Preparation method and application of filler for high-performance thermoplastic composite materials

Abstract

The present invention provides a preparation method and application of a filler for high-performance thermoplastic composite materials. The preparation method of the filler for high-performance thermoplastic composite materials comprises the following steps: S1: weighing a certain amount of copper nitrate, potassium carbonate, and deionized water, adding them to a reaction vessel, stirring and reacting at 70-90°C for 6-8 hours to obtain a mixed solution A; S2: filtering, washing, and drying the mixed solution A at 30-50°C for 4-8 hours to obtain basic copper carbonate; S3: weighing a certain amount of basic copper carbonate, ethylene glycol dimethacrylate, an initiator lauroyl peroxide, a solvent acetone, and a catalyst triethylenediamine, placing them into a reaction vessel, and reacting under UV light for 18-24 hours to obtain a solution B; S4: filtering, washing, and drying the solution B at 40-60°C for 10-12 hours to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, i.e., modified basic copper carbonate. The preparation method and application of the filler for high-performance thermoplastic composite materials provided by the present invention have the advantages of being able to synthesize new modified basic copper carbonate, and using it to modify thermoplastic plastics to obtain relatively excellent mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a preparation method and application of a filler for high-performance thermoplastic composite materials. Background Art

[0002] Basic copper carbonate has long been a common filler and an important filler for modifying thermoplastics. This modification of thermoplastics with basic copper carbonate is a popular chemical modification technology that has been recently developed. In certain specific material fields, very high physical property requirements are required, and ordinary thermoplastics can no longer meet these requirements.

[0003] Therefore, it is necessary to provide a new preparation method of fillers for high-performance thermoplastic composite materials and its application to solve the above technical problems. Summary of the Invention

[0004] The technical problem solved by the present invention is to provide a preparation method and application of a filler for high-performance thermoplastic composite materials that can synthesize a new modified basic copper carbonate and use it to modify thermoplastic plastics to obtain relatively excellent mechanical properties.

[0005] To solve the above technical problems, the present invention provides a method for preparing a filler for a high-performance thermoplastic composite material, comprising the following steps:

[0006] S1: Weigh a certain amount of copper nitrate, potassium carbonate, and deionized water into a reaction vessel, stir and react at 70-90°C for 6-8 hours to obtain a mixed solution A;

[0007] S2: Filtering, washing, and drying the mixed solution A at 30-50° C. for 4-8 hours to obtain basic copper carbonate;

[0008] S3: Weigh a certain amount of basic copper carbonate, ethylene glycol dimethacrylate, initiator lauroyl peroxide, solvent acetone, and catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 18-24 hours to obtain solution B.

[0009] S4: Filtering the solution B, washing it, and drying it at 40-60° C. for 10-12 hours to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate.

[0010] Preferably, in S1, the mass ratio of copper nitrate, potassium carbonate and deionized water is (30-40): (30-36); (70-90).

[0011] Preferably, in S3, the mass ratio of basic copper carbonate, ethylene glycol dimethacrylate, initiator lauroyl peroxide, solvent acetone, and catalyst triethylenediamine is (30-40): (12-16): (0.1-0.3): (60-80): (0.2-0.4).

[0012] The present invention also provides an application of the modified basic copper carbonate in thermoplastic plastic products, wherein the thermoplastic plastic is one of polypropylene, polybutylene terephthalate, polyethylene, polyamide 6, and styrene.

[0013] Preferably, the thermoplastic plastic and modified basic copper carbonate are melt-blended in a mass ratio of 80:20.

[0014] Compared with related technologies, the preparation method and application of fillers for high-performance thermoplastic composite materials provided by the present invention have the following beneficial effects:

[0015] (1) The preparation formula of basic copper carbonate is as follows:

[0016] Cu(NO3)2+K2CO3→CuCO3+2KNO3

[0017] 2CuCO3+H2O→CuCO3·Cu(OH)2+CO2;

[0018] (2) This patent first synthesizes a basic copper carbonate and then grafts ethylene glycol dimethacrylate onto its surface, thereby improving the interfacial compatibility between the basic copper carbonate and thermoplastics, facilitating the dispersion of the basic copper carbonate in the thermoplastics, and improving the physical properties of the thermoplastics;

[0019] (3) The modified basic copper carbonate of the present invention can greatly improve the mechanical properties of thermoplastic plastic composite materials and has great promotion value. DETAILED DESCRIPTION

[0020] The present invention will be further described below with reference to the embodiments.

[0021] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0022] Polybutylene terephthalate, i.e. PBT (model 1200-211L), was purchased from Changchun, Taiwan, China; polypropylene, i.e. PP (model Z30S), was purchased from Maoming Petrochemical; polyethylene, i.e. PE (model 5070), was purchased from Panjin Ethylene; polyamide 6, i.e. PA6 (model 1013B), was purchased from Ube, Japan; styrene, i.e. PS (model 350), was purchased from Guoqiao, Taiwan, China; deionized water was purchased from Shanghai Lianshi Chemical Reagent Co., Ltd.; copper nitrate, Jinan Yucai Chemical Co., Ltd.; potassium carbonate, Jinan Chuangshi Chemical Co., Ltd.; ethylene glycol dimethacrylate, Shandong Chuangying Chemical Co., Ltd.; lauroyl peroxide, Wanqing Chemical Technology Co., Ltd.; acetone, Jinan Xinda Chemical Co., Ltd.; triethylenediamine, Jinan Mingwei Chemical Co., Ltd.; basic copper carbonate, Jinan Mingxin Chemical Co., Ltd.

[0023] It is understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, which make the technical solution of the present invention clearer, and do not mean that the present invention can only adopt the above reagents. The specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0024] Preparation Example 1

[0025] (1) Weigh 300 g of copper nitrate, 300 g of potassium carbonate, and 700 g of deionized water into a reaction vessel and stir at 70°C for 6 h to obtain a mixed solution A;

[0026] (2) filtering the mixed solution A, washing it, and drying it at 30° C. for 4 h to obtain basic copper carbonate;

[0027] (3) Weigh 300 g of basic copper carbonate, 120 g of ethylene glycol dimethacrylate, 1 g of initiator lauroyl peroxide, 600 g of solvent acetone, and 2 g of catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 18 h to obtain solution B.

[0028] (4) Solution B was filtered, washed, and dried at 40° C. for 10 h to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate M1.

[0029] Application Example 1

[0030] 20 parts of M1 were added to 80 parts of polypropylene (PP), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PP composite material X1.

[0031] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 170°C, the temperature of zone two being 230°C, the temperature of zone three being 230°C, the temperature of zone four being 230°C, the temperature of zone five being 230°C, the temperature of zone six being 230°C, the head temperature being 230°C, and the screw speed being 220r / min.

[0032] Comparative Example 1

[0033] 20 parts of commercially available basic copper carbonate were added to 80 parts of polypropylene (PP), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PP composite material D1.

[0034] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 170°C, the temperature of zone two being 230°C, the temperature of zone three being 230°C, the temperature of zone four being 230°C, the temperature of zone five being 230°C, the temperature of zone six being 230°C, the head temperature being 230°C, and the screw speed being 220r / min.

[0035] The performance data of the PP composite materials prepared in the above Application Example 1 and Comparative Example 1 are shown in the following table:

[0036]

[0037] It can be seen from the above table that the mechanical properties of X1 are better than those of D1, which indicates that the mechanical properties of PP are better after adding the modified basic copper carbonate of the present invention.

[0038] Preparation Example 2

[0039] (1) Weigh 400 g of copper nitrate, 360 g of potassium carbonate, and 900 g of deionized water into a reaction vessel, and stir at 90° C. for 8 h to obtain a mixed solution A;

[0040] (2) filtering the mixed solution A, washing it, and drying it at 50° C. for 8 h to obtain basic copper carbonate;

[0041] (3) Weigh 400 g of basic copper carbonate, 160 g of ethylene glycol dimethacrylate, 3 g of initiator lauroyl peroxide, 800 g of solvent acetone, and 4 g of catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 24 h to obtain solution B.

[0042] (4) Solution B was filtered, washed, and dried at 60° C. for 12 h to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate M2.

[0043] Application Example 2

[0044] 20 parts of M2 were added to 80 parts of polybutylene terephthalate (PBT), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PBT composite material X2.

[0045] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 200°C, the temperature of zone two being 260°C, the temperature of zone three being 260°C, the temperature of zone four being 260°C, the temperature of zone five being 260°C, the temperature of zone six being 260°C, the head temperature being 260°C, and the screw speed being 300r / min.

[0046] Comparative Example 2

[0047] 20 parts of commercially available basic copper carbonate were added to 80 parts of polybutylene terephthalate (PBT), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PBT composite material D2.

[0048] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 200°C, the temperature of zone two being 260°C, the temperature of zone three being 260°C, the temperature of zone four being 260°C, the temperature of zone five being 260°C, the temperature of zone six being 260°C, the head temperature being 260°C, and the screw speed being 300r / min.

[0049] The performance data of the PBT composite materials prepared in the above Application Example 2 and Comparative Example 2 are shown in the following table:

[0050]

[0051] It can be seen from the above table that the mechanical properties of X2 are better than those of D2, which indicates that the mechanical properties of PBT are better after the modified basic copper carbonate of the present invention is added.

[0052] Preparation Example 3

[0053] (1) Weigh 350 g of copper nitrate, 330 g of potassium carbonate, and 800 g of deionized water into a reaction vessel, and stir at 80°C for 7 h to obtain a mixed solution A;

[0054] (2) filtering the mixed solution A, washing it, and drying it at 40° C. for 6 h to obtain basic copper carbonate;

[0055] (3) Weigh 350 g of basic copper carbonate, 140 g of ethylene glycol dimethacrylate, 2 g of initiator lauroyl peroxide, 700 g of solvent acetone, and 3 g of catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 21 h to obtain solution B.

[0056] (4) Solution B was filtered, washed, and dried at 50° C. for 11 h to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate M3.

[0057] Application Example 3

[0058] 20 parts of M3 were added to 80 parts of polyethylene (PE), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PE composite material X3.

[0059] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 120°C, the temperature of zone two being 180°C, the temperature of zone three being 180°C, the temperature of zone four being 180°C, the temperature of zone five being 180°C, the temperature of zone six being 180°C, the head temperature being 180°C, and the screw speed being 300r / min.

[0060] Comparative Example 3

[0061] 20 parts of commercially available basic copper carbonate were added to 80 parts of polyethylene (PE), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PE composite material D3.

[0062] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 120°C, the temperature of zone two being 180°C, the temperature of zone three being 180°C, the temperature of zone four being 180°C, the temperature of zone five being 180°C, the temperature of zone six being 180°C, the head temperature being 180°C, and the screw speed being 300r / min.

[0063] The performance data of the PE composite materials prepared in the above Application Example 3 and Comparative Example 3 are shown in the following table:

[0064]

[0065] It can be seen from Table 3 that the mechanical properties of X3 are better than those of D3, which indicates that the mechanical properties of PE are better after the modified basic copper carbonate of the present invention is added.

[0066] Preparation Example 4

[0067] (1) Weigh 385 g of copper nitrate, 355 g of potassium carbonate, and 885 g of deionized water into a reaction vessel, and stir at 85°C for 8 h to obtain a mixed solution A;

[0068] (2) filtering the mixed solution A, washing it, and drying it at 45° C. for 7 h to obtain basic copper carbonate;

[0069] (3) Weigh 385 g of basic copper carbonate, 155 g of ethylene glycol dimethacrylate, 2.5 g of initiator lauroyl peroxide, 775 g of solvent acetone, and 3.5 g of catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 21 h to obtain solution B.

[0070] (4) Solution B was filtered, washed, and dried at 55° C. for 11 h to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate M4.

[0071] Application Example 4

[0072] 20 parts of M4 were added to 80 parts of polyamide 6 (PA6), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PA6 composite material X4.

[0073] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 230°C, the temperature of zone two being 260°C, the temperature of zone three being 260°C, the temperature of zone four being 260°C, the temperature of zone five being 260°C, the temperature of zone six being 260°C, the head temperature being 250°C, and the screw speed being 320r / min.

[0074] Comparative Example 4

[0075] 20 parts of commercially available basic copper carbonate were added to 80 parts of polyamide 6 (PA6), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PA6 composite material D4.

[0076] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 230°C, the temperature of zone two being 260°C, the temperature of zone three being 260°C, the temperature of zone four being 260°C, the temperature of zone five being 260°C, the temperature of zone six being 260°C, the head temperature being 250°C, and the screw speed being 320r / min.

[0077] The performance data of the PA6 composite materials prepared in the above Application Example 4 and Comparative Example 4 are shown in the following table:

[0078]

[0079] It can be seen from Table 4 that the mechanical properties of X4 are better than those of D4, which indicates that the mechanical properties of PA6 are better after the modified basic copper carbonate of the present invention is added.

[0080] Preparation Example 5

[0081] (1) Weigh 315 g of copper nitrate, 345 g of potassium carbonate, and 715 g of deionized water into a reaction vessel, and stir at 85°C for 7 h to obtain a mixed solution A;

[0082] (2) filtering the mixed solution A, washing it, and drying it at 45° C. for 5 h to obtain basic copper carbonate;

[0083] (3) Weigh 335 g of basic copper carbonate, 155 g of ethylene glycol dimethacrylate, 2.5 g of initiator lauroyl peroxide, 655 g of solvent acetone, and 2.5 g of catalyst triethylenediamine, place them in a reaction vessel, and react under UV light for 20 h to obtain solution B.

[0084] (4) Solution B was filtered, washed, and dried at 55° C. for 11 h to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate M5.

[0085] Application Example 5

[0086] 20 parts of M5 were added to 80 parts of styrene (PS), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PS composite material X5.

[0087] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 160°C, the temperature of zone two being 200°C, the temperature of zone three being 200°C, the temperature of zone four being 200°C, the temperature of zone five being 200°C, the temperature of zone six being 200°C, the head temperature being 200°C, and the screw speed being 280r / min.

[0088] Comparative Example 5

[0089] 20 parts of basic copper carbonate were added to 80 parts of styrene (PS), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for blending and extrusion to obtain a PS composite material D5.

[0090] Among them, the twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one being 160°C, the temperature of zone two being 200°C, the temperature of zone three being 200°C, the temperature of zone four being 200°C, the temperature of zone five being 200°C, the temperature of zone six being 200°C, the head temperature being 200°C, and the screw speed being 280r / min.

[0091] The performance data of the PS composite materials prepared in the above-mentioned Application Example 5 and Comparative Example 5 are shown in the following table:

[0092]

[0093] It can be seen from Table 5 that the mechanical properties of X5 are better than those of D5, which indicates that the mechanical properties of PS are better after the modified basic copper carbonate of the present invention is added.

[0094] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a filler for a high-performance thermoplastic composite material, characterized in that: The following steps are involved: S1: Weigh a certain amount of copper nitrate, potassium carbonate, and deionized water into a reaction vessel, stir and react at 70-90°C for 6-8 hours to obtain a mixed solution A; S2: Filtering, washing, and drying the mixed solution A at 30-50° C. for 4-8 hours to obtain basic copper carbonate; S3: Weigh a certain amount of basic copper carbonate, ethylene glycol dimethacrylate, lauroyl peroxide (initiator), acetone (solvent), and triethylenediamine (catalyst), place them in a reaction vessel, and react under UV light for 18-24 hours to obtain solution B; S4: Filtering solution B, washing, and drying at 40-60° C. for 10-12 hours to obtain basic copper carbonate grafted with ethylene glycol dimethacrylate, namely, modified basic copper carbonate; In S1, the mass ratio of the copper nitrate, the potassium carbonate and the deionized water is 30-40:30-36:70-90; In S3, the mass ratio of the basic copper carbonate, the ethylene glycol dimethacrylate, the initiator lauroyl peroxide, the solvent acetone, and the catalyst triethylenediamine is 30-40:12-16:0.1-0.3:60-80:0.2-0.

4.

2. Application of a filler for high-performance thermoplastic composite materials, characterized in that: The invention comprises applying the preparation method of the filler for high-performance thermoplastic composite materials according to claim 1 to thermoplastic plastic products, wherein the thermoplastic plastic comprises one of polypropylene, polybutylene terephthalate, polyethylene, polyamide 6, and styrene.

3. The use of the filler for high-performance thermoplastic composite materials according to claim 2, characterized in that: The thermoplastic plastic and the filler are melt-blended at a mass ratio of 80:20.

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