UHMWPE / PLA plastic 3D printing consumable and preparation method thereof

Abstract

The invention particularly relates to a UHMWPE / PLA plastic 3D printing consumable and a preparation method thereof. The 3D printing consumable is prepared from the following raw materials in parts by weight: 35 to 55 parts of UHMWPE, 25 to 45 parts of PLA, 6 to 13 parts of PBT, 2 to 6 parts of CBT resin, 4 to 8 parts of compatilizer, 2 to 5 parts of molybdenum disulfide micro powder, 2 to 5 parts of epoxy resin, 0.5 to 3 parts of coupling agent and 0.5 to 5 parts of functional additive. Through a specific raw material ratio and a preparation process, the prepared 3D printing consumable has excellent mechanical strength, friction resistance and processability, and can be widely applied to industrial wear-resistant parts such as guide rails and sliding blocks; the raw materials adopted by the invention are environment-friendly materials and meet the green and environment-friendly requirements; the preparation method is simple in process, easy to operate and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials and its forming processing technology, in particular to a kind of UHMWPE / PLA plastic 3D printing consumables and preparation method thereof. BACKGROUND

[0002] 3D printing technology is a kind of rapid prototyping technology using layer-by-layer principle, through computer modeling of the object to be printed, then the three-dimensional model is divided into layers, and then the physical object is printed layer by layer by the printer. Among them, the fused deposition modeling method (FDM) is the most important forming method of 3D printing thermoplastic parts. The basic requirement of FDM technology for thermoplastic materials is that it has a certain fluidity during processing, and can quickly solidify after forming, and has good bonding effect. The thermoplastic parts that can be applied to FDM forming process at present include modified ABS, PA and other raw materials, but these materials still need to be improved in performance or environmental protection. UHMWPE is a kind of high polymer material with good impact resistance and friction resistance, but its processing fluidity is poor, which limits its application in the field of 3D printing. Therefore, by modifying and compounding UHMWPE, a 3D printing consumable with excellent performance is prepared, which has good market application prospect. SUMMARY

[0003] The purpose of the present application is to provide a kind of UHMWPE / PLA plastic 3D printing consumables and preparation method thereof to solve the above-mentioned problems of prior art, the 3D printing consumable has excellent mechanical strength, friction resistance and processing performance;The preparation method is simple in process and easy to operate, and is suitable for industrial production.

[0004] The purpose of the present application is achieved by the following technical scheme: a kind of UHMWPE / PLA plastic 3D printing consumables, including the following weight parts of raw materials: UHMWPE 35-55 parts, PLA 25-45 parts, PBT 6-13 parts, CBT resin 2-6 parts, compatible agent 4-8 parts, molybdenum disulfide micro powder 2-5 parts, epoxy resin 2-5 parts, coupling agent 0.5-3 parts, inorganic filler 0.2-3 parts, functional additive 0.5-5 parts.

[0005] Further, the average molecular weight of the UHMWPE is 1.8-3 million.

[0006] Further, the compatible agent is at least one of PP-g-MAH and PE-g-MAH.

[0007] Further, the coupling agent is at least one of silane coupling agent and titanate coupling agent.

[0008] Further, the silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma-mercaptopropyl trimethoxysilane.

[0009] Further, the titanate coupling agent is at least one of isopropyl triisostearyl oxyl titanate, isopropyl tri(dioctyl phosphoric acyl oxy) titanate and isopropyl tri(dioctyl pyrophosphoric acyl oxy) titanate.

[0010] Further, the inorganic filler is at least one of talcum powder, calcium carbonate, nano-alumina and nano-silica.

[0011] Further, the functional auxiliary agent is at least one of lubricant and antioxidant.

[0012] Further, the functional auxiliary agent includes 0.5-3 parts of lubricant and 0.2-2 parts of antioxidant.

[0013] Further, the lubricant is at least one of natural paraffin wax, liquid paraffin wax, microcrystalline paraffin wax and polyethylene wax.

[0014] Further, the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant.

[0015] The application also provides a preparation method of the UHMWPE / PLA plastic 3D printing consumable.

[0016] (1) raw material mixing: the raw materials are proportionally placed in a mixer and uniformly dispersed to obtain a mixture;

[0017] (2) mixing and granulation: the mixture obtained in step (1) is added to a granulator for mixing and extrusion granulation to obtain granules;

[0018] (3) drying treatment: the granules obtained in step (2) are placed in a dryer and dried at a temperature of 60-80℃ for 90-150min to reduce the water content to below 0.5%;

[0019] (4) extrusion of consumable: the granules dried in step (3) are added to an extruder for extrusion molding; the extruded filaments are cooled by pulling through a water tank and then wound into a finished product by a winding machine.

[0020] The UHMWPE / PLA plastic 3D printing consumables of the present application are prepared by using specific raw material ratio and preparation process, UHMWPE (ultra-high molecular weight polyethylene) is matched with PLA, PBT and CBT resin as main material, and is matched with compatilizer and epoxy resin, so that the raw materials are well compatible, CBT resin can form a co-crystalline network with PBT through ring-opening polymerization, and has low viscosity characteristics, which helps to improve the processing performance and mechanical properties of the UHMWPE / PLA plastic 3D printing consumables, and the addition of molybdenum disulfide powder, coupling agent and functional additives, the synergistic effect of the raw materials can give the 3D printing consumables good mechanical strength, friction resistance and processing performance. The raw materials used in the present application are environmentally friendly materials, and there is no pollution emission in the preparation process, which meets the green environmental protection requirements.

[0021] Further, in step (1), the molybdenum disulfide powder, inorganic filler and coupling agent are added to anhydrous ethanol and stirred for 20-60 min, the amount of anhydrous ethanol added is 1.5-3 times the sum of the mass of molybdenum disulfide powder, inorganic filler and coupling agent, and the anhydrous ethanol is removed by heating to obtain a premix; the premix is then mixed with other raw materials of the 3D printing consumables in a mixer.

[0022] Further, in step (2), the die temperature for extrusion and granulation is 175-200℃.

[0023] Further, in step (4), the extruder is a double-screw extruder, and the heating temperatures of each zone of the extruder are as follows: zone 1, 175-190℃; zone 2, 185-195℃; zone 3, 180-195℃; and zone 4, 165-175℃.

[0024] The present application has the following advantages: the 3D printing consumables prepared by using specific raw material ratio in the present application have excellent mechanical strength, friction resistance, dimensional stability and processing performance, and can be widely used in industrial wear-resistant parts such as guide rails, sliding blocks, etc.; the raw materials used in the present application are environmentally friendly materials, and the preparation process reduces pollution emissions, meeting the green environmental protection requirements; the preparation method of the present application is simple and easy to operate, and is suitable for industrial production. DETAILED DESCRIPTION

[0025] In order to facilitate the understanding of those skilled in the art, the present application will be further described below in conjunction with examples, and the content mentioned in the embodiments is not a limitation of the present application.

[0026] The UHMWPE / PLA plastic 3D printing consumables in some embodiments of the present application comprise the following raw materials: UHMWPE 35-55 parts, PLA 25-45 parts, PBT 6-13 parts, CBT resin 2-6 parts, compatibilizer 4-8 parts, molybdenum disulfide micro powder 2-5 parts, epoxy resin 2-5 parts, coupling agent 0.5-3 parts, inorganic filler 0.2-3 parts, and functional additive 0.5-5 parts.

[0027] In some embodiments of the present application, the average molecular weight of the UHMWPE is 1.8-3 million. The particle size of the molybdenum disulfide micro powder is 50-100 nm.

[0028] In some embodiments of the present application, the compatibilizer is at least one of PP-g-MAH and PE-g-MAH.

[0029] In some embodiments of the present application, the epoxy resin is at least one of bisphenol A type epoxy resin E-51 and bisphenol A type epoxy resin E-44.

[0030] In some embodiments of the present application, the coupling agent is at least one of silane coupling agent and titanate coupling agent.

[0031] In some embodiments of the present application, the silane coupling agent is at least one of γ-aminopropyl triethoxysilane, γ-glycidyl ether propyl trimethoxysilane, and γ-mercaptopropyl trimethoxysilane.

[0032] In some embodiments of the present application, the titanate coupling agent is at least one of isopropyl triisostearyl titanate, isopropyl tri(dioctyl phosphoric acyloxy) titanate, and isopropyl tri(dioctyl pyrophosphoric acyloxy) titanate.

[0033] In some embodiments of the present application, the inorganic filler is at least one of talc, calcium carbonate, nano-alumina, and nano-silica. The particle size of the talc and calcium carbonate is 1-3 μm. The particle size of the nano-alumina and nano-silica is 50-100 nm.

[0034] In some embodiments of the present application, the functional additive comprises lubricant 0.5-3 parts and antioxidant 0.2-2 parts.

[0035] In some embodiments of the present application, the lubricant is at least one of natural paraffin wax, liquid paraffin wax, microcrystalline paraffin wax, and polyethylene wax.

[0036] In some embodiments of the present application, the antioxidant is at least one of hindered phenolic antioxidant and phosphite antioxidant.

[0037] In some embodiments of the present application, the preparation method of the UHMWPE / PLA plastic 3D printing consumables comprises the following steps:

[0038] (1) Raw material mixing: proportionally place each raw material in a mixer and mix for 20-90 min until evenly dispersed to obtain a mixture;

[0039] (2) Mixing and granulation: add the mixture obtained in step (1) to a granulator for mixing and extrusion granulation to obtain granules; the die temperature for extrusion granulation is 175-200℃.

[0040] (3) Drying treatment: place the granules obtained in step (2) in a dryer and dry at a temperature of 60-80℃ for 90-150 min to reduce the water content to below 0.5%;

[0041] (4) Extrusion of consumables: add the dried granules in step (3) to a twin-screw extruder for extrusion molding; the heating temperatures of each zone of the extruder are: zone 1 175-190℃, zone 2 190-205℃, zone 3 185-200℃, and zone 4 165-180℃; the extruded filaments are cooled by pulling through a water tank and then wound into a finished product by a winding machine.

[0042] Further, in step (1), the molybdenum disulfide powder, inorganic filler, and coupling agent are added to anhydrous ethanol and stirred for 20-60 min; the amount of anhydrous ethanol added is 1.5-3 times the total mass of the molybdenum disulfide powder, inorganic filler, and coupling agent; the anhydrous ethanol is removed by heating to obtain a premix; the premix is then mixed uniformly with other raw materials of the 3D printing consumables.

[0043] Example 1

[0044] In this embodiment, a UHMWPE / PLA plastic 3D printing consumable comprises the following raw materials by weight: UHMWPE 53 parts, PLA 35 parts, PBT 8 parts, CBT resin 3 parts, compatibilizer 6 parts, molybdenum disulfide powder 3 parts, epoxy resin 2 parts, coupling agent 2 parts, inorganic filler 2 parts, and functional additive 3 parts. The UHMWPE used is Mitsui Chemical UHMWPE PM-20. The PLA used is Zhejiang Haizheng Biopolymer Lactic Acid REVODE110. The PBT used is Langsheng PBT PB3225 GY. The CBT resin used is Shanghai Chengzai Chemical CBT100.

[0045] In this embodiment, the compatibilizer is PP-g-MAH and PE-g-MAH in a mass ratio of 1:1. The PP-g-MAH is DuPont Komo 50E803 PP-g-MAH. The PE-g-MAH is Japan Mitsui Chemical ADMER NFQF554. The epoxy resin is bisphenol A type epoxy resin E-51, which is Baling Petrochemical Epoxy Resin E-51 CYD-128.

[0046] Further, the coupling agent is γ-aminopropyl triethoxysilane and isopropyl triisostearyl titanate in a mass ratio of 3:2. The inorganic filler is composed of talc powder and nano aluminum oxide in a mass ratio of 2:1.

[0047] Further, the functional auxiliary agent includes 1.5 parts of polyethylene wax and 1.5 parts of antioxidant. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 3:1.

[0048] In this embodiment, the preparation method of the UHMWPE / PLA plastic 3D printing consumables includes the following steps:

[0049] (1) Raw material mixing: the raw materials are placed in a mixer in proportion, mixed for 30 min to disperse uniformly, and a mixture is obtained. The molybdenum disulfide powder, inorganic filler and coupling agent are pre-mixed uniformly to obtain a pre-mixture, which is then mixed uniformly with other raw materials;

[0050] (2) Mixing and granulation: the mixture obtained in step (1) is added to a double-screw granulator for mixing and extrusion granulation to obtain granules. The die temperature of the extrusion granulation is 195°C.

[0051] (3) Drying treatment: the granules obtained in step (2) are placed in a dryer and dried at a temperature of 80°C for 120 min, so that the water content is reduced to below 0.5%.

[0052] (4) Extrusion of consumables: the granules dried in step (3) are added to a double-screw extruder for extrusion molding. The heating temperatures of each zone of the extruder are as follows: Zone 1 180°C, Zone 2 200°C, Zone 3 195°C, Zone 4 170°C. The extruded wire is cooled by pulling through a water tank and then wound into a finished product by a winding machine. The diameter of the consumable wire is 1.75±0.05 mm.

[0053] Further, in step (1), the molybdenum disulfide powder, inorganic filler and coupling agent are added to anhydrous ethanol and stirred for 30 min. The amount of anhydrous ethanol added is 2 times the sum of the mass of the molybdenum disulfide powder, inorganic filler and coupling agent. The anhydrous ethanol is removed by heating to obtain a pre-mixture. The pre-mixture is then mixed uniformly with other raw materials of the 3D printing consumables.

[0054] Embodiment 2

[0055] In this embodiment, the UHMWPE / PLA plastic 3D printing consumables include the following raw materials: UHMWPE 50 parts, PLA 38 parts, PBT 6 parts, CBT resin 3 parts, compatibilizer 6 parts, molybdenum disulfide micro powder 3 parts, epoxy resin 4 parts, coupling agent 2 parts, inorganic filler 2 parts, functional additive 3 parts.

[0056] Further, the coupling agent is γ-aminopropyl triethoxysilane. The inorganic filler is composed of talc powder and nano-alumina in a mass ratio of 2:1. The compatibilizer is PP-g-MAH.

[0057] In this embodiment, the preparation method of the UHMWPE / PLA plastic 3D printing consumables includes the following steps:

[0058] (1) Raw material mixing: place the raw materials in the proportioning machine, mix for 30 min to disperse uniformly, and obtain a mixture; wherein, the molybdenum disulfide micro powder, inorganic filler and coupling agent are pre-mixed uniformly to obtain a pre-mixture, and then mixed uniformly with other raw materials;

[0059] (2) Mixing and granulation: add the mixture obtained in step (1) to a double-screw granulator for mixing and extrusion granulation to obtain granules; the die temperature of the extrusion granulation is 200℃;

[0060] (3) Drying treatment: place the granules obtained in step (2) in a drying machine and dry at a temperature of 80℃ for 120 min to reduce the water content to below 0.5%;

[0061] (4) Extrusion consumables: add the granules dried in step (3) to a double-screw extruder for extrusion molding; the heating temperature of each zone of the extruder is respectively: zone 1 180℃, zone 2 200℃, zone 3 195℃, zone 4 170℃; the extruded wire is cooled by pulling through a water tank and then wound into a finished product by a winding machine.

[0062] Further, in step (1), the molybdenum disulfide micro powder, inorganic filler and coupling agent are added to anhydrous ethanol and stirred for 40 min, the amount of anhydrous ethanol added is 3 times the sum of the mass of molybdenum disulfide micro powder, inorganic filler and coupling agent, heated to remove anhydrous ethanol to obtain a pre-mixture; the pre-mixture is then mixed uniformly with other raw materials of the 3D printing consumables. The remaining contents of this embodiment are the same as those of embodiment 1.

[0063] Embodiment 3

[0064] The UHMWPE / PLA plastic 3D printing consumables in the embodiment include the following raw materials in parts by weight: UHMWPE 55 parts, PLA 33 parts, PBT 9 parts, CBT resin 4 parts, compatibilizer 6 parts, molybdenum disulfide micro powder 3 parts, epoxy resin 3 parts, coupling agent 2 parts, inorganic filler 2 parts, and functional additive 3 parts.

[0065] Further, the coupling agent is composed of γ-aminopropyl triethoxysilane and isopropyl triisostearyl titanate in a mass ratio of 3:2. The inorganic filler is composed of talcum powder and nano aluminum oxide in a mass ratio of 2:1.

[0066] In the embodiment, the preparation method of the UHMWPE / PLA plastic 3D printing consumables includes the following steps:

[0067] (1) Raw material mixing: the raw materials are placed in a mixer in proportion, mixed for 30 min to be uniformly dispersed to obtain a mixture; the molybdenum disulfide micro powder, inorganic filler, and coupling agent are pre-mixed uniformly to obtain a pre-mixture, which is then mixed uniformly with other raw materials;

[0068] (2) Mixing and granulation: the mixture obtained in step (1) is added to a double-screw granulator for mixing and extrusion granulation to obtain granules; the die temperature of the extrusion granulation is 195°C;

[0069] (3) Drying treatment: the granules obtained in step (2) are placed in a dryer and dried at a temperature of 80°C for 120 min to reduce the water content to below 0.5%;

[0070] (4) Extrusion of consumables: the granules dried in step (3) are added to a double-screw extruder for extrusion molding; the heating temperatures of the zones of the extruder are respectively: zone 1 180°C, zone 2 200°C, zone 3 190°C, and zone 4 175°C; the extruded filaments are cooled by being pulled through a water tank and then wound into a winding machine to form finished products.

[0071] Further, in step (1), the molybdenum disulfide micro powder, inorganic filler, and coupling agent are added to anhydrous ethanol and stirred for 30 min; the amount of anhydrous ethanol added is 2.5 times the sum of the mass of the molybdenum disulfide micro powder, inorganic filler, and coupling agent; the anhydrous ethanol is removed by heating to obtain a pre-mixture; the pre-mixture is then mixed uniformly with other raw materials of the 3D printing consumables. The remaining contents of the embodiment are the same as those of embodiment 1.

[0072] Comparative example 1

[0073] The difference between the present comparative example and embodiment 1 is that the UHMWPE / PLA plastic 3D printing consumables in the present comparative example do not contain a compatibilizer, and an equal amount of UHMWPE is used instead. The remaining contents of the present comparative example are the same as those of embodiment 1.

[0074] Comparative Example 2

[0075] The difference between the present comparative example and Example 1 is that the UHMWPE / PLA plastic 3D printing consumables in the present comparative example do not contain molybdenum disulfide micro powder, and an equal amount of UHMWPE is used instead. The rest of the content of the present example is the same as that of Example 1.

[0076] Comparative Example 3

[0077] The difference between the present comparative example and Example 1 is that the UHMWPE / PLA plastic 3D printing consumables in the present comparative example do not contain epoxy resin, and an equal amount of UHMWPE is used instead. The rest of the content of the present example is the same as that of Example 1.

[0078] Comparative Example 4

[0079] The difference between the present comparative example and Example 1 is that the UHMWPE / PLA plastic 3D printing consumables in the present comparative example do not contain CBT resin, and an equal amount of PBT is used instead. The rest of the content of the present example is the same as that of Example 1.

[0080] The 3D printing consumables prepared in Example 1 and Comparative Examples 1-3 are used for 3D printing to prepare 3D printing samples. The samples prepared in Example 1 and Comparative Examples 1-3 are tested for performance, and the data test results are shown in Table 1 below:

[0081]

[0082] The melt index is tested in accordance with GB / T 3682-2000, and the test conditions are 190℃ / 2.16kg. The tensile strength and Charpy impact strength are tested in accordance with GB / T 21461.2-2023. The wear rate is tested in accordance with GBT 3960-2016. The test method for molding shrinkage is as follows: the 3D printing consumables are printed into a sample with a size of 20*20*20mm under the condition of 23℃ / 50%RH, using a 100% filling rate, a layer thickness of 0.2mm, a printing speed of 50mm / s, and a hot bed temperature of 60℃. After printing, the sample is placed for 72h, and the X, Y and Z direction sizes are measured, and the maximum value of the shrinkage in each direction is taken as the final value. The heat distortion temperature is tested in accordance with GB / T 1634.2-2019, and the sample size is 80*10*4*mm, and the test condition is 0.45MPa. The heat distortion temperature of Example 1 is 83℃, which can meet the requirements of 3D printing. The 3D printing samples of the present application can be set to the corresponding size according to the specific provisions of the test method of each performance parameter.

[0083] To sum up, the UHMWPE / PLA plastic 3D printing consumables of the present application realizes good compatibility of each raw material, synergistic effect by matching UHMWPE, PLA, PBT, CBT resin, compatibilizer and epoxy resin and adding molybdenum disulfide powder, coupling agent and functional additives, so that the 3D printing consumables have high mechanical strength, low wear rate, good processing performance and good thermal stability.

[0084] The above specific embodiments are further illustrations of the technical solutions and beneficial effects of the present application, and are not limitations on the embodiments. Any obvious replacement without departing from the concept of the present application is within the protection scope of the present application.

Claims

1. A UHMWPE / PLA plastic 3D printing consumable, characterized in that: The raw materials include the following components by weight: UHMWPE 35-55 parts, PLA 25-45 parts, PBT 6-13 parts, CBT resin 2-6 parts, compatibilizer 4-8 parts, molybdenum disulfide powder 2-5 parts, epoxy resin 2-5 parts, coupling agent 0.5-3 parts, inorganic filler 0.2-3 parts, functional additive 0.5-5 parts.

2. The UHMWPE / PLA plastic 3D printing consumable according to claim 1, characterized in that: The compatibilizer is at least one of PP-g-MAH and PE-g-MAH.

3. The UHMWPE / PLA plastic 3D printing consumable according to claim 1, characterized in that: The coupling agent is at least one of silane coupling agent and titanate coupling agent.

4. The UHMWPE / PLA plastic 3D printing consumable according to claim 1, characterized in that: The inorganic filler is at least one of talcum powder, calcium carbonate, nano-alumina and nano-silica.

5. The UHMWPE / PLA plastic 3D printing consumable according to claim 1, characterized in that: The functional additive is at least one of lubricant and antioxidant.

6. The UHMWPE / PLA plastic 3D printing consumable according to claim 5, characterized in that: The lubricant is at least one of natural paraffin wax, liquid paraffin wax, microcrystalline paraffin wax and polyethylene wax.

7. The UHMWPE / PLA plastic 3D printing consumable according to claim 5, characterized in that: The antioxidant is at least one of hindered phenolic antioxidant and phosphite antioxidant.

8. The method for preparing UHMWPE / PLA plastic 3D printing consumables as described in any one of claims 1-7, characterized in that: The method comprises the following steps: (1) raw material mixing: proportionally placing each raw material in a mixer to disperse uniformly to obtain a mixture; (2) mixing and granulation: adding the mixture obtained in step (1) into a granulator to mix and extrude and granulate to obtain granules; (3) drying treatment: placing the granules obtained in step (2) into a dryer to perform drying treatment; (4) extruding consumables: adding the granules after drying in step (3) into an extruder to perform extrusion molding; after the extruded filaments are cooled through a water tank, they are wound into a finished product by a winding machine.

9. The method for preparing UHMWPE / PLA plastic 3D printing consumables according to claim 8, characterized in that: In step (1), the molybdenum disulfide powder, inorganic filler and coupling agent are added into anhydrous ethanol and stirred for 20-60 min; the anhydrous ethanol is added in an amount of 1.5-3 times the total mass of the molybdenum disulfide powder, inorganic filler and coupling agent; the anhydrous ethanol is removed by heating to prepare a premix; the premix is then mixed uniformly with other raw materials of the 3D printing consumables.

10. The method for preparing UHMWPE / PLA plastic 3D printing consumables according to claim 8, characterized in that: In step (4), the extruder is a double-screw extruder, and the heating temperatures of each zone of the extruder are as follows: zone 1, 175-190°C; zone 2, 190-205°C; zone 3, 185-200°C; and zone 4, 165-180°C.

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