CN110819078A - TPEE acoustic film and preparation method thereof - Google Patents
TPEE acoustic film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a TPEE acoustic film which is prepared from the following raw materials: modified TPEE sheet, antioxidant and coupling agent A; the modified TPEE sheet is prepared from the following raw materials: TPEE resin, polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol, polyformaldehyde, a crosslinking curing agent and a composite coupling agent B. The acoustic film prepared by the method has smooth and stable surface, the diameter is 2.15mm-2.52mm, and the thickness is 2.7 mu m-7.5 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 60-110mv/pa and static pressure sensitivity of 7 um/pa.
Description
Technical Field
The invention relates to the technical field of acoustic thin films, in particular to a TPEE acoustic thin 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.
TPEE (thermoplastic polyester elastomer) is a block copolymer containing polyester hard segments and polyether soft segments. Wherein the soft polyether segment and the uncrystallized polyester form amorphous phase polyester hard segment and are partially crystallized to form crystalline micro-regions which play the role of physical crosslinking points. TPEE has elasticity of rubber and strength of engineering plastics; the soft segment imparts elasticity to it, making it rubber-like; the hard segment imparts processability to it, making it plastic-like; compared with rubber, the rubber has better processing performance and longer service life; compared with engineering materials, the material has the characteristics of high strength, and better flexibility and dynamic mechanical property.
Disclosure of Invention
In order to solve the technical problems, the invention provides a TPEE acoustic film and a preparation method thereof, and aims to provide the TPEE acoustic film, wherein a TPEE material is modified by adopting polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol and polyformaldehyde, so that the toughness of the TPEE material is enhanced, and the TPEE material still has excellent mechanical properties when the ultrathin acoustic film is prepared.
The invention provides a TPEE acoustic film which is prepared from the following raw materials: modified TPEE sheet, antioxidant and coupling agent A;
the modified TPEE sheet is prepared from the following raw materials: TPEE resin, polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol, polyformaldehyde and a composite coupling agent B;
the sensitivity of the LCP acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 60-110mv/pa, and the static pressure sensitivity is less than or equal to 7 um/p.
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 TPEE sheet, 1-3 parts of antioxidant and 2-7 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 100-120 parts of TPEE resin, 20-50 parts of polybutylene terephthalate, 10-30 parts of polyether sulfone, 5-10 parts of nano calcium carbonate, 2-7 parts of nano aluminum oxide, 1-3 parts of cardanol, 10-15 parts of polyformaldehyde and 20-78 parts of a composite coupling agent B10.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 115 parts of modified TPEE sheet 105-2 parts of antioxidant and 3-6 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 115 parts of TPEE resin 105-one, 30-40 parts of polybutylene terephthalate, 15-25 parts of polyethersulfone, 6-8 parts of nano calcium carbonate, 3-6 parts of nano aluminum oxide, 1-2 parts of cardanol, 12-14 parts of polyformaldehyde, 0.002-0.004 part of crosslinking curing agent and 78-17 parts of composite coupling agent B12.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 110 parts of modified TPEE sheet, 1.5 parts of antioxidant and 4 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 110 parts of TPEE resin, 35 parts of polybutylene terephthalate, 20 parts of polyether sulfone, 7 parts of nano calcium carbonate, 5 parts of nano aluminum oxide, 1.2 parts of cardanol, 13 parts of polyformaldehyde and 15 parts of composite coupling agent B.
As a further improvement of the invention, the modified TPEE sheet is prepared by the following method:
s1, preparing a dilute solution with the concentration of 0.5-1% by using a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding polybutylene terephthalate and polyether sulfone mixed rubber after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by using a flat vulcanizing machine at 200 ℃ and 10MPa, tabletting for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
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 TPEE acoustic film has a diameter of 2.15mm to 2.52mm and a thickness of 2.7 μm to 7.5 μm.
The invention further provides a preparation method of the TPEE 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 the antioxidant, the lubricant, the flexibilizer and the light stabilizer in an ethanol water solution, dropwise adding the coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 500r/min, 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 until the hollow stainless steel tube, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
The invention has the following beneficial effects:
the crosslinking curing agent prepared by the invention is an imidazole curing agent, wherein original secondary amine is replaced by tertiary amine, and a new tertiary amine group is introduced, so that the modified imidazole curing agent is beneficial to normal-temperature curing, and can complete good curing performance even in a very small addition amount, the cost is reduced, and the product has good mechanical property and thermal property;
the acoustic film is prepared by adopting the modified TPEE material, the material contains a segmented copolymer of a polyester hard segment and a polyether soft 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 TPEE material is modified by adopting polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol, basalt and polyformaldehyde, so that the toughness of the TPEE material is enhanced, and the TPEE material still has excellent mechanical property when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein one common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with TPEE, a silane coupling agent with amino helps organic particles such as polyformaldehyde to be modified and linked with TPEE, and the modified particles and TPEE material are chemically bonded through the compounded silane coupling agent to prepare TPEE particles with better toughness and mechanical properties for later-stage preparation of TPEE acoustic membrane materials;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 2.15mm-2.52mm, and the thickness is 2.7 mu m-7.5 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 60-110mv/pa and static pressure sensitivity of 7 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 TPEE sheet, 1 part of diphenylamine and 2 parts of coupling agent A. The coupling agent A is KH 560.
Preparation of modified TPEE sheet
The raw materials comprise the following components in parts by weight: 100 parts of TPEE resin, 20 parts of polybutylene terephthalate, 10 parts of polyether sulfone, 5 parts of nano calcium carbonate, 2 parts of nano aluminum oxide, 1 part of cardanol, 10 parts of polyformaldehyde, 0.001 part of crosslinking curing agent 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, preparing a 0.5% dilute solution of a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding a crosslinking curing agent, polybutylene terephthalate and polyether sulfone rubber compound after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding and discharging the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by a flat vulcanizing machine at 200 ℃ and 10MPa for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
A method of making a TPEE acoustic film, comprising the steps of:
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 diphenylamine in an ethanol aqueous solution, dropwise adding a coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 300r/min, 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 until the hollow stainless steel tube is, 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 TPEE sheet, 3 parts of tri (cetyl alcohol) ester and 7 parts of coupling agent A. The coupling agent A is KH 570.
Preparation of modified TPEE sheet
The raw materials comprise the following components in parts by weight: 120 parts of TPEE resin, 50 parts of polybutylene terephthalate, 30 parts of polyether sulfone, 10 parts of nano calcium carbonate, 7 parts of nano aluminum oxide, 3 parts of cardanol, 15 parts of polyformaldehyde, 0.005 part of crosslinking curing agent 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, preparing a dilute solution with the concentration of 1% by using a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding a crosslinking curing agent, polybutylene terephthalate and polyether sulfone rubber compound after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding and discharging the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by a flat vulcanizing machine at 200 ℃ and 10MPa for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
A method of making a TPEE acoustic film, comprising the steps of:
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 the trihexadecyl alcohol ester in an ethanol aqueous solution, dropwise adding the 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 TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 500r/min, 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 until the hollow stainless steel tube, and curing 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 TPEE sheet, 1 part of p-phenylenediamine and 3 parts of coupling agent A. The coupling agent A is KH 792.
Preparation of modified TPEE sheet:
the raw materials comprise the following components in parts by weight: 105 parts of TPEE resin, 30 parts of polybutylene terephthalate, 15 parts of polyether sulfone, 6 parts of nano calcium carbonate, 3 parts of nano aluminum oxide, 1 part of cardanol, 12 parts of polyformaldehyde, 0.002 part of crosslinking curing agent 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, and the common silane coupling agent is DL 602.
The preparation method comprises the following steps:
s1, preparing a 0.6% dilute solution of a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding a crosslinking curing agent, polybutylene terephthalate and polyether sulfone rubber compound after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding and discharging the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by a flat vulcanizing machine at 200 ℃ and 10MPa for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
A method of making a TPEE acoustic film, comprising the steps of:
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 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 TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 350r/min, 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 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 TPEE sheet, 2 parts of tricetyl alcohol ester and 6 parts of coupling agent A. The coupling agent A is DL 171.
Preparation of modified TPEE sheet
The raw materials comprise the following components in parts by weight: 115 parts of TPEE resin, 40 parts of polybutylene terephthalate, 25 parts of polyether sulfone, 8 parts of nano calcium carbonate, 6 parts of nano aluminum oxide, 2 parts of cardanol, 14 parts of polyformaldehyde, 0.004 part of crosslinking curing agent 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 DL171, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, preparing a 0.9% dilute solution of a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding a crosslinking curing agent, polybutylene terephthalate and polyether sulfone rubber compound after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding and discharging the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by a flat vulcanizing machine at 200 ℃ and 10MPa for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
A method of making a TPEE acoustic film, comprising the steps of:
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 the trihexadecyl alcohol ester in an ethanol aqueous solution, dropwise adding the 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 TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 450r/min, 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 by adopting ultraviolet irradiation to obtain the acoustic film.
Example 5
The raw material composition (weight portion) is modified TPEE sheet 110 portions, tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1.5 portions and coupling agent A4 portions, wherein the coupling agent A is selected from one of KH550, KH560, KH570, KH792, DL602 and DL 171.
Preparation of modified TPEE sheet
The raw materials comprise the following components in parts by weight: 110 parts of TPEE resin, 35 parts of polybutylene terephthalate, 20 parts of polyether sulfone, 7 parts of nano calcium carbonate, 5 parts of nano aluminum oxide, 1.2 parts of cardanol, 13 parts of polyformaldehyde, 0.003 part of crosslinking curing agent 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 DL602, and the silane coupling agent with amino groups is KH 550.
The preparation method comprises the following steps:
s1, preparing a 0.7% dilute solution of a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding a crosslinking curing agent, polybutylene terephthalate and polyether sulfone rubber compound after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding and discharging the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by a flat vulcanizing machine at 200 ℃ and 10MPa for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
A method of making a TPEE acoustic film, comprising the steps of:
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 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 TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 400r/min, 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 by adopting ultraviolet irradiation to obtain the acoustic film.
Comparative example 1
Compared to example 5, unmodified ordinary TPEE material was used.
Comparative example 2
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 TPEE acoustic films prepared in examples 1-5 of the present invention and comparative examples 1-2 were subjected to performance tests, 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 2.15mm to 2.52mm and a thickness of 2.7 μm to 7.5 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 60-110mv/pa, static pressure sensitivity of 7um/pa and long service life of 15-20 years; the acoustic film prepared by adopting the common TPEE material in the comparative example 2 has poor mechanical property without modification, and the fracture growth rate is only 102 percent; in comparative example 3, no compound coupling agent is adopted for coupling modification, the modification effect is poor, the mechanical property is not improved much, the fracture growth rate is only 69%, and the acoustic characteristic is poor.
Compared with the prior art, the crosslinking curing agent prepared by the invention is an imidazole curing agent, wherein original secondary amine is replaced by tertiary amine, and new tertiary amine groups are introduced, so that the modified imidazole curing agent is beneficial to normal-temperature curing, and can complete good curing performance even in a very small addition amount, thereby reducing the cost and enabling the product to have good mechanical property and thermal property;
the acoustic film is prepared by adopting the modified TPEE material, the material contains a segmented copolymer of a polyester hard segment and a polyether soft 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 TPEE material is modified by adopting polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol, basalt and polyformaldehyde, so that the toughness of the TPEE material is enhanced, and the TPEE material still has excellent mechanical property when an ultrathin acoustic film is prepared;
according to the invention, two different silane modifiers are compounded to modify different particles, wherein one common silane modifier helps inorganic particles with oxygen on the surface to be modified and linked with TPEE, a silane coupling agent with amino helps organic particles such as polyformaldehyde to be modified and linked with TPEE, and the modified particles and TPEE material are chemically bonded through the compounded silane coupling agent to prepare TPEE particles with better toughness and mechanical properties for later-stage preparation of TPEE acoustic membrane materials;
the acoustic film prepared by the method has smooth and stable surface, the diameter is 2.15mm-2.52mm, and the thickness is 2.7 mu m-7.5 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 60-110mv/pa and static pressure sensitivity of 7 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 TPEE acoustic film is characterized by being prepared from the following raw materials: modified TPEE sheet, antioxidant and coupling agent A;
the modified TPEE sheet is prepared from the following raw materials: TPEE resin, polybutylene terephthalate, polyether sulfone, nano calcium carbonate, nano aluminum oxide, cardanol, polyformaldehyde and a composite coupling agent B;
the sensitivity of the LCP acoustic membrane in the sound wave frequency range of 0.025Hz-25000Hz is 60-110mv/pa, and the static pressure sensitivity is less than or equal to 7 um/pa.
2. The TPEE acoustic film as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 100-120 parts of modified TPEE sheet, 1-3 parts of antioxidant and 2-7 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 100-120 parts of TPEE resin, 20-50 parts of polybutylene terephthalate, 10-30 parts of polyether sulfone, 5-10 parts of nano calcium carbonate, 2-7 parts of nano aluminum oxide, 1-3 parts of cardanol, 10-15 parts of polyformaldehyde and 20-78 parts of a composite coupling agent B10.
3. The TPEE acoustic film as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 115 parts of modified TPEE sheet 105-2 parts of antioxidant and 3-6 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 115 parts of TPEE resin 105-one, 30-40 parts of polybutylene terephthalate, 15-25 parts of polyethersulfone, 6-8 parts of nano calcium carbonate, 3-6 parts of nano aluminum oxide, 1-2 parts of cardanol, 12-14 parts of polyformaldehyde, 0.002-0.004 part of crosslinking curing agent and 78-17 parts of composite coupling agent B12.
4. The TPEE acoustic film as claimed in claim 3, which is prepared from the following raw materials in parts by weight: 110 parts of modified TPEE sheet, 1.5 parts of antioxidant and 4 parts of coupling agent A;
the modified TPEE sheet is prepared from the following raw materials in parts by weight: 110 parts of TPEE resin, 35 parts of polybutylene terephthalate, 20 parts of polyether sulfone, 7 parts of nano calcium carbonate, 5 parts of nano aluminum oxide, 1.2 parts of cardanol, 13 parts of polyformaldehyde and 15 parts of composite coupling agent B.
5. The TPEE acoustic film as claimed in claim 1, wherein said modified TPEE sheet is prepared by the following method:
s1, preparing a dilute solution with the concentration of 0.5-1% by using a composite coupling agent B to obtain a composite coupling agent B solution;
s2, mixing and dissolving nano calcium carbonate and polyformaldehyde in an ethanol water solution, dropwise adding a composite coupling agent B solution while stirring, and after uniformly stirring, irradiating for 30min by using ultraviolet light to obtain a modifier;
s3, drying the TPEE resin in a drying oven at 100 ℃ for 2 hours, and taking out; setting an internal mixer to 200 ℃, adding TPEE resin, adding polybutylene terephthalate and polyether sulfone mixed rubber after 6min, adding the modifier prepared in the step S2 after torque is stable, mixing for 20min, discharging, feeding the discharged rubber material on and off a 200 ℃ high-temperature open mill, tabletting by using a flat vulcanizing machine at 200 ℃ and 10MPa, tabletting for 5min, and cold-pressing for 3min to obtain the modified TPEE sheet.
6. The TPEE acoustic film of claim 1, wherein said coupling agent a is selected from the group consisting of KH550, KH560, KH570, KH792, DL602, and DL 171.
7. The TPEE acoustic film as claimed in claim 1, wherein said composite coupling agent B comprises a combination of a general silane coupling agent and a silane coupling agent having an amino group, the mass ratio of the general silane coupling agent to the silane coupling agent having an amino group is 5:2, and the general silane coupling agent comprises one of KH550, KH560, KH570, KH792, DL602 and DL 171.
8. The TPEE acoustic film as set forth in claim 1, wherein said 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.
9. A TPEE acoustic film as defined in claim 1, wherein the TPEE acoustic film has a diameter of 2.15mm to 2.52mm and a thickness of 2.7 μm to 7.5 μm.
10. A method of making a TPEE acoustic film as defined in any one of claims 1-9, comprising 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 the antioxidant, the lubricant, the flexibilizer and the light stabilizer in an ethanol water solution, dropwise adding the coupling agent A solution while stirring, uniformly stirring, and irradiating for 30min by using ultraviolet light to obtain a mixed solution;
s3, dissolving the modified TPEE sheet in a DMF solution, performing 100W ultrasonic dispersion for 30min, adding the mixed solution prepared in the step S2, stirring for 30min at the rotating speed of 500r/min, 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 until the hollow stainless steel tube, and curing by adopting ultraviolet irradiation to obtain the acoustic film.
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| US20080023887A1 (en) * | 2006-07-26 | 2008-01-31 | Vollenberg Peter H | Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
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