CN111205630B - TPU acoustic film and production method thereof - Google Patents
TPU acoustic film and production method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Abstract
The invention discloses a TPU acoustic film which is characterized by comprising a modified TPU film and a bottom supporting film, wherein the modified TPU film and the bottom supporting film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 55-65 parts of TPU, 20-30 parts of modified amino-terminated polyurethane, 4-8 parts of silicone rubber with amino 107 on a side chain, 1-2 parts of L-lysine triisocyanate, 0.3-0.5 part of catalyst, 0.3-0.5 part of antioxidant, 3-5 parts of zircon powder, 1-2 parts of coupling agent and 0.5-1.5 parts of plasticizer. The invention also discloses a production method of the TPU acoustic film. The TPU acoustic film disclosed by the invention has the advantages of excellent comprehensive performance, good mechanical property, weather resistance, high temperature resistance and performance stability, high impact strength, long service life, high electroacoustic conversion efficiency and good sound transmission effect.
Description
Technical Field
The invention relates to the technical field of acoustic films, in particular to TPU acoustic production and a preparation method thereof.
Background
In mobile phones, smart phones, notebook computers, tablet computers, electronic organizers and headsets, the generation of sound, i.e. the transmission of speech, ring tones, music and other sounds and noise, takes place via so-called micro-speakers. A key component in micro-speakers is an electro-acoustic transducer, also called an acoustic transducer, which is a device that can convert an electrical signal (i.e. a voltage) into an alternating acoustic pressure (i.e. an acoustic signal), or vice versa.
The acoustic membrane is a core component of the acoustic transducer, plays a role in transduction in the acoustic transducer, participates in converting sound vibration into an electric signal, and can also convert the electric signal into a sound signal, so that transmission and detection of the sound signal are realized. The quality of which directly determines the sound transmission effect and the quality of the sound. Therefore, it is important to develop an acoustic membrane having excellent properties to maintain the nature of sound and improve the quality of sound.
The acoustic film in the prior art is generally manufactured by coating and adhering a plurality of layers of thermoplastic resin, and has the problems of low efficiency, high cost and poor consistency. In addition, the multilayer thermoplastic resin has poor heat resistance and cold resistance, is easy to generate plastic deformation at high temperature, is brittle and damaged at low temperature, has poor elasticity, larger stretching permanent deformation and low internal consumption, causes higher distortion and cannot completely restore the essence of sound. Therefore, it is imperative to seek new acoustic membranes.
TPU (thermoplastic polyurethanes) is becoming increasingly popular because of its superior properties and environmental protection concept. The material mainly comprises polyester type and polyether type, not only has excellent characteristics of high tension, toughness and aging resistance, but also has wide hardness range, wear resistance, oil resistance, high transparency, good elasticity, green and environment-friendly use, and is widely applied to the fields of daily necessities, sports goods, toys, decorative materials and the like. However, TPUs also have their own disadvantages, such as poor impact resistance and difficulty in ensuring strength. In addition, the TPU film on the market at present has poor heat resistance, and once the ambient temperature is too high, the TPU film is easily burnt, which limits the application of the TPU film to the acoustic film of the micro-speaker.
The Chinese patent with application number 201910759626.3 discloses a graphene modified antistatic TPU film, which is prepared from the following raw materials in parts by mass: 60-80 parts of polyether type TPU resin, 1-3 parts of modified graphene, 2-4 parts of heat stabilizer, 1-3 parts of lubricant, 1-2 parts of plasticizer and 0.5-2 parts of nano aluminum oxide; the graphene oxide is uniformly dispersed in the TPU resin after being modified by the silane coupling agent and reduced by the ammonia water, and meanwhile, the graphene oxide is not polymerized, so that the conductivity and impact resistance of the TPU film are enhanced; after the nano aluminum oxide is modified, the mechanical property of the nano aluminum oxide and the affinity to resin materials are enhanced; meanwhile, the dosage of the nano aluminum oxide and the graphene is less, and the manufacturing cost is reduced. The method only modifies the graphene, and does not modify inorganic materials such as nano alumina, and the like, namely, the problem of poor performance stability caused by poor dispersibility and compatibility of the inorganic materials is not solved. In addition, the heat resistance thereof is to be further improved.
Therefore, how to improve the comprehensive performance of the TPU membrane material in the prior art for being used in a high-quality TPU acoustic membrane becomes a problem to be solved urgently by researchers in the industry at present.
Disclosure of Invention
The invention mainly aims to provide a TPU acoustic film which has excellent comprehensive performance, good mechanical and mechanical properties, weather resistance, high temperature resistance and performance stability, high impact strength, long service life, high electroacoustic conversion efficiency and good sound transmission effect; meanwhile, the invention also discloses a production method of the TPU acoustic film, and the production method is simple and easy to implement, has low requirements on equipment and reaction conditions, is easy to obtain production raw materials, has high economic value and social value, and is suitable for industrial continuous production.
In order to achieve the purpose, the invention provides a TPU acoustic thin film which is characterized by comprising a modified TPU film and a bottom supporting film, wherein the modified TPU film and the bottom supporting film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 55-65 parts of TPU, 20-30 parts of modified amino-terminated polyurethane, 4-8 parts of silicone rubber with amino 107 on a side chain, 1-2 parts of L-lysine triisocyanate, 0.3-0.5 part of catalyst, 0.3-0.5 part of antioxidant, 3-5 parts of zircon powder, 1-2 parts of coupling agent and 0.5-1.5 parts of plasticizer.
Preferably, the plasticizer is at least one of epoxidized soybean oil, epoxidized butyl furoate and epoxidized acetyl methyl linoleate.
Preferably, 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.
Preferably, the particle size of the zircon powder is 200-400 meshes.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 164.
Preferably, the catalyst is any one of isopropyl titanate, zinc octoate and dibutyltin dilaurate.
Preferably, the preparation method of the silicone rubber with the amino 107 on the side chain refers to the following steps: chenfang, Huang Yong Jun and the like, synthesis and application of silicone rubber with amino 107 on side chains, and organosilicon material, 04 years in 2018.
Preferably, the preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into a high boiling point solvent, stirring for 30-40 minutes at 70-80 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and an alkaline catalyst, stirring and reacting for 4-6 hours under heat preservation, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 10-15 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 10-25 minutes, then placing the crude product under a nitrogen or inert gas atmosphere, reacting for 8-10 hours at 55-65 ℃, respectively performing ultrasonic cleaning for 3-6 times with deionized water and methanol for 0.2-0.5h each time, then placing the crude product in an oven, and drying at 80-90 ℃ to constant weight.
Furthermore, the mol ratio of the amino-terminated polyurethane, the high boiling point solvent, the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and the basic catalyst in the step S1 is 1 (6-10) to 2 (0.3-0.5).
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the alkaline catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Further, the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone in the step S2 is 1 (0.1-0.2) to 0.1 (3-5).
Further, the absorption dose in the radiation grafting process in step S2 is 200-350 kGy.
Further, the inert gas is one of helium, neon and argon.
Another object of the present invention is to provide a method for producing the TPU acoustic film, which comprises the steps of:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 5-20 mu m;
step 2: and (3) coating an adhesive on the bottom surface of the modified TPU film prepared in the step (1), then laminating the modified TPU film on a support film, pressing and hardening to obtain the TPU acoustic film.
Preferably, the hardening treatment specifically comprises: hardening for 15-25 minutes at 65-85 ℃, and then hardening for 15-20 hours at room temperature; the pressing temperature is 110-120 ℃.
Preferably, the extruder is a double-screw extruder, the temperatures of the sections are 162-.
Preferably, the adhesive is one of an ethylene-vinyl acetate copolymer adhesive, an epoxy resin adhesive and a polyurethane adhesive.
Preferably, the base film is one of a TPU film, a PTFE film, a PET film, and a PC film.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the TPU acoustic film disclosed by the invention is simple and feasible in production method, low in requirements on equipment and reaction conditions, easy in obtaining of production raw materials, high in economic value and social value, and suitable for industrial continuous production.
(2) The TPU acoustic film disclosed by the invention overcomes the defects that the traditional TPU film has poor impact resistance, the strength is difficult to ensure, and the heat resistance and the flame retardance need to be further improved, and also overcomes the technical problems that the acoustic film in the prior art has low efficiency, high cost, poor consistency, poor heat resistance and cold resistance, is easy to plastically deform at high temperature, is brittle and damaged at low temperature, has poor elasticity, larger stretching permanent deformation and low internal consumption, causes higher distortion and cannot completely restore the essence of sound.
(3) The TPU acoustic film disclosed by the invention comprises a modified TPU film and a bottom supporting film, wherein the modified TPU film and the bottom supporting film are bonded through an adhesive; the modified TPU membrane takes TPU, modified amino-terminated polyurethane and silicone rubber with amino 107 on a side chain as base materials, the TPU and the modified amino-terminated polyurethane both have polyurethane structures, and have good compatibility according to a similar compatibility principle, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride are introduced on a molecular chain through radiation grafting modification to endow the material with a cross-linking and curing reaction site, and the introduced trimethoxybenzyl and nitrile structures can endow the membrane with excellent weather resistance, high temperature resistance and performance stability under the dual effects of an electronic effect and a steric effect, and can also improve the wettability of the surface of the membrane and improve the compatibility of the membrane with other components; the introduced imidazole salt structure can catalyze the radiation grafting reaction and endow the membrane with the functions of mildew resistance, antibiosis, flame retardance, static resistance and the like; the side chain belt amino 107 silicon rubber can endow the material with excellent viscoelasticity and weather resistance and also has a lubricating effect; l-lysine triisocyanate is used as a curing agent and reacts with amino and hydroxyl on other components, so that a three-dimensional network structure is formed, and the comprehensive performance of the film is improved; the zircon powder is added, so that the strengthening effect is achieved, and the high-temperature resistance of the material can be improved.
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 TPU is polyether TPU, and the cargo number is as follows: 239a2301, available from guan dynasty new materials limited; the preparation method of the silicone rubber with the side chain having the amino 107 refers to: the synthesis and application of silicone rubber with amino 107 on the side chain, namely Chenfang, Huang Yong Jun and the like, and the silicone material is in the 04 th year 2018; the preparation of the amino-terminated polyurethane is described in: embodiment 1 of chinese invention patent CN 102432804A.
Example 1
The TPU acoustic film is characterized by comprising a modified TPU film and a backing film, wherein the modified TPU film and the backing film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 55 parts of TPU, 20 parts of modified amino-terminated polyurethane, 4 parts of silicone rubber with amino 107 at side chains, 1 part of L-lysine triisocyanate, 0.3 part of isopropyl titanate, 10100.3 parts of antioxidant, 3 parts of zircon powder, 1 part of silane coupling agent KH 5501 parts and 0.5 part of epoxidized soybean oil; the granularity of the zircon powder is 200 meshes.
The preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into dimethyl sulfoxide, stirring for 30 minutes at 70 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and sodium hydroxide, stirring for reaction for 4 hours at a constant temperature, then precipitating in water, washing the precipitated polymer with ethanol for 3 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the dimethyl sulfoxide to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the sodium hydroxide is 1:6:2: 0.3;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 10 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 10 minutes, then placing the crude product in a nitrogen atmosphere, reacting for 8 hours at 55 ℃, then performing ultrasonic cleaning for 3 times respectively by deionized water and methanol, each time for 0.2 hour, then placing the crude product in an oven, and drying at 80 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone is 1:0.1:0.1: 3; the absorbed dose during the radiation grafting process was 200 kGy.
The production method of the TPU acoustic film is characterized by comprising the following steps:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 5 mu m; the extruder is a double-screw extruder, the temperature of each section is 162 ℃, 170 ℃, 180 ℃, 200 ℃, 210 ℃ and 215 ℃ in sequence from a feed inlet, and the head temperature of the extruder is 220 ℃;
step 2: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening at 65 ℃ for 15 minutes and then at room temperature for 15 hours; the pressing temperature is 110 ℃; the adhesive is an ethylene-vinyl acetate copolymer adhesive; the base film is a TPU film.
Example 2
The TPU acoustic thin film is characterized by comprising a modified TPU film and a bottom supporting film, wherein the modified TPU film and the bottom supporting film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 57 parts of TPU, 23 parts of modified amino-terminated polyurethane, 5 parts of silicone rubber with amino 107 at a side chain, 1.2 parts of L-lysine triisocyanate, 0.35 part of zinc octoate, 1680.35 parts of antioxidant, 3.5 parts of zircon powder, KH 5601.2 parts of silane coupling agent and 0.7 part of epoxy furfuryl butyl oleate; the granularity of the zircon powder is 250 meshes.
The preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into N, N-dimethylformamide, stirring for 33 minutes at 72 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and sodium carbonate, stirring and reacting for 4.5 hours under heat preservation, then precipitating in water, washing the precipitated polymer with ethanol for 4 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the N, N-dimethylformamide to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the sodium carbonate is 1:7:2: 0.35;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 11 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 12 minutes, then placing the crude product under a helium atmosphere, reacting for 8.5 hours at 57 ℃, then respectively performing ultrasonic cleaning for 4 times by deionized water and methanol for 0.3 hour each time, then placing the crude product in an oven, and drying at 82 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone is 1:0.12:0.1: 3.5; the absorbed dose during the radiation grafting was 230 kGy.
The production method of the TPU acoustic film is characterized by comprising the following steps of:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 10 mu m; the extruder is a double-screw extruder, the temperature of each section is 164 ℃, 172 ℃, 185 ℃, 203 ℃, 213 ℃ and 216 ℃ from a charging opening in sequence, and the head temperature of the extruder is 223 DEG C
And 2, step: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening at 70 ℃ for 17 minutes and then at room temperature for 16 hours; the pressing temperature is 113 ℃; the adhesive is an epoxy resin adhesive; the support base film is a PTFE film.
Example 3
The TPU acoustic film is characterized by comprising a modified TPU film and a backing film, wherein the modified TPU film and the backing film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 60 parts of TPU, 25 parts of modified amino-terminated polyurethane, 6 parts of silicone rubber with amino 107 on a side chain, 1.5 parts of L-lysine triisocyanate, 0.4 part of dibutyltin dilaurate, 10760.4 parts of antioxidant, 4 parts of zircon powder, KH 5501.5 parts of silane coupling agent and 1 part of epoxy acetyl linseed methyl ester; the granularity of the zircon powder is 300 meshes.
The preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into N, N-dimethylacetamide, stirring for 35 minutes at 75 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and potassium hydroxide, stirring and reacting for 5 hours under heat preservation, then precipitating in water, washing the precipitated polymer with ethanol for 5 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the N, N-dimethylacetamide to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the potassium hydroxide is 1:8:2: 0.4;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 13 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 18 minutes, then placing the crude product in a neon gas atmosphere, reacting for 9 hours at 60 ℃, then performing ultrasonic cleaning for 4 times respectively by deionized water and methanol, each time for 0.35 hour, then placing the crude product in an oven, and drying at 85 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone is 1:0.15:0.1: 4; the absorbed dose during the radiation grafting process was 300 kGy.
The production method of the TPU acoustic film is characterized by comprising the following steps:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 12 mu m; the extruder is a double-screw extruder, the temperature of each section is 166 ℃, 175 ℃, 190 ℃, 205 ℃, 214 ℃ and 218 ℃ from a feed inlet in sequence, and the head temperature of the extruder is 225 ℃;
step 2: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening at 75 ℃ for 20 minutes and then at room temperature for 18 hours; the pressing temperature is 115 ℃; the adhesive is a polyurethane adhesive; the support film is a PET film.
Example 4
The TPU acoustic thin film is characterized by comprising a modified TPU film and a bottom supporting film, wherein the modified TPU film and the bottom supporting film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 64 parts of TPU, 28 parts of modified amino-terminated polyurethane, 7 parts of silicone rubber with amino on a side chain 107, 1.9 parts of L-lysine triisocyanate, 0.47 part of catalyst, 0.47 part of antioxidant, 4.7 parts of zircon powder, 1.8 parts of coupling agent and 1.4 parts of plasticizer; the plasticizer is prepared by mixing epoxidized soybean oil, epoxy butyl furoate and epoxy acetyl methyl linoleate according to the mass ratio of 1:3: 2; the coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 5; the granularity of the zircon powder is 380 meshes; the antioxidant is prepared by mixing an antioxidant 1010, an antioxidant 168, an antioxidant 1076 and an antioxidant 164 according to a mass ratio of 1:3:2: 4; the catalyst is prepared by mixing isopropyl titanate, zinc octoate and dibutyltin dilaurate according to the mass ratio of 3:2: 1.
The preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into a high-boiling-point solvent, stirring for 38 minutes at 78 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and an alkaline catalyst, keeping the temperature, stirring and reacting for 5.8 hours, then precipitating in water, washing the precipitated polymer with ethanol for 6 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the high boiling point solvent to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the basic catalyst is 1:9:2: 0.48; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:5: 3; the alkaline catalyst is prepared by mixing sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate according to the mass ratio of 1:3:5: 6;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, carrying out ultrasonic treatment for 14 minutes, then removing the N-methyl pyrrolidone by rotary evaporation, then placing the obtained crude product under an electron beam for radiation grafting for 23 minutes, then placing the crude product under an argon atmosphere, reacting for 9.7 hours at 64 ℃, then respectively carrying out ultrasonic cleaning for 5 times by using deionized water and methanol, carrying out ultrasonic treatment for 0.4 hour each time, then placing the crude product in an oven, and drying at 88 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone is 1:0.18:0.1: 4.8; the absorbed dose during the radiation grafting process was 340 kGy.
The production method of the TPU acoustic film is characterized by comprising the following steps:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 18 mu m; the extruder is a double-screw extruder, the temperature of each section is 167 ℃, 176 ℃, 195 ℃, 206 ℃, 217 ℃ and 219 ℃ in sequence from a feed inlet, and the head temperature of the extruder is 228 ℃;
step 2: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening at 80 ℃ for 23 minutes and then at room temperature for 19 hours; the pressing temperature is 118 ℃; the adhesive is an ethylene-vinyl acetate copolymer adhesive; the base film is a PC film.
Example 5
The TPU acoustic film is characterized by comprising a modified TPU film and a backing film, wherein the modified TPU film and the backing film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 65 parts of TPU, 30 parts of modified amino-terminated polyurethane, 8 parts of silicone rubber with amino 107 at side chains, 2 parts of L-lysine triisocyanate, 0.5 part of zinc octoate, 1640.5 parts of antioxidant, 5 parts of zircon powder, 5602 parts of silane coupling agent KH and 1.5 parts of epoxidized soybean oil; the granularity of the zircon powder is 400 meshes.
The preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into N-methylpyrrolidone, stirring for 40 minutes at 80 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and potassium carbonate, stirring and reacting for 6 hours under heat preservation, then precipitating in water, washing the precipitated polymer with ethanol for 7 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the N-methylpyrrolidone to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the potassium carbonate is 1:10:2: 0.5;
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 15 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 25 minutes, then placing the crude product in a nitrogen atmosphere, reacting for 10 hours at 65 ℃, then performing ultrasonic cleaning for 6 times respectively by deionized water and methanol, each time for 0.5 hour, then placing the crude product in an oven, and drying at 90 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methyl pyrrolidone is 1:0.2:0.1: 5; the absorbed dose during the radiation grafting process was 350 kGy.
The production method of the TPU acoustic film is characterized by comprising the following steps of:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 20 mu m; the extruder is a double-screw extruder, the temperature of each section is 168 ℃, 178 ℃, 198 ℃, 208 ℃, 218 ℃ and 220 ℃ from a feed inlet, and the temperature of the head of the extruder is 230 ℃;
step 2: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening at 85 ℃ for 25 minutes and then at room temperature for 20 hours; the pressing temperature is 120 ℃; the adhesive is an ethylene-vinyl acetate copolymer adhesive; the base film is a TPU film.
Comparative example 1
The invention provides a TPU acoustic membrane, the formulation and production method of which are similar to those of example 1, except that no modified amino-terminated polyurethane is added.
Comparative example 2
The invention provides a TPU acoustic membrane, the formula and the production method of which are similar to those of example 1, except that silicone rubber with amino 107 on the side chain is not added.
Comparative example 3
The invention provides a TPU acoustic film, the formula and the production method of which are similar to those of example 1, except that L-lysine triisocyanate and zircon powder are not added.
The TPU acoustic films produced in examples 1-5 and comparative examples 1-3 above were subjected to the relevant performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) thickness uniformity: about 1m was sampled in the reel direction (MD), and 4 sets of data were equally divided in the width direction (TD)4, each set of data being measured at 3 points uniformly in the reel direction (MD) and 11 points uniformly in the width direction (TD).
(2) Peeling force: randomly sampling 3 strips along the direction of a reel (MD), wherein the width of a sample strip is 25mm, and respectively testing the stripping force and then taking the average value; peeling at 180 degrees, wherein the release film is adhered on a steel plate, and the stretching speed is 300 mm/min.
(3) Young's modulus, tensile strength, elongation at break, 30% modulus, 100% modulus: the distance between the clamps of the universal material testing machine is 30mm, the stretching speed is 300mm/min, the preloading force is 0.1N (strain zero clearing and stress non zero clearing), and the test standard is ASTM D882; randomly sampling 5 strips in each direction, wherein the width of a sample strip is 15mm, the thickness of the sample strip is the thickness average value of three equidistant points at the middle position, respectively carrying out tensile test and then taking the average value, wherein the Young modulus is measured to be 3% secant modulus, and the calculation method is stress at the strain of 3%/0.03; 30% modulus: tensile stress at strain 30%; 100% modulus: tensile stress at 100% strain.
(4) Haze: and testing the film, randomly testing 3 points and taking an average value, wherein the test standard is JISK-7105.
(5) Gloss: the non-adhesive release film side was tested (with release film test), A4 white paper was placed under the film, and 3 points were randomly tested to take an average value, according to JIS-K7105.
As can be seen from Table 1, the thickness tolerance of the TPU acoustic film disclosed by the embodiment of the invention is +/-1.5 um; the stripping force is more than or equal to 2.16N/25mm, the Young modulus is more than or equal to 0.20MPa, the tensile strength is more than or equal to 16.0MPa, the breaking elongation is more than or equal to 213%, the 30% modulus is more than or equal to 2.3MPa, the 100% modulus is more than or equal to 7.2MPa, the haze is less than or equal to 0.8%, and the glossiness is more than or equal to 98%; therefore, the TPU acoustic film disclosed by the embodiment of the invention has more excellent mechanical properties and glossiness, which are the result of the synergistic effect of the components.
TABLE 1
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 (7)
1. The TPU acoustic film is characterized by comprising a modified TPU film and a backing film, wherein the modified TPU film and the backing film are bonded through an adhesive; the modified TPU film is prepared from the following raw materials in parts by weight: 55-65 parts of TPU, 20-30 parts of modified amino-terminated polyurethane, 4-8 parts of silicone rubber with amino 107 on a side chain, 1-2 parts of L-lysine triisocyanate, 0.3-0.5 part of catalyst, 0.3-0.5 part of antioxidant, 3-5 parts of zircon powder, 1-2 parts of coupling agent and 0.5-1.5 parts of plasticizer;
the preparation method of the modified amino-terminated polyurethane comprises the following steps:
step S1, adding amino-terminated polyurethane into a high boiling point solvent, stirring for 30-40 minutes at 70-80 ℃, then adding N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide and an alkaline catalyst, stirring and reacting for 4-6 hours under heat preservation, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and then removing the ethanol by rotary evaporation to obtain an intermediate product; the mol ratio of the amino-terminated polyurethane to the high boiling point solvent to the N- [ 4-cyano-3- (trifluoromethyl) phenyl ] methyl epoxy acrylamide to the basic catalyst is 1 (6-10) to 2 (0.3-0.5);
step S2, adding the intermediate product prepared in the step S1, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile and 1-allyl-3-methyl imidazole chloride into N-methyl pyrrolidone, performing ultrasonic treatment for 10-15 minutes, performing rotary evaporation to remove the N-methyl pyrrolidone, placing the obtained crude product under an electron beam for radiation grafting for 10-25 minutes, then placing the crude product in an inert gas atmosphere, reacting for 8-10 hours at 55-65 ℃, respectively performing ultrasonic cleaning for 3-6 times with deionized water and methanol for 0.2-0.5h each time, then placing the crude product in an oven, and drying at 80-90 ℃ to constant weight; the mass ratio of the intermediate product, 3-anilino-2- (3,4, 5-trimethoxybenzyl) acrylonitrile, 1-allyl-3-methyl imidazole chloride and N-methylpyrrolidone is 1 (0.1-0.2) to 0.1 (3-5); the absorption dose in the radiation grafting process in the step S2 is 200-350 kGy; the inert gas is one of nitrogen, helium, neon and argon.
2. The TPU acoustic film of claim 1 wherein the plasticizer is at least one of epoxidized soybean oil, epoxidized butyl furoate, epoxidized methyl acetyl linoleate; 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.
3. The TPU acoustic membrane of claim 1, wherein the zircon powder has a particle size of 200-400 mesh; the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 164; the catalyst is dibutyltin dilaurate.
4. The TPU acoustic film of claim 1 wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone; the alkaline catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
5. The TPU acoustic film of any of claims 1-4, wherein the process for producing the TPU acoustic film comprises the steps of:
step 1: adding the raw materials into a stirrer according to a certain proportion, uniformly mixing, performing extrusion molding by using an extruder to obtain a film, and then performing calendaring molding to prepare a modified TPU film with the thickness of 5-20 mu m;
step 2: coating an adhesive on the bottom surface of the modified TPU film prepared in the step 1, then superposing the modified TPU film on a support film, pressing, and performing hardening treatment to obtain a TPU acoustic film; the hardening treatment specifically comprises the following steps: hardening for 15-25 minutes at 65-85 ℃, and then hardening for 15-20 hours at room temperature; the pressing temperature is 110-120 ℃.
6. The TPU acoustic film as set forth in claim 5, wherein the extruder is a twin-screw extruder, and the temperatures of the sections are 162-; the adhesive is one of ethylene-vinyl acetate copolymer adhesive, epoxy resin adhesive and polyurethane adhesive; the base film is one of a TPU film, a PTFE film, a PET film and a PC film.
7. The TPU acoustic film of claim 6, wherein the TPU acoustic film thickness tolerance is ± 1.5 um; the stripping force is more than or equal to 2.16N/25mm, the Young modulus is more than or equal to 0.20MPa, the tensile strength is more than or equal to 16.0MPa, the breaking elongation is more than or equal to 213%, the 30% modulus is more than or equal to 2.3MPa, the 100% modulus is more than or equal to 7.2MPa, the haze is less than or equal to 0.8%, and the glossiness is more than or equal to 98%.
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| Synthesis and characterization of aqueous (polyurethane/aromatic polyamide sulfone) copolymer dispersions from castor oil;oilH.A. Mohamed等;《Progress in Organic Coatings》;20140501;第77卷(第5期);第965-974页 * |
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