阅读说明：本技术 一种tpee声学薄膜及其制备方法 (TPEE acoustic film and preparation method thereof ) 是由 夏超华 于 2019-10-08 设计创作，主要内容包括：本发明公开了一种TPEE声学薄膜,其特征在于,由如下重量份的各原料制成：TPEE 40-60份、基于磷酸酯聚2,3,5,6-四氟对苯二甲酸三聚氰胺-酰胺酯20-40份、环氧丙烷橡胶5-15份、硼酸三丁酯1-4份、润滑剂1-2份、抗氧剂0.2-0.6份。本发明还提供了所述TPEE声学薄膜的制备方法。本发明公开的TPEE声学薄膜力学性能、耐高低温、耐老化、耐臭氧及耐介质性能优异,制备成本低廉,阻燃性好,介电常数和介电损耗小,信号传输质量高,声电转换效率高,对高低频响应快,灵敏度高。(The invention discloses TPEE acoustic thin films, which are characterized by being prepared from the following raw materials in parts by weight of 40-60 parts of TPEE, 20-40 parts of 2,3,5, 6-tetrafluoro-terephthalic acid melamine-amide ester based on phosphate ester, 5-15 parts of propylene oxide rubber, 1-4 parts of tributyl borate, 1-2 parts of lubricant and 0.2-0.6 part of antioxidant.)

The TPEE acoustic film is characterized by being prepared from the following raw materials, by weight, 40-60 parts of TPEE, 20-40 parts of phosphate poly-2, 3,5, 6-tetrafluoro-terephthalic acid melamine-amide ester, 5-15 parts of propylene oxide rubber, 1-4 parts of tributyl borate, 1-2 parts of a lubricant and 0.2-0.6 part of an antioxidant.

2. The TPEE acoustic film of claim 1, wherein said lubricant is at least of silicone oil, polyethylene wax, ethylene bis-oleic amide.

3. The TPEE acoustic film of claim 1, wherein the antioxidant is at least of antioxidant 168, antioxidant 1076, antioxidant 1010, antioxidant 164.

4. The TPEE acoustic film of claim 1, wherein the TPEE is a copolymer of soft segment polytetrahydrofuran polyether and aliphatic polyester.

5. The TPEE acoustic film according to claim 1, wherein said process for the preparation of phosphate based poly 2,3,5, 6-tetrafluoro terephthalate melamine-amide ester comprises the steps of:

step S1: dissolving melamine-amide and 4- (diethoxyphosphoryl) -benzoic acid in an organic solvent to form a solution, then adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting at 25-40 ℃ for 18-24 hours, and after the reaction is finished, removing the solvent by rotary evaporation to obtain the intermediate;

step S2: adding the intermediate prepared in the step S1, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling-point solvent, stirring for 1.5-2.5 hours at the temperature of 115 ℃ and 135 ℃ to obtain a reaction solution, then transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen or inert gas, then stirring and reacting for 3-5 hours at the temperature of 130-150 ℃ under normal pressure, then decompressing to 50-100Pa, heating to 290 ℃ at 270-290 ℃, preserving heat and maintaining pressure, stirring and reacting for 18-22 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, removing ethanol by rotary evaporation, and vacuum drying at 70-80 deg.C to constant weight to obtain 2,3,5, 6-tetrafluoro-terephthalic acid melamine-amide phosphate.

6. The TPEE acoustic membrane of claim 5, wherein the mass ratio of the melamine-amide to the 4- (diethoxyphosphoryl) -benzoic acid to the organic solvent to the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline in the step S1 is 1:2.02 (9-15) to (0.4-0.6), and the organic solvent is of tetrahydrofuran, dichloromethane and acetone.

7. The TPEE acoustic film according to claim 5, wherein the mass ratio of the intermediate, the 2,3,5, 6-tetrafluoroterephthalic acid, the catalyst and the high-boiling solvent in the step S2 is 1.62:1 (0.4-0.6) to (8-14).

8. The TPEE acoustic film according to claim 5, wherein the catalyst is at least of tetrabutyl titanate, p-toluenesulfonic acid, antimony oxide and antimony acetate, the high boiling point solvent is at least of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the inert gas is of helium, neon and argon.

9. The TPEE acoustic film of any one of claims 1-8 and , wherein the method of making the TPEE acoustic film comprises the steps of:

step D1: adding TPEE, phosphate-based 2,3,5, 6-tetrafluoro terephthalic acid melamine-amide ester, tributyl borate, a lubricant and an antioxidant into a stirrer in proportion, uniformly mixing, and performing extrusion molding by using an extruder to obtain a film;

step D2: plasticizing the rubber sheet prepared in the step D1 on a high-temperature open mill at the plasticizing temperature of 180-; adding propylene oxide rubber after plasticizing completely, mixing uniformly, then cooling, banburying the mixed materials in a banbury mixer for 3-5 minutes, and discharging to obtain a dense rubber compound;

step D3: and D2, carrying out calendaring molding on the banburying adhesive prepared in the step D2 to obtain the TPEE acoustic film.

10. The TPEE acoustic film as claimed in claim 9, wherein said extruder is preferably a twin-screw extruder, and is pelletized by co-rotating twin-screw extrusion with a diameter of 40mm, and the screw aspect ratio (L/D) is: 44/1, the rotating speed is 250-350 r/min; the temperature of each section is from the charging opening to 165-.

Technical Field

The invention relates to the technical field of acoustic membrane materials, in particular to TPEE acoustic thin films and a casting method thereof.

Background

In recent years, with the development of economy and social progress, acoustic devices such as bamboo shoots in the spring after rain come into people's lives, the acoustic devices become which is a main tool for ordinary people to play at low cost, improve the quality of life and build spiritual culture, and new colors are given to colorful life paintings of the ordinary people, however, the influence of the acoustic devices such as a loudspeaker and a microphone on the acoustic quality draws attention of people , higher technical requirements are put forward on acoustic films of core components of the acoustic devices, and the development of the acoustic films with excellent performance becomes a technical problem to be solved urgently in the industry.

The traditional acoustic film is a capacitive or voltage type film, the film has capacitance or piezoelectricity, the selectivity to materials is high, and the material cannot be used in the occasions of high magnetic field and high electromagnetism.

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 gives it processability, making it like plastic; 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. However, this material is extremely flammable and drops significantly, is not easily manufactured with low hardness, has narrow processing conditions, requires relatively precise processing machinery, and is expensive. It can be seen that the TPEE material has high feasibility of being applied to the acoustic membrane by using the advantages of the TPEE material, but the disadvantages of the TPEE material need to be improved by modification in order to have more excellent overall properties than the acoustic membrane in the prior art.

The invention discloses high-wear-resistance TPEE thermoplastic polyester elastomer with the authorized publication number of CN105131536B, which comprises (wt%) 59-69% of TPEE, 15-25% of PTFE, 7-12% of lubricant, 0.2-1.0% of antioxidant and the balance of silicon dioxide.

Therefore, the development of novel TPEE acoustic films with better comprehensive performance has very important practical significance.

Disclosure of Invention

The invention mainly aims to provide TPEE acoustic films which have excellent mechanical property, high and low temperature resistance, aging resistance, ozone resistance and medium resistance, low preparation cost, good flame retardance, small dielectric constant and dielectric loss, high signal transmission quality, high sound-electricity conversion efficiency, quick response to high and low frequencies and high sensitivity, and also discloses a preparation method of the TPEE acoustic film.

In order to achieve the purpose, the invention provides TPEE acoustic films, which are characterized by being prepared from the following raw materials, by weight, 40-60 parts of TPEE, 20-40 parts of phosphate-based poly (2, 3,5, 6-tetrafluoro-terephthalic acid melamine-amide ester, 5-15 parts of propylene oxide rubber, 1-4 parts of tributyl borate, 1-2 parts of a lubricant and 0.2-0.6 part of an antioxidant.

, the lubricant is at least of organic silicone oil, polyethylene wax and ethylene bisoleic acid amide.

, the antioxidant is at least of antioxidant 168, antioxidant 1076, antioxidant 1010 and antioxidant 164.

Preferably, the TPEE is a copolymer of soft segment polytetrahydrofuran polyether and aliphatic polyester.

, the preparation method based on phosphoric acid ester poly-2, 3,5, 6-tetrafluoro terephthalic acid melamine-amide ester comprises the following steps:

step S1: dissolving melamine-amide and 4- (diethoxyphosphoryl) -benzoic acid in an organic solvent to form a solution, then adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting at 25-40 ℃ for 18-24 hours, and after the reaction is finished, removing the solvent by rotary evaporation to obtain the intermediate;

step S2: adding the intermediate prepared in the step S1, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling-point solvent, stirring for 1.5-2.5 hours at the temperature of 115 ℃ and 135 ℃ to obtain a reaction solution, then transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen or inert gas, then stirring and reacting for 3-5 hours at the temperature of 130-150 ℃ under normal pressure, then decompressing to 50-100Pa, heating to 290 ℃ at 270-290 ℃, preserving heat and maintaining pressure, stirring and reacting for 18-22 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, removing ethanol by rotary evaporation, and vacuum drying at 70-80 deg.C to constant weight to obtain 2,3,5, 6-tetrafluoro-terephthalic acid melamine-amide phosphate.

, the mass ratio of the melamine-amide, the 4- (diethoxyphosphoryl) -benzoic acid, the organic solvent and the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline in the step S1 is 1:2.02 (9-15): 0.4-0.6.

Preferably, the organic solvent is of tetrahydrofuran, dichloromethane and acetone.

, the mass ratio of the intermediate, 2,3,5, 6-tetrafluoroterephthalic acid, catalyst and high-boiling point solvent in the step S2 is 1.62:1 (0.4-0.6) to (8-14).

Preferably, the catalyst is at least of tetrabutyl titanate, p-toluenesulfonic acid, antimony oxide and antimony acetate.

Preferably, the high boiling point solvent is at least of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the inert gas is kinds of helium, neon and argon.

Another objects of the invention are to provide a method for preparing the TPEE acoustic film, which comprises the steps of:

step D1: adding TPEE, phosphate-based 2,3,5, 6-tetrafluoro terephthalic acid melamine-amide ester, tributyl borate, a lubricant and an antioxidant into a stirrer in proportion, uniformly mixing, and performing extrusion molding by using an extruder to obtain a film;

step D2: plasticizing the rubber sheet prepared in the step D1 on a high-temperature open mill at the plasticizing temperature of 180-; adding propylene oxide rubber after plasticizing completely, mixing uniformly, then cooling, banburying the mixed materials in a banbury mixer for 3-5 minutes, and discharging to obtain a dense rubber compound;

step D3: and D2, carrying out calendaring molding on the banburying adhesive prepared in the step D2 to obtain the TPEE acoustic film.

, the extruder is preferably a double-screw extruder, co-rotating double-screw extrusion granulation with a diameter of 40mm is adopted, the length-diameter ratio (L/D) of the screw is 44/1, the rotation speed is 250-350r/min, the temperatures of all sections are 165-170 ℃, 175-185 ℃, 190-200 ℃, 205-210 ℃, 215-220 ℃ and 215-220 ℃ in sequence from the charging opening, and the head temperature of the extruder is 215-230 ℃.

Due to the application of the technical scheme, the invention has the following beneficial effects:

(1) the TPEE acoustic film disclosed by the invention has the advantages of simple preparation method, simple process, convenience in operation, high preparation efficiency and product qualification rate, low requirements on equipment dependence and reaction conditions, high economic value and social value and capability of meeting the continuous large-scale production requirements.

(2) The TPEE acoustic film disclosed by the invention overcomes the technical problems that the acoustic film in the prior art generally has complex preparation process, high cost, low-frequency response, low sensitivity, poor sensitivity, great limitation on the application in the fields with higher requirements on sensitivity and sensitivity, such as voiceprint recognition, heart-related sound acquisition in the medical field and the like, and overcomes the defects that the TPEE material on the market is extremely easy to burn and obviously drip, is difficult to obtain low-hardness manufacturing, has narrow processing conditions, needs more precise processing machinery and is expensive, and has the advantages of excellent mechanical property, high and low temperature resistance, aging resistance, ozone resistance and medium resistance, low preparation cost, good flame retardance, small dielectric constant and dielectric loss, high signal transmission quality, high acoustoelectric conversion efficiency, quick response to high frequency and low frequency and high sensitivity.

(3) The TPEE acoustic film disclosed by the invention takes TPEE as a base material, adds 2,3,5, 6-tetrafluoro terephthalic acid melamine-amide ester phosphate, propylene oxide rubber and other additives, firstly, the molecular chain of the 2,3,5, 6-tetrafluoro terephthalic acid melamine-amide ester phosphate contains a polyester structure, the propylene oxide rubber contains a polyether structure, the TPEE contains both the polyester structure and the polyether structure, and after the three are mixed, the compatibility is good due to the existence of similar structures, so that an organic whole is formed, the comprehensive performance of the film is favorably improved, the performance stability of the film is favorably improved, the flame retardance of the film is improved due to the triazine structure contained in the 2,3,5, 6-tetrafluoro terephthalic acid melamine-amide ester phosphate, the aging resistance and the weather resistance of the film are favorably improved, the fluorobenzene structure is favorably contained, the weather resistance and the mechanical property of the film are favorably improved, a phosphorus-containing ester side chain is introduced, the phosphorus-containing ester side chain is synergistically acted with triazine with the multi-nitrogen structure, the flame retardance of the film is improved, the phosphorus ester structure can become a crosslinking site, the ester exchange crosslinking reaction with tributyl borate is generated, the comprehensive performance of the material is further improved, boron elements are introduced, the elements and the antioxidant is further, the service life of the film is better, the flame retardance is better, and the service life.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.

In the embodiment of the invention, the raw materials are all purchased commercially; the propylene oxide rubber is prepared in advance, and the preparation method refers to the following steps: the preparation performance and the application field of the propylene oxide rubber, the world rubber industry, the brook orchid, article numbers: 1671-8232(2013) 05-0010-05; the TPEE is a copolymer of soft-segment polytetrahydrofuran polyether and aliphatic polyester.