A helical carbon nanotube / zinc oxide / pctg master batch and a pctg composite containing the master batch

Abstract

The present application belongs to the technical field of polymer composite material, and particularly relates to a spiral carbon tube / zinc oxide / PCTG master batch and a PCTG composite material containing the master batch. A PCTG material loaded with spiral carbon tubes and four acicular zinc oxide is prepared through in-situ polymerization reaction as a spiral carbon tube / zinc oxide / PCTG master batch, wherein the content of the spiral carbon tube is 0.01-10wt% of the mass of the master batch, the content of the zinc oxide is 0.01-20wt% of the mass of the master batch, the PCTG composite material comprises PCTG raw material 50-90 parts, spiral carbon tube / zinc oxide / PCTG master batch 10-40 parts, glass fiber 10-45 parts, and antioxidant 0.1-1 part, which maximally reduces the structural damage of the spiral carbon tube and the zinc oxide in the blending process, makes them uniformly dispersed in the PCTG matrix, and significantly improves the mechanical properties and antibacterial effect of the PCTG composite material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer composite materials, and particularly relates to a spiral carbon tube / zinc oxide / PCTG master batch and a PCTG composite material containing the master batch. BACKGROUND

[0002] Amorphous copolyester polyethylene terephthalate / cyclohexane dimethylol (PCTG) has one more comonomer (1,4-cyclohexane dimethylol, CHDM) compared with PET. With the increase of CHDM content, the melting point of the material decreases, the glass transition temperature rises, and the crystallinity decreases, and finally an amorphous polymer is formed. Due to the difference in chemical structure, PCTG exhibits significantly different properties from PET. PCTG has good heat resistance, high transparency of products, excellent impact resistance and excellent processing performance, but its strength is reduced, so it can only partially replace the application of PET.

[0003] At present, the modification of PCTG material is mainly carried out by melt blending. The reinforcing filler used for modification and PCTG material are mixed by double screw mixing to prepare a reinforced composite material. For nanofillers, surface modification can promote their dispersion in the polymer matrix to some extent, but the agglomeration of nanofillers will still affect their distribution, especially for some nanofillers with special structure. Direct melt blending can easily cause the structure of the nanofillers to be destroyed in the double screw blending process, thereby losing their original properties.

[0004] A low warping glass fiber reinforced polyester composite material is disclosed in Chinese patent application file (publication number: CN102863749A), which comprises the following raw material components by weight: PCTG resin 50-80, glass fiber 10-50, toughening agent 0-10, antioxidant 0.2-0.6, and auxiliary agent 0.5-1. The raw materials are uniformly mixed and then placed in a double screw extruder. Alkali-free glass fiber is added downstream of the extruder, and the product is obtained by melting, mixing, extruding, cooling, drying and granulating. Glass fiber is used to reinforce and modify PCTG, but direct blending of glass fiber and PCTG matrix material does not have strong interfacial bonding between the two, which can lead to fiber floating and ultimately affect the mechanical properties of the material.

[0005] An electronic atomizer antibacterial suction nozzle made of PCTG material containing modified oleophobic nano-silver ion antibacterial agent is disclosed in Chinese patent application file (publication number: CN113402855A). The PCTG material is prepared by simple mixing and conventional injection molding in a surface modification manner to form a composite with the oleophobic nano-silver ion antibacterial agent, which promotes the dispersion of nano-silver ions in the PCTG matrix to some extent. However, the silver-based antibacterial agent can cause skin allergy when in contact with the skin. SUMMARY

[0006] The present application aims at the problems of poor strength of PCTG material and modification methods, and provides a spiral carbon tube / zinc oxide / PCTG master batch and a PCTG composite material containing the master batch, so as to enhance and modify the PCTG material, so that the material has high strength and high modulus on the basis of maintaining the original super-high toughness, and has excellent antibacterial performance, thereby further widening the application field of the PCTG material.

[0007] The spiral carbon tube / zinc oxide / PCTG master batch in the technical scheme of the present application is a PCTG material loaded with spiral carbon tubes and zinc oxide, wherein the content of the spiral carbon tubes is 0.01-10wt% of the mass of the master batch, and the content of the zinc oxide is 0.01-20wt% of the mass of the master batch.

[0008] Further, the zinc oxide is tetrapod-shaped zinc oxide, the root size is 1-10μm, and the needle length is 20-60μm, preferably the root size is 1-5μm, and the needle length is 20-30μm.

[0009] The tetrapod-shaped zinc oxide can significantly improve the mechanical properties and wear resistance of the PCTG composite material due to its extremely high mechanical strength and elastic modulus, and simultaneously acts as a physical crosslinking point of the glass fiber, plays a crosslinking role between the glass fibers in the stress process, prevents the interface slip of the glass fiber and the occurrence of floating fibers, in addition, the sharp end of the tetrapod-shaped zinc oxide has nano activity, can efficiently kill and eliminate bacterial debris, and the killing rate of common bacteria is more than 99%, which can obviously improve the antibacterial performance of the material and does not cause adverse reactions. The special structure of the spiral carbon tube can cause physical entanglement between the tetrapod-shaped zinc oxide whiskers and the glass fiber, enhance the interaction between them, and further prevent the occurrence of floating fiber phenomenon, and the conduction performance can promote the transfer of hydroxyl radicals generated in the tetrapod-shaped zinc oxide particles, and enhance the photocatalytic antibacterial effect.

[0010] Further, the preparation method of the zinc oxide is to mix zinc powder and carbon powder according to a mass ratio of 4-5:1, and heat in a muffle furnace at 950-1050℃ for 10-20min.

[0011] Further, the spiral diameter of the spiral carbon tube is 5-50nm, the pitch is 20-100nm, the diameter is 20-150nm, and the length is 2-10μm, preferably the spiral diameter is 10-20nm, the pitch is 30-50nm, the diameter is 80-120nm, and the length is 3-5μm.

[0012] The present application also provides a preparation method of the above spiral carbon tube / zinc oxide / PCTG master batch, comprising the following steps:

[0013] A1: add the helical carbon tube into the inorganic acid solution for acidification treatment, stir at room temperature, filter, separate the helical carbon tube, clean and dry, add the helical carbon tube treated by acidification into hydrogen peroxide for ultrasonic dispersion, filter, separate the helical carbon tube, clean and dry;

[0014] A2: mix the helical carbon tube obtained in the above step with four needle-like zinc oxide and ethylene glycol to obtain ethylene glycol containing the helical carbon tube and the four needle-like zinc oxide, add terephthalic acid, 1,4-cyclohexanedimethanol and a catalyst into a reaction kettle, stir after inert gas is introduced, perform esterification reaction by heating, discharge the water after reaction, and discharge the raw material from the reaction kettle to obtain PCTG master batch by pelletizing.

[0015] The PCTG material loaded with the helical carbon tube and the four needle-like zinc oxide is prepared by in-situ esterification reaction, which can effectively reduce the structure damage of the helical carbon tube and the four needle-like zinc oxide in the blending process, and fully play the mechanical property and photocatalytic antibacterial effect of the helical carbon tube and the four needle-like zinc oxide reinforcing material.

[0016] Further, the inorganic acid in step A1 is one of nitric acid, hydrochloric acid and sulfuric acid, and the concentration of the inorganic acid solution is 1-3 mol / L.

[0017] Further, the concentration of the hydrogen peroxide in step A1 is 30-40 wt%, which is used as an oxidizing agent to generate oxidizing groups on the surface of the helical carbon tube, so that the hydrophilicity of the helical carbon tube is better and the dispersion in water is more uniform.

[0018] Further, the amounts of the helical carbon tube, the four needle-like zinc oxide and the ethylene glycol in step A2 are 1-10 parts, 1-10 parts and 20-30 parts, respectively.

[0019] Further, the molar ratio of the ethylene glycol containing the helical carbon tube and the four needle-like zinc oxide, terephthalic acid and 1,4-cyclohexanedimethanol in step A2 is 1:0.5:2, and the content of the catalyst is 0.01-1% of the total mass of terephthalic acid, the mixture and 1,4-cyclohexanedimethanol.

[0020] Further, the catalyst in step A2 is one or more of titanium catalyst, antimony catalyst and aluminum catalyst, the titanium catalyst is one or more of potassium hexafluorotitanate, potassium oxalate titanate, titanate and titanium carboxylate, the antimony catalyst is one or more of antimony trioxide, antimony acetate and antimony ethylene glycol, and the aluminum catalyst is one or more of aluminum carboxylate, aluminate and inorganic aluminum salt.

[0021] Further, the temperature of the esterification reaction in step A2 is 240-270 DEG C, and the pressure is 0.25-0.3 MPa. The esterification reaction is started by the self-catalysis of terephthalic acid in the reactor, and water is discharged after 2 hours. The esterification conversion rate is determined according to the water amount, and the esterification is considered to be completed when the water amount exceeds 90% of the theoretical value.

[0022] Another object of the present application is to provide a PCTG composite material comprising the following components by weight:

[0023]

[0024] Further, the PCTG raw material is a broken piece of virgin PCTG particle or recycled PCTG, including nozzle broken or plate broken, etc.

[0025] Further, the glass fiber is alkali-free short-cut glass fiber, with a diameter of 9-15 μm and a length of 3-20 mm, preferably a diameter of 9-12 μm and a length of 5-12 mm.

[0026] Further, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 1098, and antioxidant 225.

[0027] The preparation method of the above PCTG composite material is to mix the PCTG master batch, PCTG raw material, antioxidant, and glass fiber in a high-speed blender, and to use a double-screw extruder for extrusion granulation to obtain the high-strength antibacterial PCTG composite material.

[0028] Further, the double-screw extruder has a total of 9 temperature zones, with temperatures of 215-225 DEG C / 225-235 DEG C / 230-240 DEG C / 230-240 DEG C / 235-245 DEG C / 235-245 DEG C / 235-245 DEG C / 235-245 DEG C / 245-255 DEG C, and a screw rotation speed of 200-350 rpm.

[0029] Compared with the prior art, the technical scheme of the present application has the following beneficial effects:

[0030] (1) The in-situ esterification reaction is used to prepare the PCTG master batch loaded with helical carbon tubes and four-needle-shaped zinc oxide, which is compounded with PCTG and glass fiber, thereby greatly reducing the structural damage of the helical carbon tubes and zinc oxide in the blending process, making them uniformly dispersed in the PCTG matrix, and significantly improving the mechanical properties and antibacterial effect of the PCTG composite material;

[0031] (2) The four-needle-shaped zinc oxide with a special microstructure effectively improves the mechanical properties and wear resistance of the PCTG composite material due to its good mechanical strength and elastic modulus;

[0032] (3) The special structure of the spiral carbon tube can cause physical entanglement between the four-needle-shaped zinc oxide whiskers and the glass fibers, enhance the interaction between them, and further prevent the interface slip of the glass fibers and the occurrence of the floating fiber phenomenon;

[0033] (4) The four-needle-shaped zinc oxide tips have nano activity, can efficiently kill and eliminate bacterial debris, and have a bacteria killing rate of more than 99% for common bacteria, can obviously improve the antibacterial performance of the material and will not cause adverse reactions;

[0034] (5) The good conduction performance of the spiral carbon tube can promote the transfer of hydroxyl radicals generated in the four-needle-shaped zinc oxide particles, and enhance the photocatalytic antibacterial effect. DETAILED DESCRIPTION

[0035] The technical solutions of the present application will be further described and illustrated by specific examples. It should be understood that the specific examples described herein are only used to help understand the present application, and are not used to limit the specific embodiments of the present application. If not specifically stated, the raw materials used in the embodiments of the present application are all commonly used raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.

[0036] The glass fibers used in the following examples and comparative examples are Gao Shi Company 534A, the spiral carbon tube is XFM59 of Xianfeng Nanometer Company, and the antioxidant is IRGANOX1010 of BASF Company.

[0037] Example 1

[0038] The preparation method of the spiral carbon tube / zinc oxide / PCTG master batch of this embodiment is as follows:

[0039] A1: 5 parts of spiral carbon tube were added to 150 parts of 3 mol / L nitric acid solution and stirred at room temperature for 2 h. The spiral carbon tube was separated by filtration and washed with deionized water and anhydrous ethanol for 3 times. The acid-treated spiral carbon tube was dried at 100℃ for 24 h, and then added to 150 parts of 30 vol.% hydrogen peroxide solution and ultrasonically dispersed for 2 h. The spiral carbon tube was separated by filtration and washed with deionized water until the pH was neutral. The spiral carbon tube was dried by filtration.

[0040] A2: 5 parts of the above spiral carbon nanotubes, 10 parts of four needle-like zinc oxide and 30 parts of ethylene glycol were pre-mixed by mechanical stirring for 1 h, the mixture was added into a reaction kettle according to the ratio of 0.5:1:2 with terephthalic acid and 1,4-cyclohexanedimethanol, the catalyst content was 0.1wt% of the total mass of the three, nitrogen was introduced until the pressure in the reaction kettle was 0.1 MPa, the mechanical stirring was opened, the temperature of the reaction kettle was set to 260℃, the pressure was raised to 0.27 MPa for esterification, after 2 h, water began to be discharged, when the water discharge amount exceeded 90% of the theoretical value, the esterification was considered to be completed, the pressure in the reaction kettle was reduced to normal pressure, and the raw materials were discharged from the reaction kettle to obtain spiral carbon nanotube / zinc oxide / PCTG master batch.

[0041] The preparation method of the zinc oxide is to mix zinc powder and carbon powder according to a mass ratio of 4:1, and heat at 950℃ in a muffle furnace for 20 min.

[0042] Example 2

[0043] The preparation method of the spiral carbon nanotube / zinc oxide / PCTG master batch in this example is as follows:

[0044] A1: 5 parts of spiral carbon nanotubes were added into 150 parts of a nitric acid solution with a concentration of 3 mol / L for stirring at room temperature for 2 h, the spiral carbon nanotubes were separated by filtration, washed repeatedly with deionized water and anhydrous ethanol for 3 times, and dried at 100℃ for 24 h, the acid-treated spiral carbon nanotubes were added into 150 parts of a hydrogen peroxide solution with a concentration of 30vol.% for ultrasonic dispersion for 2 h, the spiral carbon nanotubes were separated by filtration, washed repeatedly with deionized water until the pH was neutral, and dried by filtration;

[0045] A2: 2 parts of the above spiral carbon nanotubes, 10 parts of four needle-like zinc oxide and 30 parts of ethylene glycol were pre-mixed by mechanical stirring for 1 h, the mixture was added into a reaction kettle according to the ratio of 0.5:1:2 with terephthalic acid and 1,4-cyclohexanedimethanol, the catalyst content was 0.15wt% of the total mass of the three, nitrogen was introduced until the pressure in the reaction kettle was 0.1 MPa, the mechanical stirring was opened, the temperature of the reaction kettle was set to 265℃, the pressure was raised to 0.25 MPa for esterification, after 2 h, water began to be discharged, when the water discharge amount exceeded 90% of the theoretical value, the esterification was considered to be completed, the pressure in the reaction kettle was reduced to normal pressure, and the raw materials were discharged from the reaction kettle to obtain spiral carbon nanotube / zinc oxide / PCTG master batch;

[0046] The preparation method of the zinc oxide is to mix zinc powder and carbon powder according to a mass ratio of 4:1, and heat at 950℃ in a muffle furnace for 20 min.

[0047] Example 3

[0048] The preparation method of the spiral carbon nanotube / zinc oxide / PCTG master batch in this example is as follows:

[0049] A1: 5 parts of the helical carbon tube were added to 150 parts of a nitric acid solution with a concentration of 3 mol / L and stirred at room temperature for 2 h. The helical carbon tube was separated by filtration and repeatedly cleaned with deionized water and anhydrous ethanol for 3 times. The acid-treated helical carbon tube was dried at 100°C for 24 h. The acid-treated helical carbon tube was added to 150 parts of hydrogen peroxide with a concentration of 30 vol.% and ultrasonically dispersed for 2 h. The helical carbon tube was separated by filtration and repeatedly cleaned with deionized water until the pH was neutral. The helical carbon tube was dried by filtration;

[0050] A2: 1 part of the helical carbon tube obtained in the above step, 10 parts of tetrapod-shaped zinc oxide, and 30 parts of ethylene glycol were mechanically stirred for 1 h for pre-mixing. The mixture was added to a reaction kettle with terephthalic acid and 1,4-cyclohexanedimethanol in a ratio of 0.5:1:2. The catalyst content was 0.15 wt% of the total mass of the three. Nitrogen was introduced until the pressure in the reaction kettle was 0.1 MPa. The mechanical stirring was turned on. The temperature of the reaction kettle was set to 265°C, and the pressure was increased to 0.25 MPa for esterification. After 2 h, water began to be released. When the amount of water released exceeded 90% of the theoretical value, the esterification was considered complete. The pressure in the reaction kettle was reduced to atmospheric pressure. The raw materials were discharged from the reaction kettle and pelletized to obtain the helical carbon tube / zinc oxide / PCTG master batch.

[0051] The preparation method of the zinc oxide was to mix zinc powder and carbon powder in a mass ratio of 4:1 and heat them in a muffle furnace at 1000°C for 20 min.

[0052] Example 4

[0053] The preparation method of the helical carbon tube / zinc oxide / PCTG master batch in this example was as follows:

[0054] A1: 10 parts of the helical carbon tube were added to 300 parts of a nitric acid solution with a concentration of 3 mol / L and stirred at room temperature for 2 h. The helical carbon tube was separated by filtration and repeatedly cleaned with deionized water and anhydrous ethanol for 3 times. The acid-treated helical carbon tube was dried at 100°C for 24 h. The acid-treated helical carbon tube was added to 300 parts of hydrogen peroxide with a concentration of 30 vol.% and ultrasonically dispersed for 2 h. The helical carbon tube was separated by filtration and repeatedly cleaned with deionized water until the pH was neutral.

[0055] A2: 10 parts of the helical carbon tube obtained in the above step, 2 parts of tetrapod-shaped zinc oxide, and 30 parts of ethylene glycol were mechanically stirred for 1 h for pre-mixing. The mixture was added to a reaction kettle with terephthalic acid and 1,4-cyclohexanedimethanol in a ratio of 0.5:1:2. The catalyst content was 0.15 wt% of the total mass of the three. Nitrogen was introduced until the pressure in the reaction kettle was 0.1 MPa. The mechanical stirring was turned on. The temperature of the reaction kettle was set to 265°C, and the pressure was increased to 0.25 MPa for esterification. After 2 h, water began to be released. When the amount of water released exceeded 90% of the theoretical value, the esterification was considered complete. The pressure in the reaction kettle was reduced to atmospheric pressure. The raw materials were discharged from the reaction kettle and pelletized to obtain the helical carbon tube / zinc oxide / PCTG master batch.

[0056] The preparation method of the zinc oxide is to mix zinc powder and carbon powder in a mass ratio of 5:1, heat in a muffle furnace at 1050°C for 15 min.

[0057] Example 5

[0058] The preparation method of the spiral carbon tube / zinc oxide / PCTG master batch in this example is as follows:

[0059] A1: 10 parts of spiral carbon tubes were added to 300 parts of a nitric acid solution with a concentration of 3 mol / L and stirred at room temperature for 2 h. The spiral carbon tubes were separated by filtration and repeatedly washed with deionized water and anhydrous ethanol for 3 times. The acid-treated spiral carbon tubes were dried at 100°C for 24 h. The spiral carbon tubes were added to 300 parts of hydrogen peroxide with a concentration of 30 vol.% and ultrasonically dispersed for 2 h. The spiral carbon tubes were separated by filtration and repeatedly washed with deionized water until the pH was neutral. The spiral carbon tubes were dried by filtration.

[0060] A2: 10 parts of the spiral carbon tubes obtained in the above step, 1 part of tetrapod-shaped zinc oxide, and 30 parts of ethylene glycol were mechanically stirred for 1 h for pre-mixing. The mixture was added to a reaction kettle in a ratio of 0.5:1:2 with terephthalic acid and 1,4-cyclohexanedimethanol. The catalyst content was 0.1 wt% of the total mass of the three. Nitrogen was introduced into the reaction kettle until the pressure in the reaction kettle was 0.1 MPa. The mechanical stirring was turned on. The temperature of the reaction kettle was set to 265°C, and the pressure was increased to 0.25 MPa for esterification. After 2 h, water began to be discharged. When the water discharge amount exceeded 90% of the theoretical value, the esterification was considered to be completed. The pressure in the reaction kettle was reduced to normal pressure, and the raw materials were discharged from the reaction kettle for pelletizing to obtain spiral carbon tube / zinc oxide / PCTG master batch.

[0061] The preparation method of the zinc oxide is to mix zinc powder and carbon powder in a mass ratio of 5:1, heat in a muffle furnace at 1050°C for 15 min.

[0062] Example 6

[0063] The preparation method of the PCTG composite material in this example is as follows: 30 parts of the spiral carbon tube / zinc oxide / PCTG master batch obtained in Example 1, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant were added to a high-speed mixer and mixed for 5 min. Then, they were added to a twin-screw extruder for melt blending. The PCTG composite material was obtained by extrusion and granulation. The temperatures of the 9 temperature zones of the twin-screw extruder were 220°C / 230°C / 235°C / 235°C / 240°C / 240°C / 240°C / 240°C / 250°C, respectively. The screw rotation speed was 300 rpm.

[0064] Example 7

[0065] The preparation method of the PCTG composite material in this example is to add 30 parts of the helical carbon tube / zinc oxide / PCTG master batch obtained in Example 2, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant into a high-speed mixer and mix for 5 min, and then add into a twin-screw extruder for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin-screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0066] Example 8

[0067] The preparation method of the PCTG composite material in this example is to add 30 parts of the helical carbon tube / zinc oxide / PCTG master batch obtained in Example 2, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant into a high-speed mixer and mix for 5 min, and then add into a twin-screw extruder for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin-screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0068] Example 9

[0069] The preparation method of the PCTG composite material in this example is to add 30 parts of the helical carbon tube / zinc oxide / PCTG master batch obtained in Example 2, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant into a high-speed mixer and mix for 5 min, and then add into a twin-screw extruder for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin-screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0070] Example 10

[0071] The preparation method of the PCTG composite material in this example is to add 30 parts of the helical carbon tube / zinc oxide / PCTG master batch obtained in Example 2, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant into a high-speed mixer and mix for 5 min, and then add into a twin-screw extruder for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin-screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0072] Example 11

[0073] The preparation method of the PCTG composite material in this example is as follows: 20 parts of the spiral carbon nanotube / zinc oxide / PCTG master batch obtained in Example 1, 30 parts of glass fiber, 50 parts of PCTG raw material, and 0.03 parts of antioxidant are added into a high-speed mixer and mixed for 5 min, and then added into a twin screw for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0074] Example 12

[0075] The preparation method of the PCTG composite material in this example is as follows: 20 parts of the spiral carbon nanotube / zinc oxide / PCTG master batch obtained in Example 1, 30 parts of glass fiber, 50 parts of PCTG raw material, and 0.03 parts of antioxidant are added into a high-speed mixer and mixed for 5 min, and then added into a twin screw for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0076] Example 13

[0077] The preparation method of the PCTG composite material in this example is as follows: 20 parts of the spiral carbon nanotube / zinc oxide / PCTG master batch obtained in Example 1, 30 parts of glass fiber, 50 parts of PCTG raw material, and 0.03 parts of antioxidant are added into a high-speed mixer and mixed for 5 min, and then added into a twin screw for melt blending, extrusion and granulation to obtain the PCTG composite material. The temperatures of the 9 temperature zones of the twin screw extruder are 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed is 300 rpm.

[0078] Comparative Example 1

[0079] The preparation method of the PCTG composite material in this example is as follows:

[0080] (1) 15 parts of tetrapod-shaped zinc oxide and 30 parts of ethylene glycol were pre-mixed by mechanical stirring for 1 h, and the mixture was added into a reaction kettle with terephthalic acid, 1,4-cyclohexanedimethanol according to a ratio of 0.5:1:2, the catalyst content was 0.1 wt% of the total mass of the three, nitrogen was introduced into the reaction kettle until the pressure in the reaction kettle was 0.1 MPa, the mechanical stirring was turned on, the temperature of the reaction kettle was set to 260°C, and the pressure was increased to 0.27 MPa for esterification reaction, water began to be discharged after 2 h, and when the water discharge amount exceeded 90% of the theoretical value, the esterification was considered to be completed, the pressure in the reaction kettle was reduced to normal pressure, and the raw materials were discharged from the reaction kettle to obtain spiral carbon nanotube / zinc oxide / PCTG master batch;

[0081] (2) 30 parts of PCTG master batch, 30 parts of glass fiber, 40 parts of PCTG raw material, and 0.03 parts of antioxidant were added into a high-speed mixer and mixed for 5 min, and then added into a twin-screw extruder for melt blending to obtain a PCTG composite material, the temperature of the nine temperature zones of the twin-screw extruder was 220°C / 230°C / 235°C / 235°C / 240°C / 240°C / 240°C / 240°C / 250°C, and the screw rotation speed was 300 rpm.

[0082] Comparative Example 2

[0083] The preparation method of the PCTG composite material of the present comparative example was as follows:

[0084] (1) 5 parts of spiral carbon nanotubes were added into 150 parts of nitric acid solution with a concentration of 3 mol / L and stirred at room temperature for 2 h, and then the spiral carbon nanotubes were separated by filtration and washed with deionized water and anhydrous ethanol for 3 times, and then dried at 100°C for 24 h, and then the acid-treated spiral carbon nanotubes were added into 150 parts of hydrogen peroxide solution with a concentration of 30 vol.% and ultrasonically dispersed for 2 h, and then the spiral carbon nanotubes were separated by filtration and washed with deionized water until the pH was neutral, and then dried by filtration;

[0085] (2) 15 parts of the spiral carbon nanotubes obtained in the above step and 30 parts of ethylene glycol were pre-mixed by mechanical stirring for 1 h, and the mixture was added into a reaction kettle with terephthalic acid, 1,4-cyclohexanedimethanol according to a ratio of 0.5:1:2, the catalyst content was 0.1 wt% of the total mass of the three, nitrogen was introduced into the reaction kettle until the pressure in the reaction kettle was 0.1 MPa, the mechanical stirring was turned on, the temperature of the reaction kettle was set to 260°C, and the pressure was increased to 0.27 MPa for esterification reaction, water began to be discharged after 2 h, and when the water discharge amount exceeded 90% of the theoretical value, the esterification was considered to be completed, the pressure in the reaction kettle was reduced to normal pressure, and the raw materials were discharged from the reaction kettle to obtain PCTG master batch;

[0086] (3) 30 parts of helical carbon tube / zinc oxide / PCTG masterbatch, 30 parts of glass fiber, 40 parts of PCTG raw material, 0.03 parts of antioxidant were added into a high-speed mixer and mixed for 5 min, and then added into a twin screw for melt blending, and extrusion granulation to obtain a PCTG composite material. The temperature of the 9 temperature zones of the twin screw extruder was 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed was 300 rpm.

[0087] Comparative Example 3

[0088] The preparation method of the PCTG composite material of the present comparative example was as follows:

[0089] (1) 5 parts of helical carbon tube were added into 150 parts of nitric acid solution with a concentration of 3 mol / L and stirred at room temperature for 2 h. The helical carbon tube was separated by filtration, washed repeatedly with deionized water and anhydrous ethanol for 3 times, and dried at 100℃ for 24 h. The acid-treated helical carbon tube was added into 150 parts of hydrogen peroxide solution with a concentration of 30 vol.%, and ultrasonically dispersed for 2 h. The helical carbon tube was separated by filtration, washed repeatedly with deionized water until the pH was neutral, and dried by filtration.

[0090] (2) 2 parts of the helical carbon tube obtained in the above step, 5 parts of four-needle zinc oxide, 30 parts of glass fiber, 60 parts of PCTG raw material, and 0.03 parts of antioxidant were added into a high-speed mixer and mixed for 5 min, and then added into a twin screw for melt blending, and extrusion granulation to obtain a PCTG composite material. The temperature of the 9 temperature zones of the twin screw extruder was 220℃ / 230℃ / 235℃ / 235℃ / 240℃ / 240℃ / 240℃ / 240℃ / 250℃, and the screw rotation speed was 300 rpm.

[0091] Comparative Example 4

[0092] The difference between Comparative Example 4 and Example 6 was only that the addition amount of helical carbon tube / zinc oxide / PCTG masterbatch was 50 parts.

[0093] The tensile strength of the PCTG composite material obtained in the above examples and comparative examples was tested according to the ASTM D638 standard, the bending strength test standard was ASTM D790, the notched impact strength test standard was ASTM D256, the antibacterial test was tested by culture method, and the test bacteria were Escherichia coli and Staphylococcus aureus.

[0094] Table 1 Mechanical properties and antibacterial properties of each example and comparative example

[0095]

[0096] As shown in Table 1, the high-strength antibacterial PCTG composite material obtained in Examples 6-13 exhibits excellent mechanical properties and antibacterial properties, the tensile strength is greater than 48 MPa, the elongation at break is greater than 245%, the bending strength is greater than 55 MPa, the impact strength is greater than 117 KJ / m 2 The bactericidal rate of E. coli and Staphylococcus is greater than 93%, and the mechanical properties decrease as the amount of helical carbon tube / zinc oxide / PCTG masterbatch decreases. Comparative Example 1 does not add helical carbon tubes, but only adds PCTG masterbatch formed by four needle-shaped zinc oxide, which has poor physical entanglement effect on glass fibers and cannot well improve the floating fiber phenomenon, and the mechanical properties of the composite material are poor. Comparative Example 2 does not add zinc oxide, but only has PCTG masterbatch formed by helical carbon tubes, which also has limited physical entanglement effect on glass fibers, and the mechanical properties of the composite material are poor. Comparative Example 3 directly adds helical carbon tubes and zinc oxide to PCTG raw materials without preparing PCTG masterbatch through in-situ esterification reaction, which cannot obtain uniform dispersion in the composite material, and the mechanical properties and antibacterial effect of the composite material are poor. Comparative Example 4 adds excessive helical carbon tube / zinc oxide / PCTG masterbatch, which makes the composite material brittle and the mechanical properties decrease seriously. Thus, it is shown that the PCTG masterbatch loaded with helical carbon tubes and four needle-shaped zinc oxide whiskers is prepared through in-situ esterification reaction in the present application, the four needle-shaped zinc oxide whiskers have good mechanical strength and elastic modulus, effectively improving the mechanical properties and wear resistance of the PCTG composite material, the special structure of the helical carbon tubes can cause physical entanglement between the four needle-shaped zinc oxide whiskers and the glass fibers, enhancing the interaction between them, further preventing the interface slip of the glass fibers and the occurrence of the floating fiber phenomenon, and the two are compounded with PCTG and glass fibers, which maximally reduces the structural damage of the helical carbon tubes and the four needle-shaped zinc oxide whiskers in the blending process, makes them uniformly dispersed in the PCTG matrix, significantly improves the mechanical properties of the PCTG composite material, and the four needle-shaped zinc oxide whisker tips have nano activity, the killing rate of common bacteria is more than 99%, which can significantly improve the antibacterial properties of the material.

[0097] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the present application and are not intended to limit the embodiments of the present application. Those skilled in the art of the present application can make various modifications or supplements to the described embodiments or replace them with similar ways. Here, it is not necessary or possible to fully exemplify all embodiments. However, any additional limitations that can be interpreted as being contrary to the spirit of the present application are within the scope of protection of the present application.

Claims

1. A spiral carbon tube / zinc oxide / PCTG masterbatch, characterized in that: The masterbatch is a PCTG material loaded with helical carbon tubes and zinc oxide, wherein the content of the helical carbon tubes in the PCTG masterbatch is 0.01-10wt%, and the content of the zinc oxide is 0.01-20wt%. The zinc oxide is a tetrapod-shaped zinc oxide with a root size of 1-10um and a needle length of 20-60um. The helical carbon tubes have a helical diameter of 5-50nm, a helical pitch of 20-100nm, a diameter of 20-150nm, and a length of 2-10um. The masterbatch is prepared by an in-situ esterification method.

2. The masterbatch according to claim 1, characterized in that The zinc oxide is prepared by mixing zinc powder and carbon powder and heating the mixture in a muffle furnace at 950-1050° C. for 10-20 minutes.

3. The masterbatch according to claim 2, characterized in that The zinc powder and carbon powder are mixed in a mass ratio of 4-5:

1.

4. A method for preparing the spiral carbon tube / zinc oxide / PCTG masterbatch according to any one of claims 1 to 3, characterized in that: The steps include: A1: Add the spiral carbon nanotubes to a nitric acid solution and stir at room temperature. Filter and separate the spiral carbon nanotubes, wash and dry them. Add the acidified spiral carbon nanotubes to hydrogen peroxide for ultrasonic dispersion, filter and separate them, and then wash and dry them. A2: The spiral carbon tubes obtained in the above steps are mixed with zinc oxide and ethylene glycol to obtain mixture 1. Mixture 1, terephthalic acid, 1,4-cyclohexanedimethanol and a catalyst are added to a reactor. An inert gas is introduced for stirring. The temperature is increased to carry out an esterification reaction. After the reaction, water is discharged. The raw materials are discharged from the reactor and pelletized to obtain spiral carbon tube / zinc oxide / PCTG masterbatch.

5. The method for preparing a spiral carbon tube / zinc oxide / PCTG masterbatch according to claim 4, characterized in that: In step A2, the amounts of the spiral carbon tube, zinc oxide, and ethylene glycol are 1-10 parts, 1-10 parts, and 20-30 parts, respectively.

6. The method for preparing a spiral carbon tube / zinc oxide / PCTG masterbatch according to claim 4, characterized in that: In step A2, the molar ratio of mixture 1, terephthalic acid, and 1,4-cyclohexanedimethanol is 1:0.5:

2.

7. The method for preparing a spiral carbon tube / zinc oxide / PCTG masterbatch according to claim 4, characterized in that: The catalyst content in A2 is 0.01-1% of the total mass of terephthalic acid, mixture 1, and 1,4-cyclohexanedimethanol.

8. The method for preparing a spiral carbon tube / zinc oxide / PCTG masterbatch according to claim 4, characterized in that: The temperature of the esterification reaction in step A2 is 240-270° C. and the pressure is 0.25-0.3 MPa.

9. A high-strength antibacterial PCTG composite material, characterized in that: The invention comprises 50-90 parts of PCTG, 10-45 parts of glass fiber, 0.1-1 part of antioxidant and 10-40 parts of the spiral carbon tube / zinc oxide / PCTG masterbatch as claimed in claim 1.

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