CN110819103A - TPU acoustic film and preparation method thereof - Google Patents
TPU acoustic film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a TPU acoustic film which is prepared from the following raw materials: modified TPU particles, polylactic acid, an antioxidant and a coupling agent A; the modified TPU granules are prepared from the following raw materials: oligomer dihydric alcohol, isophorone diisocyanate, a chain initiator, a chain terminator, nano calcium carbonate, polyformaldehyde and a composite coupling agent B. The acoustic film prepared by the method has smooth and stable surface, the diameter is 1.55mm-2.72mm, and the thickness is 2.5 mu m-7.2 mu m; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 50-100mv/pa and static pressure sensitivity of 9 um/pa.
Description
Technical Field
The invention relates to the technical field of acoustic films, in particular to a TPU acoustic film and a preparation method thereof.
Background
The sound wave is a mechanical wave generated by the vibration of a sound source, the space for sound wave propagation is a sound field, and sound is a longitudinal wave when propagating in gas and liquid media, but may be mixed with a transverse wave when propagating in a solid medium. The frequency of the sound waves audible to the human ear is typically between 20Hz and 20000 Hz. Below 20Hz is infrasonic and above 20kHz is ultrasonic. The sound waves of different frequency bands have different purposes in the practical application process, and infrasound has important purposes in the aspects of ground sound exploration and ultrasound in the aspects of nondestructive testing, ultrasonic imaging and the like. When the sound waves are transmitted by the air, the density of the air is changed, and the air pressure is changed periodically; the effective method for detecting the sound wave is to convert sound vibration into an electric signal or an optical signal by utilizing the periodic change of the air pressure through the transduction of a film, and achieve the purpose of detecting the sound signal by detecting the electric signal or the optical signal; the common sound wave frequency detection means in the prior art is to use a capacitance type or piezoelectric type film for transduction, the weak pressure difference at two sides of the film is sensed by the film, the deformation of the film causes the change of the capacitance and the voltage of the film, and the change of the electric signal is consistent with the change of the sound signal; the capacitive or voltage type thin film requires that the thin film material has capacitance or piezoelectricity, the selectivity to the material is high, and the material cannot be used in the high magnetic field and high electromagnetic field.
In recent years, optical fiber microphones are widely researched, and particularly, partial performances of an acoustic sensing technology based on FP interference are equivalent to those of piezoelectricity or capacitance, and the optical fiber microphone has the characteristics of small volume, wide dynamic range, electromagnetic interference resistance, severe environment resistance and the like. The FP microphone film does not require piezoelectricity or capacitance, and various materials can be used for preparing acoustic films, such as silver films, silicon films, graphene films, polymer films, glycosyl films and the like; the sensitivity of an acoustic membrane is inversely proportional to the third power of the membrane thickness and directly proportional to the fourth power of the membrane radius; considering the size of the sensor, the thickness of the acoustic film is often smaller, and at the level of micron or even nanometer, the radius of the film is difficult to increase, the preparation process of the film is also complex, the cost is high, the low-frequency response is low, and the preparation of the acoustic film is a difficult point for the development of the acoustic sensor.
TPU, also known as thermoplastic polyurethane rubber or thermoplastic polyurethane elastomer, is a linear block copolymer composed of an oligomeric polyol soft segment and an isocyanate hard segment. The macromolecule dihydric alcohol and the isocyanate are connected to form a long-chain structure, and the long-chain structure shows flexibility, so that a soft segment structure in the whole macromolecule chain is formed; the small molecular polyol and the isocyanate are connected to form a short chain structure, and the short chain structure presents rigidity due to the short molecular chain, so that a hard segment structure in a macromolecular chain structure is formed. The good resilience of the TPU is due to the relative movement of the molecular chains, which is particularly evident in the low-temperature flexibility. The motion performance of the molecular chain depends greatly on the chemical property of the soft segment and the length of the chain, and the more amorphous the soft segment is, the better the flexibility is.
Disclosure of Invention
In order to solve the technical problems, the invention provides a TPU acoustic film and a preparation method thereof, and aims to provide the TPU acoustic film, wherein the toughness of the TPU material is enhanced by adopting nano calcium carbonate and polyformaldehyde to synergistically modify the TPU material, so that the TPU acoustic film still has excellent mechanical properties when the TPU acoustic film is prepared into an ultrathin acoustic film.
The invention provides a TPU acoustic film which is prepared from the following raw materials: modified TPU particles, polylactic acid, an antioxidant and a coupling agent A;
the modified TPU granules are prepared from the following raw materials: oligomer dihydric alcohol, isophorone diisocyanate, a chain initiator, a chain terminator, nano calcium carbonate, polyformaldehyde and a composite coupling agent B;
the oligomeric diol is polyethylene glycol with the number average molecular weight of 1000-2000 and/or polytetramethylene glycol with the number average molecular weight of 1000-2000;
the sensitivity of the TPU acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 50-100mv/pa, and the static pressure sensitivity is less than or equal to 9 um/pa.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 100-120 parts of modified TPU particles, 12-15 parts of polylactic acid, 1-3 parts of antioxidant and 10-10 parts of coupling agent A5;
the modified TPU granules are prepared from the following raw materials in parts by weight: 50-70 parts of oligomer dihydric alcohol, 30-50 parts of isophorone diisocyanate, 3-5 parts of chain initiator, 2-4 parts of chain terminator, 12-15 parts of nano calcium carbonate, 20-40 parts of polyformaldehyde and 78-20 parts of composite coupling agent B10.
Preferably, the feed additive is prepared from the following raw materials in parts by weight: 115 parts of modified TPU particles 105, 13-14 parts of polylactic acid, 1-2 parts of antioxidant and 6-9 parts of coupling agent A;
the modified TPU granules are prepared from the following raw materials in parts by weight: 55-65 parts of oligomer dihydric alcohol, 35-45 parts of isophorone diisocyanate, 3.5-4.5 parts of chain initiator, 2.5-3.5 parts of chain terminator, 13-15 parts of nano calcium carbonate, 25-35 parts of polyformaldehyde and 12-17 parts of composite coupling agent B.
Preferably, the feed additive is prepared from the following raw materials in parts by weight: 110 parts of modified TPU particles, 13.5 parts of polylactic acid, 1.5 parts of antioxidant and 7 parts of coupling agent A;
the modified TPU granules are prepared from the following raw materials in parts by weight: 58 parts of oligomer dihydric alcohol, 39 parts of isophorone diisocyanate, 4 parts of chain initiator, 3 parts of chain terminator, 14 parts of nano calcium carbonate, 30 parts of polyformaldehyde and 15 parts of composite coupling agent B.
As a further improvement of the invention, the modified TPU particles are made by the process of:
s1, adding a chain initiator into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator into the prepolymer to terminate the reaction, so as to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5-1% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
As a further improvement of the invention, the coupling agent A is selected from one of KH550, KH560, KH570, KH792, DL602 and DL 171.
As a further improvement of the invention, the composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with an amino group, the mass ratio of the common silane coupling agent to the silane coupling agent with the amino group is 5:2, and the common silane coupling agent comprises one of KH550, KH560, KH570, KH792, DL602 and DL 171.
As a further improvement of the invention, the antioxidant is selected from one or a mixture of more of diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide, tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, trioctyl ester, tridecyl ester, tri-dodecyl alcohol ester or tri-hexadecyl alcohol ester.
As a further improvement of the invention, the chain initiator is one or a mixture of several selected from ethylene glycol, 1-propylene glycol, 1, 4-butanediol, 2, 3-butanediol or 1, 5-pentanediol.
As a further improvement of the invention, the chain terminator is selected from one or a mixture of several of diethylamine, dipropylamine, ethanolamine or n-hexylamine.
As a further improvement of the invention, the TPU acoustic film has a diameter of 1.55mm to 2.72mm and a thickness of 2.5 μm to 7.2 μm.
The invention further provides a preparation method of the TPU acoustic film, which comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2-0.4% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and an antioxidant in an ethanol aqueous solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in the N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300-500r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 3-7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out the hollow stainless steel tube until the hollow stainless steel tube is cured by adopting ultraviolet irradiation, and obtaining the acoustic film.
The invention has the following beneficial effects:
the invention adopts the modified TPU material to prepare the acoustic film, the TPU material is composed of an oligomer polyol soft segment and an isocyanate hard segment, the most main absorption form is weak coupling between local vibration and a sound wave radiation mode generated by the action of soft and hard phase media, and the acoustic film has good acoustic characteristics and high sensitivity; the TPU material is synergistically modified by adopting the nano calcium carbonate and the polyformaldehyde, so that the toughness of the TPU material is enhanced, and the TPU material still has excellent mechanical properties when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein a common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with TPU, a silane coupling agent with amino helps organic particles such as polyformaldehyde to be modified and linked with TPU, and the modified particles are chemically bonded with TPU materials through the compounded silane coupling agent to prepare TPU particles with better toughness and mechanical properties for later-stage preparation of TPU sound film materials;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 1.55mm-2.72mm, and the thickness is 2.5 mu m-7.2 mu m; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 50-100mv/pa and static pressure sensitivity of 9 um/pa.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1
The raw materials comprise the following components in parts by weight: 100 parts of modified TPU particles, 12 parts of polylactic acid, 1 part of p-phenylenediamine and 5 parts of coupling agent A. The coupling agent A is KH 560.
Preparation of modified TPU pellets:
the raw materials comprise the following components in parts by weight: 50 parts of oligomer dihydric alcohol, 30 parts of isophorone diisocyanate, 3 parts of chain initiator 1, 4-butanediol, 2 parts of chain terminator ethanolamine, 12 parts of nano calcium carbonate, 20 parts of polyformaldehyde and 10 parts of composite coupling agent B. The composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH560, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, adding a chain initiator 1, 4-butanediol into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator ethanolamine into the prepolymer to terminate the reaction to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
A preparation method of a TPU acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and p-phenylenediamine in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in a N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 3S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Example 2
The raw materials comprise the following components in parts by weight: 120 parts of modified TPU particles, 15 parts of polylactic acid, 3 parts of trioctyl ester and 10 parts of coupling agent A. The coupling agent A is KH 570.
Preparation of modified TPU pellets:
the raw materials comprise the following components in parts by weight: 70 parts of oligomer dihydric alcohol, 50 parts of isophorone diisocyanate, 5 parts of chain initiator 2, 3-butanediol, 4 parts of chain terminator dipropylamine, 15 parts of nano calcium carbonate, 40 parts of polyformaldehyde and 20 parts of composite coupling agent B. The composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH570, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, adding a chain initiator 2, 3-butanediol into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator dipropylamine into the prepolymer to terminate the reaction, so as to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 1% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
A preparation method of a TPU acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.4% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and trioctyl ester in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in a N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 500r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Example 3
The raw materials comprise the following components in parts by weight: 105 parts of modified TPU particles, 13 parts of polylactic acid, 1 part of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and 6 parts of coupling agent A. The coupling agent A is KH 792.
Preparation of modified TPU pellets:
the raw materials comprise the following components in parts by weight: 55 parts of oligomer dihydric alcohol, 35 parts of isophorone diisocyanate, 3.5 parts of chain initiator 1, 5-pentanediol, 2.5 parts of chain terminator n-hexylamine, 13 parts of nano calcium carbonate, 25 parts of polyformaldehyde and 12 parts of composite coupling agent B. The composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is KH792, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, adding a chain initiator 1, 5-pentanediol into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator n-hexylamine into the prepolymer to terminate the reaction, so as to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.6% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
A preparation method of a TPU acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.25% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in a N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 350r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 4S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Example 4
The raw materials comprise the following components in parts by weight: 115 parts of modified TPU particles, 14 parts of polylactic acid, 2 parts of dihydroquinoline and 9 parts of coupling agent A. The coupling agent A is DL 602.
Preparation of modified TPU pellets:
the raw materials comprise the following components in parts by weight: 65 parts of oligomer dihydric alcohol, 45 parts of isophorone diisocyanate, 4.5 parts of chain initiator 2, 3-butanediol, 3.5 parts of chain terminator ethanolamine, 15 parts of nano calcium carbonate, 35 parts of polyformaldehyde and 17 parts of composite coupling agent B. The composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is one of DL171, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, adding a chain initiator 2, 3-butanediol into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator ethanolamine into the prepolymer to terminate the reaction to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.9% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
A preparation method of a TPU acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.35% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and dihydroquinoline in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in a N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 450r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 6S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Example 5
The material composition includes (by weight portion) 110 portions of modified TPU granules, 13.5 portions of polylactic acid, 1.5 portions of tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 7 portions of coupling agent A, wherein the coupling agent A is DL 171.
Preparation of modified TPU pellets:
the raw materials comprise the following components in parts by weight: 58 parts of oligomer dihydric alcohol, 39 parts of isophorone diisocyanate, 4 parts of chain initiator ethylene glycol, 3 parts of chain terminator diethylamine, 14 parts of nano calcium carbonate, 30 parts of polyformaldehyde and 15 parts of composite coupling agent B. The composite coupling agent B comprises a common silane coupling agent and a silane coupling agent with amino groups, the mass ratio of the common silane coupling agent to the silane coupling agent with amino groups is 5:2, the common silane coupling agent is DL171, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, adding a chain initiator ethylene glycol into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator diethylamine into the prepolymer to terminate the reaction, so as to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.7% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
A preparation method of a TPU acoustic film comprises the following steps:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.3% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in an ethanol water solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in a N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 400r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 5S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out until the hollow stainless steel tube is fully covered with the mixed solution, and curing the hollow stainless steel tube by adopting ultraviolet irradiation to obtain the acoustic film.
Comparative example 1
Compared with example 5, a common TPU material was used.
Comparative example 2
Compared to example 5, no polylactic acid was added.
Comparative example 3
In comparison with example 5, the composite coupling agent B was not used, and a single silane coupling agent a171 was used.
Test example 1
The TPU acoustic films prepared in inventive examples 1-5 and comparative examples 1-3 were subjected to performance testing and the results are shown in Table 1.
Table 1 table of performance test results
As can be seen from the above table, the acoustic thin films prepared in examples 1 to 5 of the present invention have a diameter of 1.55mm to 2.72mm and a thickness of 2.5 μm to 7.2 μm; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 50-100mv/pa, static pressure sensitivity of 9um/pa and long service life of 15-20 years; in the acoustic film prepared by adopting the common TPU material in the comparative example 2, the rigid structure and the flexible structure are not suitable for being used as acoustic film materials, the value of the diameter is smaller than that of the upper thickness, and the acoustic characteristic is poor; in the comparative example 3, the TPU material is modified, so that the mechanical property is poor, and the fracture growth rate is only 67%; comparative example 4 does not adopt a compound coupling agent for coupling modification, has poor modification effect, little improvement on mechanical properties, a fracture growth rate of only 82% and poor acoustic characteristics.
Compared with the prior art, the acoustic film is prepared by adopting the modified TPU material, the TPU material is composed of an oligomer polyol soft segment and an isocyanate hard segment, the most main absorption form is weak coupling between local vibration and a sound wave radiation mode generated by the action of soft and hard phase media, and the acoustic film has good acoustic characteristics and high sensitivity; the TPU material is synergistically modified by adopting the nano calcium carbonate and the polyformaldehyde, so that the toughness of the TPU material is enhanced, and the TPU material still has excellent mechanical properties when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein a common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with TPU, a silane coupling agent with amino helps organic particles such as polyformaldehyde to be modified and linked with TPU, and the modified particles are chemically bonded with TPU materials through the compounded silane coupling agent to prepare TPU particles with better toughness and mechanical properties for later-stage preparation of TPU sound film materials;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 1.55mm-2.72mm, and the thickness is 2.5 mu m-7.2 mu m; the diameter of the pressure sensor is larger than the thickness of the pressure sensor, the pressure sensor has good acoustic characteristics, good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, sensitivity of 50-100mv/pa and static pressure sensitivity of 9 um/pa.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (10)
1. The TPU acoustic film is characterized by being prepared from the following raw materials: modified TPU particles, polylactic acid, an antioxidant and a coupling agent A;
the modified TPU granules are prepared from the following raw materials: oligomer dihydric alcohol, isophorone diisocyanate, a chain initiator, a chain terminator, nano calcium carbonate, polyformaldehyde and a composite coupling agent B;
the oligomeric diol is polyethylene glycol with the number average molecular weight of 1000-2000 and/or polytetramethylene glycol with the number average molecular weight of 1000-2000;
the sensitivity of the TPU acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 50-100mv/pa, and the static pressure sensitivity is less than or equal to 9 um/pa.
2. The TPU acoustic film of claim 1, which is prepared from the following raw materials in parts by weight: 100-120 parts of modified TPU particles, 12-15 parts of polylactic acid, 1-3 parts of antioxidant and 10-10 parts of coupling agent A5;
the modified TPU granules are prepared from the following raw materials in parts by weight: 50-70 parts of oligomer dihydric alcohol, 30-50 parts of isophorone diisocyanate, 3-5 parts of chain initiator, 2-4 parts of chain terminator, 12-15 parts of nano calcium carbonate, 20-40 parts of polyformaldehyde and 78-20 parts of composite coupling agent B10.
3. The TPU acoustic film of claim 1, wherein the modified TPU particles are made by the process of:
s1, adding a chain initiator into oligomer dihydric alcohol and isophorone diisocyanate, and carrying out prepolymerization to obtain a prepolymer;
s2, adding a chain terminator into the prepolymer to terminate the reaction, so as to obtain a TPU high polymer material;
s3, preparing the composite coupling agent B into a dilute solution with the concentration of 0.5-1% to obtain a composite coupling agent B solution;
and S4, mixing and dissolving the nano calcium carbonate and the polyformaldehyde in an ethanol aqueous solution, dropwise adding the composite coupling agent B solution while stirring, uniformly stirring, irradiating by using ultraviolet light for 30min, adding the TPU high polymer material prepared in the step S2, uniformly mixing, and curing to obtain the modified TPU particles.
4. The TPU acoustic membrane of claim 1, wherein coupling agent a is selected from one of KH550, KH560, KH570, KH792, DL602, and DL 171.
5. The TPU acoustic membrane of claim 1, wherein the composite coupling agent B comprises a composite of a common silane coupling agent and a silane coupling agent with an amino group, the mass ratio of the common silane coupling agent to the silane coupling agent with the amino group is 5:2, and the common silane coupling agent comprises one of KH550, KH560, KH570, KH792, DL602 and DL 171.
6. The TPU acoustic film of claim 1, wherein the antioxidant is selected from the group consisting of diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-t-butyl-4-methylphenol, bis (3, 5-t-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ β - (3, 5-t-butyl-4-hydroxyphenyl) propionate ], trioctyl ester, tridecyl ester, tridodecyl ester, and trihexadecyl ester.
7. The TPU acoustic membrane of claim 1, wherein the chain initiator is selected from the group consisting of ethylene glycol, 1-propylene glycol, 1, 4-butanediol, 2, 3-butanediol, and 1, 5-pentanediol, or a mixture thereof.
8. The TPU acoustic film of claim 1, wherein the chain terminator is selected from one or a mixture of diethylamine, dipropylamine, ethanolamine, or n-hexylamine.
9. The TPU acoustic film of claim 1, wherein the TPU acoustic film is 1.55mm to 2.72mm in diameter and 2.5 μm to 7.2 μm thick.
10. A method of making a TPU acoustic film as set forth in any of claims 1-9 including the steps of:
s1, preparing a coupling agent A into a dilute solution with the concentration of 0.2-0.4% to obtain a coupling agent A solution;
s2, dissolving polylactic acid and an antioxidant in an ethanol aqueous solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating by using ultraviolet light for 30min to obtain a mixed solution;
s3, dissolving the modified TPU particles in the N, N-dimethylformamide solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring at the rotating speed of 300-500r/min for 30min, then immersing the tail end of the hollow stainless steel tube into the mixed solution for 3-7S until the outside of the hollow stainless steel tube is fully covered with the mixed solution, taking out the hollow stainless steel tube until the hollow stainless steel tube is cured by adopting ultraviolet irradiation, and obtaining the acoustic film.
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