CN106977711A - A kind of selective laser sintering PA66/PA6 copolymeric materials and preparation method - Google Patents
A kind of selective laser sintering PA66/PA6 copolymeric materials and preparation method Download PDFInfo
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- 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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Abstract
A kind of selective laser sintering PA66/PA6 copolymeric materials that the present invention is provided, by adipic acid hexamethylene diamine salt and caprolactam in mass ratio 95:15 polycondensations are formed, the material can also mixed flow auxiliary agent and/or antioxidant as needed, improve its mobility and antioxygenic property.Present invention also offers a kind of selective laser sintering PA66/PA6 copolymeric material preparation methods, by by adipic acid hexamethylene diamine salt and caprolactam in mass ratio 95:15 add reactor, molecular weight regulator, antioxidant and water are added simultaneously, and antistatic additive is added as needed on, copolyreaction is carried out under certain condition, and the copolymerization pellet obtained is subjected to deep cooling crush, sieve the dusty material that average grain diameter is 45 80 μm, so as to obtain the PA66/PA6 copolymeric materials for selective laser sintering, the preparation method technique is simple, and cost is relatively low, copolymeric material fusing point easily adjusts control, suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of copolymeric material and preparation method thereof, and in particular to a kind of selective laser sintering PA66/
PA6 copolyamides powder and preparation method.
Background technology
Selective laser sintering is a kind of method that three-dimensional body is manufactured by optionally fusing multiple powder beds, should
Method allows that only the multiple heavy of laser sintering powder need to be passed through according to the 3-D view of object to be produced without using tool processes
Lamination, to obtain 3D solid.This method is mainly completed using thermoplastic polymer, patent US6136948 and WO9606881
The method that this use polymer powder manufactures three-dimensional body is described in detail.The technology is in Aero-Space, doctor
The fields such as treatment, footwear, industrial design and building are applied.
One of the problem of being existed at present using the technology is：Using the technology prepare Three-dimensional Entity Components cost compared with
Height, limits business promotion to a certain extent.A major reason for causing 3 d part cost high is to use the technology
Material price it is high.With the PA12 of current main flow（Nylon 12）Exemplified by, the PA12 costs of raw material itself are higher, and for selecting
The laser sintered PA12 dusty materials process for making of selecting property is complicated, and single batch output is less, prepares cost high.In addition,
Dusty material undergoes in selective laser sintering process to be heated repeatedly, and the recycling performance of powder declines, and causes powder material
Expect overall utilization it is relatively low be also influence price the reason for one of.
The content of the invention
It is cheap it is an object of the invention to provide a kind of PA66/PA6 copolymeric materials for selective laser sintering,
It is functional, and its fusing point can be adjusted according to the raw material ratio of copolymeric material, and the selective laser that is particularly suitable for use in burns
Knot.
Present invention also offers the preparation method of the PA66/PA6 copolymeric materials, by using adipic acid hexamethylene diamine salt and oneself
Lactams polycondensation obtains copolymeric material, then crushes and screens dusty material needed for acquisition, and the preparation method technique is simple, prepares cost
It is low.
A kind of selective laser sintering PA66/PA6 copolymeric materials that the present invention is provided, the PA66/PA6 copolymeric materials by
Adipic acid hexamethylene diamine salt and caprolactam polycondensation are formed, and wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 9-5:1-
5, the ratio range can by the control of the fusing points of PA66/PA6 copolymeric materials 170 DEG C -245 DEG C this be conducive to laser sintered temperature
In the range of degree.It is preferred that the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 7-5：3-5, the copolymeric material in this ratio range
The closest PA12 of Laser Processing temperature, and PA12 is then the main flow material that current Selective Laser Sintering business is used
Material.If controlling PA66/PA6 copolymeric materials fusing point and processing temperature to be approached with PA12, without to the selectivity based on PA12
Laser sintered equipment is modified, while without extra sintering parameter adjustment is carried out in the materials process is processed, can pole
Big raising research and development and production efficiency.
Further, the PA66/PA6 copolymeric materials also include flow promortor and/or antioxidant, and flow promortor is helped
In the mobility for improving laser sintering powder, it is ensured that the stability that powder paving is sent in sintering process, so that sintering finished rate is improved,
Antioxidant is then favorably improved the inoxidizability of powder.
In Selective Laser Sintering field, the mobile performance of powder is to determine that can powder well sinter three-dimensional zero into
One important indicator of part.In general, powder flowbility can effectively reduce well the generation of powder agglomeration, agglomerated powder is improved
The paving of powder material send effect, and then improves the uniformity and compactness of powder bed, thus the 3 d part surface quality of sintering and
Related mechanical properties can have been lifted, in addition because of the reduction of agglomeration, and the recycling rate of waterused of powder can also have been lifted, energy
Reduce powder cost.
The antioxidant effect of powder can have been lifted the 3 d part quality of sintering, and three are not processed to while can reduce
The powder of dimension part is oxidized degree, and there is provided powder recycling rate of waterused.Particularly, some color or color and luster are required three
Part is tieed up, the addition of antioxidant can also increase the whiteness of 3 d part.
Further, the flow promortor is aerosil, gas phase alundum (Al2O3) or nano titanium oxide, accounts for total
The 0.1-0.9% of quality of materials.
Further, the antioxidant is Hinered phenols oxidant or phosphorous acid lipid antioxidant, accounts for total material matter
The 0.2-1.0% of amount, wherein hindered phenol anti-oxidants are 1,3,5- trimethyls -2,4,6- tri-（3,5- di-t-butyl -4- hydroxyls
Benzyl）Benzene, 2,6- di-t-butyl -4- methyl-phenols, N, N '-two（3,5- di-tert-butyl-hydroxy phenyl propionamides）In one
Plant or several, phosphorous acid lipid 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.
Further, the PA66/PA6 copolymeric materials also include antistatic additive.Appropriate antistatic additive is added can not only
3 d part is possessed anti-static function, meet and such as weave, illuminate the use in field, and sintering can be improved to a certain extent
Flow of powder performance, reduces powder agglomeration, improves the recycling rate of waterused of powder.
Further, the antistatic additive is interior mixcibility antistatic additive, and alkyl, alkaryl have nonpolar antistatic
One or several kinds in agent, preferably ethoxylated alkylamine or ethoxylated alkyl acid amide or the cruel amine of ethyoxyl bay, account for total
The 0.3-3.6% of quality of materials.
Present invention also offers a kind of selective laser sintering PA66/PA6 copolymeric material preparation methods, including following step
Suddenly:
（1）By raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator and water add reactor, wherein adipic acid oneself
The mass ratio of diamine salts and caprolactam is 9-5:1-5, molecular weight regulator accounts for the 0.3-1.5% of raw material gross mass, and water accounts for raw material
The 20-50% of gross mass；
（2）Closed reactor, is excluded after gas reactor, and it is 0.10-0.15MPa to be passed through pressure in inert gas to kettle, then is controlled
Be warming up to 185-245 DEG C in kettle, pressure to 1.1-1.6MPa, 1-3 hour of pressurize, then slow release of pressure risen in kettle to normal pressure
Temperature is kept for 1-3 hour of reaction to 240-280 DEG C, and cooling obtains copolymer nylon pellet；
（3）To step（2）Obtained copolymer nylon pellet carries out deep cooling crush, and screening obtains the choosing that average grain diameter is 45-80 μm
Selecting property laser sintering powder material.
Further, the molecular weight regulator is SA, dodecanedioic acid, 14 carbon diacid, thapsic acid, ten
One kind in eight carbon diacid, molecular weight regulator, as end-capping reagent, controls the size of copolymer nylon molecular weight in polycondensation process,
The stability of copolymer nylon is improved simultaneously.
Further, step（1）Middle raw material also includes antistatic additive.
Further, the antistatic additive is interior mixcibility antistatic additive, and alkyl, alkaryl have nonpolar antistatic
One or several kinds in agent, preferably ethoxylated alkylamine or ethoxylated alkyl acid amide or the cruel amine of ethyoxyl bay, account for total
The 0.3-3.6% of quality of materials.
Further, the water in raw material is deionized water, preferably through the water of secondary purification.
Further, step（1）Described in antioxidant be Hinered phenols oxidant or phosphorous acid lipid antioxidant, its
Middle hindered phenol anti-oxidants are 1,3,5- trimethyls -2,4,6- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）Benzene, the uncles of 2,6- bis-
Butyl -4- methyl-phenols, N, N '-two（3,5- di-tert-butyl-hydroxy phenyl propionamides）In one or more, phosphorous acid
Lipid antioxidant is 2,2 '-ethylenebis（4,6- di-tert-butyl-phenyls）Fluorophosphite, four（2,4- di-tert-butyls
Base）- 4, the one or more in 4 '-xenyl bis-phosphite.
Further, step is passed through（3）The selective laser sintering dusty material of acquisition can also add flow promortor and/
Or antioxidant, for selective laser sintering.
A kind of selective laser sintering PA66/PA6 copolymeric materials that the present invention is provided, by adipic acid hexamethylene diamine salt and oneself
Lactams polycondensation is formed, and its fusing point can be adjusted according to the adding proportion of adipic acid hexamethylene diamine salt and caprolactam, its former material
Expect with low cost, processing characteristics and satisfactory mechanical property, be particularly suitable for use in Selective Laser Sintering.The material can be with root
According to mixed flow auxiliary agent and/or antioxidant is needed, improve its mobility and antioxygenic property, copolymeric material addition is anti-quiet in addition
Electric agent can not only make the 3 d part of manufacture meet the antistatic use requirement in some fields, and can further improve powder material
The mobile performance of material, improves the recycling rate of waterused of powder, reduces materials'use price.
A kind of selective laser sintering PA66/PA6 copolymeric material preparation methods that the present invention is provided, by by adipic acid
Hexamethylene diamine salt and caprolactam add reactor according to a certain ratio, while molecular weight regulator, antioxidant and water are added, and
Antistatic additive is added as needed on, copolyreaction is carried out under certain condition, the copolymerization pellet obtained is subjected to deep cooling crush,
Particle diameter needed for screening is so as to obtain the PA66/PA6 copolymeric materials for selective laser sintering.The preparation method technique is simple,
Cost is relatively low, and copolymeric material fusing point easily adjusts control, suitable for industrialized production.
Embodiment
The present invention is described in further detail below by specific embodiment.
Embodiment 1
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 9:1（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 0.3%, deionized water is that 20%, antioxidant is 1.5%.Closed reactor is simultaneously excluded
Gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.15MPa.245 DEG C, air pressure are warming up in control kettle
To 1.6MPa, 1 hour of pressurize, then slowly it is deflated in normal pressure, kettle and is warming up to 280 DEG C of holding 1 hours of reaction, stop adding
Heat, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 45 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.1% of gross mass,
Antioxidant accounts for the 0.2% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
Embodiment 2
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 8:2（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 0.6%, deionized water is that 30%, antistatic additive is that 0.3%, antioxidant is 1.2%.
Closed reactor simultaneously excludes gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.1MPa.Control in kettle
210 DEG C are warming up to, air pressure to 1.5MPa, is then slowly deflated in normal pressure, kettle and is warming up to 270 DEG C of holdings 1.5 hours of pressurize
1.5 hours are reacted, stop heating, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 50 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.3% of gross mass,
Antioxidant accounts for the 0.4% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
Embodiment 3
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 7:3（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 0.8%, deionized water is that 40%, antioxidant is 0.8%.Closed reactor is simultaneously excluded
Gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.12MPa.200 DEG C, air pressure are warming up in control kettle
To 1.4MPa, 2 hours of pressurize, then slowly it is deflated in normal pressure, kettle and is warming up to 260 DEG C of holding 2 hours of reaction, stop adding
Heat, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 60 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.5% of gross mass,
Antioxidant accounts for the 0.6% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
Embodiment 4
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 6:4（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 1.0%, deionized water is that 40%, antistatic additive is that 3.6%, antioxidant is 0.6%.
Closed reactor simultaneously excludes gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.14MPa.Control in kettle
200 DEG C are warming up to, air pressure to 1.3MPa, is then slowly deflated in normal pressure, kettle and is warming up to 250 DEG C of holdings instead 3 hours of pressurize
Answer 2.5 hours, stop heating, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 70 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.7% of gross mass,
Antioxidant accounts for the 0.8% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
Embodiment 5
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 6:4（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 1.0%, deionized water is that 40%, antioxidant is 0.6%.Closed reactor is simultaneously excluded
Gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.14MPa.200 DEG C, air pressure are warming up in control kettle
To 1.3MPa, 3 hours of pressurize, then slowly it is deflated in normal pressure, kettle and is warming up to 250 DEG C of holding 2.5 hours of reaction, stop
Heating, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 70 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.7% of gross mass,
Antioxidant accounts for the 0.8% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
Embodiment 6
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, deionized water, antioxidant are added to reaction
In kettle.Wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 5:5（By 10 parts of calculating）, other raw materials account for gross mass
Percentage is respectively：Molecular weight regulator is that 1.5%, deionized water is that 50%, antioxidant is 0.2%.Closed reactor is simultaneously excluded
Gas reactor, then pass to it is CO 2 gas-shielded to air pressure in kettle be 0.15MPa.185 DEG C, air pressure are warming up in control kettle
To 1.1MPa, 3 hours of pressurize, then slowly it is deflated in normal pressure, kettle and is warming up to 240 DEG C of holding 3 hours of reaction, stop adding
Heat, water cooling tie rod discharging, pelletizing obtains copolymer nylon pellet；
（2）Made pellet is passed through into deep cooling crush, dried, sieve classification, the copolymer nylon powder that average grain diameter is 80 μm is obtained
Material；
（3）Obtained nylon powder material is added into flow promortor and antioxidant, wherein flow promortor accounts for the 0.9% of gross mass,
Antioxidant accounts for the 1.0% of gross mass, obtains the copolymer nylon dusty material for selective laser sintering.
The PA12 materials and embodiment 1-6 of the selective laser sintering of commercialization in the market are prepared
PA66/PA6 copolymeric material melting temperature Tm are to such as table 1：
Table 1
Contrast is prepared under same processing conditions using PA66/PA6 copolymeric materials made from PA12 materials and embodiment 1-6
The correlated performance of selective laser sintering 3 d part, such as table 2：
Table 2
It can be seen that, the selective laser sintering copolymer nylon dusty material of embodiment 4 and embodiment 5, melting temperature and selection
Property laser sintered temperature and PA12 materials it is basically identical, the setting of machined parameters is also basically identical during actual processing, but real
The 3 d part performance for applying example 4 and embodiment 5 is better than PA12 materials.
Claims (13)
1. a kind of selective laser sintering PA66/PA6 copolymeric materials, it is characterised in that the PA66/PA6 copolymeric materials by
Adipic acid hexamethylene diamine salt and caprolactam polycondensation are formed, and wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 9-5:1-
5。
2. PA66/PA6 copolymeric materials according to claim 1, it is characterised in that the PA66/PA6 copolymeric materials are by oneself
Diacid hexamethylene diamine salt and caprolactam polycondensation are formed, and wherein the mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 7-5：3-5.
3. PA66/PA6 copolymeric materials according to claim 1 or 2, it is characterised in that the PA66/PA6 copolymeric materials
Also include flow promortor and/or antioxidant.
4. PA66/PA6 copolymeric materials according to claim 3, it is characterised in that the flow promortor is gas phase titanium dioxide
Silicon, gas phase alundum (Al2O3) or nano titanium oxide, account for the 0.1-0.9% of total quality of materials.
5. PA66/PA6 copolymeric materials according to claim 3, it is characterised in that the antioxidant is Hinered phenols oxygen
Agent or phosphorous acid lipid antioxidant, account for the 0.2-1.0% of total quality of materials, wherein hindered phenol anti-oxidants are 1,3,5-
Trimethyl -2,4,6- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）Benzene, 2,6- di-t-butyl -4- methyl-phenols, N, N '-two
（3,5- di-tert-butyl-hydroxy phenyl propionamides）In one or more, phosphorous acid lipid antioxidant be 2,2 '-ethylidene
It is double（4,6- di-tert-butyl-phenyls）Fluorophosphite, four（2,4- di-tert-butyl-phenyls）- 4, in 4 '-xenyl bis-phosphite
One or more.
6. the PA66/PA6 copolymeric materials according to claim any one of 1-5, it is characterised in that the PA66/PA6 copolymerization
Material also includes antistatic additive.
7. PA66/PA6 copolymeric materials according to claim 6, it is characterised in that the antistatic additive is ethoxylation alkane
Base amine, accounts for the 0.3-3.6% of total quality of materials.
8. a kind of selective laser sintering PA66/PA6 copolymeric material preparation methods, it is characterised in that comprise the following steps:
（1）Raw material adipic acid hexamethylene diamine salt, caprolactam, molecular weight regulator, antioxidant and water are added into reactor, wherein
The mass ratio of adipic acid hexamethylene diamine salt and caprolactam is 9-5:1-5, molecular weight regulator accounts for the 0.3-1.5% of raw material gross mass,
Antioxidant accounts for the 0.2-1.0% of raw material gross mass, and water accounts for the 20-50% of raw material gross mass；
（2）Closed reactor, is excluded after gas reactor, and it is 0.10-0.15MPa to be passed through pressure in inert gas to kettle, then is controlled
Be warming up to 185-245 DEG C in kettle, pressure to 1.1-1.6MPa, 1-3 hour of pressurize, then slow release of pressure risen in kettle to normal pressure
Temperature is kept for 1-3 hour of reaction to 240-280 DEG C, and cooling obtains copolymer nylon pellet；
（3）To step（2）Obtained copolymer nylon pellet carries out deep cooling crush, and screening obtains the choosing that average grain diameter is 45-80 μm
Selecting property laser sintering powder material.
9. preparation method according to claim 8, it is characterised in that the molecular weight regulator is SA, 12 carbon
One kind in diacid, 14 carbon diacid, thapsic acid, 18 carbon diacid.
10. preparation method according to claim 8, it is characterised in that the antioxidant be Hinered phenols oxidant or
Phosphorous acid lipid antioxidant, wherein hindered phenol anti-oxidants are 1,3,5- trimethyls -2,4,6- tri-（3,5- di-t-butyls-
4- hydroxybenzyls）Benzene, 2,6- di-t-butyl -4- methyl-phenols, N, N '-two（3,5- di-tert-butyl-hydroxy phenyl propionamides）
In one or more, phosphorous acid lipid antioxidant be 2,2 '-ethylenebis（4,6- di-tert-butyl-phenyls）Fluoro phosphorous acid
Ester, four（2,4- di-tert-butyl-phenyls）- 4, the one or more in 4 '-xenyl bis-phosphite.
11. preparation method according to claim 8, it is characterised in that step（1）Middle raw material also includes antistatic additive.
12. preparation method according to claim 11, it is characterised in that the antistatic additive be ethoxylated alkylamine or
One or more in ethoxylated alkyl acid amide or the cruel amine of ethyoxyl bay, account for the 0.3-3.6% of total quality of materials.
13. the preparation method according to claim any one of 8-12, it is characterised in that pass through step（3）The selection of acquisition
Property laser sintering powder material can also add flow promortor and/or antioxidant, for selective laser sintering.
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| 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 |
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| CN107513161A (en) * | 2017-08-01 | 2017-12-26 | 湖南华曙高科技有限责任公司 | A kind of preparation method of selective laser sintering in-situ polymerization type halogen-free flame-retardant nylon material |
| CN109722008A (en) * | 2017-10-31 | 2019-05-07 | 合肥杰事杰新材料股份有限公司 | A kind of nylon 6 composition material and preparation method thereof |
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| CN112771118B (en) * | 2018-09-26 | 2024-03-15 | 巴斯夫欧洲公司 | A Sintered Powder (SP) comprising a first polyamide component (PA 1) and a second polyamide component (PA 2), wherein the melting point of the second polyamide component (PA 2) is higher than the melting point of the first polyamide component (PA 1) |
| CN112771118A (en) * | 2018-09-26 | 2021-05-07 | 巴斯夫欧洲公司 | Sinter Powder (SP) comprising a first polyamide component (PA1) and a second polyamide component (PA2), wherein the melting point of the second polyamide component (PA2) is higher than the melting point of the first polyamide component (PA1) |
| CN109517376A (en) * | 2018-11-09 | 2019-03-26 | 湖南华曙高科技有限责任公司 | Nylon powder material preparation method 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 |
| CN109593355B (en) * | 2018-11-09 | 2022-01-14 | 湖南华曙高科技有限责任公司 | Nylon polymer powder material and preparation method thereof |
| CN109593355A (en) * | 2018-11-09 | 2019-04-09 | 湖南华曙高科技有限责任公司 | Nylon polymer dusty material and preparation method thereof |
| CN114874434A (en) * | 2021-02-05 | 2022-08-09 | 天津科技大学 | Method for preparing copolyamide PA6/66 by two-stage polymerization at medium-low pressure and normal pressure |
| CN113121819A (en) * | 2021-04-01 | 2021-07-16 | 华东理工大学 | PA4-66 copolymer material and preparation method thereof |
| CN113667130A (en) * | 2021-08-19 | 2021-11-19 | 郑州大学 | Thermoplastic polyamide elastomer powder for selective laser sintering and preparation method 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 |
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