Antibacterial thermoplastic resin composite material and preparation method thereof

Abstract

The invention discloses an antibacterial thermoplastic resin composite material and a preparation method thereof. The antibacterial thermoplastic resin composite material is prepared from the following components in parts by weight: 90-110 parts of thermoplastic resin, 10-16 parts of modified potassium titanate whiskers, 2-4 parts of an antibacterial agent and 0.1-0.5 part of an antioxidant. The thermoplastic resin composite material with good mechanical property and antibacterial property is innovatively synthesized, and the thermoplastic resin composite material has good mechanical property and antibacterial property. The method has very important practical significance for expanding the application field of the thermoplastic resin composite material.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and specifically to an antibacterial thermoplastic resin composite material and a preparation method thereof. Background Art

[0002] Thermoplastic resins have advantages such as good fatigue resistance, relatively good heat resistance, and excellent dimensional stability, and are widely used. However, in some specific application fields, high requirements are placed on the mechanical properties and antibacterial properties of the resin, which limits the application of thermoplastic resin composites in specific fields such as automotive interior materials, specifically materials such as armrest boxes and instrument panels. Summary of the Invention

[0003] In view of this, the present invention provides an antibacterial thermoplastic resin composite material and a preparation method thereof to solve the problems raised in the above background art. A thermoplastic resin composite material with good mechanical properties and antibacterial properties is innovatively synthesized. This thermoplastic resin composite material has very good mechanical properties and antibacterial properties. This has very important practical significance for expanding the application fields of thermoplastic resin composites.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] On the one hand, the present invention discloses an antibacterial thermoplastic resin composite material, which is composed of the following components in parts by weight:

[0006]

[0007] As a further scheme of the present invention: The preparation method of the modified potassium titanate whiskers includes the following steps:

[0008] (1) Add lanthanum chloride hexahydrate to an acetone solution to prepare a LaCl 3 solution;

[0009] (2) Put potassium titanate whiskers and the LaCl 3 solution into concentrated acid, react for 4 - 6 h under the water bath condition of 60 - 80 °C, and wash and dry the obtained product to obtain modified potassium titanate whiskers.

[0010] Among them: The mass ratio of lanthanum chloride hexahydrate to the acetone solution in step (1) is (30 - 40):(90 - 130); the mass ratio of potassium titanate whiskers, the LaCl 3 solution, and concentrated phosphoric acid in step (2) is (30 - 40):(100 - 120):(40 - 60).

[0011] The concentration of the acetone solution in step (1) is 70-80%; the concentrated acid in step (2) is concentrated phosphoric acid with a concentration of 80-86%, and the concentrated phosphoric acid is used to remove impurities on the surface of potassium titanate whiskers.

[0012] As a further solution of the present invention: the preparation method of the antibacterial agent includes the following steps:

[0013] (1) Add indium acetate, sodium bicarbonate, and deionized water into a reaction vessel, stir and react at 50-70 °C for 10-16 h to obtain solution A;

[0014] (2) Filter, wash, vacuum dry, cool, grind, and sieve solution A to obtain indium oxide;

[0015] (3) Stir and react the obtained indium oxide with lanthanum nitrate, ammonia water, and deionized water at 60-80 °C for 6-8 h to obtain solution B;

[0016] (4) Filter, wash, and vacuum dry solution B to obtain In 2 O 3 / La 2 O 3 type antibacterial agent.

[0017] Among them, the mass ratio of indium acetate, sodium bicarbonate, and deionized water in step (1) is (20-24):(26-30):(100-120); the mass ratio of indium oxide, lanthanum nitrate, ammonia water, and deionized water in step (3) is (30-36):(32-36):(30-40):(120-160).

[0018] As a further solution of the present invention: the antioxidant is at least one of Irganox168, Irganox1010, and Irganox1330.

[0019] As a further solution of the present invention: the thermoplastic resin is one of polyethylene, polypropylene, polystyrene, polybutylene terephthalate, and polyamide 6.

[0020] On the other hand, the present invention discloses a preparation method of an antibacterial thermoplastic resin composite material as described in any one of the above, including the following steps:

[0021] (1) Weigh the thermoplastic resin, modified potassium titanate whiskers, antibacterial agent, and antioxidant according to parts by weight, mix and stir evenly to obtain a mixture;

[0022] (2) Extrude and granulate the mixture from an extruder to obtain a thermoplastic resin composite material with good mechanical properties and antibacterial properties.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] (1) The present invention modifies potassium titanate whiskers with a rare earth solution (lanthanum chloride) to obtain potassium titanate whiskers treated with the rare earth solution, which have better dispersibility and more excellent mechanical properties when used to modify thermoplastic resins. The outer electron layer structure of rare earth element La has many empty orbitals that are not filled with electrons, which can act as the central ion to accept the lone pair electrons of the ligand. At the same time, the rare earth metal La ion has a large ionic radius and mainly forms ionic coordination bonds with inorganic or organic ligands through electrostatic attraction, with outstanding chemical activity, which can clean and activate the surface of potassium titanate whiskers and enhance the wettability between potassium titanate whiskers and the thermoplastic resin matrix. At the same time, the rare earth compounds present at the interface play a pinning role, further improving the compatibility between potassium titanate whiskers and the thermoplastic resin matrix.

[0025] (2) The present invention synthesizes an antibacterial agent of the In 2 O 3 / La 2 O 3 type, which can better improve the antibacterial performance of thermoplastic resin composites compared with commercially available common antibacterial agents ， . The synthesis equation of this antibacterial agent is as follows:

[0026] In(CH 3 COO) 3 +3NaHCO 3 →3CH 3 COONa+In(HCO 3 ) 3

[0027] 2In(HCO 3 ) 3 →In 2 O 3 +6CO 2 +3H 2 O

[0028] La(NO 3 ) 3 +NH 3 ·H 2 O→La(OH) 3 +NH 4 NO 3

[0029] 2La(OH) 3 →La 2 O 3 +3H 2 O Specific embodiments

[0030] For the convenience of understanding the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the disclosure of the present invention more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0032] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0033] Polybutylene terephthalate (PBT), model 1100-211M; Polypropylene (PP), model Z30S, Maoming Petrochemical; Polyethylene (PE), model 5070, Panjin Ethylene; Polyamide 6 (PA6), model IM, Russia Kuby; Polystyrene (PS), model 350; Deionized water, Xiamen Aoquan Environmental Protection Technology Co., Ltd.; Lanthanum chloride hexahydrate, Shandong Desheng New Materials Co., Ltd.; Acetone solution, Hubei Jiufenglong Chemical Co., Ltd.; Potassium titanate whiskers, Jinan Zian Chemical Co., Ltd.; Concentrated phosphoric acid, Jining Bocheng Chemical Co., Ltd.; Indium acetate, Hubei Chengfeng Chemical Co., Ltd.; Sodium bicarbonate, Shandong Runyue Chemical Co., Ltd.; Lanthanum nitrate, Shandong Desheng New Materials Co., Ltd.; Ammonia water, Jinan Guangyu Chemical Co., Ltd.; Chitosan, Qingdao Yuekang Biotechnology Co., Ltd.; Sodium hydroxide, Chengdu Zhongzhi Chemical Co., Ltd.; Antioxidants (models Irganox168, Irganox1010, Irganox1330), BASF.

[0034] The following test instruments are used in the following examples and comparative examples:

[0035] ZSK30 twin-screw extruder, manufactured by W&P Company, Germany; JL-1000 tensile testing machine, produced by Guangzhou Guangcai Experimental Instrument Co., Ltd.; HTL900-T-5B injection molding machine, produced by Haitai Plastic Machinery Co., Ltd.; XCJ-500 impact testing machine, produced by Chengde Testing Machine Factory; QT-1196 tensile tester, Dongguan Gaotai Testing Instruments Co., Ltd.; QD-GJS-B12K high-speed mixer, Beijing Heng'ao Instrument Co., Ltd.

[0036] It can be understood that the above raw material reagents are only examples of some specific embodiments of the present invention to make the technical solution of the present invention clearer, and do not represent that the present invention can only use the above reagents. The specific scope is subject to the scope in the claims. In addition, the "parts" mentioned in the examples and comparative examples refer to parts by weight unless otherwise specified.

[0037] Any range described in the present invention includes the end values, any numerical value between the end values, and any sub-range constituted by any numerical value between the end values or the end values.

[0038] Preparation Example 1

[0039] (1) Weigh 300 g of lanthanum chloride hexahydrate and 900 g of acetone solution. Add lanthanum chloride hexahydrate to the acetone solution to prepare a LaCl 3 solution;

[0040] (2) Put 300 g of potassium titanate whiskers and 1.0 kg of LaCl 3 solution into a reaction vessel containing 400 g of concentrated phosphoric acid. Place the reaction vessel in a water bath at 60 °C and react for 4 h. Then wash the surface with deionized water until the pH value is close to neutral to obtain modified potassium titanate whiskers.

[0041] (3) Put the modified potassium titanate whiskers into a vacuum drying oven at 60 °C and dry for 2 h to obtain potassium titanate whiskers M1 treated with rare earth solution.

[0042] Preferably, the concentration of the acetone solution is 70%, and the concentration of the concentrated phosphoric acid is 80%.

[0043] Preparation Example 2

[0044] (1) Weigh 200 g of indium acetate, 260 g of sodium bicarbonate, and 1.0 kg of deionized water. Add them to a reaction vessel and stir and react at 50 °C for 10 h to obtain solution A.

[0045] (2) Filter, wash solution A, place it in a vacuum drying oven and dry at 50 °C for 6 h. Cool and grind it through an 800-mesh sieve to obtain indium oxide.

[0046] (3) Weigh 300 g of indium oxide, 320 g of lanthanum nitrate, 300 g of ammonia water, and 1.2 kg of deionized water. Add them to a reaction vessel and stir and react at 60 °C for 6 h to obtain solution B.

[0047] (4) Filter, wash solution B, place it in a vacuum drying oven and dry at 70 °C for 10 h to obtain In 2 O 3 / La 2 O 3 type antibacterial agent N1.

[0048] Example 1

[0049] (1) Weigh 90 parts of PP, 10 parts of modified potassium titanate whiskers M1, 2 parts of antibacterial agent N1, and 0.1 part of Irganox 1010, mix and stir evenly to obtain a mixture;

[0050] (2) Extrude and pelletize the mixture obtained in step (1) from the extruder to obtain the PP composite material P1.

[0051] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 170 °C, the temperature of the second temperature zone is 220 °C, the temperature of the third temperature zone is 230 °C, the temperature of the fourth temperature zone is 230 °C, the temperature of the fifth temperature zone is 230 °C, the temperature of the sixth temperature zone is 230 °C, the head temperature of the twin-screw extruder is 230 °C, and the screw speed is 220 r / min.

[0052] Comparative Example 1

[0053] (1) Weigh 90 parts of PP, 10 parts of potassium titanate whiskers, 2 parts of antibacterial agent N1, and 0.1 part of Irganox 1010, mix and stir evenly to obtain a mixture;

[0054] (2) Extrude and pelletize the mixture obtained in step (1) from the extruder to obtain the PP composite material D1.

[0055] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 170 °C, the temperature of the second temperature zone is 220 °C, the temperature of the third temperature zone is 230 °C, the temperature of the fourth temperature zone is 230 °C, the temperature of the fifth temperature zone is 230 °C, the temperature of the sixth temperature zone is 230 °C, the head temperature of the twin-screw extruder is 230 °C, and the screw speed is 220 r / min.

[0056] Comparative Example 2

[0057] (1) Weigh 90 parts of PP, 10 parts of modified potassium titanate whiskers M1, 2 parts of commercially available antibacterial agent chitosan, and 0.1 part of Irganox 1010, mix and stir evenly to obtain a mixture;

[0058] (2) Extrude and pelletize the mixture obtained in step (1) from the extruder to obtain the PP composite material D2.

[0059] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 170 °C, the temperature of the second temperature zone is 220 °C, the temperature of the third temperature zone is 230 °C, the temperature of the fourth temperature zone is 230 °C, the temperature of the fifth temperature zone is 230 °C, the temperature of the sixth temperature zone is 230 °C, the head temperature of the twin-screw extruder is 230 °C, and the screw speed is 220 r / min.

[0060] The PP composite materials prepared in Example 1 and Comparative Examples 1-2 above were made into splines by an injection molding machine for testing, and the test data are shown in Table 1 below:

[0061] Table 1

[0062]

[0063] As can be seen from the above table, generally speaking, the mechanical properties and antibacterial properties of Example 1 are stronger.

[0064] Preparation Example 3

[0065] (1) Weigh 400 g of lanthanum chloride hexahydrate and 1.3 kg of acetone solution. Add lanthanum chloride hexahydrate to the acetone solution to prepare a LaCl 3 solution;

[0066] (2) Put 400 g of potassium titanate whiskers and 1.2 k of gdLaCl 3 solution into a reaction vessel containing 600 g of concentrated phosphoric acid. Place the reaction vessel in a water bath at 80 °C and react for 6 h. Then wash the surface with deionized water until the pH value is close to neutral to obtain modified potassium titanate whiskers.

[0067] (3) Put the modified potassium titanate whiskers into a vacuum drying oven at 80 °C and dry for 4 h to obtain potassium titanate whiskers M2 treated with rare earth solution.

[0068] Preferably, the concentration of the acetone solution is 80%, and the concentration of the concentrated phosphoric acid is 86%.

[0069] Preparation Example 4

[0070] (1) Weigh 240 g of indium acetate, 300 g of sodium bicarbonate, and 1.2 kg of deionized water. Add them to a reaction vessel and stir and react at 70 °C for 16 h to obtain solution A.

[0071] (2) Filter, wash solution A, place it in a vacuum drying oven and dry at 70 °C for 8 h, cool and grind it through an 800-mesh sieve to obtain indium oxide.

[0072] (3) Weigh 360 g of indium oxide, 360 g of lanthanum nitrate, 400 g of ammonia water, and 1.2 kg of deionized water. Add them to a reaction vessel and stir and react at 80 °C for 8 h to obtain solution B.

[0073] (4) Filter, wash solution B, place it in a vacuum drying oven and dry at 90 °C for 12 h to obtain In 2 O 3 / La 2 O 3 type antibacterial agent N2.

[0074] Example 2

[0075] (1) Weigh 110 parts of PBT, 16 parts of modified potassium titanate whisker M2, 4 parts of antibacterial agent N2, 0.1 part of antioxidant Irganox1010, 0.2 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1330, mix them evenly, and obtain a mixed material;

[0076] (2) Extrude and pelletize the mixed material obtained in step (1) from an extruder to obtain the PBT composite material P2.

[0077] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 200 °C, the temperature of the second temperature zone is 230 °C, the temperature of the third temperature zone is 240 °C, the temperature of the fourth temperature zone is 240 °C, the temperature of the fifth temperature zone is 240 °C, the temperature of the sixth temperature zone is 240 °C, the head temperature of the twin-screw extruder is 240 °C, and the screw speed is 300 r / min.

[0078] Comparative Example 3

[0079] (1) Weigh 110 parts of PBT, 16 parts of potassium titanate whisker, 4 parts of antibacterial agent N2, 0.1 part of antioxidant Irganox1010, 0.2 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1330, mix them evenly, and obtain a mixed material;

[0080] (2) Extrude and pelletize the mixed material obtained in step (1) from an extruder to obtain the PBT composite material D3.

[0081] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 200 °C, the temperature of the second temperature zone is 230 °C, the temperature of the third temperature zone is 240 °C, the temperature of the fourth temperature zone is 240 °C, the temperature of the fifth temperature zone is 240 °C, the temperature of the sixth temperature zone is 240 °C, the head temperature of the twin-screw extruder is 240 °C, and the screw speed is 300 r / min.

[0082] Comparative Example 4

[0083] (1) Weigh 110 parts of PBT, 16 parts of modified potassium titanate whisker M2, 4 parts of commercially available antibacterial agent chitosan, 0.1 part of antioxidant Irganox1010, 0.2 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1330, mix them evenly, and obtain a mixed material;

[0084] (2) Extrude and pelletize the mixed material obtained in step (1) from an extruder to obtain the PBT composite material D4.

[0085] Among them, the twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 200 °C, the temperature of the second temperature zone is 230 °C, the temperature of the third temperature zone is 240 °C, the temperature of the fourth temperature zone is 240 °C, the temperature of the fifth temperature zone is 240 °C, the temperature of the sixth temperature zone is 240 °C, the head temperature of the twin-screw extruder is 240 °C, and the screw speed is 300 r / min.

[0086] The PBT composites prepared in the above Example 2 and Comparative Examples 3-4 were made into splines for testing with an injection molding machine, and the test data are shown in Table 2 below:

[0087] Table 2

[0088]

[0089] As can be seen from the above table, generally speaking, the mechanical properties and antibacterial properties of Example 2 are better than those of Comparative Examples 3-4.

[0090] Preparation Example 5

[0091] (1) Weigh 350 g of lanthanum chloride hexahydrate and 1.1 kg of acetone solution. Add lanthanum chloride hexahydrate to the acetone solution to prepare a LaCl 3 solution;

[0092] (2) Put 350 g of potassium titanate whiskers and 1.1 kg of LaCl 3 solution into a reaction vessel containing 500 g of concentrated phosphoric acid. Place the reaction vessel in a water bath at 70 °C and react for 5 h. Then wash the surface with deionized water until the pH value is close to neutral to obtain modified potassium titanate whiskers.

[0093] (3) Put the modified potassium titanate whiskers into a vacuum drying oven at 70 °C and dry for 3 h to obtain potassium titanate whiskers M3 treated with rare earth solution.

[0094] Preferably, the concentration of the acetone solution is 75%, and the concentration of the concentrated phosphoric acid is 83%.

[0095] Preparation Example 6

[0096] (1) Weigh 220 g of indium acetate, 280 g of sodium bicarbonate, and 1.1 kg of deionized water. Add them to a reaction vessel and stir and react at 60 °C for 13 h to obtain solution A.

[0097] (2) Filter, wash solution A, place it in a vacuum drying oven at 60 °C and dry for 7 h, cool and grind it through an 800-mesh sieve to obtain indium oxide.

[0098] (3) Weigh 330 g of indium oxide, 340 g of lanthanum nitrate, 350 g of ammonia water, and 1.4 kg of deionized water. Add them to a reaction vessel and stir at 70 °C for 7 h to obtain solution B.

[0099] (4) Filter and wash solution B, and place it in a vacuum drying oven to dry at 80 °C for 11 h to obtain In 2 O 3 / La 2 O 3 type antibacterial agent N3.

[0100] Example 3

[0101] (1) Weigh 100 parts of PE, 13 parts of modified potassium titanate whiskers M3, 3 parts of antibacterial agent N3, 0.1 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1010, mix and stir evenly to obtain a mixed material;

[0102] (2) Extrude and pelletize the mixed material obtained in step (1) from an extruder to obtain PE composite material P3.

[0103] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 120 °C, the temperature of the second temperature zone is 180 °C, the temperature of the third temperature zone is 180 °C, the temperature of the fourth temperature zone is 180 °C, the temperature of the fifth temperature zone is 180 °C, the temperature of the sixth temperature zone is 180 °C, the head temperature of the twin-screw extruder is 180 °C, and the screw speed is 300 r / min.

[0104] Comparative Example 5

[0105] (1) Weigh 100 parts of PE, 13 parts of potassium titanate whiskers, 3 parts of antibacterial agent N3, 0.1 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1010, mix and stir evenly to obtain a mixed material;

[0106] (2) Extrude and pelletize the mixed material obtained in step (1) from an extruder to obtain PE composite material D5.

[0107] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 120 °C, the temperature of the second temperature zone is 180 °C, the temperature of the third temperature zone is 180 °C, the temperature of the fourth temperature zone is 180 °C, the temperature of the fifth temperature zone is 180 °C, the temperature of the sixth temperature zone is 180 °C, the head temperature of the twin-screw extruder is 180 °C, and the screw speed is 300 r / min.

[0108] Comparative Example 6

[0109] (1) Weigh 100 parts of PE, 13 parts of potassium titanate whiskers, 3 parts of commercially available antibacterial agent chitosan, 0.1 part of antioxidant Irganox168, and 0.2 part of antioxidant Irganox1010, mix them evenly and stir well to obtain a mixed material;

[0110] (2) Extrude and granulate the mixed material obtained in step (1) from an extruder to obtain the PE composite material D6.

[0111] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 120 °C, the temperature of the second temperature zone is 180 °C, the temperature of the third temperature zone is 180 °C, the temperature of the fourth temperature zone is 180 °C, the temperature of the fifth temperature zone is 180 °C, the temperature of the sixth temperature zone is 180 °C, the head temperature of the twin-screw extruder is 180 °C, and the screw speed is 300 r / min.

[0112] The PE composite materials prepared in Example 3 and Comparative Examples 5-6 above were made into splines for testing by an injection molding machine, and the test data are shown in Table 3 below:

[0113] Table 3

[0114]

[0115] As can be seen from the above table, generally speaking, the mechanical properties and antibacterial properties of Example 3 are better than those of Comparative Examples 5-6.

[0116] Preparation Example 7

[0117] (1) Weigh 385 g of lanthanum chloride hexahydrate and 1.25 kg of acetone solution, add lanthanum chloride hexahydrate to the acetone solution to prepare a LaCl 3 solution;

[0118] (2) Put 365 g of potassium titanate whiskers and 1.18 kg of LaCl 3 solution into a reaction vessel containing 525 g of concentrated phosphoric acid, place the reaction vessel in a water bath at 78 °C, react for 5 h, and then wash the surface with deionized water until the pH value is close to neutral to obtain modified potassium titanate whiskers.

[0119] (3) Put the modified potassium titanate whiskers into a vacuum drying oven at 75 °C and dry for 3 h to obtain the potassium titanate whiskers M4 treated with a rare earth solution.

[0120] Preferably, the concentration of the acetone solution is 79%, and the concentration of the concentrated phosphoric acid is 85%.

[0121] Preparation Example 8

[0122] (1) Weigh 235 g of indium acetate, 295 g of sodium bicarbonate, and 1.15 kg of deionized water. Add them to a reaction vessel and stir and react at 65 °C for 15 h to obtain solution A.

[0123] (2) Filter and wash solution A, place it in a vacuum drying oven and dry at 65 °C for 7 h, then cool and grind it through an 800-mesh sieve to obtain indium oxide.

[0124] (3) Weigh 335 g of indium oxide, 345 g of lanthanum nitrate, 345 g of ammonia water, and 1.55 kg of deionized water. Add them to a reaction vessel and stir and react at 65 °C for 7 h to obtain solution B.

[0125] (4) Filter and wash solution B, place it in a vacuum drying oven and dry at 85 °C for 11 h to obtain In 2 O 3 / La 2 O 3 type antibacterial agent N4.

[0126] Example 4

[0127] (1) Weigh 95 parts of PA6, 15 parts of modified potassium titanate whisker M4, 3.5 parts of antibacterial agent N4, 0.1 part of antioxidant Irganox1010, and 0.2 part of antioxidant Irganox1330, mix and stir evenly to obtain a mixture.

[0128] (2) Extrude and pelletize the mixture obtained in step (1) from an extruder to obtain PA6 composite material P4.

[0129] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 210 °C, the temperature of the second temperature zone is 260 °C, the temperature of the third temperature zone is 260 °C, the temperature of the fourth temperature zone is 260 °C, the temperature of the fifth temperature zone is 260 °C, the temperature of the sixth temperature zone is 260 °C, the head temperature of the twin-screw extruder is 260 °C, and the screw speed is 320 r / min.

[0130] Comparative Example 7

[0131] (1) Weigh 95 parts of PA6, 15 parts of potassium titanate whisker, 3.5 parts of commercially available antibacterial agent chitosan, 0.1 part of antioxidant Irganox1010, and 0.2 part of antioxidant Irganox1330, mix and stir evenly to obtain a mixture.

[0132] (2) Extrude and pelletize the mixture obtained in step (1) from an extruder to obtain PA6 composite material D7.

[0133] Among them, the twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 210 °C, the temperature of the second temperature zone is 260 °C, the temperature of the third temperature zone is 260 °C, the temperature of the fourth temperature zone is 260 °C, the temperature of the fifth temperature zone is 260 °C, the temperature of the sixth temperature zone is 260 °C, the head temperature of the twin-screw extruder is 260 °C, and the screw speed is 320 r / min.

[0134] Comparative Example 8

[0135] (1) Weigh 95 parts of PA6, 15 parts of potassium titanate whiskers, 3.5 parts of commercially available antibacterial agent chitosan, 0.1 part of antioxidant Irganox1010, and 0.2 part of antioxidant Irganox1330, mix and stir evenly to obtain a mixture.

[0136] (2) Extrude and pelletize the mixture obtained in step (1) from the extruder to obtain the PA6 composite material D8.

[0137] Among them, the twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 210 °C, the temperature of the second temperature zone is 260 °C, the temperature of the third temperature zone is 260 °C, the temperature of the fourth temperature zone is 260 °C, the temperature of the fifth temperature zone is 260 °C, the temperature of the sixth temperature zone is 260 °C, the head temperature of the twin-screw extruder is 260 °C, and the screw speed is 320 r / min.

[0138] The PA6 composite materials prepared in the above Example 4 and Comparative Examples 7-8 were made into splines for testing by an injection molding machine, and the test data are shown in Table 4 below:

[0139] Table 4

[0140]

[0141]

[0142] As can be seen from the above table, generally speaking, the mechanical properties and antibacterial properties of Example 4 are better than those of Comparative Examples 7-8.

[0143] Preparation Example 9

[0144] (1) Weigh 335 g of lanthanum chloride hexahydrate and 1.25 kg of acetone solution, add lanthanum chloride hexahydrate to the acetone solution to prepare a LaCl 3 solution;

[0145] (2) Add 385 g of potassium titanate whiskers and 1.18 kg of LaCl 3The solution was put into a reactor vessel containing 555 g of concentrated phosphoric acid. The reactor vessel was placed in a water bath at 65 °C and reacted for 5 h. Then, the surface was washed with deionized water until the pH value was close to neutrality, and modified potassium titanate whiskers were obtained.

[0146] (3) The modified potassium titanate whiskers were placed in a vacuum drying oven at 75 °C and dried for 3 h, and then potassium titanate whiskers M5 treated with the rare earth solution were obtained.

[0147] Preferably, the concentration of the acetone solution is 75%, and the concentration of the concentrated phosphoric acid is 84%.

[0148] Preparation Example 10

[0149] (1) Weigh 225 g of indium acetate, 295 g of sodium bicarbonate, and 1.19 kg of deionized water, add them to a reactor vessel, and stir and react at 65 °C for 15 h to obtain solution A.

[0150] (2) Solution A was filtered, washed, placed in a vacuum drying oven and dried at 65 °C for 7 h, cooled and ground through an 800-mesh sieve to obtain indium oxide.

[0151] (3) Weigh 335 g of indium oxide, 345 g of lanthanum nitrate, 395 g of ammonia water, and 1.58 kg of deionized water, add them to a reactor vessel, and stir and react at 78 °C for 6 h to obtain solution B.

[0152] (4) Solution B was filtered, washed, placed in a vacuum drying oven and dried at 85 °C for 11 h to obtain In 2 O 3 / La 2 O 3 type antibacterial agent N5.

[0153] Example 5

[0154] (1) Weigh 105 parts of PS, 15 parts of modified potassium titanate whiskers M5, 2.5 parts of antibacterial agent N5, 14 parts of functional filler M5, 0.1 part of antioxidant Irganox1010, and 0.1 part of antioxidant Irganox168, mix and stir evenly to obtain a mixture.

[0155] (2) The mixture obtained in step (1) was extruded and pelletized from an extruder to obtain PS composite material P5.

[0156] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 180°C, the temperature of the second temperature zone is 220°C, the temperature of the third temperature zone is 220°C, the temperature of the fourth temperature zone is 220°C, the temperature of the fifth temperature zone is 220°C, the temperature of the sixth temperature zone is 220°C, the temperature of the head of the twin-screw extruder is 220°C, and the screw rotation speed is 280 r / min.

[0157] Comparative Example 9

[0158] (1) Weigh 105 parts of PS, 15 parts of potassium titanate whiskers, 2.5 parts of antibacterial agent N5, 0.1 part of antioxidant Irganox1010, and 0.1 part of antioxidant Irganox168, mix and stir evenly to obtain a mixed material.

[0159] (2) Extrude and pelletize the mixed material obtained in step (1) from the extruder to obtain the PS composite material D9.

[0160] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 180°C, the temperature of the second temperature zone is 220°C, the temperature of the third temperature zone is 220°C, the temperature of the fourth temperature zone is 220°C, the temperature of the fifth temperature zone is 220°C, the temperature of the sixth temperature zone is 220°C, the temperature of the head of the twin-screw extruder is 220°C, and the screw rotation speed is 280 r / min.

[0161] Comparative Example 10

[0162] (1) Weigh 105 parts of PS, 15 parts of modified potassium titanate whiskers M5, 2.5 parts of commercially available antibacterial agent chitosan, 0.1 part of antioxidant Irganox1010, and 0.1 part of antioxidant Irganox168, mix and stir evenly to obtain a mixed material.

[0163] (2) Extrude and pelletize the mixed material obtained in step (1) from the extruder to obtain the PS composite material D10.

[0164] The twin-screw extruder includes six temperature zones arranged in sequence. The temperature of the first temperature zone is 180°C, the temperature of the second temperature zone is 220°C, the temperature of the third temperature zone is 220°C, the temperature of the fourth temperature zone is 220°C, the temperature of the fifth temperature zone is 220°C, the temperature of the sixth temperature zone is 220°C, the temperature of the head of the twin-screw extruder is 220°C, and the screw rotation speed is 280 r / min.

[0165] The PS composites prepared in the above Example 5 and Comparative Examples 9-10 were made into splines by an injection molding machine for testing, and the test data are shown in Table 5 below:

[0166] Table 5

[0167]

[0168] As can be seen from the above table, generally speaking, the mechanical properties and antibacterial properties of Example 5 are better than those of Comparative Examples 9-10.

[0169] This shows that the thermoplastic resin composite prepared by the method provided by the present invention has good mechanical properties and antibacterial properties, and can expand the application fields of thermoplastic resin composites.

[0170] Although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0171] Therefore, the above are only the preferred embodiments of the present application, and are not used to limit the scope of implementation of the present application; that is, all equivalent transformations made according to the scope of the claims of the present application are within the protection scope of the claims of the present application.

Claims

1. An antibacterial thermoplastic resin composite material, characterized in that, it is composed of the following components by weight:

2. The antibacterial thermoplastic resin composite material according to claim 1, characterized in that, the preparation method of the modified potassium titanate whiskers comprises the following steps: (1) Add lanthanum chloride hexahydrate to an acetone solution to prepare a LaCl 3 solution; (2) Put potassium titanate whiskers and LaCl 3 solution into concentrated acid, react for 4 - 6 h under the water bath condition at 60 - 80 °C, wash and dry the obtained product to obtain modified potassium titanate whiskers.

3. The antibacterial thermoplastic resin composite material according to claim 2, characterized in that, The mass ratio of lanthanum chloride hexahydrate to acetone solution in step (1) is (30 - 40):(90 - 130); the mass ratio of potassium titanate whiskers, LaCl 3 solution to concentrated phosphoric acid in step (2) is (30 - 40):(100 - 120):(40 - 60).

4. The antibacterial thermoplastic resin composite material according to claim 2, characterized in that, the concentration of the acetone solution in step (1) is 70-80%; the concentrated acid in step (2) is concentrated phosphoric acid, and its concentration is 80-86%.

5. The antibacterial thermoplastic resin composite material according to claim 1, characterized in that, the preparation method of the antibacterial agent comprises the following steps: (1) Add indium acetate, sodium bicarbonate, and deionized water into a reaction vessel, stir and react at 50-70 °C for 10-16 h to obtain solution A; (2) Filter, wash, vacuum dry, cool, grind, and sieve solution A to obtain indium oxide; (3) Stir and react the indium oxide, lanthanum nitrate, ammonia water, and deionized water at 60-80 °C for 6-8 h to obtain solution B; (4) Filter, wash, and vacuum dry Solution B to obtain In 2 O 3 / La 2 O 3 type antibacterial agent.

6. The antibacterial thermoplastic resin composite material according to claim 5, characterized in that, the mass ratio of indium acetate, sodium bicarbonate, and deionized water in step (1) is (20-24):(26-30):(100-120); the mass ratio of indium oxide, lanthanum nitrate, ammonia water, and deionized water in step (3) is (30-36):(32-36):(30-40):(120-160).

7. The antibacterial thermoplastic resin composite material according to claim 1, characterized in that, the antioxidant is at least one of Irganox168, Irganox1010, and Irganox1330.

8. The antibacterial thermoplastic resin composite material according to claim 1, characterized in that, the thermoplastic resin is one of polyethylene, polypropylene, polystyrene, polybutylene terephthalate, and polyamide 6.

9. The preparation method of an antibacterial thermoplastic resin composite material according to any one of claims 1-8, characterized in that, it comprises the following steps: (1) Weigh the thermoplastic resin, modified potassium titanate whiskers, antibacterial agent, and antioxidant according to weight, mix and stir evenly to obtain a mixture; (2) Extrude and pelletize the mixture from an extruder to obtain a thermoplastic resin composite material with good mechanical properties and antibacterial properties.

Images