CN107286338A - A kind of selective laser sintering polyamide material and preparation method thereof - Google Patents
A kind of selective laser sintering polyamide material and preparation method thereof Download PDFInfo
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- CN107286338A CN107286338A CN201710627427.8A CN201710627427A CN107286338A CN 107286338 A CN107286338 A CN 107286338A CN 201710627427 A CN201710627427 A CN 201710627427A CN 107286338 A CN107286338 A CN 107286338A
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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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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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Abstract
A kind of selective laser sintering polyamide material and preparation method thereof, wherein polyamide material includes short carbon chain nylon salt, and first, second different classes of long carbon chain nylon salt, selective laser sintering polyamide material is made by copolyreaction in short carbon chain nylon salt, first, second long carbon chain nylon salt.The present invention by copolyreaction by short carbon chain nylon salt, first, second long carbon chain nylon salt by being made selective laser sintering polyamide material, copolymer nylon is obtained because three kinds of nylon salts carry out copolymerization, the symmetry and regularity of its macromolecular chain are poor, cause copolymer nylon crystallinity poor, heat endurance is poor, energy needed for melting is lower, therefore, the present invention selective laser sintering with polyamide material at lower operating temperatures, also selective sintering can be carried out, so as to require lower to agglomerating plant.In addition, polyamide material cost of the present invention is low, industrial production can be widely applied to.
Description
Technical field
The invention belongs to increases material manufacturing technology field, and in particular to a kind of selective laser sintering polyamide material and its
Preparation method.
Background technology
3D printing technique is the common name of increases material manufacturing technology, be one have Digitized manufacturing, highly flexible and adaptability,
The advanced manufacturing technology for the distinguishing feature such as direct CAD model driving, quick, material type be rich and varied, it can be by the several of prototype
The combined information of what shape, structure and selected materials sets up digitization descriptive model, and these information are output to computer afterwards
The electromechanical integrated manufacturing system of control carries out pointwise, by-line, the three-dimensional packing shaping production 3D solid by face.Relative to tradition
Subtract material manufacture process technology, increases material manufacturing technology can just pass through without proembryo and mould directly by computer model data
The method being successively superimposed produces any required physical member, can effectively simplify the fabrication schedule of product, shorten grinding for product
In the cycle processed, improve efficiency and reduce cost.3D printing technique is widely used to Aero-Space, automobile making, Making mold, life
The numerous areas such as thing engineering and medical treatment, building, art manufacture.Selective Laser Sintering（SLS）It is common in the market
A kind of 3D printing method, the method can produce high-precision manufacture parts, by many field extensive uses.
Be commonly used in selective laser sintering consumptive material in the market is generally polyamide（It is commonly called as nylon）Material, nylon
Material is as current first large-engineering plastics, and most of kinds are to contain amido link in Crystalline plastics, macromolecular chain, can shape
Into hydrogen bond, more than 90% material is to use nylon material in existing market.When preparing workpiece using selective laser sintering, usually
In the presence of due to the incomplete melted powder particle of laser so that sintered part has porosity, result in the toughness of nylon workpiece compared with
Difference, greatly limit the application of the nylon workpiece of selective laser sintering manufacture.In addition, existing nylon material due to fusing point compared with
Height, powder heat endurance is higher, and required operating temperature is higher, causes higher to equipment requirement.
The content of the invention
The above-mentioned technical problem existed for prior art, has compared with low melting point the invention provides one kind, and causes system
Part has selective laser sintering polyamide material of more preferable toughness and preparation method thereof.
In order to solve the above technical problems, the invention provides a kind of selective laser sintering polyamide material, including it is short
Carbon chain nylon salt, and different classes of the first long carbon chain nylon salt, the second long carbon chain nylon salt, and short carbon chain nylon salt,
Selective laser sintering polyamide material is made by copolyreaction in one long carbon chain nylon salt and the second long carbon chain nylon salt.
It is used as present invention further optimization scheme, first long carbon chain nylon salt, the second long carbon chain nylon salt, short carbon
The weight ratio of chain nylon salt is 1:1:0.2-0.8.
As present invention further optimization scheme, first long carbon chain nylon salt be nylon 11 salt, the salt of nylon 11 12,
The salt of nylon 11 13, Nylon-1010 Salt, the salt of nylon 1011, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt or
Nylon 1313 salt；Second long carbon chain nylon salt is nylon 11 salt, the salt of nylon 11 12, the salt of nylon 11 13, Nylon-1010 Salt, Buddhist nun
Imperial 1011 salt, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt or nylon 1313 salt.
As present invention further optimization scheme, the short carbon chain nylon salt is caprolactam or hexamethylene diamine adipate
Salt.
Present invention also offers a kind of preparation method of selective laser sintering polyamide material, comprise the following steps：
Step 1: by short carbon chain nylon salt, and different classes of the first long carbon chain nylon salt, the second long carbon chain nylon salt are carried out
Polyamide pellet is made in copolyreaction；
Step 2: above-mentioned polyamide pellet is obtained into selective laser sintering polyamide powder by crushing.
It is used as present invention further optimization scheme, the short carbon chain nylon salt, the first long carbon chain nylon salt and the second length
The weight ratio of carbon chain nylon salt is 1:1:0.2-0.8.
It is used as present invention further optimization scheme, the short carbon chain nylon salt, the first long carbon chain nylon salt and the second length
Carbon chain nylon salt is reacted by ternary polymerization is made polyamide pellet.
As present invention further optimization scheme, the short carbon chain nylon salt is caprolactam or hexamethylene diamine adipate
Salt.
As present invention further optimization scheme, in the polymerisation in above-mentioned steps one, also added with molecular weight
Conditioning agent and/or the first antioxidant, wherein molecular weight regulator account for short carbon chain nylon salt, the first long carbon chain nylon salt and second
The 0.2-0.8% of long carbon chain nylon salt gross weight, the first antioxidant accounts for short carbon chain nylon salt, the first long carbon chain nylon salt and
The 0.2-1.0% of two long carbon chain nylon salt gross weights.
As present invention further optimization scheme, in the selective laser sintering polyamide powder that step 2 is obtained
Powder flow aid and/or the second antioxidant are also added with, powder flow aid accounts for short carbon chain nylon salt, the first Long carbon chain Buddhist nun
The 0.2-2.0% of imperial salt and the second long carbon chain nylon salt gross weight, the second antioxidant accounts for short carbon chain nylon salt, the first Long carbon chain
The 0.2-0.8% of nylon salt and the second long carbon chain nylon salt gross weight.
Selective laser sintering polyamide material of the present invention and preparation method thereof has the advantages that：
（1）, by by carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt pass through copolyreaction be made choosing
The laser sintered use polyamide material of selecting property, copolymer nylon is obtained because three kinds of nylon salts carry out copolymerization, its macromolecular chain it is symmetrical
Property and regularity are poor, cause copolymer nylon crystallinity poor, heat endurance is poor.Inventor herein is had found such that due to short carbon chain
The addition of nylon, can make the symmetry of the macromolecular chain of different classes of the first long carbon chain nylon salt and the second long carbon chain nylon salt
It is more preferable by destruction with regularity, so that under the crystallizing power of selective laser sintering polyamide material made from copolymerization
Drop, or even completely lose.So that the energy needed for powder melts is lower, the requirement to agglomerating plant is reduced.
（2）, simultaneously because powder is thermally-stabilised poor, powder at lower operating temperatures, by it is laser sintered when, powder
It can completely melt, so as to improve the mobility of molten mass, reduce sintered molten body space, and then may be such that selective laser
Workpiece made from sintering polyamide material has higher toughness effect；
（3）, selective laser sintering polyamide material of the present invention and preparation method thereof, cost is low, it is easy to accomplish, and can be extensive
Applied to industrial production.
Brief description of the drawings
Fig. 1 is the DSC curve figure for the selective laser sintering polyamide material that the embodiment of the present invention 1 is provided.
Embodiment
The invention provides a kind of selective laser sintering polyamide material, including short carbon chain nylon salt, and difference
The first long carbon chain nylon salt, the second long carbon chain nylon salt of classification, and short carbon chain nylon salt, the first long carbon chain nylon salt and second
Selective laser sintering polyamide material is made by copolyreaction in long carbon chain nylon salt.Preferably, first Long carbon chain
Nylon salt, the second long carbon chain nylon salt, the weight ratio of short carbon chain nylon salt are 1:1:0.2-0.8, can so be better assured that poly-
The low melting point of acid amides powder, and pass through the high tenacity of the polyamide powder sintering product.
Preferably, the short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt are common by ternary
Polyamide pellet is made in poly- reaction, in specific implementation, and first long carbon chain nylon salt is nylon 11 salt, the salt of nylon 11 12, Buddhist nun
Imperial 1113 salt, Nylon-1010 Salt, the salt of nylon 1011, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt or Buddhist nun
Imperial 1313 salt；Second long carbon chain nylon salt is nylon 11 salt, the salt of nylon 11 12, the salt of nylon 11 13, Nylon-1010 Salt, nylon
1011 salt, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt or nylon 1313 salt.Herein it should be noted that,
Specific a kind of nylon salt selected by first long carbon chain nylon salt and the second long carbon chain nylon salt is different, such as when the first Long carbon chain
Nylon salt elects nylon 11 salt as, then the nylon salt that the second long carbon chain nylon salt can be outside blanking nylon 11 salt, such as Nylon-1010 Salt
Or the salt of nylon 11 12.
In specific implementation, the short carbon chain nylon salt can be caprolactam or adipic acid hexamethylene diamine salt, can also be certainly
Other nylon salts for possessing short carbon chain property.
Preferably, above-mentioned selective laser sintering also includes molecular weight regulator with polyamide material, and it accounts for above-mentioned first
Long carbon chain nylon salt, the second long carbon chain nylon salt, the 0.2-0.8% of short carbon chain nylon salt gross weight, such molecular weight regulator exist
As end-capping reagent in polycondensation process, the size of copolymer nylon molecular weight is can control, while improving the stability of copolymer nylon.Tool
Body, the molecular weight regulator is the one or more in adipic acid, SA, dodecanedioic acid.
It is further preferred that above-mentioned selective laser sintering also includes the first antioxidant with polyamide material, it is accounted for
State the first long carbon chain nylon salt, the second long carbon chain nylon salt, the 0.2-1.0% of short carbon chain nylon salt gross weight, it is therefore an objective to prevent oxygen
The harmful effect of gas.Specifically, first antioxidant be Hinered phenols oxidant or phosphite antioxidant, wherein
Hindered phenol anti-oxidants are 1,3,5- trimethyls -2,4,6- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）Benzene, the tertiary fourths of 2,6- bis-
Base -4- methyl-phenols, N, N '-two（3,5- di-tert-butyl-hydroxy phenyl propionamides）In one or more, phosphite
Class antioxidant is 2,2 '-ethylenebis（4,6- di-tert-butyl-phenyls）Fluorophosphite, four（2,4- di-tert-butyl-phenyls）-
4, the one or more in 4 '-xenyl bis-phosphite.
It is further preferred that above-mentioned selective laser sintering also includes powder flow aid with polyamide material, it is accounted for
The first long carbon chain nylon salt, the second long carbon chain nylon salt, the 0.2-2.0% of short carbon chain nylon salt gross weight are stated, so can be obvious
The mobility of polyamide material processing is improved, so as to add the production efficiency of polyamide processing, and then polyamide is improved and adds
The surface gloss and quality of item of work product.Specifically, the powder flow aid is gas phase alundum (Al2O3), gas phase dioxy
One or more in SiClx, gas phase titanium dioxide.
It is further preferred that above-mentioned selective laser sintering also includes the second antioxidant with polyamide material, it is accounted for
State the first long carbon chain nylon salt, the second long carbon chain nylon salt, the 0.2-0.8% of short carbon chain nylon salt gross weight, second antioxygen
Agent is phase same material with the first antioxidant.
Herein it should be noted that, above-mentioned molecular weight regulator and the first antioxidant above-mentioned first long carbon chain nylon salt,
Added before second long carbon chain nylon salt, the polymerization of short carbon chain nylon salt, and participate in polymerisation together and polyamide pellet is made；And
When polyamide pellet crushes last for Silon, above-mentioned powder flow aid and the second antioxidant are added, so as to improve poly-
The mobility and inoxidizability of acid amides powder.
Present invention also offers a kind of preparation method of selective laser sintering polyamide material, comprise the following steps：
Step 1: by short carbon chain nylon salt, and different classes of the first long carbon chain nylon salt, the second long carbon chain nylon salt are carried out
Polyamide pellet is made in copolyreaction；
In the step one, the weight ratio of the short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt can
Preferably 1:1:0.2-0.8, can so better assure that the low melting point of polyamide powder, and sinter by the polyamide powder
The high tenacity of product.It is further preferred that in order to ensure low melting point and the beneficial effect of high tenacity, the short carbon chain nylon salt,
First long carbon chain nylon salt and the second long carbon chain nylon salt are reacted by ternary polymerization is made polyamide pellet.
In specific implementation, the short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt pass through three
Polyamide pellet is made in first copolyreaction, in specific implementation, and first long carbon chain nylon salt is nylon 11 salt, nylon 11 12
Salt, the salt of nylon 11 13, Nylon-1010 Salt, the salt of nylon 1011, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt
Or nylon 1313 salt；Second long carbon chain nylon salt be nylon 11 salt, the salt of nylon 11 12, the salt of nylon 11 13, Nylon-1010 Salt,
The salt of nylon 1011, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon 1212 salt or nylon 1313 salt.It should be noted herein
It is that specific a kind of nylon salt selected by first long carbon chain nylon salt and the second long carbon chain nylon salt is different, such as when the first length
Carbon chain nylon salt elects nylon 11 salt as, then the nylon salt that the second long carbon chain nylon salt can be outside blanking nylon 11 salt, such as nylon
1010 salt or the salt of nylon 11 12.
The short carbon chain nylon salt can be caprolactam or adipic acid hexamethylene diamine salt, can also possess short carbon to be other certainly
The nylon salt of chain property.
Step 2: above-mentioned polyamide pellet is obtained into selective laser sintering polyamide powder by crushing.
Preferably, polyamide pellet is by deep cooling crush in the step 2, and it is 50 that dry, sieve classification, which obtains average grain diameter,
μm copolymer nylon powder.
Preferably, it is also anti-oxidant added with molecular weight regulator and/or first in the polymerisation in above-mentioned steps one
Agent, wherein molecular weight regulator account for short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight
0.2-0.8%, the first antioxidant accounts for short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight
0.2-1.0%.
It is further preferred that being also added with powder stream in the selective laser sintering polyamide powder that step 2 is obtained
Dynamic auxiliary agent and/or the second antioxidant, powder flow aid account for short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon
The 0.2-2.0% of chain nylon salt gross weight, the second antioxidant accounts for short carbon chain nylon salt, the first long carbon chain nylon salt and the second length
The 0.2-0.8% of carbon chain nylon salt gross weight.
In order to allow those skilled in the art to more fully understand and realize technical scheme, below by way of specific reality
Example is applied to be described in further details.
Embodiment 1
Calculated with weight ratio meter, prepare the material of following part by weight：
Caprolactam:Nylon 11 salt:Nylon-1010 Salt=0.2:1:1
The above-mentioned caprolactam got ready, nylon 11 salt, Nylon-1010 Salt are loaded in polymeric kettle, is well mixed, adds following
Additive carries out copolyreaction：
Adipic acid, addition is gross weight（Gross weight herein is the gross weight of caprolactam, nylon 11 salt and Nylon-1010 Salt
Amount）0.2%.
Hindered phenol anti-oxidants, addition is gross weight（Gross weight herein is caprolactam, nylon 11 salt and nylon
The gross weight of 1010 salt）0.2%.
After being vacuumized to the polymeric kettle equipped with reactant, nitrogen dioxide gas is filled to 0.3-0.4Mpa, is then exhausted from after gas
Heating.When temperature in the kettle rises to 220 DEG C, pressure reaches 1.5Mpa, 1.5 hours dwell times in kettle.240 are reached Deng temperature in the kettle
Decompression is begun to after DEG C.Pressure is down to 0 Mpa in 120min, 0.5h is incubated, is re-filled with nitrogen dioxide gas to 0.2-
0.3Mpa, Open valve discharging.Cool down, be cut into pellet.
Above-mentioned pellet is put into freezing crusher, crushed under liquid nitrogen environment, then it is i.e. available by drying, screening
Desired powder.
Again the powder is added to stir in vertical stirrer with gas phase alundum (Al2O3), hindered phenol anti-oxidants and mixed
3h, wherein gas phase alundum (Al2O3) account for powder gross weight（Gross weight herein is caprolactam, nylon 11 salt and Nylon-1010 Salt
Gross weight）0.2%, hindered phenol anti-oxidants account for powder gross weight（Gross weight herein is caprolactam, nylon 11 salt
With the gross weight of Nylon-1010 Salt）0.2%.100 mesh sieves are crossed after material is well mixed, selective laser sintering polyamides is obtained
Amine powder, so that the polyamide powder has cryogenic effect, and sintered part has high tenacity effect.The selectivity of the embodiment
The DSC curve figure of laser sintered use polyamide material is as shown in Figure 1.
Embodiment 2
Calculated with weight ratio meter, prepare the material of following part by weight：
Caprolactam:Nylon 11 salt:Nylon 1212 salt=0.4:1:1
Caprolactam, nylon 11 salt, nylon 1212 salt are loaded in polymeric kettle, are well mixed, following additive is added and carries out
Copolyreaction：
Adipic acid, addition is gross weight（Gross weight herein is the gross weight of caprolactam, nylon 11 salt and nylon 1212 salt
Amount）0.4%.
Hindered phenol anti-oxidants, addition is gross weight（Gross weight herein is caprolactam, nylon 11 salt and nylon
The gross weight of 1212 salt）0.4%.
After being vacuumized to the polymeric kettle equipped with reactant, nitrogen dioxide gas is filled to 0.3-0.4Mpa, is then exhausted from after gas
Heating.When temperature in the kettle rises to 225 DEG C, pressure reaches 1.6Mpa, 2 hours dwell times in kettle.250 DEG C are reached Deng temperature in the kettle
Decompression is begun to afterwards.Pressure is down to 0 Mpa in 130min, nitrogen dioxide gas is filled with to 0.2-0.3Mpa, opening valve
Door discharging.Cool down, be cut into pellet.
Above-mentioned pellet is put into freezing crusher, crushed under liquid nitrogen environment, then it is i.e. available by drying, screening
Desired powder.
Again the powder is added to stir in vertical stirrer with aerosil, hindered phenol anti-oxidants and mixed
4h, wherein aerosil account for powder gross weight（Gross weight herein is caprolactam, nylon 11 salt and nylon 1212 salt
Gross weight）0.8%, hindered phenol anti-oxidants account for powder gross weight（Gross weight herein be caprolactam, nylon 11 salt and
The gross weight of nylon 1212 salt）0.4%.100 mesh sieves are crossed after material is well mixed, selective laser sintering polyamide is obtained
Powder, so that the polyamide powder has cryogenic effect, and sintered part has high tenacity effect.
Embodiment 3
Calculated with weight ratio meter, prepare the material of following part by weight:
Caprolactam:The salt of nylon 11 12:Nylon-1010 Salt=0.6:1:1
Preparation method：Caprolactam, the salt of nylon 11 12, Nylon-1010 Salt are well mixed, following additive is added and is total to
Poly- reaction：
Adipic acid, addition is gross mass（Gross weight herein is the gross weight of caprolactam, the salt of nylon 11 12 and Nylon-1010 Salt
Amount）0.6%.
Hindered phenol anti-oxidants, addition is gross mass（Gross weight herein is caprolactam, the salt of nylon 11 12 and Buddhist nun
The gross weight of imperial 1010 salt）0.6%.
After being vacuumized to the polymeric kettle equipped with reactant, nitrogen dioxide gas is filled to 0.3-0.4Mpa, is then exhausted from after gas
Heating.When temperature in the kettle rises to 230 DEG C, pressure reaches 1.6Mpa, 2 hours dwell times in kettle.250 DEG C are reached Deng temperature in the kettle
Decompression is begun to afterwards.Pressure is down to 0 Mpa in 140min, nitrogen dioxide gas is filled with to 0.2-0.3Mpa, opening valve
Door discharging.Cool down, be cut into pellet.
Above-mentioned pellet is put into freezing crusher, crushed under liquid nitrogen environment, then it is i.e. available by drying, screening
Desired powder.
The powder and gas phase alundum (Al2O3), phosphite antioxidant are added in vertical stirrer again and stir mixed
5h is closed, wherein gas phase alundum (Al2O3) accounts for powder gross weight（Gross weight herein is caprolactam, the salt of nylon 11 12 and nylon
The gross weight of 1010 salt）1.4%, phosphite antioxidant accounts for powder gross weight（Gross weight herein be caprolactam,
The gross weight of the salt of nylon 11 12 and Nylon-1010 Salt）0.6%.100 mesh sieves are crossed after material is well mixed, selective laser is obtained
Sintering polyamide powder, so that the polyamide powder has cryogenic effect, and sintered part has high tenacity effect.
Embodiment 4
Calculated with weight ratio meter, prepare the material of following part by weight:
Caprolactam:The salt of nylon 11 12:Nylon 1212 salt=0.8:1:1
Preparation method：Caprolactam, the salt of nylon 11 12, nylon 1212 salt are well mixed, following additive is added and is total to
Poly- reaction：
Adipic acid molecular weight regulator, addition is gross mass（Gross weight herein is caprolactam, the salt of nylon 11 12 and nylon
The gross weight of 1212 salt）0.8%.
Hindered phenol anti-oxidants, addition is gross mass（Gross weight herein is caprolactam, the salt of nylon 11 12 and Buddhist nun
The gross weight of imperial 1212 salt）0.8%
After being vacuumized to the polymeric kettle equipped with reactant, nitrogen dioxide gas is filled to 0.3-0.4Mpa, is then exhausted from heating after gas.
When temperature in the kettle rises to 220 DEG C, pressure reaches 1.6Mpa, 1.5 hours dwell times in kettle.Deng temperature in the kettle reach 240 DEG C it
After begin to decompression.Pressure is down to 0 Mpa. in 140min and is filled with nitrogen dioxide gas to 0.2-0.3Mpa, Open valve
Discharging.Cool down, be cut into pellet.
Above-mentioned pellet is put into freezing crusher, crushed under liquid nitrogen environment, then it is i.e. available by drying, screening
Desired powder.
Again the powder is added to stir in vertical stirrer with gas phase titanium dioxide, phosphite antioxidant and mixed
3h, wherein gas phase titanium dioxide account for powder gross weight（Gross weight herein is caprolactam, the salt of nylon 11 12 and nylon 1212 salt
Gross weight）2%, phosphite antioxidant accounts for powder gross weight（Gross weight herein is caprolactam, nylon 11 12
The gross weight of salt and nylon 1212 salt）0.6%.100 mesh sieves are crossed after material is well mixed, selective laser sintering is obtained and uses poly-
Acid amides powder, so that the polyamide powder has cryogenic effect, and sintered part has high tenacity effect.
The selective laser sintering system prepared using the selective laser sintering of above-described embodiment 1 to 4 with polyamide powder
The correlation performance parameters of part are described in table 1 below.
Table 1：The selective laser sintering product that the selective laser sintering of embodiment 1 to 4 is prepared with polyamide powder
Performance parameter
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but not generation
Limitation of the table to the scope of the claims of the present invention.For the person of ordinary skill of the art, before present inventive concept is not departed from
Put, various modifications and improvements can be made, these belong to protection scope of the present invention, therefore, the guarantor of patent of the present invention
Shield scope should be determined by the appended claims.
Claims (10)
1. a kind of selective laser sintering polyamide material, it is characterised in that including short carbon chain nylon salt, and it is different classes of
The first long carbon chain nylon salt, the second long carbon chain nylon salt, and short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon
Selective laser sintering polyamide material is made by copolyreaction in chain nylon salt.
2. selective laser sintering polyamide material according to claim 1, it is characterised in that first Long carbon chain
Nylon salt, the second long carbon chain nylon salt, the weight ratio of short carbon chain nylon salt are 1:1:0.2-0.8.
3. selective laser sintering polyamide material according to claim 2, it is characterised in that first Long carbon chain
Nylon salt is nylon 11 salt, the salt of nylon 11 12, the salt of nylon 11 13, Nylon-1010 Salt, the salt of nylon 1011, Nylon 1012 salt, nylon
1013 salt, the salt of nylon 12, nylon 1212 salt or nylon 1313 salt；Second long carbon chain nylon salt is nylon 11 salt, nylon
1112 salt, the salt of nylon 11 13, Nylon-1010 Salt, the salt of nylon 1011, Nylon 1012 salt, the salt of nylon 1013, the salt of nylon 12, nylon
1212 salt or nylon 1313 salt.
4. the selective laser sintering polyamide material according to any one of claims 1 to 3, it is characterised in that described
Short carbon chain nylon salt is caprolactam or adipic acid hexamethylene diamine salt.
5. a kind of preparation method of selective laser sintering polyamide material, it is characterised in that comprise the following steps：
Step 1: by short carbon chain nylon salt, and different classes of the first long carbon chain nylon salt, the second long carbon chain nylon salt are carried out
Polyamide pellet is made in copolyreaction；
Step 2: above-mentioned polyamide pellet is obtained into selective laser sintering polyamide powder by crushing.
6. the preparation method of selective laser sintering polyamide material according to claim 5, it is characterised in that described
The weight ratio of short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt is 1:1:0.2-0.8.
7. the preparation method of selective laser sintering polyamide material according to claim 6, it is characterised in that described
Short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt are reacted by ternary polymerization is made polyamide grain
Material.
8. the preparation method of selective laser sintering polyamide material according to claim 7, it is characterised in that described
Short carbon chain nylon salt is caprolactam or adipic acid hexamethylene diamine salt.
9. the preparation method of the selective laser sintering polyamide material according to any one of claim 5 to 8, its feature
It is, in the polymerisation in above-mentioned steps one, also added with molecular weight regulator and/or the first antioxidant, wherein dividing
Son amount conditioning agent accounts for the 0.2-0.8% of short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight,
First antioxidant accounts for the 0.2- of short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight
1.0%。
10. the preparation method of selective laser sintering polyamide material according to claim 9, it is characterised in that
It is also anti-oxidant added with powder flow aid and/or second in the selective laser sintering polyamide powder that step 2 is obtained
Agent, powder flow aid accounts for the 0.2- of short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight
2.0%, the second antioxidant accounts for short carbon chain nylon salt, the first long carbon chain nylon salt and the second long carbon chain nylon salt gross weight
0.2-0.8%。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320716A (en) * | 2018-09-10 | 2019-02-12 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method applied to selective laser sintering |
| CN109517370A (en) * | 2018-09-10 | 2019-03-26 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method for selective laser sintering |
| CN110591343A (en) * | 2019-09-02 | 2019-12-20 | 湖南华曙高科技有限责任公司 | High-molecular powder material, preparation method thereof and method for preparing workpiece by using material |
| CN110615892A (en) * | 2019-09-09 | 2019-12-27 | 杭州聚合顺新材料股份有限公司 | Low-temperature-resistant multi-component copolymerized nylon resin and synthetic method thereof |
| CN110878139A (en) * | 2018-09-06 | 2020-03-13 | 华峰集团有限公司 | Low-melting-point high-flow ternary random copolymer polyamide modified base resin and preparation method thereof |
| CN115707728A (en) * | 2021-08-20 | 2023-02-21 | 中国石油化工股份有限公司 | Preparation method of long carbon chain nylon and long carbon chain nylon |
| CN115926441A (en) * | 2022-12-08 | 2023-04-07 | 中国石油化工股份有限公司 | Transparent copolymerized nylon film and biaxial stretching film forming process thereof |
| CN116003782A (en) * | 2022-04-26 | 2023-04-25 | 湖南世博瑞高分子新材料有限公司 | Synthesis method and application of high-flow low-temperature-resistant PA66 resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5712079A (en) * | 1980-06-27 | 1982-01-21 | Toray Ind Inc | Hot melt adhesive |
| CN1410499A (en) * | 2001-12-21 | 2003-04-16 | 淄博广通化工有限责任公司 | Long carbon chain nylon thermosol and its preparation method |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
| CN104559909A (en) * | 2015-01-29 | 2015-04-29 | 上海化工研究院 | Low-melting-point copolyamide hot melt adhesive and preparation method thereof |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
-
2017
- 2017-07-28 CN CN201710627427.8A patent/CN107286338A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5712079A (en) * | 1980-06-27 | 1982-01-21 | Toray Ind Inc | Hot melt adhesive |
| CN1410499A (en) * | 2001-12-21 | 2003-04-16 | 淄博广通化工有限责任公司 | Long carbon chain nylon thermosol and its preparation method |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
| CN104559909A (en) * | 2015-01-29 | 2015-04-29 | 上海化工研究院 | Low-melting-point copolyamide hot melt adhesive and preparation method thereof |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈继民等: "《激光现代制造技术》", 31 October 2007, 国防工业出版社 * |
Cited By (11)
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|---|---|---|---|---|
| CN110878139A (en) * | 2018-09-06 | 2020-03-13 | 华峰集团有限公司 | Low-melting-point high-flow ternary random copolymer polyamide modified base resin and preparation method thereof |
| CN110878139B (en) * | 2018-09-06 | 2022-06-17 | 华峰集团有限公司 | Low-melting-point high-flow ternary random copolymer polyamide modified base resin and preparation method thereof |
| CN109320716A (en) * | 2018-09-10 | 2019-02-12 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method applied to selective laser sintering |
| CN109517370A (en) * | 2018-09-10 | 2019-03-26 | 湖南华曙高科技有限责任公司 | A kind of nylon powder material preparation method for selective laser sintering |
| 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 |
| CN110591343A (en) * | 2019-09-02 | 2019-12-20 | 湖南华曙高科技有限责任公司 | High-molecular powder material, preparation method thereof and method for preparing workpiece by using material |
| CN110615892A (en) * | 2019-09-09 | 2019-12-27 | 杭州聚合顺新材料股份有限公司 | Low-temperature-resistant multi-component copolymerized nylon resin and synthetic method thereof |
| CN115707728A (en) * | 2021-08-20 | 2023-02-21 | 中国石油化工股份有限公司 | Preparation method of long carbon chain nylon and long carbon chain nylon |
| CN116003782A (en) * | 2022-04-26 | 2023-04-25 | 湖南世博瑞高分子新材料有限公司 | Synthesis method and application of high-flow low-temperature-resistant PA66 resin |
| CN115926441A (en) * | 2022-12-08 | 2023-04-07 | 中国石油化工股份有限公司 | Transparent copolymerized nylon film and biaxial stretching film forming process thereof |
| CN115926441B (en) * | 2022-12-08 | 2024-03-12 | 中国石油化工股份有限公司 | Transparent copolymerized nylon film and biaxially oriented film forming process thereof |
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