preserving heat for 60min at 55-65 ℃, filtering, washing to neutrality, and vacuum drying to obtain methylolated lignin.
Preferably, the mass concentration of the formaldehyde solution is 37%; the mass ratio of the alkali lignin to the formaldehyde solution is 1 (0.25-0.75).
By adopting the technical scheme, the alkali lignin molecular chain contains various groups such as oxygen groups, phenolic hydroxyl groups, aldehyde groups, carboxyl groups and the like, but the hydroxyl content is limited, and the reaction of the alkali lignin and formaldehyde is used for improving the hydroxyl content on the lignin molecular chain, so that the reaction activity and the hydrophilicity of lignin molecules are improved.
Preferably, the sepiolite fiber is subjected to an activation treatment before the modification operation, and the activation treatment step includes: calcining sepiolite fiber at 200-300 deg.C for 10-20min, placing calcined sepiolite fiber in sodium hydroxide solution, ultrasonic treating for 20-40min, suction filtering, washing, and drying to obtain activated sepiolite fiber.
By adopting the technical scheme, the zeolite water in the sepiolite fiber can be removed by high-temperature activation, the pore diameter of the sepiolite fiber is increased, and the strength and the number of the surface activation centers are increased; and then the sepiolite fiber is treated by sodium hydroxide solution, so that soluble impurities in the sepiolite fiber are reduced, a large number of hydroxyl groups are formed on the surface of the sepiolite fiber, and the reactivity of the sepiolite fiber is improved.
Preferably, the toughening agent is hydroxyethyl acrylate.
By adopting the technical scheme, the hydroxyethyl acrylate can form a hydrogen bond with lignin molecules loaded on TPU and modified sepiolite fibers to participate in a hydrogen bond crosslinking network, so that a short flexible chain is increased, and the toughness and the tensile strength of the TPU film are improved.
Preferably, the antioxidant comprises hindered phenol antioxidant and phosphite antioxidant with mass ratio of 1 (1-3).
By adopting the technical scheme, the oxygen aging rate of the TPU film is slowed down.
In a second aspect, the application provides a processing technology of a TPU film with moisture permeability, which adopts the following technical scheme:
a processing technology of TPU film with moisture permeability comprises the following steps:
Mixing a thermoplastic polyurethane elastomer, modified sepiolite fibers, a toughening agent, an antioxidant and an anti-sticking agent according to a proportion to form a mixture;
extruding, cooling and granulating the mixture to obtain premixed particles;
And extruding, casting and forming the premixed particles to obtain the TPU film with moisture permeability.
Preferably, the screw speed of the casting molding step of the premixed particles is 100-300r/min, the extrusion temperature is 80-200 ℃, the die head temperature is 100-200 ℃, and the roller speed is 300-500m/min.
By adopting the technical scheme, the TPU film with good moisture permeability, better toughness and tensile strength can be prepared, the application range of the TPU film is enlarged, and the application effect is enhanced.
In summary, the application has the following beneficial effects:
1. In the application, the modified sepiolite fiber is dispersed in the TPU system to form a network-shaped inorganic framework structure, so that the improvement of the mechanical property of the TPU film is promoted, and the tensile strength of the TPU film is enhanced; lignin loaded on the surface of the modified sepiolite fiber can be cross-linked with a thermoplastic polyurethane elastomer, a toughening agent and the like to form an organic network structure, so that the dispersion uniformity of the modified sepiolite fiber in a TPU system is improved, and the organic system is connected with an inorganic sepiolite fiber skeleton system to further promote the improvement of the tensile strength of the TPU film, thereby being beneficial to enhancing the use effect of the TPU film and expanding the application range;
2. In the application, the methylolated lignin is preferably adopted, so that the hydroxyl content on lignin molecular chains is improved, the reactivity and hydrophilicity of lignin molecules are improved, the water absorption of the TPU film is improved, the moisture permeability of the TPU film is further improved, the hydrogen bond crosslinking between the methylolated lignin and small molecules of the TPU and the toughening agent is improved, and the toughness of the TPU film is improved.
3. In the application, the sepiolite fiber is preferably activated before modification operation, so that the pore space of the water channel and the pore space of the sepiolite fiber is enlarged, the surface activity of the sepiolite fiber is improved, the loading of the sepiolite fiber on lignin is promoted, and the moisture permeability and the tensile strength of the TPU film are further improved.
Detailed Description
To further assist understanding of the technical solution of the present invention, the technical solution of the present invention will be described in more detail below by providing several specific examples of implementation, all of which are only some of the embodiments of the present invention, but not all;
The following embodiments may be combined with each other, and the same or similar concepts or processes may not be described in detail in some embodiments; the reaction apparatus, monomer compounds, organic solvents, and the like according to the following examples are commercially available.
The following specific embodiments may be combined with each other and may not be described in detail in some embodiments for the same or similar concepts or processes therein.
The following examples are further illustrative of the invention, which is not limited thereto. The embodiment is not specifically described, and the percentage content is mass percentage.
Preparation example
Preparation example 1
The preparation example provides a modified sepiolite fiber, which is prepared by the following steps:
Adding 1.2kg of wheat straw alkali lignin and 1.8kg of high molecular surfactant into 7kg of water, stirring and mixing uniformly, and carrying out ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
Immersing 2kg of sepiolite fiber into the modified solution, stirring and dispersing uniformly, dripping 0.1mol/L hydrochloric acid solution to adjust the pH value to 5, performing ultrasonic treatment at 65 ℃ for 2 hours, performing suction filtration, and performing vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
In the preparation example, the high molecular surfactant is glycerol polyoxyethylene ether G-18, and the model is keplerian kpl-30434.
Preparation example 2
The preparation example differs from the preparation example only in that the preparation method of the modified sepiolite fiber is as follows:
Adding 0.5kg of wheat straw alkali lignin and 1kg of glycerol polyoxyethylene ether into 8.5kg of water, stirring and mixing uniformly, and carrying out ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
immersing 1.5kg of sepiolite fiber into the modified solution, stirring and dispersing uniformly, adjusting the pH value to 5, carrying out ultrasonic treatment for 2 hours at 65 ℃, carrying out suction filtration, and carrying out vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
Preparation example 3
The preparation example differs from the preparation example only in that the preparation method of the modified sepiolite fiber is as follows:
adding 1.5kg of wheat straw alkali lignin and 2.5kg of glycerol polyoxyethylene ether into 8.5kg of water, stirring and mixing uniformly, and carrying out ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
Immersing 3kg of sepiolite fiber into the modified solution, stirring and dispersing uniformly, regulating the pH value to 5, carrying out ultrasonic treatment for 2 hours at 65 ℃, carrying out suction filtration, and carrying out vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
Preparation example 4
The present preparation example differs from preparation example 1 only in that the polymeric surfactant is a carboxymethyl chitosan derivative. The preparation method of the carboxymethyl chitosan derivative comprises the following steps:
Dissolving 2kg of carboxymethyl chitosan in 7L of water, dropwise adding 0.2mol/L sodium hydroxide solution to adjust the pH value to 10.5, adding 2L of dodecyl glycidyl ether into the solution, stirring and uniformly mixing, reacting for 6 hours at the temperature of 75 ℃, dropwise adding 10% acetic acid solution to adjust the pH value to 4.5, adding 5L of acetone, standing for 12 hours, filtering until the reactant is completely precipitated, washing with acetone for three times, filtering, and drying in vacuum at the temperature of 50 ℃ to obtain the carboxymethyl chitosan derivative.
The preparation method of the modified sepiolite fiber comprises the following steps:
Adding 1.2kg of wheat straw alkali lignin and 1.8kg of carboxymethyl chitosan derivative into 7kg of water, stirring and mixing uniformly, and carrying out ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
Immersing 2kg of sepiolite fiber into the modified solution, stirring and dispersing uniformly, dripping 0.1mol/L hydrochloric acid solution to adjust the pH value to 5, performing ultrasonic treatment at 65 ℃ for 2 hours, performing suction filtration, and performing vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
Preparation example 5
The present preparation differs from preparation 4 only in that lignin is methylolated lignin, and the preparation method is as follows:
Dissolving 2kg of wheat straw alkali lignin in 8L of 0.2mol/L sodium hydroxide solution, dispersing uniformly, regulating the pH value to 11 by using 20wt% sodium hydroxide solution, adding 1kg of formaldehyde solution with the concentration of 37%, uniformly mixing, reacting at 80 ℃ for 120min, regulating the pH value of the reaction solution to 3.5 by using 10wt% hydrochloric acid solution, preserving heat for 60min at 60 ℃, performing hot filtration, washing to be neutral, and performing vacuum drying at 45 ℃ to obtain the methylolated lignin.
The preparation method of the modified sepiolite fiber comprises the following steps:
Adding 1.2kg of methylolated lignin and 1.8kg of carboxymethyl chitosan derivative into 7kg of water, stirring and mixing uniformly, and performing ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
Immersing 2kg of sepiolite fiber into the modified solution, stirring and dispersing uniformly, dripping 0.1mol/L hydrochloric acid solution to adjust the pH value to 5, performing ultrasonic treatment at 65 ℃ for 2 hours, performing suction filtration, and performing vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
Preparation example 6
The present preparation example differs from preparation example 5 only in that the preparation method of methylolated lignin is as follows:
Dissolving 2kg of wheat straw alkali lignin in 8L of 0.2mol/L sodium hydroxide solution, dispersing uniformly, regulating the pH value to 11 by using 20wt% sodium hydroxide solution, adding 0.5kg of 37% formaldehyde solution into the solution, uniformly mixing, reacting at 80 ℃ for 120min, regulating the pH value of the reaction solution to 3.5 by using 10wt% hydrochloric acid solution, preserving heat for 60min at 60 ℃, filtering thermally, washing to be neutral, and drying in vacuum at 45 ℃ to obtain the methylolated lignin.
Preparation example 7
The present preparation example differs from preparation example 5 only in that the preparation method of methylolated lignin is as follows:
Dissolving 2kg of wheat straw alkali lignin in 8L of 0.2mol/L sodium hydroxide solution, dispersing uniformly, regulating the pH value to 11 by using 20wt% sodium hydroxide solution, adding 1.5kg of 37% formaldehyde solution into the solution, uniformly mixing, reacting at 80 ℃ for 120min, regulating the pH value of the reaction solution to 3.5 by using 10wt% hydrochloric acid solution, preserving heat for 60min at 60 ℃, filtering thermally, washing to be neutral, and drying in vacuum at 45 ℃ to obtain the methylolated lignin.
Preparation example 8
The present preparation example differs from preparation example 5 only in that the sepiolite fiber is subjected to an activation treatment prior to the modification operation, the activation treatment operation being as follows:
2.5kg of sepiolite fiber is placed in a condition of 260 ℃ for calcination for 15min, then the calcined sepiolite fiber is placed in 5L of 0.2mol/L sodium hydroxide solution, ultrasonic treatment is carried out for 30min, suction filtration, water washing is carried out to neutrality, and vacuum drying is carried out at 60 ℃ to obtain the activated sepiolite fiber.
The preparation method of the modified sepiolite fiber comprises the following steps:
Adding 1.2kg of methylolated lignin and 1.8kg of carboxymethyl chitosan derivative into 7kg of water, stirring and mixing uniformly, and performing ultrasonic treatment at 45 ℃ for 20min to obtain a modified solution;
Immersing 2kg of activated sepiolite fiber into the modified solution, stirring and dispersing uniformly, dripping 0.1mol/L hydrochloric acid solution to adjust the pH value to 5, performing ultrasonic treatment at 65 ℃ for 2 hours, performing suction filtration, and performing vacuum drying at 70 ℃ to obtain lignin modified sepiolite fiber.
Examples
Example 1
The embodiment discloses a TPU film with moisture permeability, which comprises the following components in mass: 10kg of thermoplastic polyurethane elastomer, 1.5kg of modified sepiolite fiber, 0.6kg of toughening agent, 0.25kg of antioxidant and 1kg of anti-sticking agent.
In this example, the thermoplastic polyurethane elastomer comprises 2.5kg of the peak HF-90MVT-7,7.5kg of Reed 7263; the modified sepiolite fiber was prepared by the method of preparation example 1; the toughening agent is hydroxyethyl acrylate; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 1:2; the anti-sticking agent is purchased from Junyue New Material technologies Co., ltd.
The processing technology of the TPU film with the moisture permeability is as follows:
Adding the thermoplastic polyurethane elastomer, the modified sepiolite fiber, the toughening agent, the antioxidant and the anti-sticking agent with the mass into a mixer, and uniformly stirring and mixing at 85 ℃ to form a mixture;
Extruding the mixture in a double-screw extruder, cooling and granulating to obtain premixed particles;
and (3) putting the premixed particles into a casting machine for extrusion casting, wherein the screw speed is 100r/min, the extrusion temperature is 200 ℃, the die head temperature is 100 ℃, and the roll speed is 300m/min, so that the TPU film with moisture permeability is obtained.
Example 2
This example differs from example 1 only in that the TPU film with moisture vapor permeability comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 1kg of modified sepiolite fiber, 0.4kg of toughening agent, 0.4kg of antioxidant and 1.2kg of anti-sticking agent.
Example 3
This example differs from example 1 only in that the TPU film with moisture vapor permeability comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 2kg of modified sepiolite fiber, 1kg of toughening agent, 0.1kg of antioxidant and 0.8kg of anti-sticking agent.
Example 4
This example differs from example 1 only in that the modified sepiolite fiber was prepared by the method of preparation example 2.
Example 5
This example differs from example 1 only in that the modified sepiolite fiber was prepared by the method of preparation example 3.
Example 6
This example differs from example 1 only in that the modified sepiolite fiber was prepared by the method of preparation example 4.
Example 7
This example differs from example 1 only in that the modified sepiolite fiber was prepared by the method of preparation example 5.
Example 8
This example differs from example 1 only in that the modified sepiolite fiber was prepared by the method of preparation example 6.
Example 9
This example differs from example 1 only in that modified sepiolite fibers were prepared as in example 7.
Example 10
This example differs from example 1 only in that modified sepiolite fibers were prepared in accordance with the method of example 8.
Comparative example
Comparative example 1
This comparative example differs from example 1 only in that the TPU film comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 0.6kg of toughening agent, 0.25kg of antioxidant and 1kg of anti-sticking agent.
The TPU film processing technology is as follows:
Putting the thermoplastic polyurethane elastomer, the toughening agent, the antioxidant and the anti-sticking agent with the mass into a mixer, and uniformly stirring and mixing at 85 ℃ to form a mixture;
Extruding the mixture in a double-screw extruder, cooling and granulating to obtain premixed particles;
And (3) putting the premixed particles into a casting machine for extrusion casting and forming to obtain the TPU film with the moisture permeability.
Comparative example 2
This comparative example differs from example 1 only in that the TPU film comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 1.5kg of sepiolite fiber, 0.6kg of toughening agent, 0.25kg of antioxidant and 1kg of anti-sticking agent.
The TPU film processing technology is as follows:
putting the thermoplastic polyurethane elastomer, sepiolite fiber, a toughening agent, an antioxidant and an anti-sticking agent with the mass into a mixer, and uniformly stirring and mixing at 85 ℃ to form a mixture;
Extruding the mixture in a double-screw extruder, cooling and granulating to obtain premixed particles;
And (3) putting the premixed particles into a casting machine for extrusion casting and forming to obtain the TPU film with the moisture permeability.
Comparative example 3
This comparative example differs from example 1 only in that the TPU film comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 1.5kg of lignin, 0.6kg of toughening agent, 0.25kg of antioxidant and 1kg of anti-sticking agent.
The TPU film processing technology is as follows:
Adding the thermoplastic polyurethane elastomer, lignin, a toughening agent, an antioxidant and an anti-sticking agent with the mass into a mixer, and uniformly stirring and mixing at 85 ℃ to form a mixture;
Extruding the mixture in a double-screw extruder, cooling and granulating to obtain premixed particles;
And (3) putting the premixed particles into a casting machine for extrusion casting and forming to obtain the TPU film with the moisture permeability.
Comparative example 4
This comparative example differs from example 1 only in that the TPU film comprises the following components by mass: 10kg of thermoplastic polyurethane elastomer, 1kg of sepiolite fiber, 0.5kg of lignin, 0.6kg of toughening agent, 0.25kg of antioxidant and 1kg of anti-sticking agent.
The TPU film processing technology is as follows:
adding the thermoplastic polyurethane elastomer, sepiolite fiber, lignin, a toughening agent, an antioxidant and an anti-sticking agent with the mass into a mixer, and uniformly stirring and mixing at 85 ℃ to form a mixture;
Extruding the mixture in a double-screw extruder, cooling and granulating to obtain premixed particles;
And (3) putting the premixed particles into a casting machine for extrusion casting and forming to obtain the TPU film with the moisture permeability.
Performance test
The cut edges of the TPU films prepared in each example and each comparative example are cut into test samples with the same size, and the following tests are carried out: test one: moisture permeability test: the MVTR (moisture vapor transmission rate) of the TPU film samples of each example and each comparative example was measured by a fabric moisture permeameter according to the International Standard ASTM-E96BW water vapor inverted cup method;
And II, testing: tensile strength test: the TPU film samples of each example, each comparative example, were tested for transverse tensile strength and elongation at break with reference to International Standard ASTM-D882-18, with a sample film thickness of 0.016mm, a sample width of 25mm, a collet distance of 50mm, and a test speed of 500mm/min.
The test results are summarized in table 1.
TABLE 1
As can be seen by combining examples 1-5 and combining Table 1, the TPU film prepared by the formula and the method disclosed by the application has an MVTR value of more than 6800 g/(m 2 multiplied by 24 h), an elongation at break of more than 500%, and high tensile strength, which indicates that the TPU film with moisture permeability has better moisture permeability, good toughness and excellent tensile property, and is beneficial to expanding the service scene of the TPU film.
It can be seen in combination with example 1 and comparative examples 1-4, and with Table 1, that the addition of lignin-modified sepiolite fibers to the TPU film system can promote improved moisture permeability and tensile strength of the TPU film; the lignin is grafted with the sepiolite fiber through the high molecular surfactant, so that the compatibility of the sepiolite fiber and a TPU system is improved, the uniform dispersion of the sepiolite fiber is promoted, and the organic cross-linked network system is connected with the inorganic fiber network structure, so that the toughness and the tensile strength of the TPU film are improved; in addition, the lignin enriches hydrophilic groups in the TPU film system, enhances the hydrophilicity of the TPU film, enables the TPU film to adsorb water molecules on the high-humidity side, and rapidly transfers the water molecules to the low-humidity side for desorption through the water channel structure of sepiolite fibers, thereby promoting the improvement of the moisture permeability of the TPU film.
As can be seen from the combination of example 1 and example 6 and the combination of table 1, the use of the methylol chitosan derivative as the polymeric surfactant helps to promote the further improvement of the moisture permeability and toughness of the TPU film, which is probably due to the strong hydrophilicity and reactivity of the methylol chitosan derivative, which is beneficial to promote the loading of the sepiolite fiber to lignin.
It can be seen from the combination of examples 1 and 7-9 and the combination of table 1 that the methylolated lignin is selected, so that hydrophilic groups of the TPU film can be further enriched, the improvement of the hydrophilicity of the TPU film is promoted, the moisture permeability of the TPU film is further improved, and the hydrogen bond crosslinking between the methylolated lignin and small molecules of the TPU and the toughening agent can be promoted, so that the toughness of the TPU film is improved.
As can be seen from the combination of example 1, example 10 and table 1, the activation treatment of the sepiolite fibers is beneficial to promote the improvement of the moisture permeability and tensile strength of the TPU film, probably because the activation treatment enlarges the pores of the water channels and holes of the sepiolite fibers and improves the surface activity of the sepiolite fibers, which helps to promote the loading of the sepiolite fibers to lignin.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The TPU film with the moisture permeability is characterized by comprising the following components in parts by mass:
100 parts of thermoplastic polyurethane elastomer,
10-20 Parts of modified sepiolite fiber,
4-10 Parts of toughening agent,
1-4 Parts of antioxidant,
8-12 Parts of an anti-sticking agent;
the modified sepiolite fiber is lignin modified sepiolite fiber.
2. The TPU film having moisture permeability according to claim 1, wherein: the preparation method of the modified sepiolite fiber comprises the following steps:
adding lignin and a macromolecular surfactant into a solvent, uniformly mixing, and performing ultrasonic treatment at 30-50 ℃ for 5-20min to obtain a modified solution;
Immersing sepiolite fiber into the modified solution, uniformly mixing, adjusting the pH value to 4.5-6, performing ultrasonic treatment at 60-90 ℃ for 60-120min, performing suction filtration, and drying to obtain lignin modified sepiolite fiber.
3. The TPU film having moisture permeability according to claim 2, wherein: in the modified solution, the mass fraction of lignin is 5-15%, and the mass fraction of the macromolecular surfactant is 10-25%; the mass of the sepiolite fiber is 15-30% of that of the modifying solution.
4. The TPU film having moisture permeability according to claim 2, wherein: the high molecular surfactant is carboxymethyl chitosan derivative, and the preparation method of the carboxymethyl chitosan derivative comprises the following steps:
Dissolving carboxymethyl chitosan in water, regulating pH to 10-11, adding dodecyl glycidyl ether, mixing, reacting at 60-80 deg.c for 6-8 hr, regulating pH to 4-5, precipitating with acetone, washing the product, filtering, and vacuum drying to obtain carboxymethyl chitosan derivative.
5. The TPU film having moisture permeability according to claim 2, wherein: the lignin is methylolated lignin.
6. The TPU film having moisture permeability according to claim 2, wherein: the sepiolite fiber is subjected to an activation treatment before the modification operation, and the activation treatment step comprises the following steps:
Calcining sepiolite fiber at 200-300 deg.C for 10-20min, placing calcined sepiolite fiber in sodium hydroxide solution, ultrasonic treating for 20-40min, suction filtering, washing, and drying to obtain activated sepiolite fiber.
7. The TPU film having moisture permeability according to claim 1, wherein: the toughening agent is hydroxyethyl acrylate.
8. The TPU film having moisture permeability according to claim 1, wherein: the antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-3).
9. A process for the processing of a TPU film having moisture vapor permeability according to any one of claims 1-8, wherein: the method comprises the following steps:
Mixing a thermoplastic polyurethane elastomer, modified sepiolite fibers, a toughening agent, an antioxidant and an anti-sticking agent according to a proportion to form a mixture;
Extruding, cooling and granulating the mixture to obtain premixed particles;
And extruding, casting and forming the premixed particles to obtain the TPU film with moisture permeability.
10. The process for producing a TPU film having moisture permeability according to claim 9, wherein: the screw speed of the casting molding step of the premixed particles is 100-300r/min, the extrusion temperature is 80-200 ℃, the die head temperature is 100-200 ℃, and the roller speed is 300-500m/min.
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