CN112852127A - Composition for 3D printing, 3D printed product and preparation method thereof - Google Patents
Composition for 3D printing, 3D printed product and preparation method thereof Download PDFInfo
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- CN112852127A CN112852127A CN201911101705.1A CN201911101705A CN112852127A CN 112852127 A CN112852127 A CN 112852127A CN 201911101705 A CN201911101705 A CN 201911101705A CN 112852127 A CN112852127 A CN 112852127A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention relates to the field of high polymer materials, and discloses a composition for 3D printing, a 3D printed product and a preparation method thereof, wherein the composition comprisesThe refractive index of the polymer I is smaller than that of the polymer II, and the difference between the refractive indexes of the polymer II and the polymer I is 0.05-0.14; the absolute value of the difference between the solubility parameters of the polymer I and the polymer II is 0.6 (J-cm) or more‑3)1/2(ii) a The weight ratio of the polymer I to the polymer II is (2-5) to 1; the polymer II is a thermoplastic elastomer, and a 3D printed product prepared from the composition has an obvious pearlescent effect, and also has high mechanical property and low die shrinkage.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a composition for 3D printing, a 3D printed product and a preparation method thereof.
Background
The high polymer material can be used as a raw material for 3D printing, the existing 3D printing material is used for improving the glossiness of a 3D printing product, so that the 3D printing product has a pearly luster effect, inorganic fillers such as titanium dioxide, zinc oxide and mica are often required to be added into the 3D printing material, the inorganic fillers are uniformly dispersed in a matrix of the 3D printing product, on one hand, a free volume is formed inside the material, the performance is reduced, and the inorganic fillers such as the mica can diffuse into the environment along with the aging and damage of the 3D printing product, so that the environment is polluted, on the other hand, the inorganic fillers such as the mica are carcinogenic, and influence is caused on the health of people.
Therefore, there is a need in the art to solve the problems of environmental pollution and toxicity caused by the addition of inorganic fillers to 3D printed materials in order to obtain 3D printed products with high gloss and pearlescent effects.
Disclosure of Invention
The invention aims to solve the problems of toxicity and influence on mechanical property caused by inorganic filler added in a 3D printing material in the prior art, and provides a composition for 3D printing, a 3D printing product and a preparation method thereof.
The inventors of the present invention found in their studies that when the difference between the refractive indices of the polymer II and the polymer I is 0.05 to 0.14, the absolute value of the difference between the bulk density parameters of the polymer I and the polymer II is 0.6 (J. cm. or more)-3)1/2And polymer I and polymer II are (2-4): 1, preparing a wire material, and performing 3D printing on the wire material by a melt accumulation method to obtain a 3D printed product with a better pearling effect.
In order to achieve the above object, a first aspect of the present invention provides a composition for 3D printing, the composition comprising a polymer I and a polymer II, wherein,
the refractive index of the polymer I is smaller than that of the polymer II, and the difference between the refractive indexes of the polymer II and the polymer I is 0.05-0.14;
the absolute value of the difference between the solubility parameters of the polymer I and the polymer II is 0.6 (J-cm) or more-3)1/2；
The weight ratio of the polymer I to the polymer II is (2-5) to 1;
the polymer II is a thermoplastic elastomer.
In a second aspect, the present invention provides a method of making a 3D printed article, the method comprising the steps of:
(1) blending, drying, extruding and drawing the composition to obtain a wire material for 3D printing;
(2) and carrying out melt stacking molding on the wire material on a 3D printer to obtain a 3D printed product.
The invention provides a 3D printed product prepared by the method.
According to the technical scheme, the 3D printing product is internally provided with the sea-island structure, and the polymer I and the polymer II in the sea-island structure have different refractive indexes (the difference between the refractive indexes of the polymer II and the polymer I is 0.05-0.14) and solubility parameters (the absolute value of the difference between the solubility parameters is more than or equal to 0.6 (J-cm)-3)1/2) According to the invention, the 3D printed product can have a pearly luster effect without adding inorganic filler and/or pearl powder into the composition, meanwhile, the tensile strength of the 3D printed product can reach more than 34MPa, the Shore A hardness is more than 60, the shrinkage rate of a mold can reach less than 2%, the 3D printed product does not raise dust in the preparation process, the use process has the characteristics of safety and no toxicity, and no powder is dispersed into the environment after the material is aged and damaged.
Drawings
Fig. 1 is an SEM image of a 3D printed article of example 1;
FIG. 2 is a 3D printed article prepared in example 1;
fig. 3 is an SEM image of the 3D printed article prepared in comparative example 4 after aging.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composition for 3D printing, which comprises a polymer I and a polymer II, wherein,
the refractive index of the polymer I is smaller than that of the polymer II, and the difference between the refractive indexes of the polymer II and the polymer I is 0.05-0.14;
the absolute value of the difference between the solubility parameters of the polymer I and the polymer II is 0.6 (J-cm) or more-3)1/2；
The weight ratio of the polymer I to the polymer II is (2-5) to 1;
the polymer II is a thermoplastic elastomer.
In the present invention, the refractive index is the ratio of the speed of light in vacuum to the speed of light in polymer I or polymer II, and in the present invention, the refractive index can be determined by extrapolation, specifically referring to "measurement of refractive index of high polymer" (Shenmin et al, proceedings of the national academy of metrology of China [ J ], 1997(1):71-75), preferably, the refractive index of polymer I is smaller than that of polymer II, and the difference between the refractive indices of polymer II and polymer I is 0.05-0.14.
In the present invention, the refractive index of the polymer I may be 1.3 or more and less than 1.53, preferably 1.45 or more and less than 1.53; the refractive index of the polymer II may be 1.51 to 1.7, preferably 1.54 to 1.67.
In the present invention, the solubility parameter is a solubility parameter of a polymer, and the greater the absolute value of the difference in solubility parameters between polymers is, the poorer the compatibility between polymers is, and preferably, the absolute value of the difference in solubility parameters between the polymer I and the polymer II is 0.6(J · cm) or more (J · cm) or less-3)1/2More preferably 0.6 to 1.4(J · cm)-3)1/2。
In the present invention, the solubility parameters of the polymer I and the polymer II may be each independently 7.4 to 14 (J. cm)-3)1/2。
According to a preferred embodiment of the present invention, the thermoplastic elastomer has a solubility parameter ranging from 7.4 to 8.6 (J-cm)-3)1/2. In the present invention, the solubility parameter can be obtained by calculation in the present invention, with particular reference to "method for determining solubility parameter of substance" (periodic recovery, oil drilling and production process [ J)]，1991(3):63-70)。
According to a preferred embodiment of the invention, the weight ratio of polymer I to polymer II is (2-4): 1.
in the present invention, the polymer I may be selected from polypropylene, polyethylene, polylactic acid, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyamide, polyethylene terephthalate, and preferably at least one of polylactic acid, polyethylene, and polypropylene.
In the present invention, it is preferable that the polymer I is at least one selected from the group consisting of polylactic acid, polypropylene and polyethylene, and when the polymer I is polypropylene, the polymer II is not a thermoplastic polyester elastomer.
In the present invention, the polymer II may be at least one of a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, and a styrenic thermoplastic elastomer.
In the present invention, the refractive index of the polypropylene may be 1.48 to 1.52, and the solubility parameter may be 7.4 to 7.8 (J. cm)-3)1/2(ii) a The polyethylene may have a solubility parameter of 7.8 to 8.2 (J.cm)-3)1/2The refractive index may be 1.45-1.48; the refractive index of the polylactic acid can be 1.44-1.48, and the solubility parameter can be 9.8-10.2 (J.cm)-3)1/2(ii) a The refractive index of the polymethyl acrylate can be 1.46-1.49, and the solubility parameter can be 9.6-10.2 (J.cm)-3)1/2(ii) a The refractive index of the polyethylacrylate can be 1.45-1.49, and the solubility parameter can be 9.4-9.8 (J.cm)-3)1/2(ii) a The polyvinyl acetate has a refractive index of 1.45-1.49 and a solubility parameter of 9.2-9.6 (J. cm)-3)1/2(ii) a The polyamide may have a refractive index of 1.51 to 1.55 and a solubility parameter of 13.2 to 13.8 (J-cm)-3)1/2(ii) a The polyethylene terephthalate may have a solubility parameter of 10.8 to 11.2(J cm)-3)1/2The refractive index may be 1.58-1.6; the thermoplastic polyurethane elastomer may have a solubility parameter of 8.4 to 8.7 (J-cm)-3)1/2The refractive index may be 1.56-1.58; the styrene-based elastomer may have a solubility parameter of 7.6 to 8.9(J · cm)-3)1/2The refractive index may be 1.54-1.58; the styrene-butadiene-styrene block copolymer may have a solubility parameter of 8.5 to 8.7 (J. cm)-3)1/2The refractive index may be 1.53-1.55; the hydrogenated styrene-butadiene block copolymerThe solubility parameter of the substance can be 7.6-8.9(J · cm)-3)1/2The refractive index may be 1.56-1.57; the thermoplastic polyester elastomer may have a solubility parameter of 7.2 to 7.5 (J. cm)-3)1/2The refractive index may be 1.54-1.59.
In the present invention, the polyamide may include at least one of polyamide 6, polyamide 66, polyamide 56, polyamide 11, polyamide 12, polyamide 46, polyamide 610, polyamide 612, and polyamide l 010.
In the present invention, it is preferable that the styrene-based thermoplastic elastomer is at least one selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer and a styrene-ethylene-propylene-styrene type block copolymer, and is preferably a styrene-butadiene-styrene block copolymer.
In the present invention, when the polymer I is polylactic acid, the polymer II may be at least one selected from the group consisting of a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, and a styrene-butadiene-styrene block copolymer, and is preferably a thermoplastic polyurethane elastomer.
In the present invention, when the polymer I is polyethylene, the polymer II may be a thermoplastic polyurethane elastomer and/or a thermoplastic polyester elastomer, preferably a thermoplastic polyester type elastomer.
In the present invention, when the polymer I is polypropylene, the polymer II may be a thermoplastic polyurethane elastomer and/or a styrene-butadiene-styrene block copolymer, preferably a styrene-butadiene-styrene block copolymer.
In the present invention, the sources of the polymer I and the polymer II are not particularly limited, and they may be synthesized by the prior art or commercially available.
In a second aspect, the present invention provides a method of making a 3D printed article, the method comprising the steps of:
(1) blending, drying, extruding and drawing the composition to obtain a wire material for 3D printing;
(2) and carrying out melt stacking molding on the wire material on a 3D printer to obtain a 3D printed product.
In the present invention, the melt blending, extrusion and drawing processes in the step (1) are not particularly limited, and may be performed in a twin-screw extruder, for example.
In the present invention, when the composition is melt blended, general-purpose auxiliaries such as an antioxidant, an antioxidant and the like may be added to the composition.
In the invention, the mixing speed of blending is 50-200r/min, and the mixing time is 2-4 min.
In the invention, the process conditions for extruding the master batch in the twin-screw extruder comprise: the extrusion temperature is 170-210 ℃, the extrusion speed is 5-30rpm, the melt pressure is 3-35bar, the length-diameter ratio of the twin-screw extruder is more than or equal to 30, for example, 32, 35 or 45, and the rotation speed is 50-100r/min (any value in the range of 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min and any two of the values).
Preferably, the process conditions of the twin-screw extruder further comprise that the temperatures of the feeding section, the melting section, the mixing section, the exhaust section and the homogenizing section are respectively 155-165 ℃, 165-175 ℃, 175-185 ℃, 165-175 ℃ and 155-165 ℃.
In the invention, the drawing ratio of the drawn yarn is 1: (1-5), the diameter of the wire obtained by wire drawing is 1.75mm +/-0.01 mm.
The invention provides a 3D printing product prepared by the method.
In the invention, the 3D printed product has at least two glass transition temperatures, the glass transition temperatures are measured by a DSC method, for example, a DSC Q200 type thermal analyzer, specifically, the 3D printed product is crushed and ground into a powder sample with the particle size of 0.2-0.5mm, 5mg of the powder sample is weighed by an analytical balance and sealed in an aluminum dish, high-purity nitrogen is introduced into a sample chamber as a protective atmosphere, the preset initial temperature is-100 ℃, the finishing temperature is 300 ℃, and the heating rate is 10 ℃/min.
In the present invention, the structure formed by the polymer I and the polymer II is a sea-island structure under the observation of the 3D printed product by a scanning electron microscope, wherein the polymer I with a high component content is a "sea" structure, and the polymer II with a low component content is an "island" structure.
In the invention, due to the island-in-sea structure formed by the polymer I and the polymer II in the 3D printed product, the different refractive indexes and the different solubility parameters of the polymer I and the polymer II, when incident light enters the island-in-sea structure formed by the polymer I and the polymer II, the incident light performs a retro-reflection process in the product, so that the emergent light is enhanced, and the product can achieve a pearlescent effect macroscopically.
The present invention will be described in detail below by way of examples.
In the following examples of the present invention,
tensile Strength determination according to GB/T1040.2-2006 tensile Properties part 2: test conditions for molded and extruded plastics, ";
impact strength was determined according to GB/T1043.1-2008 Plastic simple Beam impact Performance part 1: the method of non-instrumental impact test is adopted for determination;
the molding shrinkage is according to ISO 294-4: 2001 injection molding of a sample of a plastic thermoplastic material, part 4 measurement of mold shrinkage;
polylactic acid is available from Nature Works, USA under the trade name 4032D, and has a refractive index of 1.45 and a solubility parameter of 10 (J. cm)-3)1/2；
Polyethylene available from Yanshan petrochemical under the designation 226 has a refractive index of 1.45 and a solubility parameter of 8 (J. cm)-3)1/2；
Polypropylene available from Yanshan petrochemical under the designation K4925, polypropylene having a refractive index of 1.49 and a solubility parameter of 7.5 (J. cm)-3)1/2；
Thermoplastic polyurethane elastomer (TPU) available from Wanhua chemical under the designation WHT-1480, has a refractive index of 1.58 and a solubility parameter of 8.6 (J. cm)-3)1/2Glass transition temperature of 106℃；
The styrene-butadiene-styrene block copolymer was purchased from Nomamoto, and has a trade designation of F675, a refractive index of 1.54, and a solubility parameter of 8.6 (J. cm)-3)1/2The glass transition temperatures of the two phases are-83 ℃ and 80 ℃ respectively;
the hydrogenated styrene-butadiene block copolymer was obtained from the Barlingpetrochemical company under the trade designation YH-503, the hydrogenated styrene-butadiene block copolymer had a refractive index of 1.57 and a solubility parameter of 8.4 (J. cm)-3)1/2The glass transition temperatures of the two phases are-60 ℃ and 63 ℃ respectively;
the thermoplastic polyester elastomer (TPEE) is available from DuPont under the trade designation 55D, has a refractive index of 1.59 and a solubility parameter of 7.4(J cm)-3)1/2。
Example 1
1) Mixing the components in a weight ratio of 4: 1, adding polylactic acid (polymer I, purchased from Nature Works, USA, with the trade name of 4032D) and a thermoplastic polyurethane elastomer (TPU) (polymer II, purchased from Wanhua chemical, with the trade name of WHT-1480) into a double-screw extruder, mixing for 2mIn at room temperature (25 ℃, the same below) and at the mixing speed of 50r/mIn, drying the obtained material in an oven at 80 ℃, adding the obtained material into the double-screw extruder for blending extrusion, wherein the extrusion temperature is 210 ℃, the extrusion speed is 5rpm, the melt pressure is 30bar, the length-diameter ratio of the double-screw extruder is 30, the rotating speed is 100r/mIn, directly drawing the filament after extruding the master batch, and the drawing ratio of the filament is 1: 1, the diameter of the obtained wire is 1.75 mm;
2) feeding the wire obtained in the step 1) into a 3D printer, melting the wire again at 190 ℃, then ejecting the melted wire from a nozzle of the 3D printer, and performing stacking molding according to a preset track of each layer of the product until the product is manufactured, so as to obtain the 3D printed product (shown in figure 2, having a strong pearl effect).
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article was measured using a scanning electron microscope, as shown in fig. 1, having a sea-island structure.
Example 2
1) Mixing the following components in percentage by weight: adding polyethylene (polymer I, purchased from Yanshan petrochemical company and having a trademark of 226) and a thermoplastic polyester elastomer (TPEE) (polymer II, purchased from DuPont and having a trademark of 55D) into a double-screw extruder, mixing for 4mIn at room temperature and at a mixing speed of 200r/mIn, drying in an oven at 60 ℃, granulating to obtain a master batch, extruding the master batch in the double-screw extruder at an extrusion temperature of 170 ℃, an extrusion speed of 30rpm, a melt pressure of 35bar, a length-diameter ratio of 40 and a rotation speed of 50r/mIn, directly drawing the master batch after extruding, wherein a drawing ratio of the drawing is 1: 5, the diameter of the obtained wire is 1.75 mm;
2) feeding the wire obtained in the step 1) into a 3D printer, melting the wire again at 190 ℃, then ejecting the melted wire from a nozzle of the 3D printer, and performing stacking molding according to a preset track of each layer of the product until the product is manufactured, so as to obtain the 3D printed product (similar to the product shown in FIG. 2, and having a strong pearl effect).
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article, similar to fig. 1, having a sea-island structure was measured using a scanning electron microscope.
Example 3
1) Mixing the components in a weight ratio of 3: adding polypropylene (polymer I, purchased from Yanshan petrochemical company and having a brand number of K4925) and a styrene-butadiene-styrene block copolymer (polymer II, purchased from Maominai petrochemical company and having a brand number of F675) of 1 into a double-screw extruder, mixing for 3mIn at a room temperature mixing speed of 100r/mIn, drying, granulating to obtain a master batch, extruding the master batch in the double-screw extruder, wherein the extrusion temperature is 210 ℃, the extrusion speed is 20rpm, the melt pressure is 3bar, the length-diameter ratio of the double-screw extruder is 35, the rotation speed is 85r/mIn, directly drawing the master batch after extrusion, and the drawing ratio of the drawing is 1: 2, the diameter of the obtained wire is 1.75 mm;
2) feeding the wire obtained in the step 1) into a 3D printer, melting the wire again at 190 ℃, then ejecting the melted wire from a nozzle of the 3D printer, and performing stacking molding according to a preset track of each layer of the product until the product is manufactured, so as to obtain the 3D printed product (similar to the product shown in FIG. 2, and having a strong pearl effect).
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article, similar to fig. 1, having a sea-island structure was measured using a scanning electron microscope.
Example 4
A 3D printed article was prepared according to the method of example 1, except that polymer II was a hydrogenated styrene-butadiene block copolymer (polymer II, available from the holy petrochemical under the designation YH-503) to obtain the 3D printed article.
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article, similar to fig. 1, having a sea-island structure was measured using a scanning electron microscope.
Comparative example 1
A 3D printed article was prepared according to the method of example 1 except that the weight ratio of polylactic acid (polymer I, available from Nature Works, usa under the designation 4032D) to the thermoplastic polyurethane elastomer polyester Type (TPU) (polymer II, available from wawa chemical under the designation WHT-1480) was 1: 1, obtaining the 3D printed product.
Tensile strength, impact strength, and mold shrinkage of the 3D printed article were measured, and the pearl effect of the article was observed with the naked eye, and the results are shown in table 1.
Comparative example 2
A 3D printed article was prepared according to the method of example 1 except that the weight ratio of polylactic acid (polymer I, available from Nature Works, usa under the designation 4032D) to the thermoplastic polyurethane elastomer polyester Type (TPU) (polymer II, available from wawa chemistry under the designation WHT-1480) was 6: 1, obtaining the 3D printed product.
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article, similar to fig. 1, having a sea-island structure was measured using a scanning electron microscope.
Comparative example 3
A 3D printed article was prepared according to the method of example 1 except that the weight ratio of polylactic acid (polymer I, available from Nature Works, usa under the designation 4032D) to the thermoplastic polyurethane elastomer polyester Type (TPU) (polymer II, available from wawa chemical under the designation WHT-1480) was 1: and 4, obtaining the 3D printed product.
Tensile strength, impact strength, and molding shrinkage of the 3D printed article were measured, and pearl effects of the article were visually observed, and as a result, as shown in table 1, a microstructure of the 3D article, similar to fig. 1, having a sea-island structure was measured using a scanning electron microscope.
Comparative example 4
A3D printed article was prepared according to the method of example 1, except that Polymer II was a polyolefin thermoplastic elastomer (TPO) (Polymer II, available from Exxon under the designation HMU202, refractive index 1.48, and solubility parameter 8(J cm)-3)1/2) And obtaining the 3D printed product.
Tensile strength, impact strength, and mold shrinkage of the 3D printed article were measured, and the pearl effect of the article was observed with the naked eye, and the results are shown in table 1.
Comparative example 5
A 3D printed article was prepared according to the method of example 1 except that no thermoplastic polyurethane elastomer (TPU) (polymer II, available from wawa chemical under the designation WHT-1480) was added with 2 parts by weight of mica powder.
The tensile strength, impact strength and molding shrinkage of the 3D printed product were measured, and the pearl effect of the product was observed with naked eyes, and the results are shown in table 1, and the microstructure of the 3D printed product was measured with a scanning electron microscope, as shown in fig. 3, it can be seen that the obtained product had a damaged structure due to the addition of mica powder.
TABLE 1
| Example numbering | Tensile Strength (MPa) | Hardness (Shao A) | Molding shrinkage (%) | Pearlescent effect |
| Example 1 | 36 | 75 | 1.2 | Is strong and strong |
| Example 2 | 35 | 61 | 1.8 | Is strong and strong |
| Example 3 | 38 | 70 | 1.5 | Is strong and strong |
| Example 4 | 35 | 63 | 1.9 | Weak is weak |
| Comparative example 1 | 34 | 76 | 2 | Is not provided with |
| Comparative example 2 | 32 | 71 | 1.5 | Is not provided with |
| Comparative example 3 | 35 | 66 | 1.4 | Is not provided with |
| Comparative example 4 | 33 | 72 | 1.5 | Is not provided with |
| Comparative example 5 | 12 | 95 | 1.8 | Is strong and strong |
As can be seen from the results of Table 1, examples 1-4, comparative examples 1-5 and FIGS. 1-3, the 3D printed product has a pearly luster effect, the tensile strength can reach more than 34MPa, the mold shrinkage can reach less than 2%, and the results of examples 1-3 show that the 3D printed product prepared by the preferred embodiment of the invention has a significantly better pearly luster effect, and particularly, as can be seen from comparative example 2, the addition of mica powder in the composition can enable the 3D printed product to have a strong pearly luster effect, but the addition of natural mica powder not only reduces the mechanical properties of the 3D printed product, but also the material is easy to age in the long-term use process of the 3D product, and powder is dispersed in the environment after being damaged to generate toxic and harmful substances.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for 3D printing, comprising a polymer I and a polymer II, wherein,
the refractive index of the polymer I is smaller than that of the polymer II, and the difference between the refractive indexes of the polymer II and the polymer I is 0.05-0.14;
the absolute value of the difference between the solubility parameters of the polymer I and the polymer II is 0.6 (J-cm) or more-3)1/2；
The weight ratio of the polymer I to the polymer II is (2-5) to 1;
the polymer II is a thermoplastic elastomer.
2. The composition of claim 1, wherein the refractive index of polymer I is 1.3 or more and less than 1.53 and the refractive index of polymer II is 1.51 to 1.7.
3. The composition of claim 1 or 2, wherein the solubility parameters of polymer I and polymer II are each 7.4-14 (J-cm)-3)1/2；
PreferablyThe solubility parameter of the polymer II is 7.4 to 8.6(J · cm)-3)1/2。
4. The composition of claim 3, wherein the weight ratio of polymer I to polymer II is (2-4): 1.
5. the composition of any one of claims 1-4, wherein the polymer I is selected from at least one of polylactic acid, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polybutadiene, and polyvinyl acetate;
the polymer II is at least one selected from thermoplastic polyurethane elastomer, thermoplastic polyester elastomer and styrene thermoplastic elastomer.
6. The composition according to claim 5, wherein the polymer I is at least one selected from the group consisting of polylactic acid, polypropylene and polyethylene, and when the polymer I is polypropylene, the polymer II is not a thermoplastic polyester elastomer.
7. The composition according to claim 5, wherein the styrenic thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer SBS, styrene-isoprene-styrene block copolymer SIS, styrene-ethylene-butylene-styrene block copolymer SEBS and styrene-ethylene-propylene-styrene type block copolymer SEPS, preferably styrene-butadiene-styrene block copolymer SBS.
8. A method of making a 3D printed article, the method comprising the steps of:
(1) blending, drying, extruding and drawing a composition according to any one of claims 1 to 7 to obtain a 3D printing wire;
(2) and carrying out melt stacking molding on the wire material on a 3D printer to obtain a 3D printed product.
9. The method of claim 8, wherein the temperature of blending is 10-30 ℃, the mixing speed of blending is 50-200r/min, and the mixing time is 2-4 min; the extrusion conditions include: the extrusion temperature is 170 ℃ and 250 ℃, the extrusion speed is 5-30rpm, and the melt pressure is 3-35 bar.
10. A 3D printed article prepared by the method of claim 8 or 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113584630A (en) * | 2021-09-02 | 2021-11-02 | 杭州卓普新材料科技有限公司 | Pearlescent 3D printing material and preparation method thereof |
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| CN106633723A (en) * | 2016-11-22 | 2017-05-10 | 福建师范大学 | 3D printing wire rod with pearl effect and preparation method thereof |
| CN107446339A (en) * | 2016-06-01 | 2017-12-08 | 黑龙江鑫达企业集团有限公司 | It is a kind of suitable for flexible material of 3D printing chest and abdomen fixing band and preparation method thereof |
| CN107987497A (en) * | 2017-12-22 | 2018-05-04 | 衢州听语信息科技有限公司 | A kind of 3D printing material |
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| CN107446339A (en) * | 2016-06-01 | 2017-12-08 | 黑龙江鑫达企业集团有限公司 | It is a kind of suitable for flexible material of 3D printing chest and abdomen fixing band and preparation method thereof |
| CN106633723A (en) * | 2016-11-22 | 2017-05-10 | 福建师范大学 | 3D printing wire rod with pearl effect and preparation method thereof |
| CN107987497A (en) * | 2017-12-22 | 2018-05-04 | 衢州听语信息科技有限公司 | A kind of 3D printing material |
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| CN113584630A (en) * | 2021-09-02 | 2021-11-02 | 杭州卓普新材料科技有限公司 | Pearlescent 3D printing material and preparation method thereof |
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