CN113667295A - Preparation method of poly (urethane-urea-amide) elastomer powder for selective laser sintering and product - Google Patents

Preparation method of poly (urethane-urea-amide) elastomer powder for selective laser sintering and product Download PDF

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CN113667295A
CN113667295A CN202110957158.8A CN202110957158A CN113667295A CN 113667295 A CN113667295 A CN 113667295A CN 202110957158 A CN202110957158 A CN 202110957158A CN 113667295 A CN113667295 A CN 113667295A
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polyamide
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amide
urethane
urea
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付鹏
李震
梅树翔
刘民英
赵清香
崔喆
张晓朦
庞新厂
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Zhengzhou University
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Abstract

The invention belongs to the technical field of additive manufacturing, and discloses poly (urethane-urea-amide) elastomer powder for selective laser sintering and a preparation method thereof. The preparation method comprises the following steps: 1) pre-cooling the poly (urethane-urea-amide) elastomer granules by liquid nitrogen, and then crushing; 2) sieving the powder, wherein the particle size of the powder is selected to be 0-300 μm; 3) uniformly mixing the screened poly (urethane-urea-amide) elastomer powder with a flow aid and an antioxidant according to a certain mass ratio to obtain the poly (urethane-urea-amide) elastomer powder for selective laser sintering printing, which has the advantages of good fluidity, wide printing window, antistatic property, excellent mechanical property and water resistance of products. The material can be applied to the fields of aerospace, medical treatment orthopedic, sports equipment and the like.

Description

Preparation method of poly (urethane-urea-amide) elastomer powder for selective laser sintering and product
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a preparation method of poly (urethane-urea-amide) elastomer powder for selective laser sintering and an elastomer powder product obtained by the method.
Background
Selective Laser Sintering (SLS) is a typical 3D printing and forming technology using powder as a raw material, and the principle is to selectively irradiate and heat the powder material by high-energy laser according to a three-dimensional image of an object to be produced, so that the powder is fused and consolidated point by point, line by line and plane by plane to produce a three-dimensional entity. Compared with other 3D printing technologies, the SLS has the remarkable advantages of high forming precision, complex and various formable structures, no need of additional support and the like, and is widely applied to the fields of aerospace, biomedical treatment, automobile manufacturing, moving devices, mold casting and the like.
Thermoplastic elastomers (TPEs) have both the elasticity of rubber and the ability to be repeatedly processed by thermoplastics and are known as "third generation synthetic rubbers". Thermoplastic poly (urethane-urea-amide) elastomer (PUUA) is a late TPE, has the advantages of high tensile strength, good flexibility, high elastic recovery rate, good solvent resistance, good chemical resistance, high low-temperature impact strength, easy molding processing, toughness, wear resistance and the like, and is developed rapidly in recent years.
Currently, polyamide powder and polyurethane elastomer powder are relatively popular SLS polymer powder materials. CN 107236295B, CN 107722618B, CN107722617B, US 20210187839A1, EP 3523117B1 and the like are all polyamide powders. However, polyamide powders have the disadvantage of insufficient resilience. Because the antistatic performance of the polyamide powder is poor, the particle size range for 3D printing is narrow, in order to improve the powder utilization rate, the polyamide powder is generally prepared by a solvent precipitation method, the solvent recovery can improve the production cost, and the three-waste discharge amount is increased.
CN 111995861A, CN 108164719A, CN 108164983A, IN 366983B, US20210187933a1 and the like are all polyurethane elastomer powder, which is a polymer material developed relatively well, but the polyurethane powder has high water absorption rate, and the powder is easy to bond in SLS molding process, so the molding cylinder temperature is low, higher laser power is required to melt the powder, and the powder is easy to decompose and generate smoke in printing process.
CN112745461A mentions a composite powder which takes polystyrene as a matrix and can be used for SLS processing, the powder particles are composed of continuous phase polystyrene, disperse phase ethylene vinyl acetate copolymer and dispersed nano zinc oxide, and the particle size is several micrometers to dozens of micrometers;
CN107141769A takes cryogenic pulverized TPU powder as a main research object, improves the printing processability of TPU and the mechanical property of a formed part by mixing nylon powder, a flow aid and the like, but has wider particle size distribution.
CN106554473B has developed a kind of SEBS elastomer material that can be directly used to selectivity laser sintering processing, and SEBS passes through acetone swelling back, through spray drying, obtains the nucleocapsid structure elastomer powder who has good sphericity degree, but used a large amount of organic solvents in the preparation powder process, and the mechanical properties of printing the goods awaits improvement.
Disclosure of Invention
The invention aims to provide a novel poly (urethane-urea-amide) elastomer powder for selective laser sintering printing. The polymer powder material for SLS printing is single, easy to warp and generate smoke, narrow in printing window, poor in antistatic property, and poor in product flexibility, rebound resilience and water resistance.
In order to achieve the purpose, the invention provides the following scheme:
a method of preparing a poly (urethane-urea-amide) elastomer powder for selective laser sintering, comprising the steps of:
1) pre-cooling the poly (urethane-urea-amide) elastomer granules by liquid nitrogen, and then crushing;
2) sieving the crushed powder, wherein the particle size of the powder is selected to be 0-300 mu m;
3) mixing the undersize product obtained in the step 2) with a flow aid and an antioxidant in proportion to obtain the finished product.
The flow aid is one or more than two of gas-phase titanium dioxide, gas-phase nano silicon dioxide, talcum powder, calcium stearate and glass beads, and the addition amount of the flow aid accounts for 0.2-2.0 wt% of the total amount of the mixed powder; the antioxidant is one or more than two of sodium hypophosphite, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenol and 2, 2' -methylenebis (4-methyl-6-tert-butylphenol), and the addition amount of the antioxidant accounts for 0.2-1.0 wt% of the total amount of the mixed powder.
The poly (urethane-urea-amide) elastomer is a segmented block copolymer composed of a polyamide segment and a polyurethane segment, and the molecular chain repeating unit of the segmented block copolymer has the following structure:
Figure BDA0003220773350000021
wherein R is1、R2、R3Respectively, polyether and/or polyester, diisocyanate, polyamide.
The polyurethane consists of polyether and/or polyester with double hydroxyl groups and diisocyanate; the diisocyanate is one or more than two of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, 4 '-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate.
The polyamide is double-end amino polyamide; the double-end amino polyamide is one or more of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1011, polyamide 1012, polyamide 1013, polyamide 1111, polyamide 1112, polyamide 1113, polyamide 1212, polyamide 1213, polyamide 1313 and polyamide 1414.
The polyether and/or polyester is hydroxyl-terminated polyether and/or polyester; the polyether and/or polyester with double hydroxyl groups at the two ends is one or more than two of polytetrahydrofuran ether glycol, polypropylene oxide glycol, poly adipic acid-1, 6-hexanediol glycol, poly adipic acid-1, 4-butanediol glycol and tetrahydrofuran-propylene oxide copolymerization glycol.
The relative molecular weight of the polyamide is 500-8000; the relative molecular weights of the polyethers and polyesters are 750-.
In the step 1), the pre-cooling temperature and the crushing temperature are both-140 to-80 ℃, the pre-cooling time is 1 to 30min, and the frequency of a crushing cutter head is 30 to 50 Hz.
A poly (urethane-urea-amide) elastomer powder product for selective laser sintering is obtained according to said process.
The relative viscosity of the poly (urethane-urea-amide) elastomer powder is 1.5-3.0, and the melt index is 3.0-30.0.
Compared with the prior art, the invention has the following technical advantages:
1. this patent provides a novel thermoplastic elastomer powder, namely poly (urethane-urea-amide) elastomer powder, that can be used for selective laser sintering 3D printing formation. The poly (urethane-urea-amide) elastomer structurally has the inherent advantages of softness, hardness and adjustable melting point, has the toughness and wear resistance of nylon besides excellent flexibility and rebound resilience, and also has the advantages of low density, low water absorption, static resistance and the like. The invention develops the selective laser sintering 3D printing powder of the poly (urethane-urea-amide) elastomer and expands the application range of the powder in the field of additive manufacturing. When the prepared powder is close to the melting point of the material, the prepared powder still can keep good powder flowability, does not adhere or agglomerate and has high printing speed. The thermal stability is good, and the product can not be heated and decomposed when being printed. The product has physical and mechanical properties equivalent to those of melt molding.
2. The invention provides a new method for preparing PUUA selective laser sintering 3D printing powder by a freezing and crushing method for the first time. The good antistatic properties of PUUA make it possible to obtain a wide range of printable powder particle sizes (0-300 μm), and therefore its powder can be prepared by the freeze-milling method. By using the preparation method of the invention, the single utilization rate of the powder is higher than 60%, and the production cost is greatly reduced. Compared with the traditional solvent precipitation method, the method does not need an organic solvent, further improves the production safety, and reduces the three-waste discharge and the raw material cost. Through the screening optimization of the flow aid and the antioxidant, the PUUA powder disclosed by the invention has good fluidity, high powder laying efficiency and high speed. The powder has good thermal stability, no decomposition, no yellowing and good repeated processability in the processing process.
3. The invention provides poly (urethane-urea-amide) elastomer powder applicable to selective laser sintering printing and a preparation method thereof by adopting a cryogenic grinding method to prepare PUUA powder and screening an antioxidant, a flow additive, a filler and the like. Compared with the traditional solvent method, the cryogenic grinding method adopted by the invention can be used for preparing the poly (urethane-urea-amide) elastomer powder in an environment-friendly and efficient manner.
PUUA powder is a novel polymer material for SLS printing. PUUA is a segmented block copolymer with polyamide as a hard segment and polyether and/or polyester as a soft segment, wherein the hard segment crystal region has high melting point and crystallinity, so that PUUA powder has a wider SLS printing window. The polyamide is used as a hard segment to endow the material with rigidity, and a hard segment crystal region forms physical support in the elastomer, so that the dimensional stability of a printed product is improved; the soft segment has lower glass transition temperature and segment flexibility, and endows the copolymer with excellent flexibility.
5. Compared with the traditional TPU powder, the PUUA powder has better thermal stability and low temperature resistance, wider adjustable hardness range and good antistatic property. The PUUA powder has a wider usable particle size range (0-300 mu m) in the SLS printing process, and is high in powder utilization rate and good in fluidity, so that the problems that the powder is easy to yellow at high temperature, easy to generate static electricity, poor in fluidity and low in powder utilization rate in SLS printing can be effectively solved.
And 6, the PUUA has a narrow melting range, and the obtained powder can still keep good powder flowability, does not adhere or agglomerate when the melting point of the material is close to the melting point of the material. Therefore, the preheating temperature of the powder can be close to the melting point, and the laser power required during printing is low. The advantage is that printing speed is fast, and the product is not heated and is decomposed when printing. Compared with polyurethane, the polyurethane begins to bond powder at about 70 ℃, so the preheating temperature is about 60 ℃, the difference between the preheating temperature and the melting point is more than 100 ℃, the required laser power is high, the printing speed is low, high-power laser can cause the powder to be decomposed during printing, and besides smoke, the product performance can be reduced.
Drawings
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following briefly introduces the drawings needed for embodiments or prior art descriptions, and obviously, the drawings in the following description are only some embodiments of the present invention:
FIG. 1 is a FT-IR diagram of a poly (urethane-urea-amide) elastomer provided in example 1 of the present invention;
FIG. 2 is a DSC of the poly (urethane-urea-amide) elastomer provided in example 1 of the present invention, respectively.
Detailed Description
In order that the invention may be more clearly understood, embodiments of the invention will now be further described with reference to the accompanying drawings. In the present invention, the preparation method of the poly (urethane-urea-amide) elastomer comprises: a) keeping the polyamide salt and the diamine end-capping reagent at the temperature of 280 ℃ of 190 ℃ and the pressure of 1.0-2.0MPa for 0.5-3 hours in the inert gas atmosphere, then reducing the system pressure to the normal pressure within 1-5 hours, and discharging to obtain the diamine end-capped polyamide; b) Mixing diisocyanate and hydroxyl-terminated polyether and/or polyester according to a molar ratio of 2:1, and reacting at a constant temperature of 60-90 ℃ for 1-3h in an inert gas atmosphere to obtain polyurethane; c) mixing the diamino terminated polyamide in the step 1) and the polyurethane in the step 2) according to the mol ratio (0.98-1.02):1, adding the mixture into an extruder, reacting at the temperature of 175-280 ℃ for 2-15min, and extruding and granulating to obtain the polyurea amide elastomer granules.
In each embodiment of the invention, the extruder adopts a double-screw extruder, and the extrusion parameters of the double-screw extruder are as follows: the temperatures of the first, second, third and fourth zones are 175 deg.C, 195 deg.C and 180 deg.C respectively, the screw rotation speed is set to 30r/min, and the extrusion time is 2 min. The patent CN1255507A describes the preparation method of the nylon salt in detail, and is not described in detail here.
Example 1
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering, wherein the poly (urethane-urea-amide) elastomer is a segmented block copolymer of amino-terminated polyamide 1212 and isocyanate-terminated polyurethane, wherein the polyurethane is composed of 1, 6-hexamethylene diisocyanate and polytetrahydrofuran ether glycol; the polyamide 1212 had a relative molecular weight of 1000 and the polytetrahydrofuran ether glycol had a relative molecular weight of 2000.
The preparation method comprises the following steps:
1) pre-cooling 10kg of poly (urethane-urea-amide) elastomer granules by liquid nitrogen, keeping the temperature for 5min when the freezing temperature reaches-100 ℃, then opening a freezing crusher, mechanically crushing the granules at-100 ℃ with the frequency of a cutter head of 45Hz, and finally discharging the materials to obtain 9.5kg of coarse powder;
2) sieving the powder with 100 mesh electric sieving machine to obtain powder with particle size of 0-150 μm, drying at 80 deg.C for 5 hr, and testing water content below 0.1%.
3) 0.8 wt% of fumed nano silica and 0.2 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] were added to the dried poly (urethane-urea-amide) elastomer powder, and the mixture was uniformly mixed to obtain poly (urethane-urea-amide) elastomer powder for selective laser sintering, which was labeled PUUA 1.
PUUA1 had a repose angle of 35 ° and a bulk density of 0.45g/cm3。
Example 2
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the polyamide 1212 has a relative molecular weight of 500 and the polytetrahydrofuran ether glycol has a relative molecular weight of 750. The resulting product is labeled PUUA 2.
PUUA2 had a repose angle of 45 DEG and a bulk density of 0.5g/cm3。
Example 3
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the polyamide 1212 has a relative molecular weight of 5000 and the polytetrahydrofuran ether glycol has a relative molecular weight of 5000. The resulting product is labeled PUUA 3.
PUUA3 had a repose angle of 42 DEG and a bulk density of 0.3g/cm3。
Example 4
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the pre-cooling temperature and the pulverization temperature are-80 ℃. The resulting product is labeled PUUA 4.
PUUA4 had a repose angle of 36 ° and a bulk density of 0.47g/cm3。
Example 5
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the pre-cooling temperature and the pulverization temperature are-120 ℃. The resulting product is labeled PUUA 4.
PUUA5 had a repose angle of 40 DEG and a bulk density of 0.49g/cm3。
Example 6
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the pre-cooling temperature and the pulverization temperature are-140 ℃. The resulting product is labeled PUUA 6.
PUUA6 had a repose angle of 41 DEG and a bulk density of 0.49g/cm3。
Example 7
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that fumed nano silica is added in an amount of 0.2 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 7. PUUA7 had a repose angle of 38 DEG and a bulk density of 0.48g/cm3。
Example 8
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that fumed nano silica is added in an amount of 1.4 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 8. PUUA8 had a repose angle of 36 ° and a bulk density of 0.49g/cm3。
Example 9
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that fumed nano silica is added in an amount of 2.0 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 9. PUUA9 had a repose angle of 34 ° and a bulk density of 0.49g/cm3。
Example 10
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differs from example 1 only in that the flow aid is fumed titanium dioxide and is added in an amount of 0.8 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 10. Rest of PUUA10The angle was 37 ℃ and the bulk density was 0.46g/cm3。
Example 11
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is added in an amount of 0.6 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 11. PUUA11 had a repose angle of 36 ° and a bulk density of 0.46g/cm3。
Example 12
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is added in an amount of 0.8 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 12. PUUA12 had a repose angle of 34 ° and a bulk density of 0.47g/cm3。
Example 13
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is added in an amount of 1.0 wt%.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 13. PUUA13 had a repose angle of 35 ° and a bulk density of 0.49g/cm3。
Example 14
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, which differ from example 1 only in that the hydroxyl-terminated polyether is polyoxypropylene glycol; the relative molecular weight of the polyoxypropylene diol was 2000.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 14. PUUA14 had a repose angle of 36 ℃ and a bulk density of 0.48g/cm3。
Example 15
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the hydroxyl-terminated polyester is poly 1, 6-hexanediol adipate diol; the relative molecular weight of the poly (1, 6-hexanediol adipate) glycol is 2000.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 15. PUUA15 had a repose angle of 35 ° and a bulk density of 0.47g/cm3。
Example 16
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is a double-terminal amino group polyamide 6.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 16. PUUA16 had a repose angle of 39 DEG and a bulk density of 0.49g/cm3。
Example 17
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is amino-terminated polyamide 12.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 17. PUUA17 had a repose angle of 35 ° and a bulk density of 0.44g/cm3。
Example 18
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is amino-terminated polyamide 66.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 18. PUUA18 had a repose angle of 37 ℃ and a bulk density of 0.47g/cm3。
Example 19
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is a double-ended amino group polyamide 612.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 19. PUUA19 had a repose angle of 38 DEG and a bulk density of 0.45g/cm3。
Example 20
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is a double-terminal amino polyamide 1010.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 20. PUUA20 had a repose angle of 37 ℃ and a bulk density of 0.43g/cm3。
Example 21
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is amino-terminated polyamide 1012.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 21. PUUA21 had a repose angle of 34 ° and a bulk density of 0.40g/cm3。
Example 22
This example provides a poly (urethane-urea-amide) elastomer powder for selective laser sintering and a method for preparing the same, differing from example 1 only in that the polyamide is a double-ended amino polyamide 1313.
The resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering is designated PUUA 22. PUUA22 had a repose angle of 36 ° and a bulk density of 0.41g/cm3。
Examples of the experiments
In the examples of the present invention, the physical properties of part of the resulting poly (urethane-urea-amide) elastomer powder for selective laser sintering were characterized, and the test instruments and test standards used for each characterization are shown below.
TABLE 1 test items, instruments and standards
Figure BDA0003220773350000091
Figure BDA0003220773350000101
The SLS printed article properties of the poly (urethane-urea-amide) elastomer powder obtained in the examples are shown in table 2.
TABLE 2 physical Properties of the Poly (urethane-urea-amide) elastomer powders obtained in the examples
Figure BDA0003220773350000102
As can be seen from fig. 1, fig. 2 and table 2, the poly (urethane-urea-amide) elastomer powder for selective laser sintering, which is obtained by the preparation method, has good fluidity, wide printing window and excellent mechanical properties of printed products, is obtained by performing a part of physical property characterization tests on the poly (urethane-urea-amide) elastomer powder obtained in the 22 examples. Wherein the PUUA1 powder yield (0-150 μm) is up to 63%, the repose angle is 35 DEG, the bulk density is 0.45, the tensile strength is 14.5MPa, and the elongation at break is 253%.
The above-described embodiments describe several embodiments of the present invention in more detail and specifically, but do not represent limitations to the scope of the invention. The protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method for preparing a poly (urethane-urea-amide) elastomer powder for selective laser sintering, comprising the steps of:
1) pre-cooling the poly (urethane-urea-amide) elastomer granules by liquid nitrogen, and then crushing;
2) sieving the crushed powder, wherein the particle size of the powder is selected to be 0-300 mu m;
3) mixing the undersize product obtained in the step 2) with a flow aid and an antioxidant in proportion to obtain the finished product.
2. The preparation method of the poly (urethane-urea-amide) elastomer powder for selective laser sintering according to claim 1, wherein the flow aid is one or more of fumed titanium dioxide, fumed nano-silica, talc powder, calcium stearate and glass beads, and the addition amount of the flow aid is 0.2-2.0 wt% of the total amount of the mixed powder; the antioxidant is one or more than two of sodium hypophosphite, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenol and 2, 2' -methylenebis (4-methyl-6-tert-butylphenol), and the addition amount of the antioxidant accounts for 0.2-1.0 wt% of the total amount of the mixed powder.
3. The method according to claim 1, wherein the poly (urethane-urea-amide) elastomer is a segmented block copolymer of a polyamide segment and a polyurethane segment, and the repeating unit of the molecular chain has the following structure:
Figure FDA0003220773340000011
wherein R is1、R2、R3Respectively, polyether and/or polyester, diisocyanate, polyamide.
4. The process for preparing a poly (urethane-urea-amide) elastomer powder for selective laser sintering according to claim 3, wherein the polyurethane consists of hydroxyl terminated polyethers and/or polyesters, diisocyanates; the diisocyanate is one or more than two of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, 4 '-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate.
5. The method of claim 3, wherein the polyamide is a double-ended amino polyamide; the double-end amino polyamide is one or more of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1011, polyamide 1012, polyamide 1013, polyamide 1111, polyamide 1112, polyamide 1113, polyamide 1212, polyamide 1213, polyamide 1313 and polyamide 1414.
6. The method of claim 3, wherein the polyether and/or polyester is a hydroxyl terminated polyether and/or polyester; the polyether and/or polyester with double hydroxyl groups at the two ends is one or more than two of polytetrahydrofuran ether glycol, polypropylene oxide glycol, poly adipic acid-1, 6-hexanediol glycol, poly adipic acid-1, 4-butanediol glycol and tetrahydrofuran-propylene oxide copolymerization glycol.
7. The method for preparing poly (urethane-urea-amide) elastomer powder for selective laser sintering as claimed in claim 3, wherein the relative molecular weight of the polyamide is 500-8000; the relative molecular weights of the polyethers and polyesters are 750-.
8. The method for preparing poly (urethane-urea-amide) elastomer powder for selective laser sintering according to any one of claims 1 to 7, wherein in step 1), the pre-cooling temperature and the crushing temperature are both-140 ℃ to-80 ℃, the pre-cooling time is 1 to 30min, and the frequency of a crushing cutter is 30 Hz to 50 Hz.
9. A poly (urethane-urea-amide) elastomer powder product for selective laser sintering obtained according to the method of claim 8.
10. The poly (urethane-urea-amide) elastomer powder product for selective laser sintering according to claim 9, wherein the relative viscosity of the poly (urethane-urea-amide) elastomer powder is 1.5 to 3.0, and the melt index is 3.0 to 30.0.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1255887A (en) * 1997-03-18 2000-06-07 纳幕尔杜邦公司 Laser sinterable thermoplastic power
CN112961305A (en) * 2021-03-12 2021-06-15 郑州大学 Preparation method of polyureauramide elastomer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1255887A (en) * 1997-03-18 2000-06-07 纳幕尔杜邦公司 Laser sinterable thermoplastic power
CN112961305A (en) * 2021-03-12 2021-06-15 郑州大学 Preparation method of polyureauramide elastomer

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