A modified polyethylene composite material, its preparation method and application in 3D printing

Abstract

The present invention discloses a modified impact-resistant filler, a modified polyethylene composite material, a preparation method thereof, and an application thereof in 3D printing. The modified impact-resistant filler is obtained by ball milling glass fiber, calcite powder, and wear-resistant auxiliaries; the wear-resistant auxiliaries are fluorocarbon surfactants and / or dodecyl bis(hydroxyethyl)methyl ammonium chloride; the weight ratio of the glass fiber to the calcite powder is 2-4:1; the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of the wear-resistant auxiliaries is 1-2:1. The modified polyethylene composite material is prepared from raw materials including the following components: polyethylene resin, polycaprolactone resin, impact-resistant filler, phosphor, compatibilizer, coupling agent; the impact-resistant filler is composed of glass fiber and calcite powder or is the modified impact-resistant filler of the present invention. The modified polyethylene composite material has luminescent properties and good impact resistance, and is particularly suitable for use as a material for 3D printing.

Description

Technical Field

[0001] The present invention belongs to the field of composite materials, and particularly relates to a modified polyethylene composite material, a preparation method thereof, and an application thereof in 3D printing. Background Art

[0002] Polyethylene is a thermoplastic resin obtained by polymerizing ethylene monomers. Due to its excellent low-temperature resistance and chemical stability, it is widely used in manufacturing films, packaging materials, containers, pipes, wires and cables, daily necessities, etc. In addition, polyethylene is also a commonly used raw material for 3D printing.

[0003] Patent document CN109721786A discloses a polyethylene composite material and a preparation method thereof. Its raw materials include: polyethylene, polycaprolactone, compatibilizer, coupling agent, inorganic nano-fillers and antioxidant; and provides a preparation method of the polyethylene composite material, including: Step 1) mixing polyethylene, polycaprolactone, compatibilizer, coupling agent, inorganic nano-fillers and antioxidant in proportion to obtain a mixture; 2) melt-extruding, cooling and pelletizing the mixture to obtain the polyethylene composite material. The polyethylene composite material has the characteristics of low melting point, low shrinkage rate, high modulus and high strength, and is particularly suitable for use as a 3D printing material. However, this material does not have a light-emitting function, and its impact resistance also needs to be further improved. Summary of the Invention

[0004] Based on this, the present invention provides a modified polyethylene composite material, which has a light-emitting property and good impact resistance, and is particularly suitable for use as a 3D printing material.

[0005] The present invention includes the following technical solutions.

[0006] On the one hand, the present invention provides a modified impact-resistant filler, which is obtained by ball-milling glass fiber, calcite powder and wear-resistant auxiliary agent;

[0007] The wear-resistant auxiliary agent is a fluorocarbon surfactant and / or dodecyldihydroxyethylmethylammonium chloride;

[0008] The weight ratio of the glass fiber to the calcite powder is 2-4:1;

[0009] The weight ratio of the total weight of the glass fiber and the calcite powder to the weight of the wear-resistant auxiliary agent is 1-2:1.

[0010] In some embodiments, the wear-resistant auxiliary agent is composed of a fluorocarbon surfactant and dodecyldihydroxyethylmethylammonium chloride with a weight ratio of 1:0.3-3.

[0011] In some of these embodiments, the wear-resistant auxiliary agent is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methyl ammonium chloride with a weight ratio of 1:0.5 to 1.5.

[0012] In some of these embodiments, the wear-resistant auxiliary agent is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methyl ammonium chloride with a weight ratio of 1:0.8 to 1.2.

[0013] In some of these embodiments, the wear-resistant auxiliary agent is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methyl ammonium chloride with a weight ratio of 1:1.

[0014] In some of these embodiments, the fluorocarbon surfactant is a non-ionic fluorocarbon surfactant.

[0015] In some of these embodiments, the fluorocarbon surfactant is a fluorocarbon surfactant with the model number Capstone TM FS-3100.

[0016] In some of these embodiments, the weight ratio of the glass fiber to the calcite powder is 2.5 to 3.5:1.

[0017] In some of these embodiments, the weight ratio of the glass fiber to the calcite powder is 3:1.

[0018] In some of these embodiments, the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of the wear-resistant auxiliary agent is 1 to 1.5:1.

[0019] In some of these embodiments, the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of the wear-resistant auxiliary agent is 1.1 to 1.3:1.

[0020] In some of these embodiments, the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of the wear-resistant auxiliary agent is 5:4.

[0021] Second aspect, the present invention provides a method for preparing the modified impact-resistant filler, comprising the following steps:

[0022] (1) Take the glass fiber and the calcite powder, mix them and add water to mix evenly to obtain a mixed material liquid;

[0023] (2) Add the ball milling auxiliary agent to the mixed material liquid, put it into a ball mill for ball milling, and dry the obtained ball milling slurry to obtain the impact-resistant filler.

[0024] In some of these embodiments, in step (1), the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of water is 1:2 to 5.

[0025] In some of these embodiments, the weight ratio of the total weight of glass fiber and calcite powder to the weight of water in step (1) is 1:2.5 to 3.5.

[0026] In some of these embodiments, the weight ratio of the total weight of glass fiber and calcite powder to the weight of water in step (1) is 1:3.

[0027] In some of these embodiments, the time for ball milling in step (2) is 1 to 2 h.

[0028] In a third aspect, the present invention provides a modified polyethylene composite material, which is prepared from raw materials comprising the following components in parts by weight:

[0029]

[0030] The impact-resistant filler is composed of glass fiber and calcite powder with a mass ratio of 2 to 4:1; or the impact-resistant filler is the modified impact-resistant filler of the present invention.

[0031] In some of these embodiments, the modified polyethylene composite material is prepared from raw materials comprising the following components in parts by weight:

[0032]

[0033] In some of these embodiments, the modified polyethylene composite material is prepared from raw materials comprising the following components in parts by weight:

[0034]

[0035] In some of these embodiments, the modified polyethylene composite material is prepared from raw materials comprising the following components in parts by weight:

[0036]

[0037] In some of these embodiments, the weight ratio of the glass fiber to the calcite powder is 2.5 to 3.5:1.

[0038] In some of these embodiments, the weight ratio of the glass fiber to the calcite powder is 3:1.

[0039] In some of these embodiments, the compatibilizer is maleic anhydride grafted polyethylene.

[0040] In some of these embodiments, the coupling agent is coupling agent KH-560.

[0041] In a fourth aspect, the present invention provides a preparation method of the modified polyethylene composite material, comprising the following steps:

[0042] After uniformly mixing the polyethylene resin, polycaprolactone resin, impact-resistant filler, phosphor, compatibilizer, and coupling agent, put them into a twin-screw extruder for melt extrusion to obtain the modified polyethylene composite material.

[0043] In some embodiments, the temperature of the melt extrusion is 160°C - 200°C, preferably 170°C - 190°C.

[0044] In a fifth aspect, the present invention also provides the application of the above-mentioned modified polyethylene composite material in the preparation of 3D printed articles.

[0045] By adding phosphor to the modified polyethylene composite material, the articles prepared after 3D printing using the obtained modified polyethylene composite material can have luminescent properties. In addition, by adding an impact-resistant filler composed of glass fiber and calcite powder, the obtained modified polyethylene composite material can also have good impact resistance.

[0046] The inventors further found in the research that adding a modified impact-resistant filler obtained by ball-milling modification of glass fiber and calcite powder with the ball-milling aid described in the present invention to the modified polyethylene composite material can further significantly improve the impact resistance of the modified polyethylene composite material compared to adding an unmodified impact-resistant filler composed of glass fiber and calcite powder; and it was found that the ball-milling aid of the present invention is very crucial. Only the modified impact-resistant filler prepared with a ball-milling aid composed of a fluorocarbon surfactant and dodecyldihydroxyethylmethylammonium chloride can further significantly improve the impact resistance of the modified polyethylene composite material; the modified impact-resistant filler prepared with only a single fluorocarbon surfactant or a single dodecyldihydroxyethylmethylammonium chloride as the ball-milling aid cannot further significantly improve the impact resistance of the modified polyethylene composite material. Detailed Embodiments

[0047] The technical solutions of the present invention will be further described below through specific examples. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0048] Unless otherwise defined, all technical and scientific terms used in the present invention 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 description of the present invention are only for the purpose of describing specific embodiments and are not used to limit the present invention.

[0049] The term "comprising" and "having" and any variations thereof in the present invention are intended to cover non-exclusive inclusion. For example, a process, method, device, product or equipment that includes a series of steps is not limited to the listed steps or modules, but optionally further includes steps not listed, or optionally further includes other steps inherent to these processes, methods, products or equipment.

[0050] The "plurality" mentioned in the present invention refers to two or more. "And / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. The character " / " generally represents an "or" relationship between the associated objects before and after.

[0051] The raw materials used in the following examples are described as follows: The polyethylene resin used is the polyethylene resin with the grade of 1C7A from Sinopec Yanshan Company; the polycaprolactone resin used is the polycaprolactone resin with the grade of 6800 from Solvay of the United States; the fluorocarbon surfactant used is the fluorocarbon surfactant of Capstone TM FS-3100 from Chemours; the glass fiber used is 200-mesh glass fiber powder; the fluorescent powder used is the ultraviolet anti-counterfeiting fluorescent powder (blue light) with the product number of ZB92 from Chenlai Company, the compatibilizer is maleic anhydride grafted polyethylene; the coupling agent is coupling agent KH-560.

[0052] The remaining raw materials without specified sources are conventional raw materials that can be obtained by those skilled in the art through regular purchase channels.

[0053] The following are specific examples.

[0054] Example 1 Preparation of Modified Polyethylene Composite

[0055] The raw material composition of the modified polyethylene composite provided in this example is as follows (by weight):

[0056]

[0057] Among them, the impact-resistant filler is composed of glass fiber and calcite powder with a weight ratio of 3:1.

[0058] The preparation method of the modified polyethylene composite provided in this example is as follows: After uniformly mixing the polyethylene resin, polycaprolactone resin, impact-resistant filler, fluorescent powder, compatibilizer and coupling agent, put them into a twin-screw extruder and melt-extrude at 180 °C to obtain the modified polyethylene composite.

[0059] Example 2 Preparation of Modified Polyethylene Composite

[0060] The raw material composition of the modified polyethylene composite provided in this embodiment is as follows (in parts by weight):

[0061]

[0062] The impact-resistant filler is a modified impact-resistant filler, and the modified impact-resistant filler is prepared by the following method:

[0063] (1) Take glass fiber and calcite powder, mix them and then add them to water and mix evenly to obtain a mixed material liquid; among them, the weight ratio of glass fiber to calcite powder is 3:1; the total weight of glass fiber and calcite powder to the weight of water is 1:3;

[0064] (2) Add a ball milling aid to the mixed material liquid, put it into a ball mill and ball mill for 1.5 h to obtain a ball mill slurry, and dry the ball mill slurry to obtain the modified impact-resistant filler; among them, the weight ratio of the mixed material liquid to the ball milling aid is 10:2 (that is, the total weight of glass fiber and calcite powder to the weight of the ball milling aid is 2.5:2); the ball milling aid is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methyl ammonium chloride with a weight ratio of 1:1.

[0065] The preparation method of the modified polyethylene composite provided in this embodiment is as follows: Mix the polyethylene resin, polycaprolactone resin, impact-resistant filler, fluorescent powder, compatibilizer and coupling agent evenly, then put them into a twin-screw extruder and melt-extrude at 180 °C to obtain the modified polyethylene composite.

[0066] Preparation of the Modified Polyethylene Composite in Example 3

[0067] The raw material composition of the modified polyethylene composite provided in this embodiment is as follows (in parts by weight):

[0068]

[0069] The impact-resistant filler is a modified impact-resistant filler, and the modified impact-resistant filler is prepared by the following method:

[0070] (1) Take glass fiber and calcite powder, mix them and then add them to water and mix evenly to obtain a mixed material liquid; among them, the weight ratio of glass fiber to calcite powder is 3:1; the total weight of glass fiber and calcite powder to the weight of water is 1:3;

[0071] (2) Add a ball milling aid to the mixed material liquid, put it into a ball mill and ball mill for 1.5 h to obtain a ball mill slurry, and dry the ball mill slurry to obtain the modified impact-resistant filler; among them, the weight ratio of the mixed material liquid to the ball milling aid is 10:2; the ball milling aid is a fluorocarbon surfactant.

[0072] The preparation method of the modified polyethylene composite provided in this embodiment is as follows: Mix polyethylene resin, polycaprolactone resin, impact-resistant filler, phosphor, compatibilizer, and coupling agent evenly, and then put them into a twin-screw extruder and melt-extrude at 180 °C to obtain the modified polyethylene composite.

[0073] Preparation of the Modified Polyethylene Composite in Example 4

[0074] The raw material composition of the modified polyethylene composite provided in this embodiment is as follows (by weight):

[0075]

[0076] The impact-resistant filler is a modified impact-resistant filler, and the modified impact-resistant filler is prepared by the following method:

[0077] (1) Take glass fiber and calcite powder, mix them and add them to water to mix evenly to obtain a mixed slurry; among them, the weight ratio of glass fiber to calcite powder is 3:1; the total weight of glass fiber and calcite powder to the weight of water is 1:3;

[0078] (2) Add a ball milling aid to the mixed slurry, put it into a ball mill and ball mill for 1.5 h to obtain a ball mill slurry, and dry the ball mill slurry to obtain the modified impact-resistant filler; among them, the weight ratio of the mixed slurry to the ball milling aid is 10:2; the ball milling aid is dodecyl bis(hydroxyethyl)methyl ammonium chloride;

[0079] The preparation method of the modified polyethylene composite provided in this embodiment is as follows: Mix polyethylene resin, polycaprolactone resin, impact-resistant filler, phosphor, compatibilizer, and coupling agent evenly, and then put them into a twin-screw extruder and melt-extrude at 180 °C to obtain the modified polyethylene composite.

[0080] Print the modified polyethylene composites prepared in Examples 1-4 into splines using a 3D printer, and refer to the method in GB / T 1043.1-2008 to test their impact strength using the simply supported cantilever beam method. The test results are shown in Table 1.

[0081] Table 1. Impact Strength of the Modified Polyethylene Composite

[0082] Spline Impact strength Modified polyethylene composite material prepared in Example 1 <![CDATA[23.5KJ / m 2 > Modified polyethylene composite material prepared in Example 2 <![CDATA[41.3KJ / m 2 > Modified polyethylene composite material prepared in Example 3 <![CDATA[27.6KJ / m 2 > Modified polyethylene composite material prepared in Example 4 <![CDATA[29.1KJ / m 2 >

[0083] It can be seen from the experimental results in Table 1 that the impact strength of the modified polyethylene composite prepared in Example 1 reached 23.5 KJ / m 2 ; This shows that: by adding an impact-resistant filler composed of glass fiber and calcite powder, the modified polyethylene composite of the present invention can have better impact resistance.

[0084] As can be seen from the experimental results in Table 1, the impact strength of the modified polyethylene composite prepared in Example 2 is much higher than that of the modified polyethylene composite prepared in Example 1. This shows that adding the modified impact-resistant filler obtained by modifying glass fiber and calcite powder by the method described in the present invention to the modified polyethylene composite can further significantly improve the impact resistance of the modified polyethylene composite compared with adding the unmodified impact-resistant filler composed of glass fiber and calcite powder.

[0085] As can be seen from the experimental results in Table 1, compared with the modified polyethylene composite prepared in Example 1, the impact strength of the modified polyethylene composites prepared in Examples 3 and 4 has increased, but the increase is not significant, and the increase amplitude is much smaller than that in Example 2. This shows that the ball milling aid of the present invention is very crucial. Only by using the modified impact-resistant filler prepared with the ball milling aid composed of fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methyl ammonium chloride can the impact resistance of the modified polyethylene composite be significantly improved. However, using only a single fluorocarbon surfactant or a single dodecyl bis(hydroxyethyl)methyl ammonium chloride as the ball milling aid to prepare the modified impact-resistant filler cannot significantly improve the impact resistance of the modified polyethylene composite.

[0086] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0087] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent should be subject to the appended claims.

Claims

1. A modified impact-resistant filler, characterized in that: It is obtained by ball milling glass fiber, calcite powder and wear-resistant additives; The wear-resistant additive is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methylammonium chloride in a weight ratio of 1:0.3-3; the fluorocarbon surfactant is a nonionic fluorocarbon surfactant; The weight ratio of the glass fiber to the calcite powder is 2-4:1; The weight ratio of the total weight of the glass fiber and the calcite powder to the wear-resistant additive is 1-2:

1.

2. The modified impact-resistant filler according to claim 1, characterized in that: The weight ratio of the glass fiber to the calcite powder is 2.5-3.5:1; and / or, The weight ratio of the total weight of the glass fiber and the calcite powder to the wear-resistant additive is 1-1.5:

1.

3. The modified impact-resistant filler according to claim 1, characterized in that: The wear-resistant additive is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methylammonium chloride in a weight ratio of 1:0.5-1.5; and / or, The fluorocarbon surfactant is a fluorocarbon surfactant of model Capstone™ FS-3100; and / or, The weight ratio of the glass fiber to the calcite powder is 3:1; and / or, The weight ratio of the total weight of the glass fiber and the calcite powder to the wear-resistant additive is 1.1-1.3:

1.

4. The modified impact-resistant filler according to claim 3, characterized in that: The wear-resistant additive is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methylammonium chloride in a weight ratio of 1:0.8-1.

2.

5. The modified impact-resistant filler according to claim 4, characterized in that: The wear-resistant additive is composed of a fluorocarbon surfactant and dodecyl bis(hydroxyethyl)methylammonium chloride in a weight ratio of 1:

1.

6. The modified impact-resistant filler according to claim 3, characterized in that: The weight ratio of the total weight of the glass fiber and the calcite powder to the wear-resistant additive is 5:

4.

7. A method for preparing the modified impact-resistant filler according to any one of claims 1 to 6, characterized in that: The steps include: (1) mixing the glass fiber and calcite powder, adding them into water and mixing them evenly to obtain a mixed liquid; (2) Adding the ball milling aid to the mixed liquid, placing the mixed liquid in a ball mill for ball milling, and drying the obtained ball milled slurry to obtain the impact-resistant filler.

8. The method for preparing the modified impact-resistant filler according to claim 7, characterized in that: In step (1), the weight ratio of the total weight of the glass fiber and the calcite powder to the water is 1:2-5; and / or, The ball milling time in step (2) is 1 to 2 hours.

9. The method for preparing the modified impact-resistant filler according to claim 8, characterized in that: In step (1), the weight ratio of the total weight of the glass fiber and the calcite powder to the water is 1:2.5-3.

5.

10. The method for preparing the modified impact-resistant filler according to claim 9, characterized in that: In step (1), the weight ratio of the total weight of the glass fiber and the calcite powder to the weight of water is 1:

3.

11. A modified polyethylene composite material, characterized in that: The composition is prepared from the following raw materials by weight: 60-80 parts of polyethylene resin; 20-40 parts of polycaprolactone resin; 5~15 parts of impact-resistant filler; 1~5 parts of phosphor; 1~3 parts of compatibilizer; 1~5 parts of coupling agent; The impact-resistant filler is the modified impact-resistant filler according to any one of claims 1 to 6.

12. The modified polyethylene composite material according to claim 11, characterized in that: The modified polyethylene composite material is prepared from raw materials including the following components in parts by weight: 70-80 parts of polyethylene resin; 20-30 parts of polycaprolactone resin; 10~14 parts of impact-resistant filler; 2~4 parts of phosphor; 1~2 parts of compatibilizer; 1~3 parts of coupling agent.

13. The modified polyethylene composite material according to claim 12, characterized in that: The modified polyethylene composite material is prepared from raw materials including the following components in parts by weight: 74-76 parts of polyethylene resin; 24-26 parts of polycaprolactone resin; 11-13 parts of impact-resistant filler; 2~4 parts of phosphor; 1~2 parts of compatibilizer; 1~3 parts of coupling agent.

14. The modified polyethylene composite material according to claim 13, characterized in that: The modified polyethylene composite material is prepared from raw materials including the following components in parts by weight: 75 parts of polyethylene resin; 25 parts of polycaprolactone resin; 12 parts of impact-resistant filler; 3 parts of phosphor; 2 parts of compatibilizer; 3 parts of coupling agent.

15. The modified polyethylene composite material according to any one of claims 11 to 14, characterized in that: The weight ratio of the glass fiber to the calcite powder is 2.5-3.5:1; The compatibilizer is maleic anhydride grafted polyethylene; The coupling agent is coupling agent KH-560.

16. A method for preparing the modified polyethylene composite material according to any one of claims 11 to 15, characterized in that: The steps include: The polyethylene resin, polycaprolactone resin, impact-resistant filler, fluorescent powder, compatibilizer and coupling agent are uniformly mixed and then put into a twin-screw extruder for melt extrusion to obtain the modified polyethylene composite material.

17. Use of the modified polyethylene composite material according to any one of claims 11 to 15 in the preparation of 3D printed products.

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