CN113337102A - TPU film with good cohesiveness and preparation method thereof - Google Patents
TPU film with good cohesiveness and preparation method thereof Download PDFInfo
- Publication number
- CN113337102A CN113337102A CN202110852325.2A CN202110852325A CN113337102A CN 113337102 A CN113337102 A CN 113337102A CN 202110852325 A CN202110852325 A CN 202110852325A CN 113337102 A CN113337102 A CN 113337102A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- film
- tpu
- parts
- nano tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a TPU film with good cohesiveness and a preparation method thereof; relates to the technical field of TPU films, and is prepared from the following components: TPU particles, a plasticizer, a lubricant, doped nano vanadium dioxide particles, modified carbon nanotubes, corn fiber glue, a compatilizer and an aminosilane coupling agent; the invention provides a TPU film with good cohesiveness and a preparation method thereof, and the prepared TPU film not only has excellent mechanical properties, but also has excellent cohesiveness, so that the application field is greatly improved.
Description
Technical Field
The invention belongs to the technical field of TPU films, and particularly relates to a TPU film with good cohesiveness and a preparation method thereof.
Background
TPU (thermoplastic polyurethanes), thermoplastic TPU elastomer, is made by extrusion and mixing MDI containing NCO functional group, POLYOL containing OH functional group, 1.4BG, because of good elasticity, good physical properties, all kinds of mechanical strength are very good, therefore, it is widely used in processing modes such as injection, extrusion, calendering and dissolving into solution type resin, etc., it is a plastic material that the plastic processing trade often uses, its product covers the range of industrial application and civil necessities.
In recent years, the use of thermoplastic PU elastomers has been increasing continuously due to the continuous development of new products, and new industrial opportunities with low cost and high added value are created for plastic processing manufacturers.
The TPU film is prepared by processes of calendering, tape casting, film blowing, coating and the like on the basis of TPU granules.
The invention patent application with application publication number CN107298843A discloses a modified TPU film, which takes TPU particles as raw materials, and also comprises a compatilizer, a filler, a flame retardant, natural polyphenol, epoxy resin and a light stabilizer, wherein the components in parts by weight are respectively as follows: 70-80 parts of TPU particles, 3-6 parts of compatilizer, 1-3 parts of filler, 2-4 parts of flame retardant, 5-8 parts of natural polyphenol, 10-20 parts of epoxy resin, 0.5-1.5 parts of light stabilizer and silica as filler.
However, the TPU film prepared by the prior art has general cohesiveness and mechanical properties which cannot meet the market demand, and therefore, further improvement of the properties is required to meet the market demand.
Disclosure of Invention
The invention aims to provide a TPU film with good cohesiveness and a preparation method thereof, so as to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the TPU film with good cohesiveness is prepared from the following components in parts by weight: 88-92 parts of TPU particles, 4-6 parts of plasticizer, 1-2 parts of lubricant, 22-26 parts of filler, 12-18 parts of corn fiber glue, 1-4 parts of compatilizer and 1-4 parts of amino silane coupling agent;
the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5.
As a further technical scheme: the preparation method of the doped nano vanadium dioxide particles comprises the following steps:
adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1-2, stirring for 30min at the rotating speed of 500r/min, then heating to 390 ℃ in an inert atmosphere, stirring for 40min at a heat preservation temperature, cooling to 230 ℃ at 220 ℃ for further heat preservation for 1 h, then heating to 460 ℃ at 440 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles.
As a further technical scheme: the inert atmosphere is argon atmosphere.
As a further technical scheme: the preparation method of the modified carbon nanotube comprises the following steps:
uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid;
heating the carbon nano tube dispersion liquid to 90-100 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid.
As a further technical scheme: the mixing mass ratio of the carbon nano tube to the toluene is 1: 12;
the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2-3.
As a further technical scheme: the plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride.
As a further technical scheme: the lubricant is stearic acid.
A preparation method of a TPU film with good cohesiveness comprises the following steps:
(1) adding the doped nano vanadium dioxide particles and the modified carbon nano tubes into a mixer, stirring and mixing, and then drying in a drying oven to obtain mixed particles;
(2) mixing the mixed particles and TPU particles, placing the mixture in a reaction kettle, setting the temperature range of the reaction kettle to be 168-one-wall 172, carrying out stirring reaction at the rotating speed of 500r/min for 7-8 hours, and discharging after the reaction is finished to obtain an intermediate material;
(3) adding the intermediate material, the plasticizer, the lubricant, the corn fiber glue, the compatilizer and the aminosilane coupling agent into a double-screw extruder, and carrying out melt mixing to obtain a mixture;
(4) adding the mixture into a casting machine, casting the mixture onto the roll surface of a casting roll to form a film, applying pressure to the film to enable the film to be smoothly attached to the roll surface of the casting roll, moving the film through a cooling device along with the casting roll to shape the film, and finally curling the shaped film.
The invention can improve the bonding strength to a certain extent by introducing the amino silane coupling agent.
The corn fiber glue is a hemicellulose B component extracted from corn bran, is soluble arabinoxylan and has good bonding performance, and the bonding performance of the TPU film can be improved to a certain extent, the bonding performance effect of the TPU film is enhanced, and the application field is improved by introducing the corn fiber glue into the preparation of the TPU film.
The carbon nano tube has a unique tube structure, the diameter of the tube is in nanometer magnitude, the length of the tube is in micrometer magnitude, the perfect hexagonal structure connection and the great length-diameter ratio are provided, and the carbon nano tube has more excellent performances and powerful sp2The hybrid C-C bond structure enables the carbon nano tube to have extraordinary ultrahigh hardness, strength and modulus, and has excellent resilience and flexibility, but the carbon nano tube has poor dispersibility and is easy to aggregate.
The filler is mixed with the doped nano vanadium dioxide particles and the modified carbon nano tubes, so that the mechanical property of the TPU film can be better improved, and particularly the tensile property is obviously improved.
Advantageous effects
The invention provides a TPU film with good cohesiveness and a preparation method thereof, and the prepared TPU film not only has excellent mechanical properties, but also has excellent cohesiveness, so that the application field is greatly improved.
Drawings
FIG. 1 is a microstructure view of the surface of a TPU film.
Detailed Description
The TPU film with good cohesiveness is prepared from the following components in parts by weight: 88-92 parts of TPU particles, 4-6 parts of plasticizer, 1-2 parts of lubricant, 22-26 parts of filler, 12-18 parts of corn fiber glue, 1-4 parts of compatilizer and 1-4 parts of amino silane coupling agent;
the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5.
Vanadium dioxide is a metal oxide with phase transition property, the phase transition temperature of the vanadium dioxide is 68 ℃, and the structural change before and after the phase transition causes reversible conversion of infrared light from transmission to reflection.
The preparation method of the doped nano vanadium dioxide particles comprises the following steps:
adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1-2, stirring for 30min at the rotating speed of 500r/min, then heating to 390 ℃ in an inert atmosphere, stirring for 40min at a heat preservation temperature, cooling to 230 ℃ at 220 ℃ for further heat preservation for 1 h, then heating to 460 ℃ at 440 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles.
The inert atmosphere is argon atmosphere.
The preparation method of the modified carbon nanotube comprises the following steps:
uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid;
heating the carbon nano tube dispersion liquid to 90-100 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid.
The mixing mass ratio of the carbon nano tube to the toluene is 1: 12;
the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2-3.
The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride.
The lubricant is stearic acid.
Stearic acid:
1. the characteristics are as follows: a white waxy transparent solid or a yellowish waxy solid. Can be dispersed into powder with slight butter smell;
2. density: 0.84g/cm3；
3. Melting point: 67-72 ℃;
4, boiling point: 361 ℃;
5. refractive index (n 20D): 1.455;
6. gas phase standard heat of combustion (enthalpy): -11446.9 kJ. mol-1；
7. Gas phase standard heat of formation (enthalpy): -781.2 kJ. mol-1；
8. Liquid phase standard heat of combustion (enthalpy): -11343.4 kJ. mol-1；
9. Liquid phase standard heat of formation (enthalpy): -884.7 kJ. mol-1；
10. Standard heat of combustion (enthalpy) of crystalline phase: -11280.4 kJ. mol-1；
11. Standard heat of formation (enthalpy) of crystalline phase: -947.7 kJ. mol-1；
A preparation method of a TPU film with good cohesiveness comprises the following steps:
(1) adding the doped nano vanadium dioxide particles and the modified carbon nano tubes into a mixer, stirring and mixing, and then drying in a drying oven to obtain mixed particles;
(2) mixing the mixed particles and TPU particles, placing the mixture in a reaction kettle, setting the temperature range of the reaction kettle to be 168-one-wall 172, carrying out stirring reaction at the rotating speed of 500r/min for 7-8 hours, and discharging after the reaction is finished to obtain an intermediate material;
(3) adding the intermediate material, the plasticizer, the lubricant, the corn fiber glue, the compatilizer and the aminosilane coupling agent into a double-screw extruder, and carrying out melt mixing to obtain a mixture;
(4) adding the mixture into a casting machine, casting the mixture onto the roll surface of a casting roll to form a film, applying pressure to the film to enable the film to be smoothly attached to the roll surface of the casting roll, moving the film through a cooling device along with the casting roll to shape the film, and finally curling the shaped film.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 88, a plasticizer 4, a lubricant 1, a filler 22, corn fiber glue 12, a compatilizer 1 and an aminosilane coupling agent 1; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1, stirring at the rotating speed of 500r/min for 30min, then heating to 385 ℃ in an inert atmosphere, preserving heat and stirring for 40min, cooling to 220 ℃, preserving heat for 1 h, then heating to 440 ℃, preserving heat for 30min, and naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 90 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15:2. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Example 2
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 92, plasticizer 6, lubricant 2, filler 26, corn fiber glue 18, compatilizer 4, and aminosilane coupling agent 4; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:2, stirring at the rotating speed of 500r/min for 30min, then heating to 390 ℃ in an inert atmosphere, preserving heat and stirring for 40min, cooling to 230 ℃, continuing to preserve heat for 1 h, then heating to 460 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 100 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 3. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Example 3
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 91, a plasticizer 5, a lubricant 1.4, a filler 25, corn fiber glue 15, a compatilizer 3 and an aminosilane coupling agent 2; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1.5, stirring at the rotating speed of 500r/min for 30min, then heating to 387 ℃ in an inert atmosphere, preserving heat and stirring for 40min, cooling to 222 ℃, continuing to preserve heat for 1 h, then heating to 445 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 93 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2.1. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Example 4
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 88, plasticizer 6, lubricant 2, filler 22, corn fiber glue 12, compatibilizer 4, aminosilane coupling agent 4; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:2, stirring at the rotating speed of 500r/min for 30min, then heating to 385 ℃ in an inert atmosphere, keeping the temperature and stirring for 40min, cooling to 220 ℃, keeping the temperature for 1 h, then heating to 460 ℃, keeping the temperature for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 100 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 3. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Example 5
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 90, a plasticizer 4.5, a lubricant 1.7, a filler 23, corn fiber glue 14, a compatilizer 2 and an aminosilane coupling agent 2; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1.6, stirring at the rotating speed of 500r/min for 30min, then heating to 388 ℃ in an inert atmosphere, preserving heat and stirring for 40min, cooling to 224 ℃, continuing to preserve heat for 1 h, then heating to 441 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 96 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2.8. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Example 6
The TPU film with good cohesiveness is prepared from the following components in parts by weight: TPU particles 89, a plasticizer 5, a lubricant 1.5, a filler 24, corn fiber glue 15, a compatilizer 1.4 and an aminosilane coupling agent 1.4; the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5. The preparation method of the doped nano vanadium dioxide particles comprises the following steps: adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1.2, stirring at the rotating speed of 500r/min for 30min, then heating to 387 ℃ in an inert atmosphere, preserving heat and stirring for 40min, cooling to 226 ℃, continuing to preserve heat for 1 h, then heating to 443 ℃, preserving heat for 30min, and naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles. The inert atmosphere is argon atmosphere. The preparation method of the modified carbon nanotube comprises the following steps: uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid; heating the carbon nano tube dispersion liquid to 92 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid. The mixing mass ratio of the carbon nano tube to the toluene is 1: 12; the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2.5. The plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride. The lubricant is stearic acid.
Test of
Oxygen transmission rate test (test with reference to GBT 1038-2000):
TABLE 1
Comparative example 1: the difference from example 1 is that no modified carbon nanotubes are added.
Comparative example 2: the difference from example 1 is that doped nano vanadium dioxide particles are not added.
As can be seen from table 1, the TPU film prepared according to the present invention has excellent oxygen barrier properties, and is capable of better preventing oxygen permeation.
Adhesive property:
t peel strength (N/15mm) test:
TABLE 2
| T Peel Strength (N/15mm) | |
| Example 1 | 41.368 |
| Example 2 | 41.312 |
| Example 3 | 42.337 |
| Example 4 | 41.300 |
| Example 5 | 42.317 |
| Example 6 | 42.325 |
| Comparative example 1 | 35.189 |
| Comparative example 2 | 32.107 |
Comparative example 1: the difference from example 1 is that no modified carbon nanotubes are added.
Comparative example 3: the difference from example 1 is that no corn fiber gum is added.
As can be seen from Table 2, the TPU film prepared by the invention has excellent bonding performance, and the bonding performance of the TPU film can be effectively improved by modifying the synergistic promotion effect of the carbon nano tube and the corn fiber glue, so that the application field of the TPU film is improved.
Tensile properties test (test with reference to GB 1302291):
TABLE 3
Comparative example 1: the difference from example 1 is that no modified carbon nanotubes are added.
Comparative example 2: the difference from example 1 is that doped nano vanadium dioxide particles are not added.
As can be seen from Table 3, the TPU film prepared by the method has excellent tensile strength, the tensile property of the TPU film can be remarkably improved by the synergistic promotion effect of the modified carbon nanotubes and the doped nano vanadium dioxide particles, the durability of the TPU film can be improved by improving the mechanical property of the TPU film, the service life is further improved, and the application environment is expanded.
And (3) ductility detection:
ductility: preparing a rectangular sample with the length of 20cm, the width of 5cm and the thickness of 2mm, clamping the sample by using a tensile testing machine to perform a linear tensile test until the sample is stretched to be broken, measuring the length L1cm of the sample after the test, calculating the length change value (L1-20) cm before and after the test, and calculating the elongation: (L1-20)/10X 100%;
TABLE 4
| Ductility% | |
| Example 1 | 470.4 |
| Example 2 | 480.1 |
| Example 3 | 480.8 |
| Example 4 | 470.0 |
| Example 5 | 490.3 |
| Example 6 | 472.6 |
| Comparative example 1 | 325.5 |
As can be seen from table 4, the TPU films prepared according to the present invention have excellent elongation properties.
The microstructure of the membrane surface was observed using a JSM-6390 LV type scanning electron microscope for example 1, as shown in FIG. 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited to the illustrated embodiments, and all the modifications and equivalents of the embodiments may be made without departing from the spirit of the present invention.
Claims (8)
1. The TPU film with good cohesiveness is characterized by being prepared from the following components in parts by weight: 88-92 parts of TPU particles, 4-6 parts of plasticizer, 1-2 parts of lubricant, 22-26 parts of filler, 12-18 parts of corn fiber glue, 1-4 parts of compatilizer and 1-4 parts of amino silane coupling agent;
the filler is formed by mixing doped nano vanadium dioxide particles and modified carbon nano tubes according to the mass ratio of 1: 5.
2. The TPU film with good adhesion as claimed in claim 1, wherein: the preparation method of the doped nano vanadium dioxide particles comprises the following steps:
adding ammonium polyvanadate and ammonium molybdate into a stirring kettle according to the mass ratio of 10:1-2, stirring for 30min at the rotating speed of 500r/min, then heating to 390 ℃ in an inert atmosphere, stirring for 40min at a heat preservation temperature, cooling to 230 ℃ at 220 ℃ for further heat preservation for 1 h, then heating to 460 ℃ at 440 ℃, preserving heat for 30min, and then naturally cooling to room temperature to obtain the doped nano vanadium dioxide particles.
3. A good adhesion TPU film as set forth in claim 2 wherein: the inert atmosphere is argon atmosphere.
4. The TPU film with good adhesion as claimed in claim 1, wherein: the preparation method of the modified carbon nanotube comprises the following steps:
uniformly dispersing the carbon nano tube into toluene to obtain a carbon nano tube dispersion liquid;
heating the carbon nano tube dispersion liquid to 90-100 ℃, preserving the heat for 30min, then adding toluene-2, 4-diisocyanate, stirring and reacting for 2 h, then naturally cooling to room temperature, carrying out suction filtration, sequentially cleaning with ethanol and clear water for 10min, and then drying at constant temperature of 50 ℃ to obtain the carbon nano tube dispersion liquid.
5. A TPU film with good adhesion as claimed in claim 4, wherein: the mixing mass ratio of the carbon nano tube to the toluene is 1: 12;
the mixing mass ratio of the carbon nano tube dispersion liquid to the toluene-2, 4-diisocyanate is 15: 2-3.
6. The TPU film with good adhesion as claimed in claim 1, wherein: the plasticizer is dibutyl phthalate, and the compatilizer is polyethylene grafted maleic anhydride.
7. The TPU film with good adhesion as claimed in claim 1, wherein: the lubricant is stearic acid.
8. The method for preparing the TPU film with good adhesion according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) adding the doped nano vanadium dioxide particles and the modified carbon nano tubes into a mixer, stirring and mixing, and then drying in a drying oven to obtain mixed particles;
(2) mixing the mixed particles and TPU particles, placing the mixture in a reaction kettle, setting the temperature range of the reaction kettle to be 168-one-wall 172, carrying out stirring reaction at the rotating speed of 500r/min for 7-8 hours, and discharging after the reaction is finished to obtain an intermediate material;
(3) adding the intermediate material, the plasticizer, the lubricant, the corn fiber glue, the compatilizer and the aminosilane coupling agent into a double-screw extruder, and carrying out melt mixing to obtain a mixture;
(4) adding the mixture into a casting machine, casting the mixture onto the roll surface of a casting roll to form a film, applying pressure to the film to enable the film to be smoothly attached to the roll surface of the casting roll, moving the film through a cooling device along with the casting roll to shape the film, and finally curling the shaped film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110852325.2A CN113337102B (en) | 2021-07-27 | 2021-07-27 | TPU film with good cohesiveness and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110852325.2A CN113337102B (en) | 2021-07-27 | 2021-07-27 | TPU film with good cohesiveness and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113337102A true CN113337102A (en) | 2021-09-03 |
| CN113337102B CN113337102B (en) | 2022-05-17 |
Family
ID=77480390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110852325.2A Active CN113337102B (en) | 2021-07-27 | 2021-07-27 | TPU film with good cohesiveness and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113337102B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114559727A (en) * | 2022-01-05 | 2022-05-31 | 武汉市天将技术有限公司 | Composite material for air-drop water bag and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440208A (en) * | 2008-12-09 | 2009-05-27 | 东华大学 | Preparation of functionalized carbon nano-tube modification polyurethane elastomer |
| CN101481142A (en) * | 2009-02-18 | 2009-07-15 | 大连理工大学 | Method for preparing hypovanadic oxide doped powder material |
| KR20140022321A (en) * | 2012-08-14 | 2014-02-24 | 주식회사 세진산업 | Protection film for display/touch panel |
| CN105315652A (en) * | 2015-11-06 | 2016-02-10 | 苏州瑞高新材料有限公司 | High-bonding-strength air permeable bacteriostatic TPU composite film and preparation method thereof |
| CN107033376A (en) * | 2016-11-23 | 2017-08-11 | 广东聚航新材料研究院有限公司 | A kind of antimicrobial form TPU is cast membrane preparation method |
| CN108715734A (en) * | 2018-06-26 | 2018-10-30 | 阜南县柳祥工艺品有限公司 | A kind of environmental protection paint that adhesive property is good |
| CN109912880A (en) * | 2017-12-13 | 2019-06-21 | 广州金发碳纤维新材料发展有限公司 | A kind of glass fiber mat reinforced thermoplastic composite and preparation method thereof |
| CN110452525A (en) * | 2019-08-16 | 2019-11-15 | 安徽嘉明新材料科技有限公司 | A kind of modified antistatic TPU membrane of graphene |
| CN110964308A (en) * | 2019-12-20 | 2020-04-07 | 山东一诺威聚氨酯股份有限公司 | Explosion-proof heat-insulation TPU film for automobile glass and preparation method thereof |
| CN112175224A (en) * | 2020-10-14 | 2021-01-05 | 泉州师范学院 | Method for improving stretching and folding resistance of FDM 3D printing TPU shoe material |
-
2021
- 2021-07-27 CN CN202110852325.2A patent/CN113337102B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440208A (en) * | 2008-12-09 | 2009-05-27 | 东华大学 | Preparation of functionalized carbon nano-tube modification polyurethane elastomer |
| CN101481142A (en) * | 2009-02-18 | 2009-07-15 | 大连理工大学 | Method for preparing hypovanadic oxide doped powder material |
| KR20140022321A (en) * | 2012-08-14 | 2014-02-24 | 주식회사 세진산업 | Protection film for display/touch panel |
| CN105315652A (en) * | 2015-11-06 | 2016-02-10 | 苏州瑞高新材料有限公司 | High-bonding-strength air permeable bacteriostatic TPU composite film and preparation method thereof |
| CN107033376A (en) * | 2016-11-23 | 2017-08-11 | 广东聚航新材料研究院有限公司 | A kind of antimicrobial form TPU is cast membrane preparation method |
| CN109912880A (en) * | 2017-12-13 | 2019-06-21 | 广州金发碳纤维新材料发展有限公司 | A kind of glass fiber mat reinforced thermoplastic composite and preparation method thereof |
| CN108715734A (en) * | 2018-06-26 | 2018-10-30 | 阜南县柳祥工艺品有限公司 | A kind of environmental protection paint that adhesive property is good |
| CN110452525A (en) * | 2019-08-16 | 2019-11-15 | 安徽嘉明新材料科技有限公司 | A kind of modified antistatic TPU membrane of graphene |
| CN110964308A (en) * | 2019-12-20 | 2020-04-07 | 山东一诺威聚氨酯股份有限公司 | Explosion-proof heat-insulation TPU film for automobile glass and preparation method thereof |
| CN112175224A (en) * | 2020-10-14 | 2021-01-05 | 泉州师范学院 | Method for improving stretching and folding resistance of FDM 3D printing TPU shoe material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114559727A (en) * | 2022-01-05 | 2022-05-31 | 武汉市天将技术有限公司 | Composite material for air-drop water bag and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113337102B (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201014880A (en) | Processing aid for thermoplastic polyurethanes | |
| CN113337102B (en) | TPU film with good cohesiveness and preparation method thereof | |
| CN114075322A (en) | Waterborne polyurethane resin emulsion and preparation method thereof | |
| CN107033827B (en) | Single-component silane modified polyether sealant for building and preparation method thereof | |
| CN113174124A (en) | PPC and PBAT composite material and preparation method thereof | |
| CN111040255A (en) | Bio-based polyethylene/starch blending modified blown film material and preparation method thereof | |
| CN112980375A (en) | Single-component silane modified polyether sealant and preparation method thereof | |
| CN111438835A (en) | Composite environment-friendly plastic particle and preparation method thereof | |
| CN109232998B (en) | Chain-shaped SiO2Preparation method of reinforced thermoplastic starch plastic | |
| CN114891183A (en) | Waterborne polyurethane modified starch dispersion liquid and preparation method thereof | |
| CN111205605A (en) | High-melt-strength polyhydroxyalkanoate blend and film, and preparation method and application thereof | |
| JP4904703B2 (en) | Heat resistant polyurethane film | |
| CN111269555B (en) | Thermoplastic polyurethane elastomer composition and preparation method thereof | |
| CN117511365A (en) | Polylactic acid/polydopamine/mica nano composite coating and preparation method and application thereof | |
| CN114075331A (en) | Polyglycolic acid composition and preparation method and application thereof | |
| CN111019217B (en) | Nano composite polymer material | |
| CN111675854A (en) | Polyurethane toughened polypropylene composite material and preparation and detection method thereof | |
| CN110539540A (en) | Flame-retardant chlorinated polyethylene waterproof coiled material and preparation method thereof | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof | |
| CN113388165A (en) | Thermoplastic starch for bioplastic and preparation method thereof | |
| CN114045146A (en) | High-thermal-conductivity waterborne polyurethane composite material and preparation method thereof | |
| CN115322538A (en) | Composition for enhanced modified polyglycolic acid, enhanced modified polyglycolic acid material, and preparation method and application thereof | |
| CN109867845A (en) | A kind of plastics and preparation method thereof of anti-aging antistatic | |
| CN111205635B (en) | High-water-resistance polyamide 6 composite material and preparation method thereof | |
| CN114773646B (en) | Fully-degradable high-toughness polyvinyl alcohol composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |