CN115612264A - PC/PCTG alloy and preparation method and application thereof - Google Patents
PC/PCTG alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a PC/PCTG alloy and a preparation method and application thereof, belonging to the technical field of high polymer materials. The material is prepared from the following raw materials in parts by weight: 10-20 parts of modified carbon fiber, 55-65 parts of PCTG, 30-45 parts of PC, 5~8 parts of MBS, 3252 parts of coupling agent, 3532 parts of antioxidant and 3425 parts of lubricant. According to the PC/PCTG alloy and the preparation method and application thereof, the problem of combination between carbon fibers and PC can be solved without an interface modifier, and the prepared alloy is good in flexibility, excellent in mechanical property and acoustic property and suitable for replacing wood to manufacture musical instruments.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a PC/PCTG alloy and a preparation method and application thereof.
Background
Most of the main materials of the traditional musical instruments are wood, the requirements on the materials are extremely high, the wood is required to have no defects such as cracking, knots, wormholes and the like, the density, the width and the annual rings are also specifically required, the log yield is low, in recent years, the wood resources are deficient, the wood for the musical instruments has poor dimensional stability and humidity resistance and heat resistance, the preparation process for preparing the musical instruments is relatively complex and the like, and the demand for finding new materials for the musical instruments capable of replacing the wood is urgent.
At present, the thermoplastic material reinforced by carbon fiber has a geometric structure similar to wood, so that a tone quality effect which is almost different from that of the wood for a traditional instrument can be obtained to a certain extent, and the carbon fiber has excellent vibration characteristics and has various advantages of high specific modulus, large bending strength, small environmental influence and the like; the PC material has excellent thermal stability, high toughness, mechanical property and dimensional stability, and the composite use of the two can enable the prepared musical instrument to have excellent properties such as high structural designability, impact resistance, corrosion resistance, high temperature resistance, good acoustic quality stability and the like.
However, the graphite crystal structure on the surface of the carbon fiber causes the carbon fiber to have poor interface performance and poor wettability and cohesiveness with resin materials such as PC and the like, so that the prepared composite material has poor flexibility, and the application of the carbon fiber and PC composite material in the manufacture of musical instruments is severely limited.
Chinese patent CN114231002A, a PC composite material and a preparation method and application thereof, discloses a PC composite material, which comprises PC, carbon fibers and an interface modifier, wherein the wettability and the cohesiveness between the carbon fibers and the PC are improved by adding the interface modifier, so that the sounding characteristic of a musical instrument is improved. However, the PC composite material needs to be added with a large amount of interface modifier, and the acoustic performance of the PC composite material needs to be further improved.
Disclosure of Invention
The invention provides a PC/PCTG alloy, a preparation method and application thereof, aiming at solving the problems that the prepared composite material is poor in flexibility and needs to be further improved due to poor wettability and cohesiveness between carbon fibers and PC in the existing carbon fiber and PC composite material, and the bonding problem between the carbon fibers and the PC can be improved without an interface modifier, so that the PC/PCTG alloy is good in flexibility and has excellent acoustic performance.
The invention aims to provide a PC/PCTG alloy.
Another object of the present invention is to provide a method for producing the above PC/PCTG alloy.
Another object of the present invention is to provide the use of the above PC/PCTG alloy in the manufacture of musical instruments.
The purpose of the invention can be realized by the following technical scheme:
a PC/PCTG alloy is prepared from the following raw materials in parts by weight:
10-20 parts of modified carbon fiber, 55-65 parts of PCTG, 30-45 parts of PC, 5~8 parts of MBS, 3252 parts of coupling agent, 3532 parts of antioxidant and 3425 parts of lubricant.
According to the method, the PC/PCTG alloy is prepared by compounding the three-dimensional structure modified carbon fiber prepared by an ultrasonic-electrochemical method with PCTG, PC, MBS and other components in a specific ratio, the wettability and the cohesiveness between the modified carbon fiber and the PC are improved by the modified carbon fiber and a coupling agent, and the mechanical property of the material is improved by the three-dimensional structure of the modified carbon fiber, so that the energy storage modulus of the material is greatly improved, the volume is louder, the impact resistance of a PC composite material is improved, and the forming processing of the material is facilitated; the MBS material is introduced as a compatilizer to enhance the compatibility between the PCTG and the PC of the amorphous resin material, improve the system fluidity, improve the balance degree of the mass distribution of the material, and improve the flexibility and the mechanical property of the material, thereby effectively improving the tone; the compounding of PCTG and PC greatly improves the defect of low notch impact strength of the composite material, greatly improves the mechanical properties of the material such as tensile strength, bending strength, storage modulus, energy consumption modulus and the like, and improves the flexibility of the material, so that the musical instrument has louder, clearer and fuller timbre and excellent acoustic performance.
As a preferred technical solution of the present invention, the modified carbon fiber is prepared by the following method:
s1, dissolving graphene oxide and ethylenediamine in N, N-dimethylformamide according to a mass ratio of 1-2 to 5-10, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as a cathode, performing ultrasonic treatment for 30min under the voltage of 20-30V, taking out the cathode material, washing, and performing vacuum drying at 80 ℃ for 6h to obtain the modified carbon fiber.
According to the method, graphene oxide and ethylenediamine are ultrasonically mixed to obtain electrolyte by an ultrasonic-electrochemical method, carbon fibers are used as a cathode and the electrolyte are subjected to ultrasonic-electrochemical deposition simultaneously, the interface bonding force of the graphene oxide, the ethylenediamine and the carbon fibers is greatly increased by chemical imidization in-situ polymerization and ultrasonic-electrochemical deposition, the carbon fibers, the graphene oxide and the ethylenediamine are constructed into a continuous micro network structure which is uniformly dispersed by taking the carbon fibers as a core framework in a micron-scale multi-scale and three-dimensional direction, namely a three-dimensional structure taking the carbon fibers as a core, the interface compatibility between modified carbon fibers and resin is increased, the mechanical properties of the modified carbon fibers and resin composite materials are greatly improved, and the acoustic properties of the materials are improved.
Preferably, the coupling agent is one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
Preferably, the antioxidant is a phosphite.
Preferably, the lubricant is one or more of silicone, calcium stearate, zinc stearate and dimethyl silicone oil.
The preparation method of the PC/PCTG alloy comprises the following steps:
adding the modified carbon fiber, PCTG, PC, MBS, a coupling agent, an antioxidant and a lubricant into a high-speed mixer according to the corresponding weight parts for melt blending to obtain a uniform material, and extruding and granulating at 220 to 250 ℃ through an extruder to obtain the PC/PCTG alloy.
Preferably, the step of premixing the PCTG, PC and MBS is also included before the melt blending.
The PC/PCTG alloy is applied to musical instrument manufacturing.
The invention has the beneficial effects that:
(1) The modified carbon fiber prepared by an ultrasonic-electrochemical method, PCTG, PC, MBS and other components are compounded in a specific ratio to prepare a PC/PCTG alloy, the wettability and the cohesiveness between the modified carbon fiber and the PC are improved by the modified carbon fiber and a silane coupling agent, the compatibility between the PCTG and the PC of an amorphous resin material is enhanced by introducing an MBS material as a compatilizer, the system flowability is improved, the compatibility among the components of the system is further improved, and the problem of combination between the carbon fiber and the resin can be solved without an interface modifier.
(2) The addition of modified carbon fiber and PCTG greatly improves the balance degree of the mass distribution of the carbon fiber reinforced composite material and the defect of low impact strength of a composite material gap, greatly improves the mechanical properties of the material such as tensile strength, bending strength, storage modulus, energy consumption modulus and the like, improves the flexibility of the material, makes the tone of the prepared musical instrument more loud, clear and full, and has excellent acoustic performance.
(3) The PC/PCTG alloy prepared by the invention is easy to form, has higher storage modulus and lower energy consumption modulus, loud volume, clear and lasting sound, excellent tone quality and tone color, is convenient to process, and is suitable for manufacturing musical instruments.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be provided in conjunction with the embodiments.
The raw materials in the examples are all commercially available; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise specified.
Example 1
A preparation method of a PC/PCTG alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 2:5 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at the voltage of 25V, taking out the cathode material, washing, and performing vacuum drying at the temperature of 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 12 parts of modified carbon fiber, 58 parts of PCTG, 35 parts of PC, 6 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melting and blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
Example 2
A preparation method of a PC/PCTG alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 1:5 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at the voltage of 25V, taking out the cathode material, washing, and performing vacuum drying at the temperature of 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 17 parts of modified carbon fiber, 61 parts of PCTG, 39 parts of PC, 7 parts of MBS, 550 parts of silane coupling agent KH, 1 part of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 240 ℃ through an extruder to obtain the PC/PCTG alloy.
Example 3
A preparation method of PC/PCTG alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in N, N-dimethylformamide according to a mass ratio of 1;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at the voltage of 30V, taking out the cathode material, washing, and performing vacuum drying at the temperature of 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 16 parts of modified carbon fiber, 64 parts of PCTG, 43 parts of PC, 6 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
Example 4
A preparation method of a PC/PCTG alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 1:8 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as a positive electrode, performing ultrasonic treatment for 30min at the voltage of 20V, taking out the cathode material, washing, and performing vacuum drying for 6h at the temperature of 80 ℃ to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 20 parts of modified carbon fiber, 61 parts of PCTG, 31 parts of PC, 8 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 220 ℃ through an extruder to obtain the PC/PCTG alloy.
Example 5
A preparation method of a PC/PCTG alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 1:6 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at a voltage of 23V, taking out the cathode material, washing, and performing vacuum drying at 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 11 parts of modified carbon fiber, 56 parts of PCTG, 44 parts of PC, 7 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melting and blending to obtain a uniform material, and extruding and granulating at 250 ℃ through an extruder to obtain the PC/PCTG alloy.
Comparative example 1
A preparation method of a PC/ABS alloy comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 2:5 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at the voltage of 25V, taking out the cathode material, washing, and performing vacuum drying at the temperature of 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/ABS alloy
Adding 12 parts of modified carbon fiber, 58 parts of ABS, 35 parts of PC, 6 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
Comparative example 2
A preparation method of a PC/PCTG alloy material comprises the following steps:
preparation of PC/PCTG alloy
Adding 12 parts of carbon fiber, 58 parts of PCTG, 35 parts of PC, 6 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
Comparative example 3
A preparation method of a PC/PCTG alloy material comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving graphene oxide and ethylenediamine in the mass ratio of 2:5 in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as an anode, performing ultrasonic treatment for 30min at the voltage of 25V, taking out the cathode material, washing, and performing vacuum drying at the temperature of 80 ℃ for 6h to obtain the modified carbon fiber.
(2) Preparation of PC/PCTG alloy
Adding 12 parts of modified carbon fiber, 58 parts of PCTG, 35 parts of PC, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melt blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
Comparative example 4
A preparation method of a PC/PCTG alloy material comprises the following steps:
(1) Preparation of modified carbon fiber
S1, dissolving ethylenediamine in N, N-dimethylformamide, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in the S1 as an electrolyte, taking a graphite electrode as a positive electrode, performing ultrasonic treatment for 30min at the voltage of 25V, taking out the cathode material, washing, and performing vacuum drying for 6h at the temperature of 80 ℃ to obtain the modified carbon fiber.
(3) Preparation of PC/PCTG alloy
Adding 12 parts of modified carbon fiber, 58 parts of PCTG, 35 parts of PC, 6 parts of MBS, 550 parts of silane coupling agent KH, 2 parts of phosphite ester and 1 part of silicone into a high-speed mixer according to the corresponding parts by weight for melting and blending to obtain a uniform material, and extruding and granulating at 230 ℃ through an extruder to obtain the PC/PCTG alloy.
According to ISO standard and GB/T16406-1996, the performance test is carried out on the materials prepared in the example 1~5 and the comparative example 1~4, the performance test result of the composite material is shown in tables 1 and 2, the tensile strength and the bending strength in each index influence the flexibility of the material, the sound quality and the timbre of the prepared musical instrument are greatly influenced, the impact strength of the notch of the simply supported beam influences the sound definition, the bass is greatly influenced, and the difference value of the storage modulus and the energy consumption modulus influences the sound persistence.
TABLE 1 Performance test results for example 1~5
TABLE 2 Performance test results for comparative example 1~4
The test results in table 1 show that the embodiments of the present invention have excellent mechanical properties, which indicates that the present invention compounds the modified carbon fiber prepared by the ultrasonic-electrochemical method with PCTG, PC, MBS and other components in a specific ratio to prepare a PC/PCTG alloy, and the specific component ratios of the modified carbon fiber and the PCTG material realize that the bonding problem between the carbon fiber and the resin can be improved without an interface modifier, and the defect of low impact strength of the notch of the simple beam of the composite material is greatly improved, so that the mechanical properties of the material, such as tensile strength, bending strength, storage modulus, energy consumption modulus and the like, are greatly improved, the flexibility, volume and tone quality of the material are improved, and the prepared musical instrument has a loud, clear and full tone and excellent acoustic properties.
The test results in table 2 show that the PCTG material in the comparative example 1 is replaced by the ABS material which is also amorphous resin, which is not well compatible with the modified carbon fiber-PC system, so that the mechanical properties of the alloy are greatly reduced, the storage modulus is low, and the volume is low; the carbon fiber used in the comparative example 2 is not modified, does not have a three-dimensional structure constructed by the carbon fiber, the graphene oxide and the ethylene diamine, has low tensile strength and bending strength, is not beneficial to processing, and the notch impact strength of the simply supported beam is less than 6 kJ/m 2 The sound is not clear enough, so that the volume attenuation is fast and the tone color is poor; compared with the comparative example 3, MBS is not added, so that the compatibility between PC and PCTG materials is poor, the PC and PCTG materials cannot be well organically combined, the mechanical property of the prepared alloy is poor, the storage modulus is low, the tone quality is poor, and the volume is low; the modified carbon fiber used in the comparative example 4 is not added with graphene oxide, the mechanical property and the interface bonding force of the modified carbon fiber are increased weakly due to the surface bonding of the ethylenediamine and the carbon fiber, the compatibility of the modified carbon fiber and a resin system is reduced, and although the prepared alloy material is superior to other comparative examples, the acoustic property is poor compared with that of the alloy prepared in the embodiment 1~5.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The PC/PCTG alloy is characterized by being prepared from the following raw materials in parts by weight:
10-20 parts of modified carbon fiber, 55-65 parts of PCTG, 30-45 parts of PC, 5~8 parts of MBS, 3252 parts of coupling agent, 3532 parts of antioxidant and 3425 parts of lubricant;
the modified carbon fiber is prepared by the following method:
s1, dissolving graphene oxide and ethylenediamine in N, N-dimethylformamide according to a mass ratio of 1-2 to 5-10, uniformly mixing, and ultrasonically stirring for 10min to prepare an electrolyte;
and S2, taking the carbon fiber as a power supply cathode, taking the electrolyte obtained in S1 as an electrolyte, taking a graphite electrode as a cathode, performing ultrasonic treatment for 30min under the voltage of 20 to 30V, taking out the cathode material, washing, and performing vacuum drying for 6h at the temperature of 80 ℃ to obtain the modified carbon fiber.
2. The PC/PCTG alloy according to claim 1, wherein the coupling agent is one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
3. The PC/PCTG alloy according to claim 1, wherein the antioxidant is phosphite.
4. The PC/PCTG alloy according to claim 1, wherein the lubricant is one or more of silicone, calcium stearate, zinc stearate and simethicone.
5. A method for producing the PC/PCTG alloy as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
adding the modified carbon fiber, PCTG, PC, MBS, a coupling agent, an antioxidant and a lubricant into a high-speed mixer according to the corresponding weight parts for melt blending to obtain a uniform material, and extruding and granulating at 220 to 250 ℃ through an extruder to obtain the PC/PCTG alloy.
6. The method of claim 5, wherein the pre-blending step comprises pre-blending PCTG, PC and MBS.
7. Use of a PC/PCTG alloy as claimed in any one of claims 1 to 4 in the manufacture of musical instruments.
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