CN107337792B - Melting point-controllable copolymerized nylon powder material and preparation method thereof - Google Patents
Melting point-controllable copolymerized nylon powder material and preparation method thereof Download PDFInfo
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- CN107337792B CN107337792B CN201710627635.8A CN201710627635A CN107337792B CN 107337792 B CN107337792 B CN 107337792B CN 201710627635 A CN201710627635 A CN 201710627635A CN 107337792 B CN107337792 B CN 107337792B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention provides a melting point controllable copolymerized nylon powder material and a preparation method thereof. The method controls the proportion of two nylon salts in the copolymerized nylon from salt preparation to obtain the copolymerized nylon salt at one time, can effectively control the melting point of the copolymerized nylon, saves the salt separation and drying operation, improves the process stability, saves the preparation time, saves the preparation cost and improves the stability of the performance of the copolymerized nylon material.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a melting point-controllable copolymerized nylon powder material and a preparation method thereof.
Background
Selective Laser Sintering (SLS) technology has been applied to industrial production, while the Sintering parameters of general Selective Laser Sintering equipment are fixed, which results in different kinds of materials and is difficult to be applied to the Selective Laser Sintering technology.
Nylon is a semicrystalline polymer, and the selective laser sintering product has excellent performances in the aspects of strength, density and the like, and is a high polymer material which is very suitable for the selective laser sintering process. At present, nylon of the selective laser sintering technology is mainly long-carbon-chain nylon, nylon 11 and nylon 12, and the market share of the nylon 11, the nylon 12 and composite materials thereof reaches 95%. Mainly because of its larger sintering window and lower temperature, it is easy to process. However, the long carbon chain nylon mainly used and produced in China, such as PA1010, PA1012, PA1212 and PA1014, cannot be well used in the existing selective laser sintering technology because the powder making is difficult and the sintering window is narrow.
The existing nylon powder material has strict requirements on sintering process and equipment, and improper control of sintering temperature can cause difficulty in controlling powder melting in the sintering process or warping and deformation of parts due to internal stress, thereby affecting the quality of selective laser sintering parts. The sintering temperature of the nylon material is mainly related to the melting point of the nylon material, and the melting point of most nylon monomers is difficult to meet the requirement. The copolymerized nylon has the advantages that the melting point required by the selective laser sintering material is achieved by changing the proportion of the nylon, and meanwhile, the copolymerized nylon has the crystallization property different from that of single nylon and has slower crystallization rate, so that the prepared powder has more regular appearance, narrower particle size distribution and faster sintering window, and the prepared nylon powder is more favorable for being applicable to the selective laser sintering technology.
In the prior art, the copolymerized nylon is generally prepared by two prepared nylon salts and then polymerized. The preparation method needs to prepare two kinds of nylon salt in advance and needs to dry, the process is complex, and the preparation period is long. In addition, during polymerization, because the two nylon salts are physically mixed and are easy to mix unevenly, the fluctuation of the melting point of the prepared granules is large, the quality fluctuation of the prepared granules is large, and the production is not facilitated.
The polyamide alloy prepared from two different nylon granules cannot rearrange molecular chains because the original molecular chains are relatively stable, and the prepared polyamide alloy is not suitable for a selective laser sintering technology.
Disclosure of Invention
The invention provides a copolymerized nylon powder material with controllable melting point and a preparation method thereof, which have low cost and easy realization and are easy to be applied to industrial production. The invention controls the proportion of two nylon salts in the copolymerized nylon from the beginning of salt preparation, obtains the copolymerized nylon salt at one time, can effectively control the melting point of the copolymerized nylon, saves the salt separation and drying operation, improves the process stability and saves the preparation time. Not only saves the preparation cost, but also improves the stability of the performance of the copolymerized nylon powder material.
The invention provides a melting point-controllable copolymerized nylon powder material which is formed by polymerizing aliphatic dibasic acid and aliphatic diamine, wherein the mass ratio of the aliphatic dibasic acid to the aliphatic diamine is 9-1: 1-9.
As a further preferable scheme of the invention, the copolymerized nylon powder material is formed by polymerizing aliphatic dibasic acid and aliphatic diamine, and the mass ratio of the aliphatic dibasic acid to the aliphatic diamine is 3-7: 7-3.
As a further preferable embodiment of the present invention, the aliphatic dibasic acid is one or two of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid.
In a further preferred embodiment of the present invention, the aliphatic diamine is one or two of decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecylenediamine, and tetradecylenediamine.
In a further preferred embodiment of the present invention, the antioxidant is a complex antioxidant composed of a hindered phenol antioxidant and a phosphite antioxidant, wherein the hindered phenol antioxidant is preferably one or two of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol, and the phosphite antioxidant is 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and/or tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylbisphosphite.
As a further preferred embodiment of the present invention, the molecular weight regulator is one or more of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and tetradecanedioic acid.
The invention also provides a preparation method of the melting point controllable copolymerized nylon powder material, which comprises the following steps:
adding aliphatic dibasic acid, aliphatic diamine and a first solvent into a reactor, generating a copolymer nylon salt solution at the temperature of 60-90 ℃, and performing centrifugal suction filtration to obtain a copolymer nylon salt;
step two, adding the copolymerized nylon salt prepared in the step one, a molecular weight regulator, deionized water and an antioxidant into a polymerization kettle, sealing the reaction kettle, vacuumizing, introducing inert gas until the pressure in the reaction kettle is 0.10-0.15 Mpa, heating to 190-235 ℃, keeping the pressure in the reaction kettle to 1.1-1.6 MPa, maintaining the pressure for 0.5-3 hours, slowly exhausting to normal pressure, heating to 230-280 ℃, keeping the reaction for 0.2-3 hours, stopping heating, cooling water, stretching strips, discharging, and granulating to obtain copolymerized nylon granules;
step three, adding the copolymerized nylon granules prepared in the step two into a polymerization kettle, adding a second solvent, stirring at the temperature of 110-170 ℃ and under the pressure of 0.9-1.8 MPa, cooling to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder, wherein the mass of the second solvent is 5-10 times that of the copolymerized nylon granules;
step four, drying and screening the copolymerized nylon powder prepared in the step three to obtain copolymerized nylon powder with the average particle size of 45-65 mu m;
and step five, mixing the copolymerized nylon powder prepared in the step four with a flow assistant and an antioxidant in a ratio of 1: 0.1-2% to 0.1-2%, uniformly mixing and screening to obtain the copolymerized nylon powder material with a controllable melting point.
As a further preferable scheme of the invention, the molar ratio of the aliphatic dibasic acid to the aliphatic diamine is 1: 1.01-1.06, the mass of the first solvent is 5-10 times of the sum of the masses of the aliphatic dibasic acid and the aliphatic diamine, and the first solvent is deionized water and/or an alcohol solvent.
As a further preferable scheme of the invention, in the second step, the mass ratio of the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant is 47.9-79.5 percent, 0.3-1.5 percent, 20-50 percent and 0.2-0.6 percent.
As a further preferable embodiment of the present invention, the second solvent is one or more of deionized water, an alcohol solvent, a ketone solvent, an amide solvent, and a sulfoxide solvent.
The invention provides a copolymerization nylon powder material with controllable melting point and a preparation method thereof, and the copolymerization nylon powder material has the following beneficial effects:
1. the invention does not need to dry nylon salt, and directly enters a polymerization kettle to be blended and polymerized, thereby reducing the operation steps and greatly reducing the production cost.
2. The invention directly determines the proportion of two nylon salts in the salt preparation process, and can accurately control the melting point of the finally prepared copolymerized nylon powder.
3. The ratio of the two nylon salts is controllable, the prepared nylon granules are more stable, the mechanical property and the thermal property of the copolymerized nylon powder are more stable, the quality controllability of the nylon powder is facilitated, and the quality of the prepared powder is more stable.
4. When two kinds of nylon salt are copolymerized, the two kinds of nylon are subjected to random copolymerization, the molecular structures of the two kinds of nylon are damaged, and the long carbon chain of the long carbon chain copolymerized nylon is lower in crystallinity and slower in crystallization rate compared with the long carbon chain of the nylon which is not copolymerized, the powder sintering window is wider, and the selective laser technology is more favorably applied to the copolymerized nylon powder; the copolymerized nylon with the long carbon chain has low crystallinity, and powder particles are easier to melt during sintering, so that the copolymerized nylon sintered piece has higher tensile elongation at break and better toughness.
Detailed Description
The present invention is described in further detail below by way of specific examples.
The first embodiment is as follows:
adding sebacic acid, sebacic diamine and dodecanedioic acid into a reactor, wherein the molar ratio of the sebacic acid to the dodecanedioic acid to the sebacic diamine is 1: 1.01, the addition amount of ethanol is 5 times of the total amount of the sebacic acid, the sebacic diamine and the dodecanedioic acid, generating a copolymerized nylon salt solution at 60 ℃, and performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1010 salt and 1012 salt, and the mass ratio of the 1010 salt to the 1012 salt is 3: 7;
step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 79.5 percent to 0.3 percent to 20 percent to 0.2 percent. Sealing, vacuumizing, and introducing inert gas to protect at 0.10 MPa. And (3) heating to 190 ℃, keeping the pressure at 1.6MPa for 0.5h, then slowly discharging gas to normal pressure, heating to 230 ℃, keeping the reaction for 3h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain the copolymerized nylon granules.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding methanol which is 5 times of the mass of the copolymerized nylon granules, stirring at the pressure of 0.9MPa and the temperature of 110 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain copolymerized nylon powder with the average particle size of 45 microns.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 0.1% to 0.1%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
Example two:
adding sebacic acid, sebacic diamine and dodecanedioic acid into a reactor, wherein the molar ratio of the sebacic acid to the dodecanedioic acid to the sebacic diamine is 1: 1.01, the addition amount of methanol is 5 times of the total amount of the sebacic acid, the sebacic diamine and the dodecanedioic acid, generating a copolymerized nylon salt solution at 60 ℃, and performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1010 salt and 1012 salt, and the mass ratio of the 1010 salt to the 1012 salt is 6: 4;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 79.5 to 0.3 to 20 to 0.2, sealing, vacuumizing, and introducing inert gas to protect the pressure of 0.10 MPa. And (3) heating to 190 ℃, keeping the pressure at 1.6MPa for 0.5h, then slowly discharging gas to normal pressure, heating to 230 ℃, keeping the reaction for 3h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain the copolymerized nylon granules.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding ethanol which is 5 times of the mass of the copolymerized nylon granules, stirring at the pressure of 0.9MPa and the temperature of 110 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain copolymerized nylon powder with the average particle size of 45 microns.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 0.1% to 0.1%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
Example three:
adding sebacic acid, sebacic diamine and tetradecanedioic acid into a reactor, wherein the molar ratio of sebacic acid to tetradecanedioic acid is 1: 1.02, the addition amount of water is 6 times of the total amount of sebacic acid, sebacic diamine and tetradecanedioic acid, generating a copolymerized nylon salt solution at 65 ℃, performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1010 salt and 1014 salt, and the mass ratio of 1010 salt to 1014 salt is 1: 9;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 74.1: 0.6: 25: 0.3, sealing, vacuumizing, and introducing inert gas to protect 0.11 MPa. Heating to 200 ℃, keeping the pressure at 1.5MPa for 1h, then slowly discharging gas to normal pressure, heating to 240 ℃, keeping the reaction for 2h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain the copolymerized nylon pellets.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding dimethylacetamide which is 6 times of the mass of the copolymerized nylon granules, stirring at the pressure of 1.1MPa and the temperature of 120 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain the copolymerized nylon powder with the average particle size of 50 microns.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 0.3% to 0.3%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
Example four:
adding sebacic acid, sebacic diamine and dodecanediamine into a reactor, wherein the molar ratio of the sebacic acid to the sebacic diamine to the dodecanediamine is 1: 1.03, the addition amount of ethanol is 7 times of the total amount of the sebacic acid to the sebacic diamine to the dodecanediamine, generating a copolymerized nylon salt solution at 70 ℃, and performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1010 salt and 1210 salt, and the mass ratio of the 1010 salt to the 1210 salt is 2: 8;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 68.7: 0.9: 30: 0.4, sealing, vacuumizing, and introducing inert gas to protect 0.12 MPa. Heating to 210 ℃, keeping the pressure at 1.4MPa for 1.5h, then slowly discharging gas to normal pressure, heating to 250 ℃, keeping the reaction for 1.5h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain copolymerized nylon granules;
step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding dimethylformamide which is 7 times of the mass of the copolymerized nylon granules, stirring at the pressure of 1.3MPa and the temperature of 130 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
drying and screening the obtained copolymerized nylon powder to obtain copolymerized nylon powder with the average particle size of 55 mu m;
and step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 0.6% to 0.6%, uniformly mixing, and screening to obtain the nylon powder for selective laser sintering.
Example five:
adding sebacic acid, sebacic diamine, dodecanediamine and dodecanedioic acid into a reactor, wherein the molar ratio of the sebacic acid to the dodecanedioic acid to the amine of the sebacic diamine to the amine of the dodecanedioic acid is 1: 1.04, the addition amount of methanol is 8 times of the total amount of the sebacic acid, the sebacic diamine, the dodecanediamine and the dodecanedioic acid, generating a copolymerized nylon salt solution at 75 ℃, performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1010 salt and 1212 salt, and the mass ratio of the 1010 salt to the 1212 salt is 5: 5;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 63.3: 1.2: 35: 0.5, and adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into the polymerization kettle. Wherein the molecular weight regulator accounts for 1.2% of the total mass of the raw materials, and the antioxidant accounts for 0.5% of the total mass of the raw materials. Wherein the total mass of the raw materials is the sum of the mass of the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant; the deionized water accounts for 35% of the total mass of the solid, wherein the total mass of the solid is the sum of the mass of the copolymerized nylon salt, the molecular weight regulator and the antioxidant. Sealing, vacuumizing, and introducing inert gas to protect 0.13 MPa. Heating to 220 ℃, keeping the pressure at 1.3MPa for 1.5h, then slowly discharging gas to normal pressure, heating to 260 ℃ for reaction for 1h, stopping heating, cooling by water, drawing strips, discharging, and pelletizing to obtain the copolymerized nylon pellets.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding methanol which is 8 times of the mass of the copolymerized nylon granules, stirring at the pressure of 1.5MPa and the temperature of 150 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain copolymerized nylon powder with the average particle size of 55 mu m.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 0.9% to 0.9%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
Example six:
step one, adding undecamide, undecamide and tridecanedioic acid into a reactor, wherein the molar ratio of the undecamide to the undecamide is 1: 1.05, the adding amount of water is 9 times of the total amount of the undecamide, the undecamide and the tridecanedioic acid, generating a copolymer nylon salt solution at 80 ℃, and performing centrifugal suction filtration to obtain the copolymer nylon salt, wherein the copolymer nylon salt is a mixture of 1111 salt and 1113 salt, and the mass ratio of 1111 salt to 1113 salt is 7: 3;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 62.9: 1.5: 35: 0.6, sealing, vacuumizing, and introducing inert gas for protection at 0.14 MPa. And (3) heating to 230 ℃, keeping the pressure at 1.2MPa for 1h, then slowly discharging gas to normal pressure, heating to 270 ℃, keeping the reaction for 0.5h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain the copolymerized nylon granules.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding 9 times of ethanol by mass of the copolymerized nylon granules, stirring at the pressure of 1.7MPa and the temperature of 160 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain the copolymerized nylon powder with the average particle size of 60 mu m.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 1.5% to 1.5%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
Example seven:
step one, adding tetradecanediamine, dodecanedioic acid and tetradecanedioic acid into a reactor, wherein the molar ratio of the dodecanedioic acid to the tetradecanedioic acid is 1: 1.06, the adding amount of ethanol is 10 times of the total amount of the tetradecanediamine, the dodecanedioic acid and the tetradecanedioic acid, generating a copolymerized nylon salt solution at 90 ℃, performing centrifugal suction filtration to obtain the copolymerized nylon salt, wherein the copolymerized nylon salt is a mixture of 1412 salt and 1214 salt, and the mass ratio of 1412 salt to 1214 salt is 9: 1;
and step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant into a polymerization kettle according to the mass ratio of 47.9: 1.5: 50: 0.6, sealing, vacuumizing, and introducing inert gas to protect 0.15 MPa. Heating to 235 ℃, keeping the pressure at 1.1MPa for 0.5h, then slowly discharging gas to normal pressure, heating to 280 ℃ for reaction for 0.2h, stopping heating, cooling by water, stretching strips, discharging, and pelletizing to obtain the copolymerized nylon granules.
Step three, preparing copolymerized nylon powder in a solvent method powder preparation mode, adding the prepared copolymerized nylon granules into a polymerization kettle, adding methanol which is 10 times of the mass of the copolymerized nylon granules, stirring at the pressure of 1.8MPa and the temperature of 170 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
and step four, drying and screening the obtained copolymerized nylon powder to obtain copolymerized nylon powder with the average particle size of 65 mu m.
And step five, mixing the obtained copolymerized nylon powder with a flow aid and an antioxidant in a ratio of 1: 2% to 2%, uniformly mixing, and screening to obtain the copolymerized nylon powder material with a controllable melting point.
The relevant performance parameters for selectively laser sintered three-dimensional parts made using the copolymerized nylon powder materials of examples one through seven above are set forth in table 1, where the copolymerized material melting temperature Tm, defined as the difference between the polyamide powder initial melting temperature Tmo and the initial crystallization temperature Tco in the sintering window in the selective laser sintering technique, is set forth in table 1.
Table 1: EXAMPLES one TO seventy Performance parameters of Selective laser sintering three-dimensional parts made from copolymerized Nylon powder materials
| Examples | Melting temperature Tm (. degree.C.) | Sintering Window (. degree. C.) | Tensile strength (Mpa) | Tensile elongation at Break (%) |
| Example one | 186 | 31 | 48 | 45 |
| Example two | 190 | 35 | 57 | 56 |
| EXAMPLE III | 171 | 25 | 42 | 37 |
| Example four | 190 | 28 | 58 | 41 |
| EXAMPLE five | 164 | 39 | 37 | 64 |
| EXAMPLE six | 163 | 32 | 37 | 57 |
| EXAMPLE seven | 157 | 33 | 33 | 58 |
Claims (4)
1. The copolymerization nylon powder material with the controllable melting point for selective laser sintering is characterized by being prepared by polymerizing aliphatic dibasic acid and aliphatic diamine, wherein the mass ratio of the aliphatic dibasic acid to the aliphatic diamine is 9-1: 1-9, the aliphatic dibasic acid is one or two of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and tetradecanedioic acid, the aliphatic diamine is one or two of decanediamine, undecanediamine, dodecanediamine, tridecanediamine and tetradecanediamine, the aliphatic dibasic acid is two and/or the aliphatic diamine is two, and the copolymerization nylon powder material is prepared by the following method:
adding a first solvent, the aliphatic dibasic acid and the aliphatic diamine into a reactor, generating a copolymer nylon salt solution at 60-90 ℃, and performing centrifugal filtration to obtain a copolymer nylon salt, wherein the first solvent is water, methanol or ethanol, the molar ratio of the aliphatic dibasic acid to the aliphatic diamine is 1: 1.01-1.06, and the mass of the first solvent is 5-10 times of the sum of the masses of the aliphatic dibasic acid and the aliphatic diamine;
step two, adding the copolymerized nylon salt, the molecular weight regulator, the deionized water and the antioxidant prepared in the step one into a polymerization kettle, wherein the mass ratio of the copolymerized nylon salt to the molecular weight regulator to the deionized water to the antioxidant is 47.9-79.5%, 0.3-1.5%, 20-50% and 0.2-0.6%, sealing the reaction kettle, vacuumizing, introducing inert gas until the pressure in the reaction kettle is 0.10-0.15 MPa, heating to 190-235 ℃, keeping the pressure in the reaction kettle at 1.1-1.6 MPa, maintaining the pressure for 0.5-3 h, slowly releasing gas to normal pressure, heating to 230-280 ℃, keeping the reaction for 0.2-3 h, stopping heating, drawing water to cool, discharging and granulating to obtain copolymerized nylon granules;
adding the copolymerized nylon granules prepared in the second step into a polymerization kettle, adding a second solvent, wherein the mass of the second solvent is 5-10 times of that of the copolymerized nylon granules, the second solvent is methanol, ethanol, dimethylacetamide or dimethylformamide, stirring at the pressure of 0.9-1.8 MPa and the temperature of 110-170 ℃, then cooling and reducing the pressure to room temperature and normal pressure, separating out powder, and carrying out centrifugal filtration to obtain copolymerized nylon powder;
step four, drying and screening the copolymerized nylon powder prepared in the step three to obtain copolymerized nylon powder with the average particle size of 45-65 mu m;
and step five, mixing the copolymerized nylon powder prepared in the step four with a flow additive and an antioxidant in a ratio of 1: 0.1-2% to 0.1-2%, uniformly mixing and screening to obtain the copolymerized nylon powder material with controllable melting point for selective laser sintering.
2. The melting point controllable copolymerized nylon powder material of claim 1, wherein the mass ratio of the aliphatic dibasic acid to the aliphatic diamine is 3-7: 7-3.
3. The melting point-controllable copolymerized nylon powder material of claim 2, wherein the antioxidant is a complex antioxidant consisting of hindered phenol antioxidant and phosphite antioxidant, wherein the hindered phenol antioxidant is preferably one or two of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol, and the phosphite antioxidant is 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and/or tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenyldiphosphite.
4. The melting point controlled copolymerized nylon powder material of claim 3, wherein the molecular weight modifier is one or more of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid.
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| CN109517370B (en) * | 2018-09-10 | 2021-07-02 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder material for selective laser sintering |
| CN109517376B (en) * | 2018-11-09 | 2021-08-03 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder material for selective laser sintering |
| CN109970969B (en) * | 2019-04-10 | 2021-06-22 | 山东广垠新材料有限公司 | Preparation method of terpolymer low-melting-point nylon |
| CN111057233B (en) * | 2019-12-29 | 2023-05-05 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
| CN111040444A (en) * | 2019-12-31 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Nylon powder for selective laser sintering and preparation method thereof |
| CN113461934A (en) * | 2021-06-18 | 2021-10-01 | 山东东辰瑞森新材料科技有限公司 | High-melting-point transparent nylon material and preparation method thereof |
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| CN115772262B (en) * | 2021-09-06 | 2024-01-19 | 成都肆零壹科技有限公司 | Continuous process for preparing aliphatic dibasic acid nylon |
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