CN113045828B - Selective laser sintering composition and three-dimensional printing method using the same - Google Patents

Selective laser sintering composition and three-dimensional printing method using the same Download PDF

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CN113045828B
CN113045828B CN202010157512.4A CN202010157512A CN113045828B CN 113045828 B CN113045828 B CN 113045828B CN 202010157512 A CN202010157512 A CN 202010157512A CN 113045828 B CN113045828 B CN 113045828B
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thermoplastic
laser sintering
selective laser
powder
rubber
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CN113045828A (en
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吴晋安
李治宏
林凡杰
简福明
陈建明
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Industrial Technology Research Institute ITRI
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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
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention provides a selective laser sintering composition and a three-dimensional printing method using the same. The selective laser sintering composition comprises a nano inorganic powder and a thermoplastic vulcanized elastomer powder. The inorganic powder has a particle size distribution D90 of 1nm to 950nm. The thermoplastic vulcanizate powder has a particle size distribution D90 of 40 μm to 100 μm and a difference (DeltaT) between the melting onset temperature and the crystallization onset temperature of 10℃or higher. The thermoplastic vulcanizate powder comprises a thermoplastic and a crosslinked polymer. The difference in melting onset temperature (DeltaT) from crystallization onset temperature of the thermoplastic is greater than or equal to 10 ℃, and the weight ratio of the thermoplastic to the crosslinked polymer is from 1:1 to 1:4.

Description

Selective laser sintering composition and three-dimensional printing method using the same
Technical Field
The invention relates to a selective laser sintering composition and a method for performing selective laser sintering three-dimensional printing by using the composition.
Background
Additive manufacturing (Additive Manufacturing, commonly known as three-dimensional (3D) printing techniques) is characterized by the absence of a mold to manufacture the part. Currently, additive manufacturing methods include fused deposition modeling (fused deposition modeling, FDM), stereolithography (SLA), and selective laser sintering (selective laser sintering, SLS).
Fused Deposition Modeling (FDM) has advantages such as low cost and simple technology, but is limited by the technology itself, and generally has disadvantages such as slow modeling, limited modeling object size, and poor precision. Stereolithography (SLA) requires a liquid plastic resin, a photopolymer, and then cured by an Ultraviolet (UV) laser. SLA is considered a slower additive manufacturing method because small parts may take hours or even days to complete.
Selective Laser Sintering (SLS) forms parts layer by using a high energy pulsed laser. First, a thin layer of material powder is provided in a chamber and is melted in a localized manner by means of a laser beam. After melting and subsequent resolidification, the chamber may be lowered and a new layer of powder applied and the above construction process repeated. Thus, the desired part can be produced by repeatedly applying new layers and selectively melting layer by layer.
One factor of particular importance in selective laser sintering is the sinterable window (sinterable window) of the material powder used for sintering. The sinterable window of the material powder should be as wide as possible to reduce warpage of the part during the laser sintering operation. Rigid Polyamide (PA) and Polyetheretherketone (PEEK) are materials that are more commonly used in SLS technology. Common soft materials are elastomers such as thermoplastic polyester elastomer (TPEE), thermoplastic Polyurethane (TPU) and thermoplastic polyamide elastomer (TPAE). However, the conventional elastomer often exhibits a relatively wide melting temperature range during the melt processing, and the crystallization speed is too high during cooling, so that the material still partially exhibits a molten state while cooling and crystallizing, thereby narrowing the processing window (SLS) of the SLS process, and affecting the sinterability and printing quality of the material.
Therefore, there is a need in the industry for a novel material powder for laser sintering to improve sinterability and print quality.
Disclosure of Invention
According to an embodiment of the present invention, there is provided a selective laser sintering composition. The selective laser sintering composition comprises a nano-inorganic powder and a thermoplastic vulcanizate (thermoplastic vulcanizate, TPV) powder. The inorganic powder has a particle size distribution (particle size distribution) D90 of 1nm to 950nm and the thermoplastic vulcanizate powder has a particle size distribution D90 of 40 μm to 100 μm. The difference DeltaT between the melting initiation temperature (the onset temperature of melting (TM set)) and the crystallization initiation temperature (the onset temperature of crystallization (TC set)) of the thermoplastic vulcanizate powder is 10℃or greater. The thermoplastic vulcanizate powder comprises a thermoplastic and a crosslinked polymer (crosslinked polymer). The difference DeltaT between the melting onset temperature and the crystallization onset temperature of the thermoplastic is greater than or equal to 10 ℃, and the weight ratio of the thermoplastic to the crosslinked polymer is from 1:1 to 1:4. The crosslinked polymer is a crosslinked rubber, a crosslinked thermoplastic elastomer, or a combination thereof.
According to embodiments of the present invention, the weight ratio of the nano-inorganic powder to the thermoplastic vulcanizate powder may be 0.2:99.8 to 0.8:99.2.
According to embodiments of the present invention, the thermoplastic vulcanizate powder may have a Shore A hardness of 50A to 98A.
According to an embodiment of the present invention, the nano-inorganic powder may be silicon oxide, aluminum oxide, titanium oxide, calcium carbonate, magnesium silicate, zinc oxide, magnesium oxide, or a combination thereof.
According to an embodiment of the invention, the thermoplastic is polypropylene (polypropylene), polyethylene (polyethylene), polyurethane (polyurethane), polyethylene terephthalate (polyethylene terephthalate), polyamide (polyamide) or a combination of the above.
According to embodiments of the present invention, the crosslinked polymer may be the product of crosslinking a rubber (and/or a thermoplastic elastomer) in the presence of a crosslinking agent and a plasticizer.
According to an embodiment of the present invention, the rubber may be ethylene-propylene-diene monomer rubber (ethylene-propylene-rubber), natural Rubber (NR), polybutadiene rubber (polybutadiene rubber, BR), nitrile rubber (nitrilebutadiene rubber, NBR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), ethylene-propylene rubber (EPR), ethylene-propylene-diene-diene monomer rubber (EPDM), or the above composition.
According to embodiments of the present invention, the crosslinking agent may be a peroxide, a phenolic resin, sulfur, a sulfide, a carbodiimide compound (carbodiimide compound), an aliphatic diamine (aliphatic diamine), or a combination thereof.
According to an embodiment of the invention, the plasticizer is a silicone oil, a mineral oil, a paraffinic oil, or a combination of the above.
According to an embodiment of the present invention, the selective laser sintering composition may further comprise an additive, wherein the additive is a dye, a pigment, an antioxidant, a stabilizer, or a combination thereof.
According to the embodiment of the invention, the invention provides a selective laser sintering three-dimensional printing method. The method comprises the following steps: (A) Forming a film layer, wherein the film layer comprises the selective laser sintering composition; (B) Selectively irradiating the film layer with a laser beam scan to cure the selective laser sintering composition to form a portion of an object; and (C) repeating steps (A) and (B) until the object is formed.
Drawings
FIG. 1 is a schematic view of a selective laser sintering composition according to an embodiment of the present invention.
[ symbolic description ]
1-a first tangent line; 2-a second tangent; 3-a third tangent; 4-fourth tangent.
Detailed Description
The selective laser sintering composition of the present invention is described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different forms of the invention. The specific components and arrangements described below are only a brief description of the present invention. These are, of course, merely examples and are not intended to be limiting. Furthermore, repeated reference numerals or designations may be used in the various embodiments. These repetition are for the purpose of simplicity and clarity in order not to obscure the invention in any way the various embodiments and/or constructions discussed.
According to an embodiment of the present invention, there is provided a selective laser sintering composition. The selective laser sintering composition comprises a nano inorganic powder and a thermoplastic vulcanized elastomer powder, wherein the thermoplastic vulcanized elastomer powder has a particle size distribution D90 of 40 μm to 100 μm and a melting initiation temperature (the onset temperature of melting (T) M Set)) and crystallization onset temperature (the onset temperature of crystallization (T) C Set)) is greater than or equal to 10 ℃. By adding this particular thermoplastic vulcanizate powder, the selective laser sintering composition of the present invention can give the object obtained by selective laser sintering three-dimensional printing the object elasticity and the same thermal property performance as hard plastic. Therefore, the invention provides an elastic material for laser sintering, which solves the problem that the traditional elastic material is difficult to perform laser sintering due to narrow sintering window.
Furthermore, since the thermoplastic vulcanizate powder used in the present invention comprises thermoplastic as the continuous phase and crosslinked polymer (comprising a crosslinked rubber, a crosslinked thermoplastic elastomer, or a combination thereof) as the dispersed phase. Thus, the selective laser sintering composition of the present invention exhibits melting behavior upon laser sintering processing from thermoplastics with a relatively sharp and broad sintering window. When cooled, the sintered product exhibits softness and elastic recovery deformation characteristics due to the dispersed phase of the rubber.
According to an embodiment of the present invention, there is provided a selective laser sintering composition. According to embodiments of the present invention, the selective laser sintering composition comprises a nano-inorganic powder and a thermoplastic vulcanizate (thermoplastic vulcanizate, TPV) powder. According to embodiments of the invention, the particle size distribution (particle size distribution) D90 of the inorganic powder may have a value of about 1nm to 950nm, for example, about 1nm, 5nm, 10nm, 20nm, 50nm, 100nm, 150nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 950nm. If the value of the particle size distribution (particle size distribution) D90 of the inorganic powder is too high, the resulting selective laser sintering composition has poor fluidity, and a film layer having a relatively uniform thickness cannot be obtained when the powder bed is carried out by an automatic powder-laying apparatus. According to embodiments of the present invention, the thermoplastic vulcanizate powder may have a particle size distribution D90 of about 40 μm to 100 μm, for example, about 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm. If the value of the particle size distribution D90 of the thermoplastic vulcanizate powder is too low, the thermoplastic vulcanizate powder tends to aggregate due to electrostatic concerns, resulting in a difficulty in uniformly dispersing the thermoplastic vulcanizate powder in the film layer. If the value of the particle size distribution D90 of the thermoplastic vulcanizate powder is too high, the accuracy of the object obtained by selective laser sintering three-dimensionally printing of the selective laser sintering composition of the present invention may be reduced. Here, the particle size distribution D90 means that 90% of the total volume of the powder has a diameter smaller than the value defined by D90. According to an embodiment of the invention, the particle size distribution D90 is determined according to the method specified in ISO 13322-1:2004.
According to embodiments of the present invention, the weight ratio of the nano-inorganic powder to the thermoplastic vulcanizate powder may be about 0.2:99.8 to 0.8:99.2, for example, may be about 0.2:99.8, 0.3:99.7, 0.4:99.6, 0.5:99.5, 0.6:99.4, 0.7:99.3, or 0.8:99.2. If the weight ratio of the nano inorganic powder to the thermoplastic vulcanizate powder is too high, the physical properties of the final printed product will be reduced by too much inorganic additives, and the material cost will be increased. If the weight ratio of the nano inorganic powder to the thermoplastic vulcanized elastomer powder is too low, the obtained selective laser sintering composition has poor fluidity, and a film layer with uniform thickness cannot be obtained when powder bed powder is carried out by automatic powder paving equipment.
According to an embodiment of the present invention, the nano-inorganic powder may be silicon oxide (silicon oxide), aluminum oxide (aluminum oxide), titanium oxide (titanium oxide), calcium carbonate (calcium carbonate), magnesium silicate (m agnesium silicate), zinc oxide (zinc oxide), magnesium oxide (magnesium oxide), or a combination thereof.
According to an embodiment of the present invention, the selective laser sintering composition may further comprise an additive, wherein the additive may be added in an amount of 0.1 to 30 parts by weight, and the total weight of the nano inorganic powder and the thermoplastic vulcanizate (thermoplastic vulcanizate, TPV) powder is 100 parts by weight. According to embodiments of the present invention, the additive may be, for example, a dye, a pigment, an antioxidant, a stabilizer (e.g., a thermal stabilizer light stabilizer, or a hydrolytic stabilizer), a fixing agent, or a combination thereof.
According to embodiments of the present invention, the selective laser sintering composition may be comprised of a nano-inorganic powder and a thermoplastic vulcanizate (thermoplastic vulcanizate, TPV) powder.
According to embodiments of the present invention, the thermoplastic vulcanizate powder may comprise a thermoplastic and a cross-linked polymer (cross-linked thermoplastic). Notably, in the thermoplastic vulcanizate powders of the present invention, the crosslinked polymer (rubber phase) forms uniform, micron-sized particles dispersed within the thermoplastic (plastic phase).
Critical in the selective laser sintering process is the melting range of the selective laser sintering composition, known as the sintering window (W). The thermoplastic plastic of the invention has a sintering window W P Whereas the thermoplastic vulcanizate powder of the present invention has a sintering window W T . The sintering window may be determined, for example, by differential scanning calorimetry (differencential scanning calorimetry, DSC) according to the method specified in ASTM D3418.
In a differential scanning calorimetry assay, the heat supplied to/removed from the sample Q is plotted as a function of temperature T to give a Differential Scanning Calorimetry (DSC) profile. A DSC diagram including a heating operation H and a cooling operation C is depicted in fig. 1 by way of example. First, a heating operation H is performed to heat the sample and the reference in a linear manner. During melting of the sample (solid-to-liquid phase), an additional amount of heat Q must be supplied to keep the sample at the same temperature as the reference. Peaks, called melting peaks, were then observed in the DSC profile. After heating operation H, cooling operation C is typically measured. During crystallization/solidification (liquid-solid phase) of the sample, a higher amount of heat Q must be removed to keep the sample at the same temperature as the reference, as heat is released during crystallization/solidification. In the DSC plot of cooling run C, a peak in the opposite direction to the melting peak, which is referred to as the crystallization peak, is then observed. DSC spectra can be used to determine the onset of melting temperature T M onset and crystallization onset temperature T C onset。
To determine the melting onset temperature T M onset, a first tangent line 1 is drawn relative to the baseline of heating run H at a temperature below the melting peak. The second tangent line 2 is drawn relative to the first inflection point of the melting peak at a temperature below the temperature at the maximum of the melting peak. The two tangents are extrapolated until they intersect. The vertical extrapolation intersecting the temperature axis represents the melting onset temperature T M onset. To determine the crystallization onset temperature T C onset, a third tangent 3 is drawn relative to the baseline of cooling run (C) at a temperature above the crystallization peak. The fourth tangent line 4 is drawn relative to the inflection point of the crystallization peak at a temperature greater than the temperature at the minimum of the crystallization peak. The two tangents are extrapolated until they intersect. The vertical extrapolation intersecting the temperature axis indicates the crystallization onset temperature T C onset. In the present invention, the sintering window is the melting initiation temperature T M onset and crystallization onset temperature T C The difference between onset. The sintering window W therefore corresponds to the following formula: w=t M onset-T C onset。
In the context of the present invention, a "sintering window (W)" and a "melting onset temperature (T M onset) and crystallization onset temperature (T C Set) has the same meaning and is used synonymously.
According to an embodiment of the invention, the thermoplastic has a melting onset temperature T M onset and crystallization onset temperature T C The difference DeltaT of onset T (i.e. the sintering window W P ) It is necessary to be greater than or equal to 10 ℃ (for example, it may be 10 ℃ to 80 ℃,10 ℃ to 70 ℃,10 ℃ to 60 ℃, 20 ℃ to 80 ℃, 20 ℃ to 70 ℃, or 20 ℃ to 60 ℃) so that the obtained thermoplastic vulcanizate powder has a relatively distinct and broad sintering window W T (melting initiation temperature T of thermoplastic vulcanizate elastomer powder) M onset (the onset temperature ofmelting) and crystallization onset temperature T C onset (the onset temperature ofcrystallization) difference Δt). Therefore, the selective laser sintering composition is easy to form an object by using the selective laser sintering three-dimensional printing method, and the obtained object has higher precision.
According to embodiments of the present invention, the thermoplastic may be a polyester elastomer, polypropylene, polyethylene, polyurethane, polyethylene terephthalate polyamide, or a combination thereof. According to embodiments of the invention, the number average molecular weight of the thermoplastic may be 50,000 to 500,000, such that the sintering window W of the thermoplastic P Greater than or equal to 10 ℃. According to an embodiment of the invention, the thermoplastic may be, for example, a sintering window W P Polypropylene, polyethylene, polyurethane, polyethylene terephthalate, polyamide, or a combination thereof at a temperature greater than or equal to 10 ℃. According to an embodiment of the invention, the thermoplastic does not comprise a thermoplastic silane-based plastic, or a thermoplastic siloxane-based plastic. In other words, the thermoplastic of the present invention is a polymer that does not contain silane groups (silane groups) or siloxane groups (siloxane groups).
According to an embodiment of the present invention, the difference DeltaT between the melting initiation temperature and the crystallization initiation temperature of the thermoplastic vulcanizate powder (i.e., the sintering window W T ) Can be greater than or equal to 10deg.C(e.g., 10 ℃ to 80 ℃,10 ℃ to 70 ℃,10 ℃ to 60 ℃, 20 ℃ to 80 ℃, 20 ℃ to 70 ℃, or 20 ℃ to 60 ℃). According to an embodiment of the present invention, the difference DeltaT between the melting initiation temperature and the crystallization initiation temperature of the thermoplastic vulcanizate powder (i.e., the sintering window W T ) A difference DeltaT from the melting onset temperature and crystallization onset temperature of the thermoplastic (i.e., sintering window W P ) Proportional to the ratio.
According to embodiments of the present invention, the weight ratio of the thermoplastic to the crosslinked polymer may be about 1:1 to 1:4, for example, about 1:1, 2:3, 1:2, 3:7, 1:3, or 1:4. If the weight ratio of the thermoplastic to the crosslinked polymer is too low (i.e., the weight ratio of the thermoplastic to the crosslinked polymer is less than 0.25), the sintering window of the resulting thermoplastic vulcanizate powder may be too narrow (i.e., the difference Δt between the melt onset temperature and the crystallization onset temperature of the thermoplastic vulcanizate powder is less than 10 ℃) or not obvious, thereby narrowing the process window (process window) of the SLS process and affecting the sinterability and print quality of the material. In addition, if the weight ratio of the thermoplastic to the crosslinked polymer is too high (i.e., the weight of the thermoplastic is greater than the weight of the crosslinked polymer), the selective laser sintering composition of the present invention results in a sintered product that has less elastic recovery deformation characteristics.
According to embodiments of the present invention, the thermoplastic vulcanizate powder may have a Shore A (Shore A) hardness of about 50A to 98A, for example, about 50A, 60A, 70A, 80A, 90A, or 95A. The surface Hardness (Shore Hardness, shore Hardness A) of the thermoplastic vulcanizate powder was determined according to the method specified in ASTM D-2240.
According to embodiments of the present invention, the crosslinked polymer may be the product of crosslinking a rubber and/or a thermoplastic elastomer in the presence of a crosslinking agent and a plasticizer.
According to an embodiment of the present invention, the rubber may be ethylene-propylene-diene monomerrubber (ethylene-propylene-rubber), natural Rubber (NR), polybutadiene rubber (polybutadiene rubber, BR), nitrile rubber (nitrile butadiene rubber, NBR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), ethylene-propylene rubber (EPR), ethylene-propylene-diene-diene monomer rubber (EPDM), or a composition thereof. According to embodiments of the present invention, the number average molecular weight of the rubber may be 80,000 to 1,000,000. According to an embodiment of the present invention, the thermoplastic elastomer may be a polyolefin elastomer (polyolefin elastomer, POE), a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene triblock copolymer (SIS), a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene-ethylene/butylene-styrene block copolymer (SEPS), or a composition of the above. According to embodiments of the present invention, the polyolefin elastomer (polyolefin elastomer, POE) can be a polymer or copolymer of an olefinic monomer (e.g., an alpha-olefinic monomer). For example, the processing unit may be configured to, the olefinic monomer may be ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, isoprene, tetrafluoroethylene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclobutene, cyclopentene cyclohexene, cyclooctene, 1, 3-butadiene, 1, 3-pentadiene, 3, 4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 1, 4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1, 4-hexadiene, 7-methyl-1, 6-octadiene, 3, 7-dimethyl-1, 6-octadiene, 5, 7-dimethyl-1, 6-octadiene, 1, 7-octadiene, 3,7, 11-trimethyl-1, 6, 10-octatriene, 6-methyl-1, 5-heptadiene, 1, 6-heptadiene, 1, 8-nonadiene, 1, 9-decadiene, or 1, 10-undecadiene. Further, according to an embodiment of the present invention, the polyolefin elastomer may be Polyethylene (PE), high Density Polyethylene (HDPE), linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), polypropylene, poly (propylene- α -olefin), ethylene-propylene copolymer (EPC), poly (ethylene- α -olefin), poly (ethylene-octene), poly (ethylene-hexene), poly (ethylene-butene), poly (ethylene-heptene), polybutene, polypentene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), or ethylene-butyl acrylate (EBA). According to embodiments of the present invention, the thermoplastic elastomer may have a number average molecular weight of 50,000 to 300,000.
According to embodiments of the present invention, the crosslinking agent may be a peroxide, a phenolic resin, sulfur, a sulfide, a carbodiimide compound (carbodiimide compound), an aliphatic diamine (aliphatic diamine), or a combination thereof.
According to embodiments of the present invention, the peroxide may be dicumyl peroxide (DCP, dicumyl peroxide), full butyl peroxide (perbutyl peroxide, PBP), dimethyl-di-t-butylperoxy hexane, t-butylethylhexyl monoperoxycarbonate, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, di-t-butylperoxy cumene, 1-di-t-butylperoxy-3, 5-trimethylcyclohexane, 4-di (t-butylperoxy) n-butyl valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl formate, diacetyl peroxide, lauroyl peroxide, t-butylcumyl peroxide, or combinations thereof. According to an embodiment of the present invention, the phenolic resin may be formed by a condensation reaction of a phenol compound and an aldehyde compound, wherein the phenol compound may be 4-t-butylphenol (4-t-butylphenol), 4-octylphenol (4-t-octylphenol), 2-ethylphenol (2-ethylphenol), 3-ethylphenol (3-ethylphenol), 4-ethylphenol (4-ethylphenol), o-cresol (o-cresol), m-cresol (m-cresol), p-cresol (p-cresol), 2,5-xylenol (2, 5-xylenol), 3,4-xylenol (3, 4-xylenol), 3,5-xylenol (3, 5-xylenol), 2,3,5-trimethylphenol (2, 3, 5-trimethylphenol), 3-methyl-6-t-butylphenol (3-methyl-6-butylphenol), 2-hydroxy-1, 3-dimethylphenol (1, 3-hydroxy-1-bisphenol a), or a combination thereof; and, the aldehyde compound may be formaldehyde (formaldehyde), para-formaldehyde (paraformaldehyde), acetoacetaldehyde (acetoaldehyde), benzaldehyde (benzaldehyde), phenylformaldehyde (phenylaldehyde), or a combination of the above. According to embodiments of the present invention, the sulfide may be tetrabenzyl thiuram disulfide (tetrabenzylthiuram disulfide), dibenzothiazyl disulfide (dibenzothiazole disulfide), or a combination thereof. According to an embodiment of the present invention, the carbodiimide compound (carbodiimide compound) may be 1-ethyl- (3-dimethylaminopropyl) carbodiimide (1-ethyl-3- (3-dimethyllanopyl) carbodiimide), N '-dicyclohexylcarbodiimide (N, N' -dicyclohexylcarbodiimide), or a combination thereof. According to embodiments of the present invention, the aliphatic diamine may be hexamethylenediamine, octanediamine, nonanediamine, decanediamine, 1, 16-hexadecanediamine (1, 16-Hexadecane diamine), 1, 18-octadecanediamine (1, 18-Octadecane diamine), or a combination thereof.
According to embodiments of the present invention, the plasticizer may be silicone oil, mineral oil, paraffin oil, or a combination thereof.
According to an embodiment of the present invention, the method for preparing the thermoplastic vulcanizate powder may include the following steps. First, a thermoplastic, and a rubber (and/or thermoplastic elastomer) are compounded into a blend. Then, a cross-linking agent and a plasticizer are added to crosslink and vulcanize the rubber (and/or thermoplastic elastomer) in the blend, and the originally continuous rubber phase is dispersed in the plastic phase by the shearing force generated during the crosslinking to form phase inversion, thus obtaining the thermoplastic vulcanized elastomer. After the process of drying, grinding and sieving the thermoplastic vulcanized elastomer, thermoplastic vulcanized elastomer powder is obtained. The term "kneading" as used herein refers to a process of uniformly mixing rubber or plastic with various agents (e.g., a crosslinking agent and a plasticizer) by mechanical action, and may be performed in a discontinuous or batch process in the kneading step.
According to embodiments of the present invention, the method of manufacturing the thermoplastic vulcanizate may be a dynamic crosslinking process. The term dynamic crosslinking refers to the process of kneading the crosslinking agent and the mixture during melt blending of the rubber and plastic in the mixture to form crosslinks between the rubber. The term "dynamic" means that the mixture imparts shear forces during the crosslinking step. In order to allow better melt blending of the rubber and plastic, the temperature during blending may be adjusted to between the melting temperature and the decomposition temperature depending on the plastic used.
The invention also provides a selective laser sintering three-dimensional printing method, and a three-dimensional printing method using the selective laser sintering composition. The method comprises the following steps: (A) Forming a film layer, wherein the film layer is composed of the selective laser sintering composition; (B) Selectively irradiating the film layer with a laser beam scan to cure the selective laser sintering composition to form a portion of an object; and (C) repeating steps (A) and (B) until the object is formed.
According to embodiments of the present invention, the film may be as thick as conventional in the selective laser sintering three-dimensional printing method, for example, 80 μm to 150 μm. Lasers suitable for selective laser sintering according to embodiments of the present invention are known to those skilled in the art, such as Nd: YAG laser (neodymium doped yttrium aluminum garnet laser, neodymium-doped yttrium aluminum garnet laser) or carbon dioxide laser.
In order to make the above and other objects, features and advantages of the present invention more comprehensible, several embodiments accompanied with figures are described in detail below:
thermoplastic vulcanizate elastomer powder
Preparation example 1:
70 parts by weight of Ethylene Propylene Diene Monomer (EPDM) (manufactured and sold by DOW under the product number NORDEL) TM 4570 30 parts by weight of polypropylene (PP) (manufactured and sold by Li Changrong chemical industry under the trade designation 9580) (having a melting initiation temperature of 147.2 ℃ and a crystallization initiation temperature of 132.6 ℃ and a difference (DeltaT) of 14.6 ℃), 1.5 parts by weight of peroxide (manufactured and sold by Legenseng, trade designation DCP) as a crosslinking agent, and 40 parts by weight of mineral oil (manufactured and sold by Legenseng, trade designation FOMI-250) as a plasticizer were fed into a kneader (model JKM-DK 10) and at a temperature of 150 ℃ and at 50-100 rpm. Kneading is carried outAfter 20 minutes, the thermoplastic vulcanized elastomer master batch was obtained by granulating with a granulator (model GZML-110L-150) at a temperature of 50 to 100℃and a screw rotation speed of 20 rpm. Next, the thermoplastic vulcanized elastomer master batch was subjected to freeze-grinding in liquid nitrogen using a grinder and sieved to obtain a thermoplastic vulcanized elastomer powder (1) having a particle size distribution D90 of about 82 μm and a thermoplastic vulcanized elastomer powder (2) having a particle size distribution D90 of about 146 μm, respectively. The hardness of the obtained thermoplastic vulcanizate powders (1) and (2) and the sintering window W were measured T The results are shown in Table 1.
Preparation example 2:
60 parts by weight of Ethylene Propylene Diene Monomer (EPDM) (manufactured and sold by DOW under the product number NORDEL) TM 4570 40 parts by weight of polypropylene (PP) (manufactured and sold by Li Changrong chemical industry under the trade designation 9580) (having a melting initiation temperature of 147.2 ℃ and a crystallization initiation temperature of 132.6 ℃ and a difference DeltaT of 14.6 ℃), 1.2 parts by weight of peroxide (manufactured and sold by Chanxin corporation under the trade designation DCP) as a crosslinking agent, and 30 parts by weight of mineral oil (manufactured and sold by Chahui corporation under the trade designation FOMI-250) as a plasticizer were fed into a kneader (model JKM-DK 10) and at a temperature of 150 ℃ and at 50-100 rpm. After kneading for 20 minutes, the thermoplastic vulcanized elastomer master batch was obtained by granulating with a granulator (model GZML-110L-150) at a temperature of 50 to 100℃and a screw rotation speed of 20 rpm. Subsequently, the thermoplastic vulcanized elastomer master batch was subjected to freeze-grinding in liquid nitrogen by a grinder and sieved to obtain a thermoplastic vulcanized elastomer powder (3) having a particle size distribution D90 of about 91. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (3) and the sintering window W were measured T The results are shown in Table 1.
Preparation example 3:
preparation example 3 was conducted in the same manner as in preparation example 2 except that the weight ratio of EPDM to PP was adjusted from 60:40 to 80:20, to obtain a thermoplastic vulcanizate powder (4) having a particle size distribution D90 of about 85. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (4) and the sintering window W were measured T The results are shown in Table 1.
Preparation example 4:
preparation example 4 was conducted in the same manner as in preparation example 2 except that the weight ratio of EPDM to PP was adjusted from 60:40 to 50:50, to obtain a thermoplastic vulcanizate powder (5) having a particle size distribution D90 of about 81. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (5) and the sintering window W were measured T The results are shown in Table 1.
TABLE 1
Preparation example 5:
70 parts by weight of styrene-ethylene/butylene-styrene block copolymer (SEBS) (manufactured and sold by Taiwan rubber Co., china under the trade name Taipol 6014), 30 parts by weight of polypropylene (PP) (manufactured and sold by Li Changrong under the trade name 8681) (having a melting initiation temperature of 142.8 ℃ C., a crystallization initiation temperature of 121.5 ℃ C., a difference (. DELTA.T) of 21.3 ℃ C.), and 1.2 parts by weight of peroxide (manufactured and sold by Arkema under the trade name Aripol 6014) were mixed101 As a crosslinking agent, and 80 parts by weight of mineral oil (manufactured and sold by super-benefit corporation under the trade designation FOMI-550) as a plasticizer, were fed into a kneader (model number JKM-DK 10) and at a temperature of 150℃and at 50-100 rpm. After kneading for 20 minutes, the thermoplastic vulcanized elastomer master batch was obtained by granulating with a granulator (model GZML-110L-150) at a temperature of 50 to 100℃and a screw rotation speed of 20 rpm. Subsequently, the thermoplastic vulcanized elastomer master batch was subjected to freeze-grinding in liquid nitrogen by a grinder and sieved to obtain a thermoplastic vulcanized elastomer powder (6) having a particle size distribution D90 of about 86. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (6) and the sintering window W were measured T The results are shown in Table 2.
Preparation example 6:
preparation example 6 was conducted in the same manner as in preparation example 5 except that SEBS was replaced with a styrene-ethylene/butylene-styrene block copolymer (SEPS) (manufactured and sold as Kraton Corporation under the trade name G1730), to obtainThe thermoplastic vulcanizate powder (7) had a particle size distribution D90 of about 79. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (7) and the sintering window W were measured T The results are shown in Table 2.
Preparation example 7:
preparation example 7 was conducted in the same manner as in preparation example 5 except that SEBS was replaced with acrylate rubber (ACM) (manufactured and sold by ZEON under the trade name AR-51) and PP was replaced with polyamide (Nylon) (manufactured and sold by China Temming. With the trade name PA 6N) (melting initiation temperature: 203.2 ℃ C., crystallization initiation temperature: 181.5 ℃ C., difference DeltaT: 21.7 ℃ C.), to obtain a thermoplastic vulcanizate powder (8) having a particle size distribution D90 of 88. Mu.m. The hardness of the obtained thermoplastic vulcanizate powder (8) and the sintering window W were measured T The results are shown in Table 2.
Preparation example 8:
preparation example 8 was conducted in the same manner as in preparation example 5 except that SEBS was replaced with Natural Rubber (NR) (manufactured and sold by the process of the patent and fly industry under the trade number 3L), to obtain a thermoplastic vulcanizate powder (9) having a particle size distribution D90 of about 95 μm. The hardness of the obtained thermoplastic vulcanizate powder (9) and the sintering window W were measured T The results are shown in Table 2.
Comparative example 1
100 parts by weight of thermoplastic polyester elastomer (TPEE) (manufactured and sold by DuPont under the trade name 4056) was subjected to freeze-grinding in liquid nitrogen using a grinder and sieved to obtain TPEE powder having a particle size distribution D90 of about 86. Mu.m. The hardness results of the TPEE powder are shown in Table 2. The obtained TPEE powder was analyzed by differential scanning calorimetry (differential scanning calorimetry, DSC), and the sintering window W could not be measured because the melting peak of the TPEE powder was too broad and very close to the crystallization peak p 。
Comparative example 2
100 parts by weight of polyurethane (TPU) (manufactured and sold by Lubrizol under the trade name S385A) was subjected to freeze-grinding in liquid nitrogen using a grinder and sieved to obtain TPU powder having a particle size distribution D90 of about 80. Mu.m. The hardness of the TPU powder is measured and the results are shown in Table 2. Scanning heat using differentialThe TPU powder obtained was analyzed by the analytical method (differential scanning calorimetry, DSC) and the sintering window W could not be measured because the melting peak of the TPU powder was too broad and very close to the crystallization peak p 。
TABLE 2
Selective laser sintering composition
Example 1
99.8 parts by weight of the thermoplastic vulcanizate powder (1) and 0.2 parts by weight of the silica powder (particle size distribution D90: 20 nm) were uniformly mixed to obtain a selective laser sintering composition (1). The fluidity of the selective laser sintering composition (1) was measured, and the results are shown in table 3. Next, the selective laser sintering composition (1) was subjected to selective laser sintering three-dimensional printing (film thickness 150 μm, powder bed temperature 140 ℃) to obtain a test piece, and the test piece was subjected to a tensile strength test and a three-dimensional printing accuracy test, and the results are shown in Table 3. The tensile strength of the test piece is measured in accordance with the manner specified in ASTM D412. The three-dimensional printing precision test was conducted by observing whether the shape of a square hole of 2mm side designed on a test piece formed by the selective laser sintering composition was complete (the shape was considered incomplete if there was a residual burr or hole deformation), and the precision test was considered to be passed if the square hole was complete.
Examples 2 to 9
Examples 2-9 the procedure was carried out as described in example 1, except that the thermoplastic vulcanizate powders (1) were replaced with the thermoplastic vulcanizate powders (2) to (9), respectively, to give the selective laser sintering compositions (2) to (9). Next, fluidity tests were conducted on the selective laser sintering compositions (2) to (9), respectively, and the results are shown in table 3. Next, three-dimensional printing (film thickness 150 μm; powder bed temperature of thermoplastic vulcanizate powders (2) - (7) and (9) 140 ℃ C., powder bed temperature of thermoplastic vulcanizate powder (8) 190 ℃ C.) was performed on each of the selective laser sintering compositions (2) - (9) to obtain test pieces, and tensile strength test and three-dimensional printing accuracy test were performed on these test pieces, and the results are shown in Table 3.
Comparative example 3
Comparative examples 3 and 4 were conducted in the same manner as described in example 1 except that the thermoplastic vulcanizate powder (1) was replaced with the TPEE powder described in comparative example 1 and the TPU powder described in comparative example 2, respectively, to obtain selective laser sintering compositions (10) and (11). Next, fluidity tests were performed on the selective laser sintering compositions (10) and (11), respectively, and the results are shown in table 3. Next, three-dimensional printing (film thickness 150 μm, powder bed temperature of TPEE powder 120 ℃ C., powder bed temperature of TPU powder 90 ℃ C.) was performed on each of the selective laser sintering compositions (10) and (11) to obtain test pieces, and the tensile strength test and the three-dimensional printing accuracy test were performed on these test pieces, and the results are shown in Table 3.
TABLE 3 Table 3
The thermoplastic vulcanizate powders used in the selective laser sintering composition (1) and the selective laser sintering composition (2) have the same material, except that the particle size distribution D90 of the thermoplastic vulcanizate powder used in the selective laser sintering composition (1) is smaller than 100 μm, and the particle size distribution D90 of the thermoplastic vulcanizate powder used in the selective laser sintering composition (2) is larger than 100. Mu.m. As can be seen from table 3, when the particle size distribution D90 of the plastic-vulcanized elastomer powder used was more than 100 μm, the obtained test piece failed the three-dimensional printing accuracy test. In addition, the tensile strength of the test pieces prepared by selectively laser sintering the composition (10) containing TPEE powder was significantly inferior. Furthermore, because TPEE powder and TPU powder do not have a sintering window WT (or the sintering window WT is less than 10 ℃), these powders are not easy to form objects using a selective laser sintering three-dimensional printing method, and the resulting objects have poor accuracy.
While the invention has been described with reference to several embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (11)

1. A selective laser sintering composition comprising:
a nano inorganic powder, wherein the particle size distribution D90 of the inorganic powder has a value of 1nm to 950nm; and
a thermoplastic vulcanizate powder, wherein the difference Δt between the melt onset temperature and the crystallization onset temperature of the thermoplastic vulcanizate powder is greater than or equal to 10 ℃, wherein the value of the particle size distribution D90 of the thermoplastic vulcanizate powder is from 40 μιη to 100 μιη, wherein the weight ratio of the nano-inorganic powder to thermoplastic vulcanizate powder is from 0.2:99.8 to 0.8:99.2, wherein the thermoplastic vulcanizate powder comprises:
a thermoplastic, wherein the difference delta T between the onset of melting and onset of crystallization of the thermoplastic is greater than or equal to 10 ℃; and
a crosslinked polymer, wherein the crosslinked polymer is a crosslinked rubber, a crosslinked thermoplastic elastomer, or a combination thereof, wherein the weight ratio of the thermoplastic to the crosslinked polymer is from 1:1 to 1:4;
the preparation method of the thermoplastic vulcanized elastomer powder comprises the steps of mixing the thermoplastic plastic with rubber and/or thermoplastic elastomer, drying, grinding and sieving.
2. The selective laser sintering composition of claim 1, wherein the thermoplastic vulcanizate powder has a shore a hardness of 50A to 98A.
3. The selective laser sintering composition of claim 1, wherein the nano-inorganic powder is silica, alumina, titania, calcium carbonate, magnesium silicate, zinc oxide, magnesium oxide, or a combination thereof.
4. The selective laser sintering composition of claim 1, wherein the thermoplastic is a polypropylene, a polyethylene, a polyurethane, a polyethylene terephthalate, a polyamide, or a combination thereof.
5. The selective laser sintering composition of claim 1 wherein the crosslinked polymer is the product of crosslinking the rubber and/or the thermoplastic elastomer in the presence of a crosslinking agent and a plasticizer.
6. The selective laser sintering composition of claim 5 wherein the rubber is ethylene propylene diene monomer rubber, natural rubber, polybutadiene rubber, nitrile rubber, styrene butadiene rubber, acrylate rubber, ethylene propylene diene monomer rubber or a combination thereof.
7. The selective laser sintering composition of claim 5 wherein the thermoplastic elastomer is a polyolefin elastomer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene-ethylene/butylene-styrene block copolymer, or a combination thereof.
8. The selective laser sintering composition of claim 5 wherein the crosslinking agent is a peroxide, a phenolic resin, sulfur, a sulfide, a carbodiimide compound, an aliphatic diamine, or a combination thereof.
9. The selective laser sintering composition of claim 5, wherein the plasticizer is silicone oil, mineral oil, paraffin oil, or a combination thereof.
10. The selective laser sintering composition of claim 1, further comprising:
an additive, wherein the additive is a dye, a pigment, an antioxidant, a stabilizer, a fixing agent, or a combination thereof.
11. A method of three-dimensional printing with a selective laser sintering composition comprising:
(A) Forming a film layer, wherein the film layer comprises the selective laser sintering composition of any of claims 1 to 10;
(B) Selectively irradiating the film layer with a laser beam scan to cure the selective laser sintering composition to form a portion of an object; and
(C) Repeating steps (a) and (B) until the object is formed.
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