CN113201215B - Selective laser sintering self-repairing polyurethane powder material and preparation method thereof - Google Patents
Selective laser sintering self-repairing polyurethane powder material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention relates to the technical field of additive manufacturing materials, and particularly relates to a selective laser sintering self-repairing polyurethane powder material and a preparation method thereof. Is prepared by compounding self-repairing polyurethane, nano powder, an antioxidant, a light stabilizer, silicone and an antistatic agent; the self-repairing polyurethane is obtained by carrying out chain extension reaction on dithiodiglycol. The reversible exchange dynamic balance reaction performance of the disulfide bond in the invention and the synergistic effect of the disulfide bond and the hydrogen bond promote the material to carry out a mechanism of damage self-repair, thereby prolonging the service life of the material.
Description
Technical Field
The invention relates to the technical field of material increase manufacturing materials, and particularly relates to a selective laser sintering self-repairing polyurethane powder material and a preparation method thereof.
Background
The selective laser sintering technology is one of the most important processing technologies for additive manufacturing, selective sintering is carried out by utilizing laser beams under the control of a computer according to layered section information, the next layer of sintering is carried out after one layer of sintering is finished, and redundant powder is removed after all the layers of sintering are finished, so that a sintered molded part entity can be obtained. Among materials that can be used for laser sintering, polymer materials are receiving attention due to their excellent properties, but polymers that can be used for selective laser sintering processes are limited, and currently, nylon, TPU, PP, and the like are mainly on the market. For polymer selective laser sintering, the sintered article is typically z-axis strength reduction, which is the greatest challenge in producing high quality parts. This is also one of the key directions for the research of selective laser sintering materials and processes.
Disclosure of Invention
The invention provides a selective laser sintering self-repairing polyurethane powder material and a preparation method thereof, and solves the problem of low interlayer bonding strength in the sintering process through the good self-repairing function of the material.
A selective laser sintering self-repairing polyurethane powder material is prepared by compounding self-repairing polyurethane, nano powder, an antioxidant, a light stabilizer, silicone and an antistatic agent; the self-repairing polyurethane is obtained by carrying out chain extension reaction on dithiodiglycol.
A preparation method of a selective laser sintering self-repairing polyurethane powder material comprises the following steps:
step 2, preparing a selective laser sintering self-repairing polyurethane powder material: after the self-repairing polyurethane elastomer is crushed, 100 parts by weight of the self-repairing polyurethane elastomer, 0.5-2 parts by weight of an antioxidant, 0.5-2 parts by weight of a light stabilizer, 1-5 parts by weight of silicone and 0.5-2 parts by weight of an antistatic agent are mixed, the mixture is extruded by a double-screw extruder for granulation, and the granules are crushed and screened to obtain the selective laser sintering self-repairing polyurethane powder material.
In one embodiment, in step 1, the polyester polyol is polytetramethylene adipate glycol with a molecular weight of 1000-; the diisocyanate is one of methylene-bis (4-phenyl isocyanate) or methylene-bis (4-cyclohexyl isocyanate). The molar ratio of the polyester polyol to the diisocyanate to the chain extender is 1 (1.5-2) to 0.5-1.
In one embodiment, in the step 1, the nanopowder is one of nanosilicon dioxide, nanosilicon oxide and nanosilicon carbide, and the particle size is 30-50 um; the addition amount of the nano powder is 3-5% of the total mass of the polyester polyol, the diisocyanate and the chain extender.
In one embodiment, in step 1, the preparation of the nanopowder comprises the following steps: preparing the nano particles into suspension with the concentration of 1-3wt% by adopting ethanol water solution, adding a silane coupling agent until the concentration is 0.5-1wt%, adding an ionic liquid containing dihydroxy until the concentration is 0.5-1wt%, carrying out grafting reaction, filtering, washing and drying a reaction product, and obtaining the nano powder of the grafted ionic liquid.
In one embodiment, the ionic liquid containing a dihydroxy group is 1, 3-dihydroxyethyl imidazole chloride.
In one embodiment, the concentration of the aqueous ethanol solution is 60 to 70 vol.%, and the silane coupling agent is KH550 or KH 560; the temperature of the grafting reaction is 45-65 ℃ and the reaction time is 2-8 h.
In one embodiment, the dehydration is carried out at the step 1 under the conditions of 120-130 ℃, the vacuum degree of-0.09 MPa or more and the dehydration time of 1-5 h.
In one embodiment, in step 1, the parameters for performing the prepolymerization are: the temperature is 70-80 ℃, and the reaction time is 1-4 h.
In one embodiment, in step 1, the chain extender is dithiodiethylene glycol, and the parameters of the chain extension reaction are: reacting at 100 ℃ and 110 ℃ for 1-5 h.
In one embodiment, the temperature of the curing process is 60-65 ℃.
In one embodiment, the antioxidant is antioxidant 1010; the light stabilizer is light stabilizer 770; the antistatic agent is polyquaternium.
In one embodiment, the screening process employs an air classifier to obtain powder particle size D90= 110-.
The selective laser sintering self-repairing polyurethane powder material is applied to 3D printing.
Advantageous effects
(1) According to the invention, the nano powder is added in the prepolymerization process, a large amount of dispersed microphase structures are formed in the composite material, a large amount of phase interfaces are created, the number of hydrogen bonds formed by hydroxyl on the surface of the powder and hydrogen groups on a polyurethane chain is increased, the association number of the hydrogen bonds is increased, the cohesive energy of the chain segment is increased, and the mechanical property of the polyurethane elastomer is also improved. Meanwhile, diol containing disulfide bonds is used as a chain extender and reacts with the polyurethane prepolymer to synthesize a polyurethane elastomer containing disulfide bonds, and the reversible exchange dynamic balance reaction performance of disulfide bonds and the synergistic effect of hydrogen bonds endow the material with good mechanical properties and initial bonding capability. Therefore, the product after sintering of the selective laser sintering self-repairing polyurethane powder material keeps good interlayer strength and has good mechanical properties.
(2) The reversible exchange dynamic balance reaction performance of the disulfide bond in the invention and the synergistic effect of the disulfide bond and the hydrogen bond promote the material to carry out a mechanism of damage self-repair, thereby prolonging the service life of the material.
(3) In the invention, the adopted nano powder is subjected to hydrolytic condensation reaction of a silane coupling agent on the surface, and because the surface of the nano powder contains abundant hydroxyl groups generated by adsorption, the grafting reaction can be carried out in the hydrolysis process of silane, and meanwhile, the coupling agent can also graft ionic liquid containing dihydroxyl; in the synthesis process of polyurethane, the grafted hydroxyl and isocyanate are subjected to condensation polymerization reaction, so that the nano powder and the polyurethane material form a three-dimensional cross-linked structure, and the physical strength and the toughness of the material are remarkably improved.
The reaction process is shown as follows, wherein MO x Represents metal oxide nanopowder.
(4) The addition of the antioxidant 1010, the light stabilizer 770, the polyquaternium and the silicone powder improves the fluidity and the aging resistance of the powder, and avoids the problems of fluffiness and poor fluidity caused by static electricity generated in the process of mixing and transmitting the powder to a printer.
Drawings
FIG. 1 is an infrared spectrum of a material
FIG. 2 is a Raman spectrum of a material
FIG. 3 is a schematic view of a spline printing method
Detailed Description
Example 1
Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃, keeping the vacuum degree above-0.09 MPa, and dehydrating for 2 hours. Adding 93.2g of nano silicon dioxide with the particle size of 30um, fully stirring for 30min, introducing nitrogen, reducing the temperature to 70 ℃, adding 4g of catalyst and 875g of methylene-bis (4-phenyl isocyanate), and reacting for 2h under the protection of nitrogen to generate the polyurethane prepolymer capped by isocyanate groups. 231.4g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 60 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating. Finally, freezing and crushing the particles by liquid nitrogen, grinding the particles by a ball mill, and screening the particles by an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 123um, wherein the infrared spectrum and the Raman spectrum of the material are shown in figures 1 and 2.
As can be seen from FIG. 1, at 2000cm -1 -2500cm- 1 In the wave number range, no characteristic peak is obvious in an infrared diagram, and the fact that no free NCO group exists in a synthesized product system is proved, so that NCO reaction is complete. 3330cm -1 Stretching vibration peak of 1730cm of N-H group forming hydrogen bond at left and right -1 Stretching and contraction of the carbonyl group, indicating the formation of hydrogen bonds and the synthesis of the polyurethane elastomer. As can be seen from FIG. 2, 512cm -1 The absorption peak of S-S appeared and 640cm -1 The absorption peak of C-S shows up, which proves the successful accessing of disulfide bond into material system.
Example 2
Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 125 ℃, keeping the vacuum degree above-0.09 MPa, and dehydrating for 2 hours. Adding 145g of nano-silica with the particle size of 50um, fully stirring for 30min, introducing nitrogen, cooling to 70 ℃, adding 4g of catalyst and 750g of methylene-bis (4-phenyl isocyanate), and reacting for 3h under the protection of nitrogen to generate the polyurethane prepolymer capped by isocyanate groups. 154.2g of dithiodiglycol is added, the temperature is rapidly raised to 110 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 65 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 0.5 part of antioxidant 1010, 2 parts of light stabilizer 770, 1 part of silicone powder and 0.5 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 127 um.
Example 3
Adding 2kg of polytetramethylene adipate glycol with molecular weight of 2000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 130 ℃ and the vacuum degree above-0.09 MPa, and dehydrating for 2 h. Adding 107g of nano alumina with the particle size of 50um, fully stirring for 30min, introducing nitrogen, cooling to 80 ℃, adding 6g of catalyst and 524.7g of methylene-bis (4-cyclohexyl isocyanate), and reacting for 3h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 154.2g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 65 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 2 parts of antioxidant 1010, 0.5 part of light stabilizer 770, 5 parts of silicone powder and 2 parts of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 120 um.
Example 4
Adding 2kg of polytetramethylene adipate glycol with molecular weight of 2000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃ and the vacuum degree above-0.09 MPa, and dehydrating for 2 h. Adding 75g of nano silicon carbide with the particle size of 30um, fully stirring for 30min, introducing nitrogen, cooling to 75 ℃, adding 6g of catalyst and 393.5g of methylene-bis (4-cyclohexyl isocyanate), and reacting for 2h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 77g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 60 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1.5 parts of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1.5 parts of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 130 um.
Example 5
Compared with the embodiment 1, the nano powder modified by the dihydroxyl ionic liquid is adopted. Preparing 2wt% suspension of nano silicon dioxide with the particle size of 30um by adopting 65vol.% ethanol water solution, adding a silane coupling agent KH550 to the concentration of 0.5wt%, adding 1, 3-dihydroxyethyl imidazole chloride ionic liquid to the concentration of 1wt%, carrying out grafting reaction at the reaction temperature of 55 ℃ for 4h, filtering, washing and drying reaction products, and obtaining the nano silicon dioxide grafted with the ionic liquid. Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃, keeping the vacuum degree above-0.09 MPa, and dehydrating for 2 hours. Adding 93.2g of nano silicon dioxide grafted with ionic liquid, fully stirring for 30min, introducing nitrogen, reducing the temperature to 70 ℃, adding 4g of catalyst and 875g of methylene-bis (4-phenyl isocyanate), and reacting for 2h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 231.4g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 60 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 123 um.
Example 6
Compared with the embodiment 1, the nano powder modified by the dihydroxyl ionic liquid is adopted. Preparing 2wt% suspension of 50um nano-silica by adopting 65vol.% ethanol water solution, adding a silane coupling agent KH550 to a concentration of 1wt%, adding 1, 3-dihydroxyethyl imidazole chloride ionic liquid to a concentration of 0.5wt%, carrying out grafting reaction at a reaction temperature of 60 ℃ for 3h, filtering, washing and drying reaction products, and obtaining the nano-silica grafted with the ionic liquid. Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 125 ℃, keeping the vacuum degree above-0.09 MPa, and dehydrating for 2 hours. Adding 145g of nano silicon dioxide grafted with ionic liquid, fully stirring for 30min, introducing nitrogen, cooling to 70 ℃, adding 4g of catalyst and 750g of methylene-bis (4-phenyl isocyanate), and reacting for 3h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 154.2g of dithiodiglycol is added, the temperature is rapidly raised to 110 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 65 ℃.
Crushing the obtained self-repairing polyurethane elastomer, then uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating the mixture. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 127 um.
Example 7
Compared with the embodiment 1, the nano powder modified by the dihydroxyl ionic liquid is adopted. Preparing a suspension with the concentration of 2wt% by adopting 65vol.% ethanol water solution to prepare 50um nano-alumina, adding a silane coupling agent KH550 to the concentration of 0.5wt%, adding 1, 3-dihydroxyethyl imidazole chloride ionic liquid to the concentration of 1wt%, carrying out grafting reaction at the reaction temperature of 55 ℃ for 5h, and filtering, washing and drying a reaction product to obtain the nano-alumina grafted with the ionic liquid. Adding 2kg of polytetramethylene adipate glycol with molecular weight of 2000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 130 ℃ and the vacuum degree above-0.09 MPa, and dehydrating for 2 h. 107g of nano alumina grafted with ionic liquid is added, the mixture is fully stirred for 30min, nitrogen is introduced, the temperature is reduced to 80 ℃, 6g of catalyst and 524.7g of methylene-bis (4-cyclohexyl isocyanate) are added, and the mixture reacts for 3h under the protection of nitrogen, so that the polyurethane prepolymer terminated by isocyanate groups is generated. 154.2g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 65 ℃.
Crushing the obtained self-repairing polyurethane elastomer, then uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating the mixture. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 120 um.
Example 8
Compared with the embodiment 1, the nano powder modified by the dihydroxyl ionic liquid is adopted. Preparing a suspension with the concentration of 2wt% from 30um nano silicon carbide by adopting 65vol.% ethanol water solution, adding a silane coupling agent KH550 to the concentration of 1wt%, adding 1, 3-dihydroxyethyl imidazole chloride ionic liquid to the concentration of 0.5wt%, carrying out grafting reaction at the temperature of 60 ℃ for 3h, filtering, washing and drying a reaction product, and obtaining the nano silicon carbide grafted with the ionic liquid. Adding 2kg of polytetramethylene adipate glycol with molecular weight of 2000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃ and the vacuum degree above-0.09 MPa, and dehydrating for 2 h. Adding 75g of nano silicon carbide grafted with ionic liquid, fully stirring for 30min, introducing nitrogen, cooling to 75 ℃, adding 6g of catalyst and 393.5g of methylene-bis (4-cyclohexyl isocyanate), and reacting for 2h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 77g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the materials are stirred and discharged, and the self-repairing polyurethane elastomer is obtained after curing and molding at 60 ℃.
Crushing the obtained self-repairing polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an air classifier to obtain the selective laser sintering self-repairing polyurethane powder material with the particle size D90 of 130 um.
Comparative example 1
The difference from example 1 is that: the chain extender used was 1, 4-butanediol.
Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃, keeping the vacuum degree above-0.09 MPa, and dehydrating for 2 hours. Adding 93.2g of nano-silica with the particle size of 30um, fully stirring for 30min, introducing nitrogen, cooling to 70 ℃, adding 4g of catalyst and 875g of methylene-bis (4-phenyl isocyanate), and reacting for 2h under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. Adding 135g of 1, 4-butanediol, quickly heating to 100 ℃, stirring, discharging, and curing and molding at 60 ℃ to obtain the polyurethane elastomer.
Crushing the obtained polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating the mixture. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering polyurethane powder material with the particle size D90 of 125 um.
Comparative example 2
The difference from example 1 is that: no nanopowder was added.
Adding 2kg of polytetramethylene adipate glycol with the molecular weight of 1000 into a reactor with stirring, heating for melting, stirring, keeping the temperature at 120 ℃, the vacuum degree at more than-0.09 MPa, and dehydrating for 2 hours. Introducing nitrogen, reducing the temperature to 70 ℃, adding 4g of catalyst and 875g of methylene-bis (4-phenyl isocyanate), and reacting for 2 hours under the protection of nitrogen to generate the polyurethane prepolymer terminated by isocyanate groups. 231.4g of dithiodiglycol is added, the temperature is rapidly raised to 100 ℃, the mixture is stirred and discharged, and the polyurethane elastomer is obtained after curing and molding at 60 ℃.
Crushing the obtained polyurethane elastomer, uniformly mixing 100 parts of crushed particles, 1 part of antioxidant 1010, 1 part of light stabilizer 770, 3 parts of silicone powder and 1 part of antistatic agent polyquaternary ammonium salt in a high-speed mixer, putting the mixture into a double-screw extruder, and extruding and granulating the mixture. And finally, freezing and crushing the particles by adopting liquid nitrogen, grinding the particles by using a ball mill, and screening the particles by using an airflow classifier to obtain the selective laser sintering polyurethane powder material with the particle size D90 of 123 um.
And (3) carrying out selective laser sintering 3D printing on the obtained polyurethane powder, setting sintering process parameters as laser power 35w, scanning speed as 3000mm/s, scanning interval as 0.1mm, layering thickness as 0.1mm, processing temperature as 125 ℃, printing the test sample strip shown in the figure 3, and carrying out tensile property test, wherein the test results are shown in Table 1.
TABLE 1
As can be seen from the above table, the self-modifying polyurethane material capable of 3D printing is successfully prepared, and as can be seen from the table 1, the material has the advantage of good physical strength; as can be seen from the comparison of example 1 and comparative example 1, the addition of the nanofiller increases the tensile strength of the material itself; it can be seen from the comparison between example 1 and comparative example 2 that the disulfide bond-containing diol is used as a chain extender and reacts with the polyurethane prepolymer to synthesize a disulfide bond-containing polyurethane elastomer, the disulfide bond-containing polyurethane elastomer has a reversible exchange dynamic balance reaction performance and a synergistic effect with a hydrogen bond, so that the material has good mechanical properties and initial bonding capability, and the strength retention of a sintered product in the Z direction is good due to the synergistic effect of the disulfide bond; it can be seen from the comparison between example 1 and example 4 that the ionic liquid with dihydroxy is introduced in the process of crosslinking the silane coupling agent on the surface of the nano inorganic powder material, so that the ionic liquid can be grafted on the surface of the nano inorganic powder material, and then the nano inorganic particles can be embedded into the three-dimensional network of polyurethane during the condensation reaction of the polyurethane material, thereby effectively improving the tensile and strength properties of the material.
Repair performance testing of polyurethane materials
Processing the prepared polyurethane material into a sample strip, quickly cutting off the sample strip from the middle part of the sample strip, attaching the fracture surface, heating to 70 ℃ for repairing for 18h, testing the tensile strength of the sample strip, and defining the ratio of the tensile strength to the original tensile strength as the repairing rate. The test results are shown in table 2:
TABLE 2
The polyurethane material prepared by the invention has good self-repairing performance, the cross-linking and self-repairing performance of the material can be effectively improved by using the diol containing the disulfide bond as the chain extender, and the repairing rate after cutting is obviously higher than that of the polyurethane material prepared by using the traditional diol chain extender.
Claims (5)
1. A selective laser sintering self-repairing polyurethane powder material is characterized in that the material is prepared by compounding self-repairing polyurethane, nano powder, an antioxidant, a light stabilizer, silicone and an antistatic agent; wherein, the self-repairing polyurethane is obtained by carrying out chain extension reaction on dithiodiglycol;
the preparation method of the selective laser sintering self-repairing polyurethane powder material comprises the following steps:
step 1, synthesis of a self-repairing polyurethane elastomer: dehydrating polyester polyol, adding nano powder, adding a catalyst and diisocyanate in an inert gas atmosphere, and carrying out prepolymerization reaction to generate an isocyanate group-terminated polyurethane prepolymer; adding a chain extender, heating to carry out chain extension reaction, discharging and curing after the chain extension reaction is finished, and obtaining the self-repairing polyurethane elastomer; the polyester polyol is polytetramethylene adipate glycol with the molecular weight of 1000-2000; the diisocyanate is one of methylene-bis (4-phenyl isocyanate) or methylene-bis (4-cyclohexyl isocyanate); the molar ratio of the polyester polyol to the diisocyanate to the chain extender is 1 (1.5-2) to 0.5-1; the adding amount of the nano powder is 3-5% of the total mass of the polyester polyol, the diisocyanate and the chain extender; the preparation steps of the nano powder are as follows: preparing 1-3wt% of suspension liquid from the nano particles by adopting ethanol water solution, adding a silane coupling agent to the concentration of 0.5-1wt%, adding an ionic liquid containing dihydroxy to the concentration of 0.5-1wt%, carrying out grafting reaction, filtering, washing and drying a reaction product to obtain nano powder of the grafted ionic liquid; the nano particles are one of nano silicon dioxide, nano aluminum oxide and nano silicon carbide, and the particle size is 30-50 mu m; the ionic liquid containing dihydroxy is 1, 3-dihydroxyethyl imidazole chloride; the concentration of the ethanol aqueous solution is 60-70 vol.%, and the silane coupling agent is KH550 or KH 560; the temperature of the grafting reaction is 45-65 ℃, and the reaction time is 2-8 h;
step 2, preparation of a selective laser sintering self-repairing polyurethane powder material: after the self-repairing polyurethane elastomer is crushed, 100 parts by weight of the self-repairing polyurethane elastomer, 0.5-2 parts by weight of an antioxidant, 0.5-2 parts by weight of a light stabilizer, 1-5 parts by weight of silicone and 0.5-2 parts by weight of an antistatic agent are mixed, the mixture is extruded by a double-screw extruder for granulation, and the granules are crushed and screened to obtain the selective laser sintering self-repairing polyurethane powder material.
2. The selective laser sintering self-repairing polyurethane powder material of claim 1, wherein in the step 1, the conditions for dehydration are 120-130 ℃, the vacuum degree is-0.09 MPa or more, and the dehydration lasts for 1-5 h; the parameters for carrying out the prepolymerization reaction are: the temperature is 70-80 ℃, and the reaction time is 1-4 h.
3. The selective laser sintering self-repairing polyurethane powder material of claim 1, wherein in the step 1, the chain extender is dithiodiglycol, and the parameters of the chain extension reaction are as follows: reacting at 100 ℃ and 110 ℃ for 1-5 h.
4. The selective laser sintering self-repairing polyurethane powder material of claim 1, wherein the temperature of the curing process is 60-65 ℃; the antioxidant is antioxidant 1010; the light stabilizer is light stabilizer 770; the antistatic agent is polyquaternium; the screening process adopts an air classifier to screen, and the powder particle size D90= 110-.
5. The application of the selective laser sintering self-repairing polyurethane powder material in 3D printing.
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