CN112500703A - Acoustic thin film and preparation method thereof - Google Patents

Acoustic thin film and preparation method thereof Download PDF

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Publication number
CN112500703A
CN112500703A CN202011424202.0A CN202011424202A CN112500703A CN 112500703 A CN112500703 A CN 112500703A CN 202011424202 A CN202011424202 A CN 202011424202A CN 112500703 A CN112500703 A CN 112500703A
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film
acoustic
modified
parts
polythioetherimide
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程旺生
雷军
邓生卫
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Hunan Qiwei Technology Co ltd
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Hunan Qiwei Technology Co ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
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    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
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    • H04R2231/00—Details of apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor covered by H04R31/00, not provided for in its subgroups
    • H04R2231/001—Moulding aspects of diaphragm or surround
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
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Abstract

The invention discloses an acoustic film which is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 60-70 parts of polythioether imide, 2-5 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 15-25 parts of D-glass fiber powder and 0.5-1.5 parts of coupling agent. The invention also discloses a preparation method of the acoustic film. The acoustic film disclosed by the invention has the advantages of good comprehensive performance, good performance stability and sound transmission effect, high sensitivity and electroacoustic conversion efficiency, and excellent weather resistance, mechanical property and high temperature resistance.

Description

Acoustic thin film and preparation method thereof
Technical Field
The invention relates to the technical field of membrane materials, in particular to an acoustic thin film and a preparation method thereof.
Background
With the development of society, the pace of life of people is gradually accelerated, and the pressure from life and work is increased. Listening to a pleasant music becomes an effective measure for the current young person in labor to relax the mind and body and relieve stress and avoid chronic diseases caused by the autonomic nervous dysfunction. The music can knock closed soul, relieve depression and stuffy mood, stimulate the brain, activate brain cells and even realize soul treatment to some extent. Music is output and propagated without leaving the acoustic device, in which an acoustic membrane is one of its key components, and an acoustic signal is generated by the movement of an acoustic membrane of a speaker mechanically driven by a voice coil. The acoustic membrane with excellent performance is a precondition for ensuring the electroacoustic conversion efficiency of the electroacoustic transducer, and the mass of the acoustic membrane directly influences the sound transmission quality and the service life of an acoustic device.
Not only is high flexural rigidity, low density, high internal damping required for an ideal acoustic film, but also excellent thermal stability, weatherability, mechanical properties, and demanding functional capacity under thermal load, and conventional film materials such as polyethylene terephthalate (PET) or Polycarbonate (PC) are more frequently at their limits and cannot meet the requirements for high quality acoustic film applications. The existing acoustic membranes are commonly used as silicone acoustic membranes and polyether ether ketone acoustic membranes, and the membrane materials are all in thousands of years, so that the defects that the heat resistance and the weather resistance are required to be further improved, and the dielectric constant at high frequency is required to be further reduced are generally existed.
The Chinese patent with application number 201911058072.0 discloses 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 ultrasonic transducer is larger than the thickness of the ultrasonic transducer, the ultrasonic transducer has good acoustic characteristics, has good responsiveness in the sound wave frequency range of 0.025Hz-25000Hz, and has the sensitivity of 60-110mv/pa and the sensitivity of 7 um/pa. However, the raw materials for preparing the film contain various components, and the components are not connected with each other by chemical bonds, so that the comprehensive performance is poor, the performance stability is poor, and the service life is short.
There is still a need in the art for an acoustic membrane with good overall performance, stable performance, good sound transmission effect, high sensitivity and electroacoustic conversion efficiency, and excellent weatherability, mechanical properties, and high temperature resistance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the acoustic film with good comprehensive performance, good performance stability and sound transmission effect, high sensitivity and electroacoustic conversion efficiency, and excellent weather resistance, mechanical property and high temperature resistance. Meanwhile, the invention also provides a preparation method of the acoustic film, and the preparation method has the advantages of simple process, convenient operation and control, small equipment investment, low energy consumption, high preparation efficiency and high qualified rate of finished products, and is suitable for industrial popularization and application.
Therefore, the invention relates to an acoustic film which is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 60-70 parts of polythioether imide, 2-5 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 15-25 parts of D-glass fiber powder and 0.5-1.5 parts of coupling agent.
In an embodiment of the present invention, the carrier film is any one of a TPU film, a PTFE film, and a PET film.
In one embodiment of the invention, the rosin-based adhesive is a rosin-based hyperbranched epoxy resin; the rosin-based hyperbranched epoxy resin is prepared by the preparation method of the rosin-based hyperbranched epoxy resin in Chinese patent application No. 201610861045.7 in patent example 4; the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
In one embodiment of the invention, the fiber diameter of the D-glass fiber powder is 3-6 μm, and the length-diameter ratio (3-6) is 1.
In one embodiment of the invention, the polythioetherimide is polythioetherimide prepared by the method of the invention patent example 1 of China application No. 201811101144.0.
In one embodiment of the present invention, the preparation method of the 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylthiophenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 65-75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and then removing the ethanol and residual water by rotary evaporation to obtain the 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3) -trifluoromethylphenyl) methacrylamide copolymer.
In one embodiment of the invention, the mass ratio of the 2-acrylamido-2-methylpropanesulfonic acid, the allyl 3, 5-diamino-1H-pyrazole-4-carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, the initiator and the high boiling point solvent is 1 (0.2-0.4):0.6:0.2:1 (0.03-0.04): 10-20).
In one embodiment of the present invention, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of helium, neon, argon and nitrogen.
Another object of the present invention is to provide a method for preparing the acoustic film, including the steps of:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 3-8 mu m by using a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then laminating the modified polythioetherimide film on a carrier film, pressing the modified polythioetherimide film at the temperature of 105-115 ℃, and hardening the modified polythioetherimide film for 15-20min at the temperature of 50-60 ℃ to obtain the acoustic film.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the acoustic film provided by the invention has the advantages of simple process, convenience in operation and control, low equipment investment, low energy consumption, high preparation efficiency and finished product qualification rate, and is suitable for industrial popularization and application.
(2) The acoustic film provided by the invention overcomes the defects that the mechanical property, the heat resistance and the weather resistance of the existing acoustic film are required to be further improved and the dielectric constant under high frequency is required to be further reduced; through the synergistic effect of the raw materials, the prepared acoustic film has the advantages of good comprehensive performance, good performance stability and sound transmission effect, high sensitivity and electroacoustic conversion efficiency, and excellent weather resistance, mechanical property and high temperature resistance.
(3) In the preparation process of the acoustic film, the modified polythioetherimide film provided by the invention, under the action of phosphorus pentoxide as a catalyst, a benzene ring on the polythioetherimide can generate a crosslinking reaction with a sulfonic acid group on a 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer to form a three-dimensional network structure, so that the comprehensive performance and the performance stability of the acoustic film are effectively improved, the two substrates are connected by chemical bonds to form an organic whole, and under the multiple actions of an electronic effect, a steric hindrance effect and a conjugation effect, the synergistic effect combines the advantages of the two, and the acoustic film is endowed with more excellent acoustic performance and durability.
(4) According to the acoustic film provided by the invention, an asymmetric structure is introduced on a 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer through random copolymerization among monomers, so that the prepared film has lower dielectric constant and dielectric loss and better sensitivity at high frequency.
(5) The addition of the D-glass fiber powder improves the mechanical property of the acoustic film, simultaneously effectively reduces the dielectric loss of the acoustic film, improves the sound transmission effect, ensures that the prepared film layer has good weather resistance, excellent mechanical property and good comprehensive performance and performance stability under the multiple actions of electronic effect, steric hindrance effect and electronic effect of each monomer in the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxy thiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, and has a thiophenol structure similar to a polythioether imide structure part, compatibility between them is enhanced; the amino group on the rosin-based adhesive can perform ring-opening reaction with the epoxy group on the rosin-based adhesive, so that the film layer and the base material have better bonding performance and longer service life.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The rosin-based adhesive is rosin-based hyperbranched epoxy resin; the rosin-based hyperbranched epoxy resin is prepared by the preparation method of the rosin-based hyperbranched epoxy resin in Chinese patent application No. 201610861045.7 in patent example 4; the polythioetherimide is prepared by the method of the Chinese patent application No. 201811101144.0, namely the patent example 1.
Example 1
The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 60 parts of polythioetherimide, 2 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 15 parts of D-glass fiber powder and 0.5 part of coupling agent; the base film is a TPU film; the coupling agent is a silane coupling agent KH 550; the diameter of the D-glass fiber powder is 3 mu m, and the length-diameter ratio is 3: 1.
The preparation method of the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 3 hours at 65 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and then performing rotary evaporation to remove the ethanol and residual water to obtain 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methyl propyl silatrane An acrylamide copolymer.
The mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid, the 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxythiophenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, the initiator and the high-boiling point solvent is 1:0.2:0.6:0.2:1:0.03: 10; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is helium.
A preparation method of the acoustic film comprises the following steps:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 3 mu m by a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then superposing the modified polythioetherimide film on a carrier film, pressing at 105 ℃, and hardening at 50 ℃ for 15min to obtain the acoustic film.
Example 2
The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 63 parts of polythioether imide, 3 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 17 parts of D-glass fiber powder and 0.7 part of coupling agent; the support base film is a PTFE film. The coupling agent is a silane coupling agent KH 560; the diameter of the D-glass fiber powder is 4 μm, and the length-diameter ratio is 4: 1.
The preparation method of the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 3.5 hours at 67 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and then performing rotary evaporation to remove ethanol and residual water to obtain 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methyl phenyl An acrylamide copolymer.
The mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the 3, 5-diamino-1H-pyrazole-4-allyl carboxylate to the methacryloxypropylsilatrane to the allyloxythiophenol to the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide to the initiator to the high boiling point solvent is 1:0.25:0.6:0.2:1:0.033: 12; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is neon.
A preparation method of the acoustic film comprises the following steps:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 4 mu m by a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then superposing the modified polythioetherimide film on a carrier film, pressing at 108 ℃, and hardening at 53 ℃ for 17min to obtain the acoustic film.
Example 3
The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 65 parts of polythioether imide, 3.5 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 20 parts of D-glass fiber powder and 1 part of coupling agent; the carrier film is a PET film; the coupling agent is a silane coupling agent KH 570; the fiber diameter of the D-glass fiber powder is 4.5 mu m, and the length-diameter ratio is 4.5: 1.
The preparation method of the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 4 hours at 70 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and then performing rotary evaporation to remove the ethanol and residual water to obtain 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methyl propyl silatrane An acrylamide copolymer.
The mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid, the 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, the methacryloxypropylsilatrane, the allyloxythiophenol, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, the initiator and the high boiling point solvent is 1:0.3:0.6:0.2:1:0.035: 15; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is argon.
A preparation method of the acoustic film comprises the following steps:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 7 mu m by a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then laminating the modified polythioetherimide film on a carrier film, pressing the base film at 113 ℃, and hardening the base film at 58 ℃ for 19min to obtain the acoustic film.
Example 4
The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 70 parts of polythioetherimide, 5 parts of phosphorus pentoxide, 25 parts of 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 8 parts of D-glass fiber powder and 1.5 parts of coupling agent.
The base film is a TPU film; the coupling agent is a silane coupling agent KH 550; the diameter of the D-glass fiber powder is 5.5 mu m, and the length-diameter ratio is 5.5: 1.
The preparation method of the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours at 73 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and then performing rotary evaporation to remove ethanol and residual water to obtain 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methyl phenyl An acrylamide copolymer.
The mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the 3, 5-diamino-1H-pyrazole-4-allyl carboxylate to the methacryloxypropylsilatrane to the allyloxythiophenol to the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide to the initiator to the high boiling point solvent is 1:0.35:0.6:0.2:1:0.038: 18; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 2: 3; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:3: 2; the inert gas is nitrogen.
A preparation method of the acoustic film comprises the following steps:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 7 mu m by a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then laminating the modified polythioetherimide film on a carrier film, pressing the base film at 113 ℃, and hardening the base film at 58 ℃ for 19min to obtain the acoustic film.
Example 5
The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 70 parts of polythioetherimide, 5 parts of phosphorus pentoxide, 25 parts of 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 8 parts of D-glass fiber powder and 1.5 parts of coupling agent; the carrier film is a PTFE film; the coupling agent is a silane coupling agent KH 570; the diameter of the D-glass fiber powder is 6 mu m, and the length-diameter ratio is 6: 1.
The preparation method of the 2-acrylamide-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 5 hours at 75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and then performing rotary evaporation to remove the ethanol and residual water to obtain 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methyl propyl silatrane An acrylamide copolymer.
The mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid, the 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxythiophenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, the initiator and the high-boiling point solvent is 1:0.4:0.6:0.2:1:0.04: 20; the initiator is azobisisobutyronitrile; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is helium.
A preparation method of the acoustic film comprises the following steps:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 8 mu m by a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then laminating the modified polythioetherimide film on a carrier film, pressing the modified polythioetherimide film at 115 ℃, and hardening the modified polythioetherimide film at 60 ℃ for 20min to obtain the acoustic film.
Comparative example 1
An acoustic film was formulated and prepared substantially as in example 1, except that polyphenylene sulfide PPS-LM-1140 was used in place of the polythioetherimide.
Comparative example 2
An acoustic film was formulated and produced in substantially the same manner as in example 1 except that the polythioetherimide was replaced with a meltable polyimide molding powder YS-20.
Comparative example 3
An acoustic film having substantially the same formulation and preparation as in example 1 except that methacryloxypropyl silatrane was not added.
Comparative example 4
An acoustic film was formulated and prepared substantially as in example 1, except that N- (4-cyano-3-trifluoromethylphenyl) methacrylamide was not added.
Comparative example 5
An acoustic film was formulated and prepared substantially as in example 1, except that allyloxythiophenol was not added.
The acoustic films prepared in examples 1 to 5 and comparative examples 1 to 5 above were subjected to the relevant performance tests, and the test results and the test methods are shown in table 1; the aging test is carried out according to GB/T14522-93; other performances are tested according to the current national standard of China, and the dielectric constant test frequency is 50 kHz.
TABLE 1
Item Tensile strength Rate of decrease in tensile Strength after aging Sensitivity of the probe Dielectric constant
Unit of MPa ％ mv/pa —
Example 1 93 2.1 86 2.7
Example 2 97 1.7 90 2.6
Example 3 101 1.3 95 2.6
Example 4 104 1.0 99 2.5
Example 5 106 0.8 105 2.4
Comparative example 1 85 4.6 74 3.9
Comparative example 2 82 5.3 78 3.7
Comparative example 3 89 5.1 81 3.5
Comparative example 4 87 4.9 83 3.3
Comparative example 5 90 4.2 83 3.1
As can be seen from table 1, the acoustic thin film disclosed in the embodiment of the present invention has more excellent mechanical properties, a lower dielectric constant, and a higher sensitivity, and increases the signal transmission speed, which is a result of the synergistic effect of the raw materials.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. The acoustic film is characterized by comprising a modified polythioether imide film and a bottom supporting film, wherein the modified polythioether imide film and the bottom supporting film are bonded through a rosin-based adhesive; the modified polythioether imide film is prepared from the following raw materials in parts by weight: 60-70 parts of polythioether imide, 2-5 parts of phosphorus pentoxide, 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer, 15-25 parts of D-glass fiber powder and 0.5-1.5 parts of coupling agent.
2. The acoustic film of claim 1, wherein the backing film is any one of a TPU film, a PTFE film, and a PET film.
3. The acoustic membrane of claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
4. An acoustic membrane according to claim 1, wherein the D-glass fiber powder has a fiber diameter of 3 to 6 μm and an aspect ratio (3 to 6): 1.
5. An acoustic membrane according to claim 1, wherein the preparation method of the 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-carboxylic acid allyl ester/methacryloxypropylsilatrane/allyloxyphenylphenol/N- (4-cyano-3-trifluoromethylphenyl) methacrylamide copolymer comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, 3, 5-diamino-1H-pyrazole-4-allyl carboxylate, methacryloxypropylsilatrane, allyloxyphenylthiophenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 65-75 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and then removing the ethanol and residual water by rotary evaporation to obtain the 2-acrylamido-2-methylpropanesulfonic acid/3, 5-diamino-1H-pyrazole-4-allyl carboxylate/methacryloxypropylsilatrane/allyloxyphenylthiophenol/N- (4-cyano-3) -trifluoromethylphenyl) methacrylamide copolymer.
6. The acoustic membrane of claim 5, wherein the mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, allyl 3, 5-diamino-1H-pyrazole-4-carboxylate, methacryloxypropylsilatrane, allyloxyphenylphenol, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, initiator and high boiling point solvent is 1 (0.2-0.4):0.6:0.2:1 (0.03-0.04): 10-20).
7. An acoustic membrane according to claim 5 wherein the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of helium, neon, argon and nitrogen.
8. An acoustic film according to any one of claims 1-7, wherein the method of making the acoustic film comprises the steps of:
step S1, preparation of modified polythioetherimide film: uniformly mixing all the raw materials, melting, and sequentially preparing a modified polythioetherimide film with the thickness of 3-8 mu m by using a clothes hanger type T-die, a chrome-plated calendering roller, a drying roller and other equipment;
and S2, coating rosin-based adhesive on the bottom surface of the modified polythioetherimide film prepared in the step S1, then laminating the modified polythioetherimide film on a carrier film, pressing the modified polythioetherimide film at the temperature of 105-115 ℃, and hardening the modified polythioetherimide film for 15-20min at the temperature of 50-60 ℃ to obtain the acoustic film.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2024109000A1 (en) * 2022-11-24 2024-05-30 安徽绿沃循环能源科技有限公司 Lithium battery separator and preparation method therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024109000A1 (en) * 2022-11-24 2024-05-30 安徽绿沃循环能源科技有限公司 Lithium battery separator and preparation method therefor

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