CN104910614B - A kind of 3D printing low-warpage nylon dragon particulate composite and preparation method thereof - Google Patents
A kind of 3D printing low-warpage nylon dragon particulate composite and preparation method thereof Download PDFInfo
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a kind of 3D printing low-warpage nylon dragon particulate composite and preparation method thereof, it is characterised in that：Feed components constitute as follows according to mass percent：Nylon66 fiber~88.6wt%, 10~30wt% of micro inorganic fillers, 1~2wt% of coupling agent, 0.1~0.5wt% of hindered phenol antioxygen, 0.2~1.0wt% of phosphite antioxidant, 0.1~0.5wt% of other auxiliary agents；Described other auxiliary agents are the one or more combination in dispersant, nucleator, lubricant.The present invention is used in combination by selecting micro inorganic fillers, coupling agent, hindered phenol antioxygen, phosphite antioxidant, and the 3D printing for being spray-dried preparation is excellent with low-warpage nylon dragon particulate composite resistance to warping, and caking property is excellent；Its spherical particle narrowly distributing, good fluidity, without layering shedding problem, and preparation efficiency is high, energy consumption is small, simple easy processing.
Description
Technical field
The present invention relates to nylon powder technical field of composite materials, more particularly to a kind of 3D printing low-warpage nylon dragon powder
Composite and preparation method thereof.
Background technology
3D printing technique is a kind of emerging rapid shaping technique, is described as that " the third time industrial revolution is most significant
The tool of production ".Selective laser sintering and moulding technology is that one kind is integrated with CAD/CAM, Numeric Control Technology, laser processing technology and material
The high-new 3D printing technique of the field such as material science newest fruits.Using this technology, irradiated by laser and be capable of achieving dusty material
Mutually bond stratification and be layering, so as to realize the rapid shaping of product.With the amorphous polymer such as polystyrene, ABS
Fusion sediment rapid shaping, the 3D printing technique of the Stereolithography Polymer material of photosensitive resin are compared, and nylon powder is multiple
The features such as selective laser sintering and moulding product of condensation material has precision higher, intensity, heat resistance and toughness, can directly use
In finished product assembling, interference detection and performance test, thus can be widely applied to the preparation of industrial functional part.
At present, the preparation method of SLS nylon powders composite mainly has situ aggregation method, dissolving precipitated method, deep cooling
Grinding method etc..These methods are disclosed description in following patents.
The A of patent CN 103980485, the A of patent CN 104031262 and the A of patent CN 104356643 disclose a kind of profit
Anionic polymerisation principle is used, amidic-salt is first prepared, a small amount of catalyst, molecular weight regulator, strand stabilizer, anti-is then added
Auxiliary agent is added in oxygen agent etc., carries out anionic polymerisation, is prepared 3D printing nylon powder and is answered by discharging stirring or dissolving cooling precipitating
The method of condensation material.
The A of patent CN 104163929, patent ZL 200710053668.2 and patent ZL 200710053667.8 are disclosed
One kind is put into nylon material, nucleator, alcohol or inorganic nano-particle suspension in closed container, under nitrogen protection,
Heating for dissolving, then prepares one by slow cooling, vacuum distillation recovered solvent, filtering, centrifugation, vacuum drying and screening
The method for planting the particle diameter macromolecule nylon particulate composite of the 3D printing between 35-50 μm.
Patent 104164080A and patent 104231607A disclose one kind and set nylon in freezing respectively with other resins
- 60 DEG C~-80 DEG C are cooled in standby, are crushed and powder is obtained；After powder surface active, bulking agent, filler, antioxidant etc. is added to help
Agent, mixed at high speed is uniform, vibrosieve, the method for preparing selective laser sintering nylon alloy particulate composite.
The A of patent CN 103205107 disclose one kind by nylon resin 40-85 parts and a small amount of pigment, filler, dispersant
Deng addition auxiliary agent blending, melting extrusion granulation, low-temperature grinding, screening, the dusty material of 60~120 mesh of collection, then with it is same
The method that binding material high-speed stirred prepared by method prepares the caking ability 3D printing moulding material high for being rich in toughness.
The A of patent CN 104250437 and patent 104250435A also disclosed a kind of by 0.1~500 μm of nylon micro-sphere
100 parts prepare modification of nylon micro-sphere material with the addition auxiliary agent mixing such as the steady agent of a small amount of light, defoamer, levelling agent, antioxidant
Method.
, there are following common deficiencies in 3D printing nylon powder composite and preparation method thereof disclosed in above-mentioned patent,
It is have impact on to promote and application.
1. powder shape is irregular, and particle diameter distribution is uneven, leads to not carry out selective laser sintering and moulding or shaping
Product buckling deformation is serious, can not meet requirement of the commercial Application to product precision and intensity.
2. complex process, high cost, need Slow cooling in powder precipitation process, and preparation efficiency is low, and energy consumption is big.
3. stirring mixed distribution is uneven, composite wood powder materials easily layering and shedding, influence the precision of 3D printing product with it is strong
Degree.
4. in print procedure, cause to print product buckling deformation because nylon crystallization occurs volume contraction, or even cannot
Printed.
The content of the invention
To solve deficiency of the prior art, present invention aim at providing, one kind is spherical, particle diameter distribution is uniform, mobility
Good, low warpage, have excellent laser sintering and moulding and mechanical performance concurrently, and preparation process is energy-saving, simple easy processing 3D
Printing low-warpage nylon dragon particulate composite and preparation method thereof.
This invention takes following technical scheme：
A kind of 3D printing low-warpage nylon dragon particulate composite, it is characterised in that：Feed components are according to quality percentage
It is as follows than constituting：
Nylon66 fiber~88.6wt%, 10~30wt% of micro inorganic fillers, 1~2wt% of coupling agent, hindered phenol antioxygen
0.1~0.5wt%, 0.2~1.0wt% of phosphite antioxidant, 0.1~0.5wt% of other auxiliary agents；
Described other auxiliary agents are the one or more combination in dispersant, nucleator, lubricant.
Described nucleator is the solid mixture that organic nucleating agent and inorganic nucleator are constituted, selected from commercially available
BRUGGOLEN P22。
Described dispersant is the one kind in alkylbenzenesulfonate or alkyl sulfate.
Described lubricant is the one kind in aliphatic compound, amide-type, paraffin or hydro carbons.
Further, the nylon is one or more in the long carbon chain nylons such as PA1010, PA1212, PA12, PA11,
Fusing point is 140-190 DEG C.
Further, the micro inorganic fillers are the one kind or several in spherical, oval white carbon, calcium carbonate
Kind, mesh number is 1250 mesh, 2500 mesh or 5000 mesh.
Further, the micro inorganic fillers are the spherical white carbon of 2500 mesh.
Further, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy
One or more in base silane, monoalkoxy aliphatic acid titanate coupling agent.
Further, the coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Further, the hindered phenol antioxygen is 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecane alcohol
Ester (antioxidant 1076), N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098),
One kind in triethylene glycol ether-two (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester (antioxidant XH-245).
Further, the hindered phenol antioxygen is antioxidant XH-245.
Further, the phosphite antioxidant is three (2,4- di-t-butyl) phenyl-phosphites (irgasfos 168), sub-
The consumption of phosphate antioxidant is the twice of the consumption of hindered phenol antioxygen.
A kind of 3D printing preparation method of low-warpage nylon dragon particulate composite, comprises the following steps：
The first step, by nylon raw material, micro inorganic fillers, coupling agent, hindered phenol antioxygen, phosphite antioxidant,
Other auxiliary agents and trifluoroethanol are put into closed container, and trifluoroethanol solvent load is nylon resin quality: trifluoroethanol is molten
The mass volume ratio of agent is 1: 1~1:5g/mL, is stirred continuously, and forms nylon lysate；
, be transported to nylon lysate in spray dryer by peristaltic pump by second step, be atomized under nitrogen protection,
Dry, powder is collected and formic acid recycling；Intake air temperature is 110~130 DEG C, and air outlet temperature is 80~90 DEG C, oxygen
Gas concentration≤1.5%.
3rd step, air drying 2-8 hours in vacuum drier, prepares 95% particle diameter normal distribution at 30-80 μm
Between 3D printing with low-warpage nylon dragon particulate composite.
Beneficial effect of the present invention is：
(1) present invention receives micro inorganic fillers, coupling agent, hindered phenol antioxygen, phosphite antioxidant by selection
Be used in combination, be spray-dried prepare 3D printing nylon powder composite, dimensional stability, resistance to warping, stretching yield stress,
IZOD notch impact strengths are increased substantially, and caking property is excellent, powder shape comparison rule, and particle diameter distribution is uniform,
The property of can be chosen laser sintering and moulding is prevented effectively from moulded products buckling deformation, meet commercial Application to product precision and
The requirement of intensity.
(2) preparation process is simple of the invention, low cost, do not need Slow cooling, preparation efficiency in powder precipitation process
Height, energy consumption is low.
(3) stirring mixed distribution is uniform, spherical particle narrowly distributing, good fluidity, without layering shedding problem, composite wood powder
Material is difficult layering and shedding, improves the precision and intensity of 3D printing product.
(4) nylon powder composite of the invention can avoid generation volume contraction and cause printing in print procedure
The phenomenon of product buckling deformation, it is ensured that printing is smoothed out.
Specific embodiment
A kind of 3D printing low-warpage nylon dragon particulate composite, it is characterised in that：Feed components are according to quality percentage
It is as follows than constituting：
Nylon66 fiber~88.6wt%, 10~30wt% of micro inorganic fillers, 1~2wt% of coupling agent, hindered phenol antioxygen
0.1~0.5wt%, 0.2~1.0wt% of phosphite antioxidant, 0.1~0.5wt% of other auxiliary agents；
The consumption of the phosphite antioxidant is the twice of the consumption of hindered phenol antioxygen；
Described other auxiliary agents are the one or more combination in dispersant, nucleator, lubricant.
In specific embodiment and comparative example formula, nylon employs the PA12 products of UBE Industries Ltd.,
Model 9048T1, fusing point is 146 DEG C；Micro inorganic fillers employ the hard charcoal in the prosperous safe micro-nano chemical plant in Shouguang City of Shandong Province
Black product, model CT-602, average grain diameter is 6 μm；Coupling agent employs the silane coupled of Nanjing You Pu Chemical Co., Ltd.s
Agent product, model KH560；Hindered phenol antioxygen employs the products of Irganox 245 of German Ciba, and fusing point is 76~
79℃；Phosphite antioxidant employs the products of Irgafos 168 of German Ciba, phosphite antioxidant and hindered phenol
Antioxidant is 1 using proportioning:2；Nucleator employs the BRUGGOLEN P22 products of Brueggemann chemical company, is nanometer
Organic and inorganic constituents the mixture of powders of level.
The constituent content such as table that 3D printing is formulated with the embodiment 1-9 and comparative example of low-warpage nylon dragon particulate composite
One.
The constituent content table of table one, embodiment 1-9 and comparative example formula
3D printing of the invention is as follows with the preparation method of low-warpage nylon dragon particulate composite：
(1) each component is weighed by the weight proportion of formula；
(2) in each component and trifluoroethanol being put into nitrogen charging closed container, trifluoroethanol solvent load is nylon resin
Quality: the mass volume ratio of trifluoroethanol solvent is 1: 1~1:5g/mL, is stirred continuously, and forms nylon lysate；
(3) lysate is transported in spray dryer by peristaltic pump, is atomized under nitrogen protection, dried, powder
Collect and formic acid recycling at end；Intake air temperature is 125 ± 2 DEG C, and air outlet temperature is 85 ± 2 DEG C DEG C, oxygen concentration≤
1.5%.
(4) powder of collection is placed in vacuum drier, air drying 3 hours is packed, obtains 3D printing with low
Warpage nylon powder composite.
The preparation method of the comparative example 1 in above-mentioned table is as follows：
(1) PA12 is weighed by the weight proportion of formula；
(2) in each component and trifluoroethanol being put into nitrogen charging closed container, it is stirred continuously, forms nylon lysate；Three
Fluoroethanol solvent load is nylon resin quality: solvent volume=1: 1~1:5；
(3) lysate is transported in spray dryer by peristaltic pump, is atomized under nitrogen protection, dried, powder
Collect and formic acid recycling at end；Intake air temperature is 125 ± 2 DEG C, and air outlet temperature is 85 ± 2 DEG C DEG C, oxygen concentration≤
1.5%.
(4) powder of collection is placed in vacuum drier, air drying 3 hours is packed, obtains 3D printing with low
Warpage nylon powder composite.
Comparative example 2 in above-mentioned table is the 3D printing of German EOS Corp. PA12 dusty materials, and product type is PA
2200。
The embodiment 1~9 of low-warpage nylon dragon particulate composite of the invention and the performance test of comparative example 1~2 are as follows：
Performance evaluation mode and implementation standard：
Nylon powder composite prepared by the above method is placed in 3D printer (EOSNIT P396), and according to state
Mark printing standard specimen, powdering thickness is 0.12mm, and preheating temperature is 174 DEG C, and laser power is 70w, sweep speed is 4 meters/
Hour.
Stretching yield stress, tensile strain at yield, elongation at break, the Izod notched impact of sample are detected according to GB
Intensity and artificial accelerated aging performance (fluorescent ultraviolet lamp, II type, exposure chamber 1, total open-assembly time 1000hrs)
By above-mentioned test, as a result such as table two.
Table two, test result contrast table
As can be seen here, 3D printing low-warpage nylon dragon particulate composite of the present invention has good molding processibility, and
Compared with without potting resin being the product that is produced of scheme of comparative example 1, dimensional stability, resistance to warping, stretching yield stress,
IZOD notch impact strengths are increased substantially.
3D printing of the present invention with low-warpage nylon dragon the mouldability of particulate composite and the color and luster of printed sample with it is existing
3D printing nylon powder material is that the product of comparative example 2 is close, but its product dimensional stability, warpage properties, tensile yield
Stress and IZOD notch impact strengths are superior to comparative example 2.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to model of the invention
Enclose and be defined, under the premise of design spirit of the present invention is not departed from, this area ordinary skill technical staff is to the technology of the present invention side
Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (8)
1. a kind of 3D printing with low-warpage nylon dragon particulate composite, it is characterised in that：Feed components are according to mass percent
Composition is as follows：
Nylon66 fiber~88.6wt%, 10~30wt% of micro inorganic fillers, 1~2wt% of coupling agent, hindered phenol antioxygen 0.1
~0.5wt%, 0.2~1.0wt% of phosphite antioxidant, 0.1~0.5wt% of other auxiliary agents；
The nylon is one or more in PA1010, PA1212, PA12, PA11 long carbon chain nylon, and the fusing point of nylon is
140-190℃；
The micro inorganic fillers are one or more in spherical, oval white carbon or calcium carbonate, micro inorganic
The mesh of fineness 1250 of filler, 2500 mesh or 5000 mesh；
Described other auxiliary agents are the one or more combination in dispersant, nucleator, lubricant.
2. 3D printing according to claim 1 with low-warpage nylon dragon particulate composite, it is characterised in that：The micron order
Inorganic filler is the spherical white carbon of 2500 mesh.
3. 3D printing according to claim 1 with low-warpage nylon dragon particulate composite, it is characterised in that：The coupling agent
It is gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane or monoalkoxy aliphatic acid titanate esters
One or more in coupling agent.
4. 3D printing according to claim 3 with low-warpage nylon dragon particulate composite, it is characterised in that：The coupling agent
It is γ-glycidyl ether oxygen propyl trimethoxy silicane.
5. 3D printing according to claim 1 with low-warpage nylon dragon particulate composite, it is characterised in that：The hindered phenol
Antioxidant is 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecanes alcohol ester, N, N'- is double-(3- (3,5- di-t-butyls-
4- hydroxy phenyls) propiono) in hexamethylene diamine or triethylene glycol ether-two (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester
It is a kind of.
6. 3D printing according to claim 5 with low-warpage nylon dragon particulate composite, it is characterised in that：The hindered phenol
Antioxidant is triethylene glycol ether-two (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester.
7. 3D printing according to claim 1 with low-warpage nylon dragon particulate composite, it is characterised in that：The phosphorous acid
Ester antioxidant is three (2,4- di-t-butyl) phenyl-phosphites, and the consumption of phosphite antioxidant is the consumption of hindered phenol antioxygen
Twice.
8. 3D printing according to claim 1 with low-warpage nylon dragon particulate composite preparation method, it is characterised in that
Specifically include following steps：
(1) nylon raw material, micro inorganic fillers, coupling agent, hindered phenol antioxygen, phosphite ester antioxygen are taken according to raw material proportioning
Agent, other auxiliary agents and trifluoroethanol are put into closed container, and trifluoroethanol solvent load is nylon resin quality: trifluoroethanol
The mass volume ratio of solvent is 1: 1~1:5g/mL, is stirred continuously, and forms nylon lysate；
(2) nylon lysate is transported in spray dryer by peristaltic pump, the intake air temperature for controlling spray dryer is
110~130 DEG C, air outlet temperature is 80~90 DEG C, and oxygen concentration≤1.5% is atomized, dried, powder under nitrogen protection
Collect and formic acid recycling at end；
(3) air drying 2-8 hours in vacuum drier, 3D of the 95% particle diameter normal distribution between 30-80 μm is prepared
Printing low-warpage nylon dragon particulate composite.
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| CN105802210B (en) * | 2016-04-12 | 2018-07-10 | 江苏思睿迪快速制造科技有限公司 | Polystyrene organic rigid-particle modification of nylon silk for 3D printing and preparation method thereof |
| JP6402810B1 (en) * | 2016-07-22 | 2018-10-10 | 株式会社リコー | Three-dimensional modeling resin powder, three-dimensional model manufacturing apparatus, and three-dimensional model manufacturing method |
| CN106221198A (en) * | 2016-07-29 | 2016-12-14 | 佛山市高明区诚睿基科技有限公司 | A kind of 3D printing composite of low warpage |
| CN107841128A (en) * | 2016-09-20 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of SLS 3D printings PA 12/GB composites |
| FR3061182B1 (en) * | 2016-12-22 | 2019-05-31 | Setup Performance | SPHERIC PARTICLE POWDER OF CROSSLINKABLE POLYAMIDE, PROCESS FOR PREPARATION AND USE WITH SELECTIVE LASER SINTERING TECHNOLOGY |
| WO2018140443A1 (en) * | 2017-01-24 | 2018-08-02 | Jabil Inc. | Multi jet fusion three dimensional printing using nylon 5 |
| CN110845814A (en) * | 2018-07-24 | 2020-02-28 | 上海杰事杰新材料(集团)股份有限公司 | Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof |
| CN109233267A (en) * | 2018-07-27 | 2019-01-18 | 会通新材料股份有限公司 | A kind of modified PA11 material, tubing and preparation method thereof |
| CN111036157A (en) * | 2019-12-09 | 2020-04-21 | 安徽工业大学 | Method for preparing nylon microspheres from nylon fibers and application |
| CN111995862B (en) * | 2020-07-06 | 2022-02-18 | 金发科技股份有限公司 | 3D printing powder and preparation method thereof |
| CN111961335B (en) * | 2020-07-06 | 2022-02-18 | 金发科技股份有限公司 | 3D printing powder and preparation method thereof |
| CN111909509B (en) * | 2020-07-06 | 2022-02-18 | 金发科技股份有限公司 | 3D printing powder and preparation method thereof |
| CN112592579A (en) * | 2020-11-19 | 2021-04-02 | 江苏博云塑业股份有限公司 | Rapid-forming polyamide composite material and preparation method thereof |
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| CN103756293A (en) * | 2013-12-24 | 2014-04-30 | 上海邦中高分子材料有限公司 | 3D (Three-dimensional) printing material |
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