CN110079010B - Shape memory polymer alloy based on fused deposition 3D printing and preparation method thereof - Google Patents
Shape memory polymer alloy based on fused deposition 3D printing and preparation method thereof Download PDFInfo
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention discloses a shape memory polymer alloy based on fused deposition 3D printing and a preparation method thereof. The polymer alloy comprises the following raw materials in percentage by weight: 30-50% of polyolefin plastic, 10-40% of nylon resin, 20-40% of thermoplastic elastomer graft, 0.1-1% of peroxide crosslinking agent, 0-5% of auxiliary crosslinking agent and 1-5% of nano filler. And (3) performing melt extrusion molding on the raw materials mixed by the high-speed mixer to obtain the polymer alloy suitable for fused deposition 3D printing. The polymer alloy prepared by the invention has excellent 3D printing performance, so that the printed product has the characteristics of low warping degree, high dimensional stability, smooth and defect-free surface, good mechanical property and heat resistance and the like, and also has an excellent thermotropic shape memory function, and the printed product has high shape fixing rate and shape recovery rate, and can meet the application requirements of the shape memory product.
Description
Technical Field
The invention relates to a 3D printing polymer consumable, in particular to a shape memory polymer alloy based on fused deposition 3D printing and a preparation method thereof.
Background
The 3D printing technology is a rapid prototyping technology that began to be developed in the 80 s of the 20 th century, and can be classified into a selective laser sintering technology, a three-dimensional photocuring technology, a fused deposition modeling technology, and the like according to the working principle. The fused deposition modeling is one of the most widely applied 3D printing technologies at present due to the characteristics of simple principle, convenient operation, low cost and the like, and can be widely applied to the fields of medical treatment, automobiles, military affairs, aerospace, electronic products, educational culture, artistic design and the like.
With the development of 3D printing technology becoming mature, people's needs have been far from satisfying the concept of "3D printing", which was proposed in 2013, and have attracted the broad interests of scholars. 4D printing, as the name implies, refers to the introduction of a fourth dimension, time, on the basis of a three-dimensional article, which may undergo changes in structure, properties, morphology, function, etc. over time under external stimuli (e.g., heat, electricity, light, magnetism, moisture, etc.). Among them, the thermal shape memory is one of the most studied 4D printing technologies at present, which means that the shape of a 3D product can change with time under thermal stimulation, and the shape memory material is the basis on which the technology is based. The shape memory polymer has the advantages different from shape memory alloy and shape memory ceramic, such as low density, low response temperature, large deformation amount, easy processing, low cost and the like, and is more suitable for fused deposition 3D printing, so the 4D printing technology is rapidly developed in recent years, and the application in various advanced fields, such as biomedicine, military air defense, mechanical sensing devices, brakes and the like, can be effectively met.
The existing commercial fused deposition 3D printing polymer consumables mainly comprise acrylonitrile-butadiene-styrene (ABS) and polylactic acid, but ABS is easy to warp and deform in the printing process and has slight 'bad' smell, and polylactic acid has the defects of large brittleness, low thermal deformation temperature and high cost of printed products, and the two materials generally lack the functions of electric conduction, heat conduction, shape memory and the like, so that the defects limit the wide application and development of fused deposition molding technology. Along with the increasing requirements of people on printing consumables, the novel consumables with low cost, high performance and multiple functions, in particular to the polymer consumables with better 3D printing performance and shape memory function, have wide application prospect.
Polyolefin is common general thermoplastic plastic, has the advantages of small relative density, good mechanical property, chemical corrosion resistance, heat resistance, easy processing, good electrical insulation property and the like, but is difficult to be applied to fused deposition molding at present due to the problems of large shrinkage rate of products and the like. Chinese patent application CN103739954A discloses a polypropylene composite material for fused deposition 3D printing and a preparation method thereof, wherein the raw materials comprise, by weight, 70-98% of polypropylene, 1-20% of transparent toughening agent, 0-10% of inorganic filler, 0.1-0.5% of nucleating agent, 0.2-2% of stabilizer and 0-5% of other additives.
The Chinese patent application CN104086891A provides a polypropylene and polyethylene composite consumable for fused deposition 3D printing, which comprises, by mass, 40-80% of polypropylene, 10-40% of polyethylene, 3-15% of an inorganic filler, 0.2-3% of a nucleating agent and 0.2-1.5% of a tackifier, and the printing consumable has good surface rigidity and scratch resistance, does not have the problem of environmental stress cracking, is high in safety, can be used for printing products with various food-grade requirements, has a water absorption rate of only 0.01% in water, and therefore, the printed products do not absorb water and damp, have good surface gloss and are easy to color; the printing consumables also have high heat resistance, high impact resistance, excellent bending resistance, corrosion resistance, voltage resistance and arc resistance.
Nylon is a typical engineering plastic, has excellent comprehensive properties such as high rigidity, small creep, high mechanical strength, good heat resistance, good electrical insulation and the like, and can be used in harsh chemical and physical environments for a long time. Theoretically, the fused deposition 3D printing consumable material can also be used as a fused deposition 3D printing consumable material, but actually, due to the large shrinkage rate, the interlayer peeling and warping in the printing process are serious, and even the printing product cannot be molded, the printed product is easy to shrink and deform, and the application of the fused deposition 3D printing consumable material is greatly limited.
The Chinese invention patent application CN106433108A discloses a high-temperature-resistant nylon wire material for fused deposition 3D printing, a preparation method thereof and a method for 3D printing by using the same, wherein the high-temperature-resistant nylon wire material comprises the following raw materials in parts by weight: the high-temperature-resistant nylon wire material for 3D printing by fused deposition is prepared by using high-strength nylon resin as a base material, carrying out physical modification on the nylon resin by using the organic modified montmorillonite, the antioxidant and the lubricant, and adjusting the synergistic effect among the components in different proportions to improve the shrinkage of the nylon resin and the thermal denaturation temperature, and has the advantages of high strength, low shrinkage, low warping deformation degree, low molding precision, high temperature resistance and easiness in removing supports.
However, the printing consumables of polyolefins or nylons such as chinese patent applications CN103739954A, CN104086891A, and CN106433108A have good comprehensive properties, but because the raw materials have single component types, only have inorganic fillers, toughening agents, additives and other components for improving printing properties and processability, and lack reversible phase and stationary phase which are necessary for a semi-crystalline polymer shape memory system, the printing consumables lack functionality such as shape memory, and the application thereof is obviously limited by functionality.
Disclosure of Invention
Aiming at the problems of the fused deposition 3D printing consumable material with the functionality, the invention aims to provide a shape memory polymer alloy which has excellent 3D printing performance such as warping degree, surface quality, mechanical property and thermal property of a product and also has a shape memory function and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a shape memory polymer alloy based on fused deposition 3D printing is characterized in that the shape memory polymer alloy comprises the following raw materials in percentage by weight: 30-50% of polyolefin plastic, 10-40% of nylon resin, 20-40% of thermoplastic elastomer graft, 0.1-1% of peroxide crosslinking agent, 0-5% of auxiliary crosslinking agent and 1-5% of nano filler;
the polyolefin plastic is high-density polyethylene, low-density polyethylene or polypropylene;
the nylon resin is nylon 6, nylon 66 or nylon 1010;
the thermoplastic elastomer graft is one or more of POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and EVA-g-MAH;
the auxiliary crosslinking agent is styrene or turpentine;
the nano filler is nano silicon dioxide or nano calcium carbonate.
To further achieve the object of the present invention, preferably, the peroxide crosslinking agent is dicumyl peroxide (DCP) or Benzoyl Peroxide (BPO).
Preferably, the low density polyethylene is a linear low density polyethylene.
The preparation method of the shape memory polymer alloy based on fused deposition 3D printing comprises the following steps:
1) weighing the raw materials according to the weight percentage;
2) drying the weighed polyolefin plastic, nylon resin, thermoplastic elastomer graft and nano filler;
3) putting the weighed raw materials into a high-speed mixer for mixing;
4) adding the mixed raw materials into a double-screw extruder for melt extrusion and granulation;
5) and drying the obtained uniformly mixed granules, and performing melt extrusion molding through a double-screw extruder to obtain the polymer alloy wire rod for 3D printing through melt deposition.
Preferably, the drying treatment in step 2) is drying in a forced air oven at 60-100 ℃ for 4-10 hours to reduce the water content of the raw material to 0.2-0.5%.
Preferably, the raw materials are put into a high-speed mixer for mixing for 10-30 minutes at the mixing temperature of 40-70 ℃.
Preferably, the extrusion temperature of the melt extrusion and granulation is 205-260 ℃, and the screw rotation speed is 50-80 r/min.
Preferably, the temperature of the melt extrusion molding is 205-260 ℃, the screw rotating speed is 40-60r/min, and the diameter of the wire rod is 1.75 +/-0.1 mm.
Preferably, the drying treatment in step 5) is drying at 60-100 ℃ for 4-10 hours.
Compared with the prior art, the invention has the following characteristics and excellent effects:
1) the polyolefin and the nylon resin used in the invention are typical semi-crystalline polymers, the nylon resin maintains the stationary phase of the original shape of the product, the mechanical property of the polyolefin plastic can be effectively improved, the polyolefin is used as the reversible phase which can be used for changing the original shape of the product to form a temporary shape, and the water absorption of the nylon resin can be greatly reduced, so that the polymer alloy material with excellent mechanical property and shape memory property can be obtained.
2) The reversible phase polyolefin plastic can generate micro-crosslinking action under the action of a crosslinking agent (and an auxiliary crosslinking agent) so as to regulate and control a crystalline phase, and the key triggering condition for changing the shape of a product is temperature generally, so that molecular chains of the polyolefin plastic can move when the temperature reaches the melting point of the polyolefin, the temporary shape of the product is endowed by rapid cooling crystallization, and after the temperature is recovered, the molecular chain crystals are melted and subjected to entropy elastic recovery, so that the shape recovery phenomenon is presented.
3) The polymer alloy prepared by the invention can be used for preparing a product with a thermotropic shape memory function by fused deposition 3D printing, namely, the product can obtain a temporary shape at a certain deformation temperature through the action of external force and is fixed by quickly cooling, the product can still be kept even after the external force is removed, and then the product can be quickly recovered to the original shape when the temperature is recovered to the deformation temperature, so that the product has high shape fixing rate and shape recovery rate.
4) The thermoplastic elastomer graft used in the invention not only serves as a compatibilizer of polyolefin and nylon resin, but also can serve as an interface modifier of a polymer and a nano filler, so that the performance of the alloy is further improved; the crystallization capability of the polymer alloy is weakened to relieve uneven volume shrinkage caused by a layer-by-layer stacking forming mode of the alloy when the alloy is used for fused deposition 3D printing, so that the generated printing warping problem is improved.
5) The polymer alloy prepared by the invention is added with a small amount of nano-filler, so that the polymer alloy is not only suitable for fused deposition 3D printing, but also has excellent printing effect and printing performance, and a printed product has the characteristics of low warping degree, high dimensional stability, smooth and free surface, good mechanical property and heat resistance and the like.
Detailed Description
For a better understanding of the present invention, the present invention is further illustrated below with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically noted in the specific examples can be performed with reference to the conventional techniques.
30-50% of polyolefin plastic, 10-40% of nylon resin, 20-40% of thermoplastic elastomer graft, 0.1-1% of peroxide crosslinking agent, 0-5% of auxiliary crosslinking agent and 1-5% of nano filler; the thermoplastic elastomer graft is one or more of POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and EVA-g-MAH;
example 1
The preparation method of the shape memory polymer alloy based on fused deposition 3D printing comprises the following steps: according to the weight percentage of the raw materials, 44 weight percent of polypropylene plastic, 30 weight percent of nylon 66, 22 weight percent of POE-g-MAH and 1 weight percent of nano-silica are dried for 5 hours at the temperature of 60 ℃, and then the materials, 0.2 weight percent of dicumyl peroxide (DCP) and 2.8 weight percent of turpentine oil are put into a high-speed mixer together for mixing, the mixing temperature is 50 ℃, and the mixing time is 20 minutes; adding the mixed raw materials into a double-screw extruder for melt extrusion and granulation, wherein the extrusion temperature is 250 ℃, and the screw rotation speed is 80 r/min; and drying the obtained granules at 60 ℃ for 6 hours, and performing melt extrusion in a double-screw extruder to obtain polymer alloy wires with the diameter of 1.75 +/-0.1 mm, wherein the extrusion temperature is 255 ℃ and the screw rotation speed is 40r/min, and the polymer alloy wires can be used for 3D printing through melt deposition.
And (3) feeding the prepared wire into a nozzle of printing equipment, introducing a code of a corresponding test sample strip model into the printing equipment, and preparing the test sample strip by fused deposition 3D printing, wherein the printing arrangement mode is +/-45 degrees, the printing filling rate is 100 percent, the nozzle temperature of the printing equipment is 260 ℃, and the hot bed temperature is 120 ℃.
The warping degree of a printed product is represented and the printing effect of the printed product is evaluated by printing a strip-shaped sample with the size of 80 multiplied by 10 multiplied by 4mm, as shown in figure 1, the alloy material obtained in the embodiment has a good printing effect, the shape of the sample can be observed to be basically consistent with that of a designed 3D model, and the forming precision is good; the sample has high dimensional stability and low warpage, and the measured warpage is only 5.3%. The method for testing the warping degree comprises the following steps: a 80 × 10 × 4mm strip-shaped article was printed out by FDM apparatus as a model of warpage test, and the measurement method is shown in fig. 2: placing the product on a platform, and measuring the highest height h of the middle position of the product from the horizontal plane1And thickness h of the intermediate position of the article2And calculating the warping degree omega according to a formula, measuring 5 samples in each group, and taking an arithmetic mean value.
By observing the surface of the sample, the surface of the sample is smooth, the filling is dense, the defects of holes, whitening and the like are avoided, and the printing quality is good.
The alloy material obtained in the embodiment has good mechanical property and heat resistance, and the tensile strength is 25.6MPa after a tensile test sample strip is printed and a tensile test is executed according to the standard ISO 527-2-20121 BA; printing a bending test sample bar according to the standard ISO 178-; printing a notch impact test sample strip according to the standard ASTM D256-2006 and executing an impact test, wherein the notch impact test sample strip shows extremely high toughness, and the impact sample strip cannot be broken by punching; vicat softening point test bars were printed and tested according to standard GB/T1633-.
The shape memory property of the material is generally characterized by two indexes of shape fixation rate and shape recovery rate, which can be measured by adopting a tensile film clamp and a controlled stress mode of DMA, and the setting program is as follows: 1) initial shape of spline becomes epsilon0Keeping the temperature of the material at the deformation temperature for 5min, and then applying a certain fixed stress sigma to deform the material; 2) immediately cooling to room temperature, and maintaining at the temperature and stress for 3min to fix the deformation to epsilon1,load(ii) a 3) Removing external force, and maintaining at the temperature for 3min to obtain epsilon1(ii) a 4) Quickly returning to the deformation temperature and keeping the temperature for 20min to finally deform to epsilon0,rec. The calculation formula of the shape fixation rate and the recovery rate is as follows:
rate of shape fixation
Shape recovery rate
The shape memory DMA test was performed by printing stretched film strips of dimensions 60X 5X 1 mm. The alloy material obtained in this example has excellent shape memory performance, and the DMA test result is shown in fig. 3, where the shape fixation rate is 90.0% and the shape recovery rate is 89.1% according to the strain. Since the shape fixation rate reflects the effectiveness of the temporary shape being fixed and the shape recovery rate reflects the closeness of the final recovered shape to the initial shape, in this example, the higher levels of both the shape fixation rate and the shape recovery rate indicate that the article made from the alloy can be stably given the temporary shape and can be substantially recovered to the initial shape when the temperature reaches the deformation temperature, with excellent shape memory properties. The shape memory polymer alloy has good mechanical property, low warping degree and high shape fixing rate and recovery rate, is combined with a fused deposition 3D printing technology, can simply and conveniently realize the preparation of a thermotropic shape memory intelligent product with a complex shape, and can be popularized and applied to advanced fields of biomedicine, aerospace, military air defense, mechanical sensing devices, brakes and the like. For example, a micro-driver used as a thrombus treatment device can be heated by a photoelectric control system after being assembled in a treatment system, so that the micro-driver can be restored to a spiral shape to pull out thrombus; for another example, the alarm can be used as a heat-sensitive alarm, and when the ambient environment reaches a certain temperature, the switch can automatically return to the off state, so that the alarm effect can be realized. The existing similar alloy materials generally do not have the shape memory function of the embodiment because of lack of a cross-linking network or lack of two phases with far different properties as a fixed phase and a reversible phase; the existing shape memory material is generally not suitable for a 3D printing technology, the technical difficulty is high when a product with a complex shape is prepared by adopting a traditional method, the manufacturing cost is high, the alloy material can be suitable for a fused deposition 3D printing technology, a complex product with almost any shape can be simply and conveniently prepared, and the alloy material has an excellent shape memory function, so that the manufacturing cost can be greatly reduced, the production efficiency is improved, and materials and energy are saved.
Example 2
Drying 35 wt% of high-density polyethylene, 30 wt% of nylon 6, 32 wt% of EPDM-g-MAH and 2.5 wt% of nano calcium carbonate at 80 ℃ for 4 hours, then putting the materials and 0.5 wt% of dicumyl peroxide (DCP) into a high-speed mixer for mixing, wherein the mixing temperature is 60 ℃, and the mixing time is 15 minutes; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature is 235 ℃, and the screw rotation speed is 70 r/min; and drying the obtained granules at 80 ℃ for 5 hours, and performing melt extrusion through a double-screw extruder to obtain polymer alloy wires with the diameter of 1.75 +/-0.1 mm and capable of being used for 3D printing through melt deposition, wherein the extrusion temperature is 235 ℃ and the screw rotation speed is 50 r/min.
Test bars were prepared by fused deposition 3D printing, with a print alignment of ± 45 °, a print fill rate of 100%, a nozzle temperature of the printing apparatus of 250 ℃, and a hot bed temperature of 110 ℃. Tests show that the sample also has higher dimensional stability, the warping degree is only 4.1%, and the surface is smooth and free of defects; the mechanical property and the heat resistance are good, the tensile strength is 23.3MPa, the bending strength is 22.3MPa, the toughness is extremely high, so that an impact sample strip cannot be broken, and the Vicat softening point is 53.8 ℃; the shape memory performance is better, the shape fixing rate is up to 91.5%, and the shape recovery rate is 80.9%.
Example 3
Drying 38 wt% of polypropylene, 30 wt% of nylon 1010, 28 wt% of SEBS-g-MAH and 3 wt% of nano-silica at 70 ℃ for 5 hours, then putting the materials, 0.3 wt% of dicumyl peroxide (DCP) and 0.7 wt% of styrene into a high-speed mixer for mixing, wherein the mixing temperature is 40 ℃, and the mixing time is 30 minutes; adding the mixed raw materials into a double-screw extruder for melt extrusion and granulation, wherein the extrusion temperature is 230 ℃, and the screw rotation speed is 60 r/min; and drying the obtained granules at 80 ℃ for 4 hours, and performing melt extrusion through a double-screw extruder to obtain polymer alloy wires with the diameter of 1.75 +/-0.1 mm, wherein the extrusion temperature is 210 ℃ and the screw rotation speed is 60r/min, and the polymer alloy wires can be used for 3D printing through melt deposition. Test bars were prepared by fused deposition 3D printing, with a print arrangement of ± 45 °, a print fill rate of 80%, a nozzle temperature of the printing equipment of 230 ℃, and a hot bed temperature of 80 ℃. Tests show that the alloy has good shape memory performance, the shape fixing rate is 84.4%, and the shape recovery rate is 88.1%, which indicates that the alloy can basically meet the use requirements of thermotropic shape memory products, and the shape memory performance is not influenced even if the printing filling rate is reduced, so that the preparation of light shape memory products with any shape can be simply realized by changing the printing filling rate.
Example 4
Drying 50 wt% of linear low-density polyethylene, 16 wt% of nylon 6, 28 wt% of EVA-g-MAH and 5 wt% of nano calcium carbonate at 60 ℃ for 6 hours, then putting the materials and 1 wt% of Benzoyl Peroxide (BPO) into a high-speed mixer for mixing, wherein the mixing temperature is 50 ℃ and the mixing time is 10 minutes; adding the mixed raw materials into a double-screw extruder for melt extrusion and granulation, wherein the extrusion temperature is 215 ℃, and the screw rotation speed is 60 r/min; and drying the obtained granules at 60 ℃ for 6 hours, and performing melt extrusion through a double-screw extruder to obtain polymer alloy wires with the diameter of 1.75 +/-0.1 mm, wherein the extrusion temperature is 215 ℃ and the screw rotation speed is 40r/min, and the polymer alloy wires can be used for 3D printing through melt deposition. Test bars were prepared by fused deposition 3D printing with a print arrangement of 0 °/90 °, a print fill rate of 100%, a nozzle temperature of the printing apparatus of 230 ℃, and a hot bed temperature of 75 ℃. Tests show that the alloy has good shape memory performance, the shape fixing rate is 82.1%, and the shape recovery rate is 80.0%, which indicates that the alloy can basically meet the use requirements of thermotropic shape memory products.
Example 5
Drying 40 wt% of low-density polyethylene, 32 wt% of nylon 6, 26 wt% of POE-g-MAH and 1.5 wt% of nano-silica at 60 ℃ for 6 hours, then putting the materials and 0.5 wt% of dicumyl peroxide (DCP) into a high-speed mixer for mixing, wherein the mixing temperature is 60 ℃ and the mixing time is 20 minutes; adding the mixed raw materials into a double-screw extruder, carrying out melt extrusion and granulation, wherein the extrusion temperature is 210 ℃, and the screw rotation speed is 80 r/min; and drying the obtained granules under the same conditions, and performing melt extrusion in a double-screw extruder to obtain polymer alloy wires with the diameter of 1.75 +/-0.1 mm, wherein the extrusion temperature is 240 ℃ and the screw rotating speed is 40r/min, and the polymer alloy wires can be used for 3D printing through melt deposition.
The solid article was prepared by fused deposition 3D printing, wherein the printing arrangement was ± 45 °, the printing fill rate was 100%, the nozzle temperature of the printing apparatus was 250 ℃, and the hot bed temperature was 100 ℃.
The flower-shaped solid article shown in fig. 4 was printed to verify the molding effect and shape memory characteristics of the solid article prepared by fused deposition 3D printing using the alloy material. Firstly, placing a flower product in a blast drying oven at 175 ℃ for 20min, then applying external force to deform the product, immediately rapidly cooling the product to room temperature by cold water to fix a temporary shape, and showing the phenomenon of 'closing' of buds; the product was placed in a forced air drying oven at 175 ℃ again, and the pictures show the shape of the product at 30, 60 and 180 seconds respectively, i.e. the phenomenon that the buds are gradually opened is shown, and the final product can return to the original shape from the temporary shape within 3 minutes at the temperature, and the shape memory performance is excellent. After verification, the alloy is applied to fused deposition 3D printing, not only can a solid product with high forming precision, good dimensional stability and complex shape structure be prepared, but also the product has good thermotropic shape memory performance, namely, the temporary shape can be effectively kept, the original shape can be automatically recovered when the temperature reaches a certain temperature, and the requirement on the shape memory function of the product in practical application is met.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. It will be appreciated by those skilled in the art that various changes, modifications, substitutions, combinations, and omissions may be made without departing from the spirit and principles of the invention and are to be considered as equivalent within the scope of the invention.
Claims (9)
1. A shape memory polymer alloy based on fused deposition 3D printing is characterized in that the shape memory polymer alloy comprises the following raw materials in percentage by weight: 30-50% of polyolefin plastic, 10-40% of nylon resin, 20-40% of thermoplastic elastomer graft, 0.1-1% of peroxide crosslinking agent, 0-5% of auxiliary crosslinking agent and 1-5% of nano filler;
the polyolefin plastic is high-density polyethylene, low-density polyethylene or polypropylene;
the nylon resin is nylon 6, nylon 66 or nylon 1010;
the thermoplastic elastomer graft is one or more of POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and EVA-g-MAH;
the auxiliary crosslinking agent is styrene or turpentine;
the nano filler is nano silicon dioxide or nano calcium carbonate.
2. A shape memory polymer alloy based on fused deposition 3D printing according to claim 1, wherein the peroxide cross-linking agent is dicumyl peroxide or benzoyl peroxide.
3. A shape memory polymer alloy based on fused deposition 3D printing according to claim 1, wherein the low density polyethylene is linear low density polyethylene.
4. A method of preparing a shape memory polymer alloy based on fused deposition 3D printing according to any of claims 1 to 3, characterized by comprising the steps of:
1) weighing the raw materials according to the weight percentage;
2) drying the weighed polyolefin plastic, nylon resin, thermoplastic elastomer graft and nano filler;
3) putting the weighed raw materials into a high-speed mixer for mixing;
4) adding the mixed raw materials into a double-screw extruder for melt extrusion and granulation;
5) and drying the obtained uniformly mixed granules, and performing melt extrusion molding through a double-screw extruder to obtain the polymer alloy wire rod for 3D printing through melt deposition.
5. The method for preparing a shape memory polymer alloy based on fused deposition 3D printing according to claim 4, wherein the drying treatment in step 2) is drying in a forced air oven at 60-100 ℃ for 4-10 hours to reduce the water content of the raw material to 0.2-0.5%.
6. The method of claim 4, wherein the raw materials are mixed in the high speed mixer for 10-30 minutes at a temperature of 40-70 ℃.
7. The method as claimed in claim 4, wherein the extrusion temperature for melt extrusion and granulation is 205-260 ℃, and the screw rotation speed is 50-80 r/min.
8. The method as claimed in claim 4, wherein the melt extrusion temperature is 205-260 ℃, the screw rotation speed is 40-60r/min, and the diameter of the wire is 1.75 ± 0.1 mm.
9. The method of claim 4, wherein the drying process of step 5) is performed at 60-100 ℃ for 4-10 hours.
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