CN112159539B - Novel polyphenylene sulfide powder for selective laser sintering, preparation method thereof and polyphenylene sulfide mixed powder - Google Patents
Novel polyphenylene sulfide powder for selective laser sintering, preparation method thereof and polyphenylene sulfide mixed powder Download PDFInfo
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Abstract
A novel polyphenylene sulfide powder for selective laser sintering, a preparation method thereof and a polyphenylene sulfide mixed powder are provided, wherein the preparation method of the novel polyphenylene sulfide powder comprises the following steps: placing polyphenylene sulfide resin, a lubricant and a main antioxidant into a mixer for mixing to obtain a mixture; putting the mixture into an extruder for melting to obtain mixed granules; drying the mixed granules, and then putting the dried mixed granules into a cryogenic pulverizer to prepare powder so as to obtain polyphenylene sulfide semi-finished product powder; and putting the polyphenylene sulfide semi-finished product powder, the flow additive, the auxiliary antioxidant and the inorganic filler into a stirrer, fully mixing, and screening to obtain the novel polyphenylene sulfide powder. The novel polyphenylene sulfide powder prepared by the invention has high-efficiency oxidation resistance to all forms of oxidation reactions, so that the crystal structure of the polyphenylene sulfide powder is kept stable; and the new polyphenylene sulfide powder and the quantitative residual powder are mixed by the stirrer, so that the antioxidant content of the polyphenylene sulfide mixed powder is kept stable, and the improvement of sintering repeatability is realized.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to novel polyphenylene sulfide powder for selective laser sintering, a preparation method of the novel polyphenylene sulfide powder and polyphenylene sulfide mixed powder.
Background
The Selective Laser Sintering (SLS) technology for manufacturing objects by layer-by-layer stacking is the most industrialized material increase technology due to the advantages of simple process, no need of support, high utilization rate and the like. It is well known that polymers are commonly used materials for SLS, wherein nylon occupies more than 90% of the market due to high laser absorption efficiency and good mechanical properties. More importantly, the nylon has low melting point and has no strict requirement on the temperature resistance of equipment, so that the nylon is widely applied to middle and low-end fields of hand plates, model manufacturing and the like. With the progress of mechanical temperature-resistant technology, high-melting point materials are receiving attention. Among them, polyphenylene sulfide (PPS), which is a special engineering plastic, has a high laser absorption efficiency as nylon does. Compared with nylon, the nylon has higher strength, temperature resistance and corrosion resistance. Is considered to be the next most commercially promising SLS material.
Although PPS has a series of performance advantages, sulfur in the molecule is divalent, and the outermost electrons are easily combined with oxygen, so that the crystal structure is damaged. PPS has been a well-established solution to this problem in the conventional art, but SLS equipment cannot completely isolate oxygen and requires long processing (about 24 hours) in a high temperature environment, and the SLS powder can only be in the micron-sized range (wanyan selective laser sintering polymer material and its product performance study). The superposition of the above characteristics further exacerbates the oxidation degree of PPS, so that the PPS processed by SLS is yellowed and is accompanied with the remarkable reduction of mechanical properties. Therefore, the improvement of oxidation resistance is one of the most critical technologies of PPS for SLS. At present, the oxidation resistance of PPS is mainly divided into a physical method and a chemical method, and the physical method mainly improves the oxidation resistance by controlling the physical properties of powder. Such as patent numbers: CN105504813A, the degree of oxidation is controlled by increasing the particle size of PPS powder, but this method has to adopt a costly spheroidizing technique to increase the sphericity of the powder to offset the negative influence of particle size on flowability. Chemical rules inhibit the degree of oxidation of PPS by the addition of antioxidants; such as the patent numbers: CN104231607A, adding an antioxidant into the PPS powder by high-speed stirring to realize the improvement of the antioxidant capacity; patent numbers: CN104650587B, through adding antioxidant by melting and mixing, the oxidation resistance of the finished PPS powder is improved, and the mechanical property is also slightly improved. However, because the oxidation form of PPS is complex, mainly including two forms of thermal oxidation reaction (chemical formula 1, 2) and radical reaction (chemical formula 3, 4), the oxidation resistance of PPS is improved by adding an auxiliary agent during one of melt mixing and high-speed stirring processes in the current methods, and the methods can only effectively inhibit one of the oxidation reactions. Therefore, even if the schemes have certain oxidation resistance to the novel polyphenylene sulfide powder, the oxidation degree of the powder is obviously improved when the powder is repeatedly used, and the problems of mechanical property reduction, yellowing of workpieces and the like of finally formed workpieces are inevitable. Obviously, the reduction of the number of repetitions will bring linear growth to the processing cost of the material, which greatly limits the commercialization of polyphenylene sulfide powder in the SLS technology field.
Disclosure of Invention
For the two oxidation forms of polyphenylene sulfide, the thermal oxidation reaction is an oxidation process in which oxygen directly participates, and the reaction mainly occurs on the surface of powder particles in an SLS forming cylinder; the radical reaction is an oxidation process catalyzed by radicals under heating and oxygen atmosphere, and mainly occurs inside the powder particles during laser sintering. The above oxidation reaction in the SLS equipment causes polyphenylene sulfide molecules to generate internal crosslinking and molecular degradation, both of which destroy the crystalline structure of the molecular chain, and finally, the mechanical properties of the molded workpiece are reduced and accompanied by yellowing.
Therefore, the innovation of the invention is that the main antioxidant for eliminating free radicals is added into the polyphenylene sulfide resin by a melt mixing method to directionally inhibit free radical reaction (see the following reaction formulas (3) and (4)), and then the auxiliary antioxidant for eliminating peroxide is efficiently loaded on the surface of the polyphenylene sulfide powder subjected to cryogenic grinding treatment by a high-speed stirring manner to directionally inhibit thermo-oxidative reaction (see the following reaction formulas (1) and (2)); thereby synergistically improving the oxidation resistance of the novel polyphenylene sulfide powder, improving the mechanical property of finished workpieces and inhibiting the yellowing of the workpieces. Meanwhile, the surface-loaded additive has the characteristic of transferability under a specific stirring condition, so that the oxidant on the surface of the new powder is transferred to the quantitative residual powder completely consumed by the auxiliary oxidant, the improvement of the repeatability of the polyphenylene sulfide powder is realized, and the manufacturing cost of the terminal product is obviously reduced.
In order to achieve the above purpose, the invention provides a novel polyphenylene sulfide powder for selective laser sintering, a preparation method thereof and a polyphenylene sulfide mixed powder, so as to solve the technical problems of insufficient oxidation resistance of the novel polyphenylene sulfide powder and poor sintering repeatability of the mixed powder in the prior art.
In order to solve the technical problems, the invention provides a preparation method of novel polyphenylene sulfide powder for selective laser sintering, which comprises the following steps:
firstly, putting polyphenylene sulfide resin, a lubricant and a main antioxidant into a mixer for mixing to obtain a mixture;
step two, putting the mixture into an extruder for melting to obtain mixed granules;
and step three, drying the mixed granules, and then putting the dried mixed granules into a cryogenic pulverizer to prepare powder so as to obtain polyphenylene sulfide semi-finished product powder.
Putting the polyphenylene sulfide semi-finished product powder, the flow additive, the auxiliary antioxidant and the inorganic filler into a stirrer, fully mixing, and screening to obtain new polyphenylene sulfide powder; wherein the content of the first and second substances,
the polyphenylene sulfide resin, the lubricant, the primary antioxidant, the secondary antioxidant, the flow assistant and the inorganic filler are as follows in parts by weight:
100 parts of polyphenylene sulfide resin
1-5 parts of lubricant
0.01-0.5 part of main antioxidant
0.01-2.5 parts of auxiliary antioxidant
0.1-5 parts of flow assistant
0-50 parts of inorganic filler.
In a further preferred embodiment of the present invention, the primary antioxidant is a phenolic antioxidant and/or an aminic antioxidant.
In a further preferred embodiment of the present invention, the phenolic antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol ester, 2,2' -methylenebis (4-methyl-6-tert-butylphenol); the amine antioxidant is one or more of octylated diphenylamine, 4 '-di (alpha, alpha-dimethylbenzyl) diphenylamine, N-phenyl-N' -isopropyl-p-phenylenediamine, N, N '-di (1, 4-dimethylpentyl) -p-phenylenediamine and N-phenyl-N' - (p-toluenesulfonyl) -p-phenylenediamine.
As a further preferable mode of the present invention, the secondary antioxidant is one or more of tris (2, 6-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, thiodipropionate distearate, ditridecanol thiodipropionate, and thiosulfinic acid.
In a more preferred embodiment of the present invention, the polyphenylene sulfide resin is a thermoplastic resin having a weight average molecular weight of 8000 to 120000.
In a further preferred embodiment of the present invention, the lubricant is one or more of zinc stearate, calcium stearate, methyl silicone oil, glycerol, graphite, molybdenum sulfide, butyl stearate, and oleamide.
As a further preferable scheme of the present invention, the drying process in the third step is: drying the mixture in a forced air drying oven at the temperature of 60-90 ℃ for 1-3 h to ensure that the water content of the mixed granules is less than 3%.
The invention also provides the novel polyphenylene sulfide powder for selective laser sintering, which is prepared by any one of the preparation methods of the novel polyphenylene sulfide powder for selective laser sintering.
The invention also provides the polyphenylene sulfide mixed powder for selective laser sintering, the novel polyphenylene sulfide powder for selective laser sintering and the residual polyphenylene sulfide powder are mixed in a stirrer to obtain the polyphenylene sulfide mixed powder, and the weight ratio of the residual polyphenylene sulfide powder to the novel polyphenylene sulfide powder is n, wherein n = (2 xM)F/MZ)-1，MFIn parts by weight of secondary antioxidant, MZIs the weight portion of the main antioxidant.
The invention relates to novel polyphenylene sulfide powder for selective laser sintering and a preparation method thereof.A polyphenylene sulfide resin, a lubricant and a main antioxidant are put into a mixer to be mixed to obtain a mixture; then putting the mixture into an extruder for melting to obtain mixed granules; and finally, placing the polyphenylene sulfide semi-finished product powder, a flow assistant, an auxiliary antioxidant and an inorganic filler into a stirrer, fully mixing and screening to obtain the novel polyphenylene sulfide powder, so that the novel polyphenylene sulfide powder prepared by the invention has high-efficiency antioxidant capacity for all forms of oxidation reactions, and the crystal structure of the polyphenylene sulfide powder is kept stable.
According to the polyphenylene sulfide mixed powder for selective laser sintering, the novel polyphenylene sulfide powder for selective laser sintering and the residual polyphenylene sulfide powder are mixed in the stirrer to obtain the polyphenylene sulfide mixed powder, so that the content of an oxidant in the mixed powder is kept relatively consistent in the process of repeated use, the repeated use performance of the powder is improved, and the problems of reduction of mechanical properties and yellowing of colors of finished workpieces are obviously reduced.
Detailed Description
In order to solve the technical problems of insufficient oxidation resistance of the novel polyphenylene sulfide powder and poor sintering repeatability of mixed powder in the prior art, the invention provides a preparation method of the novel polyphenylene sulfide powder for selective laser sintering, which comprises the following steps:
firstly, putting polyphenylene sulfide resin, a lubricant and a main antioxidant into a mixer for mixing to obtain a mixture; preferably, the mixture is obtained by fully mixing the raw materials in a mixer at the temperature of 50-120 ℃ and the speed of 50-200 r/min for 20-60 min.
Step two, putting the mixture into an extruder for melting to obtain mixed granules; the type of the extruder is a single screw extruder, a twin screw extruder or a multi-screw extruder. Wherein a double-screw extruder is preferred, and the temperature of a feeding hopper part of the extruder is 180-220 ℃; the temperature of the extruder is 250-300 ℃, the temperature of the die head is 270-350 ℃, and the time of the materials in the whole extrusion process is 3-5 min.
And step three, drying the mixed granules, and then putting the dried mixed granules into a cryogenic pulverizer to prepare powder so as to obtain polyphenylene sulfide semi-finished product powder.
Specifically, the drying method in this step is not particularly limited, but the moisture content of the dried pellets is required to be less than 3%. Preferably, the mixed granules are dried for 1 to 3 hours in a forced air drying oven at the temperature of 60 to 90 ℃ and dried for 1 to 3 hours in the forced air drying oven at the temperature of 60 to 90 ℃ so that the water content of the mixed granules is less than 3 percent. The cryogenic grinding powder preparation process comprises the step of grinding at a grinding rotor frequency of 25-50 Hz in a liquid nitrogen environment atmosphere at-100 to-160 ℃, wherein the particle size D50 of the polyphenylene sulfide semi-finished product powder is = 20-100 μm, and preferably D50= 40-80 μm.
Putting the polyphenylene sulfide semi-finished product powder, the flow additive, the auxiliary antioxidant and the inorganic filler into a stirrer, fully mixing, and screening to obtain new polyphenylene sulfide powder; preferably, the polyphenylene sulfide powder is obtained by uniformly stirring the polyphenylene sulfide powder in a stirrer at the temperature of 40-80 ℃ and the speed of 500-3000 r/min for 2-60 min. The mesh number of the screening net is 50-150 meshes. Wherein the content of the first and second substances,
the polyphenylene sulfide resin, the lubricant, the primary antioxidant, the secondary antioxidant, the flow assistant and the inorganic filler are as follows in parts by weight:
100 parts of polyphenylene sulfide resin
1-5 parts of lubricant
0.01-0.5 part of main antioxidant
0.01-2.5 parts of auxiliary antioxidant
0.1-5 parts of flow assistant
0-50 parts of inorganic filler.
Specifically, the main antioxidant is a phenol antioxidant and/or an amine antioxidant, the phenol antioxidant is N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl ] pentaerythritol ester, 2,2' -methylenebis (4-methyl-6-tert-butylphenol), the amine antioxidant is octylated diphenylamine, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N, N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N ' - (p-toluenesulfonyl) -p-phenylenediamine One or more of (a). Preferably, one of the phenolic antioxidants and one of the amine antioxidants are selected to be mixed as the primary antioxidant. The amine antioxidant and the phenol antioxidant have synergistic effect when used together, so that the main antioxidant obtained by mixing the two antioxidants is beneficial to further improving the antioxidant performance of the material.
The auxiliary antioxidant is one or more of tris (2, 6-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, thiodipropionate distearate, didodecanediol thiodipropionate and thiosulfinic acid. The flow auxiliary agent is one or more of silicon dioxide, nano silicon carbide, nano calcium oxide, nano aluminum oxide, titanium dioxide and calcium carbonate. The inorganic filler is one or more of glass beads, glass fibers, carbon fibers, mica, calcium chloride, titanium dioxide, talcum powder and the like which can reinforce nylon. The polyphenylene sulfide resin is thermoplastic resin with the weight-average molecular weight of 8000-120000. The lubricant is one or more of zinc stearate, calcium stearate, methyl silicone oil, glycerol, graphite, molybdenum sulfide, butyl stearate and oleamide.
The invention also provides the novel polyphenylene sulfide powder for selective laser sintering, which is prepared by any one of the preparation methods of the novel polyphenylene sulfide powder for selective laser sintering.
The invention also provides the polyphenylene sulfide mixed powder for selective laser sintering, the novel polyphenylene sulfide powder for selective laser sintering and the residual polyphenylene sulfide powder are mixed in a stirrer to obtain the polyphenylene sulfide mixed powder, and the weight ratio of the residual polyphenylene sulfide powder to the novel polyphenylene sulfide powder is n, wherein n = (2 xM)F/MZ)-1，MFIn parts by weight of secondary antioxidant, MZIs the weight portion of the main antioxidant.
In order to make the technical solutions of the present invention better understood and realized by those skilled in the art, the technical solutions of the present invention are described in detail below by way of examples.
Comparative example 1
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate and 0.04 part of tris (2, 6-di-tert-butylphenyl) phosphite are put into a mixer, mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, and the mixture is transferred into a double-screw extruder after complete mixing, wherein the temperature of a feeding hopper part is 220 ℃; melting and mixing for 3min under the conditions that the temperature of an extruder is 280 ℃ and the temperature of a die head is 330 ℃ for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give pellets with a water content of 1.5%. Drying the granules, putting the granules into a cryogenic grinder, grinding the granules in a liquid nitrogen environment atmosphere at minus 160 ℃ at a grinding rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.1 part of tris (2, 6-di-tert-butylphenyl) phosphite and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and performing mechanical property test on the obtained workpiece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ for 150min at a speed of 50r/min to obtain polyphenylene sulfide primary mixed powder, marking as PPS1, and repeating the processes to obtain PPS2 and PPS3. Finally, mechanical property specimens obtained by sintering the PPS8 powder were tested to complete the comparative example.
Comparative example 2
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate and 0.04 part of 2, 6-di-tert-butyl-4-methylphenol are placed into a mixer, and are mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, after the mixture is fully mixed, the mixture is transferred into a double-screw extruder, and the temperature of a feeding hopper part is 220 ℃; the extruder temperature is 280 ℃, and the die head temperature is 330 ℃ for 3min for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give a moisture content of 1.5%. Drying the granules, putting the granules into a cryogenic pulverizer, pulverizing the granules in a liquid nitrogen environment atmosphere at minus 160 ℃ at a pulverizing rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ at a speed of 50r/min for 150min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2 and PPS3. Finally, mechanical property specimens obtained by sintering the PPS8 powder were tested to complete the comparative example.
Comparative example 3
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate and 0.04 part of tris (2, 6-di-tert-butylphenyl) phosphite are put into a mixer, mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, and the mixture is transferred into a double-screw extruder after complete mixing, wherein the temperature of a feeding hopper part is 220 ℃; melting and mixing for 3min under the conditions that the temperature of an extruder is 280 ℃ and the temperature of a die head is 330 ℃ for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give pellets with a water content of 1.5%. Drying the granules, putting the granules into a cryogenic pulverizer, pulverizing the granules in a liquid nitrogen environment atmosphere at minus 160 ℃ at a pulverizing rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ and a speed of 50r/min for 150min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2, PPS3. Finally, mechanical property specimens obtained by sintering the PPS8 powder were tested to complete the comparative example.
Example 1
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate and 0.04 part of 2, 6-di-tert-butyl-4-methylphenol are put into a mixer, mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, and the mixture is transferred into a double-screw extruder after complete mixing, wherein the temperature of a feeding hopper part is 220 ℃; melting and mixing for 3min under the conditions that the temperature of an extruder is 280 ℃ and the temperature of a die head is 330 ℃ for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give pellets with a water content of 1.5%. Drying the granules, putting the granules into a cryogenic grinder, grinding the granules in a liquid nitrogen environment atmosphere at minus 160 ℃ at a grinding rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.1 part of tris (2, 6-di-tert-butylphenyl) phosphite and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ at a speed of 50r/min for 150min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2 and PPS3. The mechanical properties of the sintered specimens from the PPS8 powder were finally tested to complete the example.
Example 2
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate, 0.02 part of 2, 6-di-tert-butyl-4-methylphenol and 0.02 part of N-phenyl-N' -isopropyl-p-phenylenediamine are placed into a mixer, and are mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, and after complete mixing, the mixture is transferred into a double-screw extruder, and the temperature of a feeding hopper part is 220 ℃; melting and mixing for 3min under the conditions that the temperature of an extruder is 280 ℃ and the temperature of a die head is 330 ℃ for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give pellets with a water content of 1.5%. Drying the granules, putting the granules into a cryogenic grinder, grinding the granules in a liquid nitrogen environment atmosphere at minus 160 ℃ at a grinding rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.1 part of tris (2, 6-di-tert-butylphenyl) phosphite and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ at a speed of 50r/min for 150min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2 and PPS3. The mechanical properties of the sintered specimens from the PPS8 powder were finally tested to complete the example.
Example 3
100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 50000, 2 parts of zinc stearate and 0.04 part of 2, 6-di-tert-butyl-4-methylphenol are put into a mixer, mixed for 45min at the temperature of 80 ℃ at the speed of 100r/min, and the mixture is transferred into a double-screw extruder after complete mixing, wherein the temperature of a feeding hopper part is 220 ℃; melting and mixing for 3min under the conditions that the temperature of an extruder is 280 ℃ and the temperature of a die head is 330 ℃ for granulation; the pellets were then placed in a forced air drying oven and dried at a temperature of 90 ℃ for 1h to give pellets with a water content of 1.5%. Drying the granules, putting the granules into a cryogenic pulverizer, pulverizing the granules in a liquid nitrogen environment atmosphere at-160 ℃ at a pulverizing rotor frequency of 50Hz to obtain polyphenylene sulfide semi-finished product powder with D50=65 mu m, putting the polyphenylene sulfide semi-finished product powder, 0.5 part of silicon dioxide, 0.08 part of tris (2, 6-di-tert-butylphenyl) phosphite and 20 parts of glass beads into a stirrer, stirring the mixture for 5min at a temperature of 40 ℃ at a speed of 1500 r/min, and finally sieving the mixture by a sieve of 80 meshes to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 4:1 at a temperature of 30 ℃ at a speed of 50r/min for 150min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2 and PPS3. The mechanical properties of the sintered specimens from the PPS8 powder were finally tested to complete the example.
Example 4
100 parts of polyphenylene sulfide resin with the weight average molecular weight of 120000, 5 parts of calcium stearate, 0.05 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl ] pentaerythritol ester and 0.05 part of 4.4' -di (alpha, alpha-dimethylbenzyl) diphenylamine are put into a mixer, the mixture is mixed for 20min at the temperature of 120 ℃ and the speed of 200r/min, the mixture is transferred into a double screw extruder after the complete mixing, the mixture is melted and mixed for 5min under the conditions that the temperature of a feeding hopper part is 220 ℃, the temperature of the extruder is 300 ℃ and the temperature of a die head is 350 ℃ for granulation, then the granules are put into a blast drying box, the granules are dried for 2h at the temperature of 90 ℃, the water content of the granules is 1.5 percent, the granules are put into a cryogenic crusher after being dried, the granules are crushed in a liquid nitrogen environment at the temperature of-160 ℃ and the crushing rotor frequency of 50Hz, and the semi-finished product powder of polyphenylene sulfide with the D50=55 mu m is obtained, then placing the polyphenylene sulfide semi-finished product powder, 2 parts of nano silicon carbide, 0.2 part of didecyl diglycol thiodipropionate and 10 parts of glass fiber into a stirrer, stirring for 30min at the temperature of 80 ℃ at the speed of 500 r/min, and finally sieving by a 120-mesh sieve to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 3:1 at a temperature of 30 ℃ and at a speed of 200r/min for 30min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2, namely PPS3. The mechanical properties of the sintered specimens from the PPS8 powder were finally tested to complete the example.
Example 5
Putting 100 parts of polyphenylene sulfide resin with the weight-average molecular weight of 10000, 1 part of methyl silicone oil, 0.1 part of N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.1 part of N-phenyl-N' - (p-toluenesulfonyl) -p-phenylenediamine into a mixer, mixing at the temperature of 50 ℃ at the speed of 50r/min for 60min, transferring the mixture into a double-screw extruder after fully mixing, and controlling the temperature at a feeding hopper part to be 180 ℃; melting and mixing for 5min for granulation under the conditions that the temperature of an extruder is 250 ℃ and the temperature of a die head is 270 ℃; the pellets were then placed in a forced air drying oven and dried at a temperature of 60 ℃ for 3 hours to give pellets having a water content of 0.5%. Drying the granules, putting the granules into a cryogenic crusher, crushing and processing the granules in a liquid nitrogen environment atmosphere at-130 ℃ at a crushing rotor frequency of 25Hz to obtain polyphenylene sulfide semi-finished product powder with D50=45 mu m, then putting the polyphenylene sulfide semi-finished product powder, 0.1 part of titanium dioxide, 0.2 part of tris (nonylphenyl) phosphite and 50 parts of carbon fiber into a stirrer, stirring the mixture for 60min at a temperature of 40 ℃ at a speed of 500 r/min, and finally sieving the mixture through a 60-mesh sieve to obtain the novel polyphenylene sulfide powder.
Sintering the new polyphenylene sulfide powder in selective laser sintering equipment, and testing the mechanical properties of the obtained work piece after bale cleaning, wherein the test result is marked as PPS 0. And stirring the rest powder and the prepared new powder at a weight ratio of 1:1 at a temperature of 25 ℃ at a speed of 200r/min for 30min to obtain polyphenylene sulfide primary mixed powder which is marked as PPS1, and repeating the processes to obtain PPS2 and PPS3. The mechanical properties of the sintered specimens from the PPS8 powder were finally tested to complete the example.
Table 1: performance parameters of three-dimensional parts obtained by adopting the polyphenylene sulfide mixed powder through selective laser sintering equipment
Compared with the preparation processes of examples 1, 4 and 5, comparative example 1 is a preparation process in which only the secondary antioxidant is added, comparative example 2 is a preparation scheme in which only the primary antioxidant is added, and comparative example 3 is a preparation scheme in which the secondary antioxidant is added during the smelting process, and the primary antioxidant is added at the high-speed stirring stage; as is clear from the comparison of mechanical properties, the comparative examples are inferior in both initial properties and stability after sintering to the levels of examples 1, 4 and 5, and the powder is inferior in oxidation resistance effect because the yellowness of the work pieces is higher. Therefore, the preparation method of the polyphenylene sulfide by adding the primary antioxidant in the smelting process and adding the auxiliary antioxidant in the high-speed stirring stage has more excellent initial antioxidant capacity, can remarkably improve the sintering stability of the product, and enables the performance of a workpiece obtained by selective laser sintering of polyphenylene sulfide powder to be always maintained at a higher level.
Only one primary type antioxidant was added in example 1, while two types of primary type antioxidants were added in example 2. Comparing example 1 with example 2, it can be seen that the addition of the two main type antioxidants can eliminate both long-chain type radicals and small molecule type radicals, thereby not only synergistically enhancing the antioxidant ability but also enhancing the stability of the powder. Finally, the initial performance and the performance stability of the polyphenylene sulfide powder can be improved.
It is clear from the comparison between examples 1 and 3 that the ratio of the residual powder to the new powder in example 3 is not at the optimum addition level, so that the antioxidant in the polyphenylene sulfide mixed powder is continuously reduced during the repeated use, and finally the workpiece performance is relatively low and the yellowing degree is also increased during the repeated use.
The above-mentioned embodiments only express various embodiments of the present invention, and the description thereof is more specific and detailed, but not meant to limit the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and the scope of the invention is to be determined by the appended claims.
Claims (7)
1. The preparation method of the novel polyphenylene sulfide powder for selective laser sintering is characterized by comprising the following steps of:
firstly, putting polyphenylene sulfide resin, a lubricant and a main antioxidant into a mixer for mixing to obtain a mixture;
step two, putting the mixture into an extruder for melting to obtain mixed granules;
drying the mixed granules, and then putting the dried mixed granules into a cryogenic pulverizer to prepare powder so as to obtain polyphenylene sulfide semi-finished product powder;
putting the polyphenylene sulfide semi-finished product powder, the flow additive, the auxiliary antioxidant and the inorganic filler into a stirrer, fully mixing, and screening to obtain new polyphenylene sulfide powder; wherein the content of the first and second substances,
the polyphenylene sulfide resin, the lubricant, the primary antioxidant, the secondary antioxidant, the flow assistant and the inorganic filler are as follows in parts by weight:
100 parts of polyphenylene sulfide resin
1-5 parts of lubricant
0.01-0.5 part of main antioxidant
0.01-2.5 parts of auxiliary antioxidant
0.1-5 parts of flow assistant
0-50 parts of inorganic filler; wherein the content of the first and second substances,
the primary antioxidant is a phenol antioxidant and/or an amine antioxidant; the auxiliary antioxidant is one or more of tris (2, 6-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, thiodipropionate distearate, didodecanediol thiodipropionate and thiosulfinic acid.
2. The method of claim 1, wherein the phenolic antioxidant is N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol ester, 2,2 '-methylenebis (4-methyl-6-tert-butylphenol), the aminic antioxidant is octylated diphenylamine, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, N-phenyl-N '-isopropyl-p-phenylenediamine, N, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine, one or more of N-phenyl-N' - (p-toluenesulfonyl) -p-phenylenediamine.
3. The method for preparing the polyphenylene sulfide new powder for selective laser sintering as claimed in claim 2, wherein the polyphenylene sulfide resin is a thermoplastic resin having a weight average molecular weight of 8000 to 120000.
4. The method for preparing polyphenylene sulfide new powder for selective laser sintering as claimed in claim 1, wherein the lubricant is one or more of zinc stearate, calcium stearate, methyl silicone oil, glycerol, graphite, molybdenum sulfide, butyl stearate, and oleamide.
5. The method for preparing the polyphenylene sulfide new powder for selective laser sintering according to any one of claims 1 to 4, wherein the drying process in the third step is as follows: drying the mixture in a forced air drying oven at the temperature of 60-90 ℃ for 1-3 h to ensure that the water content of the mixed granules is less than 3%.
6. A novel polyphenylene sulfide powder for selective laser sintering, which is prepared by the method for preparing a novel polyphenylene sulfide powder for selective laser sintering according to any one of claims 1 to 5.
7. A polyphenylene sulfide mixed powder for selective laser sintering, which is prepared by mixing the novel polyphenylene sulfide powder for selective laser sintering and the residual polyphenylene sulfide powder of claim 6 in a blender, wherein the weight ratio of the residual polyphenylene sulfide powder to the novel polyphenylene sulfide powder is n, wherein n = (2 XM)F/MZ)-1，MFIn parts by weight of secondary antioxidant, MZIs the weight portion of the main antioxidant.
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