CN108164997A - A kind of 3D printing long-chain nylon composite material - Google Patents
A kind of 3D printing long-chain nylon composite material Download PDFInfo
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- CN108164997A CN108164997A CN201711464000.7A CN201711464000A CN108164997A CN 108164997 A CN108164997 A CN 108164997A CN 201711464000 A CN201711464000 A CN 201711464000A CN 108164997 A CN108164997 A CN 108164997A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention relates to a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：100 parts of long-chain nylon, 5 10 parts of kevlar chopped strands, 5 15 parts of wollastonite, 0.1 0.3 parts of coupling agent, 38 parts of toughener, 0.5 1 parts of hyperbranched resin, 0.2 1 parts of antioxidant, wire rod and printing product are exposed without apparent fiber, and print the tensile strength of product and bending strength height, heat distortion temperature is high, dimensionally stable.
Description
Technical field
The present invention relates to a kind of 3D printing long-chain nylon composite materials, belong to 3D printing field of material technology.
Background technology
3D printing technique is just changing the process of modern manufacturing industry deeply, it be one kind do not need to conventional tool, fixture and
Lathe, but based on digital model file, with adhesive materials such as powdery metal or plastics, pass through what is successively printed
Mode carrys out the technology of constructed object, and the technology is in jewelry, footwear, industrial design, building, engineering and construction (AEC), automobile, boat
Empty space flight, dentistry and medical industries, education, GIS-Geographic Information System, civil engineering, gun and other field are all applied.
Fusion sediment (FDM) technology is a kind of common technology of 3D printing, this technology is being melted using thermoplastic polymer
It under state, is squeezed out from printing head, is then frozen into profile thin layer, then being formed by stacking in layer.FDM technology requires material
With relatively low condensation shrinking percentage, steeper viscosity-temperature curve and higher intensity, rigidity, thermal stability etc., the technology is normal at present
Polymer material is polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS) and makrolon (PC) etc.,
Nylon composite materials are seldom as the document of 3D printing material.
Nylon material intensity is high and has certain flexibility, can be with the final products of printing function, some are complicated
Movable part, as long as counterpart reasonable design is, it can be achieved that one-pass molding, there is wide prospect in 3D printing field.Long-chain Buddhist nun
Imperial (such as PA11, PA12, PA1212, PA1012) has the advantages that following prominent compared with nylon66 fiber, nylon 6：(1) long-chain nylon
Water absorption rate is relatively low, and nylon66 fiber, nylon 6 are easy to absorb water, and has bigger crystallization degree, it is made to be beaten as 3D printing material
The product of print has the problem of a series of bad, such as：The next size of product water sucting belt, performance are unstable, crystallization after molding
It shrinks so that product size is less than former design size, and warpage risk for having bigger etc.；(2) fusing point of long-chain nylon is relatively low
(170-190 DEG C) can finally use on common FDM types 3D printer (general print temperature is up to 250-260 DEG C),
And the fusing point of nylon66 fiber, nylon 6 is between 220-260 DEG C, but actual conditions are 250 DEG C or so, nylon66 fiber cannot still melt completely
Change, nylon 6 does not have melt flow rate (MFR) required during 3D printing yet, and cannot be bonded on forming bottom plate, this causes nylon
66th, nylon 6 is difficult to use in the FDM type 3D printers of market popularity.But long-chain nylon is compared with nylon66 fiber, nylon 6 or poly- carbonic acid
The engineering plastics such as ester still have the disadvantages such as intensity is poor, heat resisting temperature is relatively low, shrinking percentage is larger.Therefore, it is necessary to take steps to change
The intensity, heat resistance and molding shrinkage of chain nylon material are good at, makes it that when being applied to 3D printing there is higher performance and beat
Effect is printed, widens the application field of 3D printing.
Invention content
The technical problem to be solved by the present invention is to：For solve intensity existing for existing 3D printing nylon material it is poor,
The technical issues of heat resisting temperature is relatively low, shrinking percentage is larger provides a kind of 3D printing long-chain nylon composite material.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of 3D printing long-chain nylon composite material includes the component of following parts by weight：
100 parts of long-chain nylon, 5-10 parts of kevlar chopped strands, 5-15 parts of wollastonite, 0.1-0.3 parts of coupling agent, toughening
3-8 parts of agent, 0.5-1 parts of hyperbranched resin, 0.2-1 parts of antioxidant.
Preferably, 3D printing long-chain nylon composite material includes the component of following parts by weight：
100 parts of long-chain nylon, 7-8 parts of kevlar chopped strands, 8-10 parts of wollastonite, 0.2-0.3 parts of coupling agent, toughener
5-7 parts, 0.7-1 parts of hyperbranched resin, 0.4-0.7 parts of antioxidant.
Preferably, the length of the kevlar chopped strands is 1-3mm, and diameter is no more than 15 μm.
Preferably, the draw ratio of the wollastonite raphioid fiber is more than 15.
Preferably, the long-chain nylon is at least one of PA11, PA12, PA1212, PA1012.
Preferably, the coupling agent is silane coupling agent, and the general formula of the silane coupling agent is YSiX3, X for methoxyl group or
Ethyoxyl, Y contain amino or epoxy group.
Preferably, the toughener is grafted ethylene propylene diene rubber for maleic anhydride or ethylene-acrylate-maleic anhydride is common
Polymers.
Preferably, the hyperbranched resin be polyester or polyamide hyperbranched resin, preferably Hyper C100,
Hyper HPN202 and Hyper H40 series, the Hyper H40 series include Hyper H401, Hyper H402, Hyper
H403。
Polyester or polyamide hyperbranched resin of the present invention has highly branched structure (main chain is short, branch is more),
Even if it is made to have larger molecular weight mutually to tangle without with other long chains, it is easy to move between macromolecular, it is a small amount of to be
Melt viscosity can be effectively reduced, and is not easy to be precipitated from solid polymer, can be improved because of Kevlar chopped strands and silicon ash
The melt flow rate (MFR) that stone is brought after adding in declines and reduction fiber is exposed；Although thermotropic liquid crystal polymer melts latter section of temperature
In the range of in liquid crystal state, have the order that high fluidity has part again, melt flow rate (MFR) can be improved, but thermotropic liquid crystal gathers
The melting temperature for closing object needs is very high, and long-chain nylon of the present invention is suitble to the temperature for squeezing out processing relatively low (generally not
Need more than 200 degree), thermotropic liquid crystal polymer cannot melt in the range of the suitable extrusion temperature of long-chain nylon, even if examining
Consider into screw rod be blended when because the influence of additional heat, processing aid and long-chain nylon in itself caused by shearing and rubbing is also real
The now not suitable extrusion of long-chain nylon and thermotropic liquid crystal polymer.
Preferably, the antioxidant be Hinered phenols antioxidant or phosphite ester kind antioxidant, the Hinered phenols antioxygen
Agent is preferably antioxidant 1076, antioxidant 1010, antioxidant 1790, antioxidant 330, antioxidant 2246, the phosphorous acid esters
Antioxidant is preferably irgasfos 168, antioxidant 626.
The above-mentioned 3D printing preparation method of long-chain nylon composite material of the present invention, includes the following steps：
Coupling agent solution is prepared, coupling agent ethyl alcohol or water are preferably configured to coupling agent solution, and by its pH value tune
Between 4-5.5；
The coupling agent solution of atomization is sprayed into while stirring wollastonite with the speed of 100-600r/min, after having sprayed coupling agent
Continue stirring 5-10 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2-3 hours at 90-120 DEG C, cold
But to room temperature to get coupling agent modified wollastonite；
By coupling agent modified wollastonite, long-chain nylon, kevlar chopped strands, toughener, hyperbranched resin, antioxidant with
The speed of 100-600r/min is stirred 5-15 minutes, obtains premix raw material；
Premix raw material is added in into extruding pelletization in double screw extruder and obtains modified particle, each section of temperature of double screw extruder is set
It is set to：One 170-182 DEG C of area, 183-193 DEG C of 2nd area, 187-197 DEG C of 3rd area, 190-200 DEG C of 4th area, 190-200 DEG C of 5th area, six
187-197 DEG C of area, 187-197 DEG C of 7th area, 185-195 DEG C of 8th area, 185-195 DEG C of 9th area, 183-193 DEG C of tenth area, Shi Yiqu
183-193 DEG C, 187-197 DEG C of head, engine speed 350-450r/min, feeding frequency 7-12r/min；
Modified particle is dried to moisture content no more than 0.05% at 80-105 DEG C, drying pellet is obtained, then will dry grain
Material adds in extrusion plastic melt in single screw extrusion machine, by gained plastic melt by hot water treatment, cold water cooling and shaping, wind
It is dry, obtain wire rod, each heating interval temperature setting of single screw extrusion machine is 175-185 DEG C of an area, two 187-198 DEG C of areas, three
190-200 DEG C of area, four 192-202 DEG C of areas, five 188-198 DEG C of areas, six 185-197 DEG C of areas, 45-55 DEG C of hot water temperature, cold water temperature
20-30 DEG C of degree.
Preferably, nylon, toughener, hyperbranched resin, antioxidant are first mixed into obtain mixture M 1, kevlar is chopped fibre
Dimension mixes to obtain mixture M 2 with coupling agent modified wollastonite, then by mixture M 1 from the main charge door at one area of double screw extruder
It adds in, mixture M 2 is added in from four area's side loading mouths of double screw extruder.
The beneficial effects of the invention are as follows：
The present invention 3D printing with long-chain nylon composite material by a certain proportion of long-chain nylon, kevlar chopped strands,
Wollastonite, coupling agent, toughener, hyperbranched resin and antioxidant composition, wire rod and printing product are exposed without apparent fiber, and beat
The tensile strength and bending strength of printing product are high, and heat distortion temperature is high, dimensionally stable；Specifically have the beneficial effect that：
(1) Kevlar chopped strands are the organic fibers that are spun into of Wholly aromatic polyamide of a kind of special high temperature resistant, high intensity,
Even if not doing special surface treatment and increase-volume, the Kevlar chopped strands of certain content also have good compatible with long-chain nylon
Property, and the heat resisting temperature of long-chain nylon, intensity can be increased substantially, reduce inprocess shrinkage etc., but cost is higher, and only a large amount of
It adds in Kevlar chopped strands and is not added with the wire rod of wollastonite and its 3D printing product has fiber exposed and rough surface phenomenon, 3D
Printing head is easily blocked during printing；The microstructure of wollastonite is have certain draw ratio needle-shaped, for reducing long-chain nylon
The water imbibition of material has great role, but enhancing, raising heat resistance and the effect for reducing inprocess shrinkage to long-chain nylon material
Much smaller than kevlar chopped strands, advantage is that cost is more much lower than kevlar chopped strand.Kevlar chopped strands and wollastonite
It is combined with rational ratio, in the case that of reasonable cost, intensity, thermal stability and the size of long-chain nylon can be effectively improved
Stability.
(2) kevlar chopped strands are combined with acicular wollastonite and are compared with common fiber glass packing, have following
Advantage：Thermal stability is good, and thermal deformation is low, and dimensional stability is better than glass；Needle-shaped mineral filler can solve fiber glass packing
Caused by surface floating fiber and the problem of product easy warpage；The fluidity of molten of reinforced plastics is preferable, surface gloss is high.
(3) kevlar chopped strand of the length for 1-3mm, kevlar chopped strands when being due to being applied to 3D printing are selected
It is small on melt flow rate (MFR) influence compared with kevlar long fibres, and high melt flow rate (MFR) is the important indicator of 3D printing,
And select kevlar chopped strand of the diameter no more than 15 μm that can ensure the draw ratio of fiber, it can more effectively improve long-chain
Tensile strength, bending strength and the heat distortion temperature of nylon similarly, select wollastonite raphioid fiber energy of the draw ratio more than 15
Enough effectively improve the intensity and heat distortion temperature of long-chain nylon.
(4) addition of coupling agent can improve the compatibility of long-chain nylon and wollastonite, preferably play wollastonite to Buddhist nun
The improvement result of imperial material.
(5) toughener can improve the toughness and mechanical property of nylon composite materials, why select have certain polarity
Ethylene propylene diene rubber or ethylene-acrylate-copolymer-maleic anhydride are grafted as toughener with the maleic anhydride of reactivity,
Be since long-chain nylon is the polymer with polarity, above-mentioned toughener can be well dispersed in modified process long-chain nylon it
In, and the anhydride group in the amide group and maleic anhydride in long-chain nylon has reactivity and forms the probability of hydrogen bond,
This considerably increases the compatibilities of long-chain nylon and toughener；Such toughener can also strengthen kevlar fibers, coupling agent modified
Wollastonite and nylon matrix combination.
(6) polyester or polyamide hyperbranched resin that the present invention selects can effectively reduce melt viscosity, and be not easy from solid
It is precipitated, can improve because the melt flow rate (MFR) brought after Kevlar chopped strands and wollastonite addition declines in the polymer of state
Fiber is exposed with reducing, and improves the fluidity of molten of composite material, improves the surface smooth finish of composite material.
(7) addition of antioxidant can avoid the oxidative phenomena and thus generate that long-chain nylon occurs in high temperature working processes
Hydraulic performance decline.
Specific embodiment
By embodiment, the present invention is described in further detail now.
Embodiment 1
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 5 parts of kevlar chopped strands, 10 parts of wollastonite, 0.2 part of coupling agent, 3 parts of toughener, over-expense
Change 0.5 part of resin, 0.2 part of antioxidant；The kevlar chopped strands length be 2mm, 12 μm of diameter；The needle-shaped fibre of wollastonite
The draw ratio of dimension is more than 15；The long-chain nylon is PA11；The coupling agent be silane coupling agent, structural formula NH2(CH2)3Si(OC2H5)3；The toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched resin is Hyper C100；Institute
Antioxidant is stated as antioxidant 1076.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent ethyl alcohol is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 100r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 5 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2.5 hours at 120 DEG C, is cooled to often
Temperature is to get coupling agent modified wollastonite；
By long-chain nylon, toughener, hyperbranched resin, antioxidant, kevlar chopped strands and coupling agent modified wollastonite
Raw material must be premixed by being stirred 15 minutes with the speed of 100r/min；
Raw material will be premixed to add in from the main charge door at one area of double screw extruder, double screw extruder extruding pelletization must change
Property particle, each section of temperature setting of double screw extruder are：One 176 DEG C of area, 188 DEG C of 2nd area, 191 DEG C of 3rd area, 195 DEG C of 4th area, five
195 DEG C of area, 192 DEG C of 6th area, 192 DEG C of 7th area, 190 DEG C of 8th area, 190 DEG C of 9th area, 188 DEG C of tenth area, 188 DEG C of 11st area, head 195
DEG C, engine speed 400r/min, feeding frequency 10r/min；
Modified particle is dried to moisture content no more than 0.05% at 90 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 182 DEG C of an area, two 189 DEG C of areas, three 195 DEG C of areas, 4th area
198 DEG C, five 194 DEG C of areas, six 192 DEG C of areas, 55 DEG C of hot water temperature, 25 DEG C of cold water temperature.
Embodiment 2
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 7 parts of kevlar chopped strands, 5 parts of wollastonite, 0.1 part of coupling agent, 7 parts of toughener, over-expense
Change 0.7 part of resin, 0.4 part of antioxidant；The kevlar chopped strands length be 3mm, a diameter of 10 μm；The wollastonite is needle-shaped
The draw ratio of fiber is more than 15；The long-chain nylon is PA1012；The coupling agent be silane coupling agent, structural formula NH2
(CH2)3Si(OCH3)3；The toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched resin is Hyper
H402；The antioxidant is antioxidant 330.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent water is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 300r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 8 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2.5 hours at 110 DEG C, is cooled to often
Temperature is to get coupling agent modified wollastonite；
By long-chain nylon, toughener, hyperbranched resin, antioxidant, kevlar chopped strands and coupling agent modified wollastonite
Raw material must be premixed by being stirred 10 minutes with the speed of 300r/min；
Raw material will be premixed to add in from the main charge door at one area of double screw extruder, double screw extruder extruding pelletization must change
Property particle, each section of temperature setting of double screw extruder are：One 175 DEG C of area, 193 DEG C of 2nd area, 197 DEG C of 3rd area, 200 DEG C of 4th area, five
198 DEG C of area, 197 DEG C of 6th area, 197 DEG C of 7th area, 195 DEG C of 8th area, 195 DEG C of 9th area, 193 DEG C of tenth area, 193 DEG C of 11st area, head 195
DEG C, engine speed 400r/min, feeding frequency 9r/min；
Modified particle is dried to moisture content no more than 0.05% at 100 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 185 DEG C of an area, two 195 DEG C of areas, three 197 DEG C of areas, 4th area
202 DEG C, five 198 DEG C of areas, six 196 DEG C of areas, 50 DEG C of hot water temperature, 25 DEG C of cold water temperature.
Embodiment 3
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 8 parts of kevlar chopped strands, 15 parts of wollastonite, 0.3 part of coupling agent, 3 parts of toughener, over-expense
Change 0.7 part of resin, 1 part of antioxidant；The kevlar chopped strands length be 2.5mm, 12 μm of diameter；The needle-shaped fibre of wollastonite
The draw ratio of dimension is more than 15；The long-chain nylon is PA1212；The coupling agent is silane coupling agent, and structural formula isThe toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched tree
Fat is Hyper H401；The antioxidant is antioxidant 1790.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent ethyl alcohol is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 300r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 7 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 3 hours at 100 DEG C, is cooled to room temperature,
Up to coupling agent modified wollastonite；
Long-chain nylon, toughener, hyperbranched resin, antioxidant are mixed into 15 minutes to obtain mixture with the speed of 300r/min
Kevlar chopped strands and coupling agent modified wollastonite are stirred 15 minutes to obtain mixture by M1 with the speed of 300r/min
M2；
Mixture M 1 is added in from the main charge door at one area of double screw extruder, mixture M 2 is from the side loading at 4th area
Mouth adds in, and double screw extruder extruding pelletization obtains modified particle, and each section of temperature setting of double screw extruder is：One 176 DEG C of area, two
193 DEG C of area, 196 DEG C of 3rd area, 197 DEG C of 4th area, 195 DEG C of 5th area, 195 DEG C of 6th area, 194 DEG C of 7th area, 194 DEG C of 8th area, nine areas 192
DEG C, 192 DEG C of tenth area, 193 DEG C of 11st area, 194 DEG C of head, engine speed 450r/min, feeding frequency 12r/min；
Modified particle is dried to moisture content no more than 0.05% at 95 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 180 DEG C of an area, two 192 DEG C of areas, three 195 DEG C of areas, 4th area
197 DEG C, five 193 DEG C of areas, six 192 DEG C of areas, 50 DEG C of hot water temperature, 30 DEG C of cold water temperature.
Embodiment 4
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 10 parts of kevlar chopped strands, 6 parts of wollastonite, 0.1 part of coupling agent, 8 parts of toughener, over-expense
Change 1 part of resin, 0.5 part of antioxidant；The kevlar chopped strands length be 1.7mm, 15 μm of diameter；The needle-shaped fibre of wollastonite
The draw ratio of dimension is more than 15；The long-chain nylon is PA12；The coupling agent be silane coupling agent, structural formula NH2CH2Si
(OCH3)3；The toughener is ethylene-acrylate-copolymer-maleic anhydride；The hyperbranched resin is Hyper HPN202；
The antioxidant is antioxidant 1010.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent water is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 200r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 10 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2 hours at 90 DEG C, is cooled to room temperature,
Up to coupling agent modified wollastonite；
Long-chain nylon, toughener, hyperbranched resin, antioxidant are mixed into 15 minutes to obtain mixture with the speed of 200r/min
Kevlar chopped strands and coupling agent modified wollastonite are stirred 15 minutes to obtain mixture by M1 with the speed of 200r/min
M2；
Mixture M 1 is added in from the main charge door at one area of double screw extruder, mixture M 2 is from the side loading at 4th area
Mouth adds in, and double screw extruder extruding pelletization obtains modified particle, and each section of temperature setting of double screw extruder is：One 170 DEG C of area, two
183 DEG C of area, 187 DEG C of 3rd area, 190 DEG C of 4th area, 190 DEG C of 5th area, 187 DEG C of 6th area, 187 DEG C of 7th area, 185 DEG C of 8th area, nine areas 185
DEG C, 183 DEG C of tenth area, 183 DEG C of 11st area, 187 DEG C of head, engine speed 350r/min, feeding frequency 7r/min；
The modified particle of gained is dried to moisture content no more than 0.05% at 80 DEG C, obtains drying pellet, it then will drying
Pellet adds in extrusion plastic melt in single screw extrusion machine, by gained plastic melt by hot water treatment, cold water cooling and shaping, wind
It is dry, obtain wire rod, each heating interval temperature setting of single screw extrusion machine is 175 DEG C of an area, two 187 DEG C of areas, three 190 DEG C of areas,
Four 192 DEG C of areas, five 188 DEG C of areas, six 185 DEG C of areas, 45 DEG C of hot water temperature, 20 DEG C of cold water temperature.
Embodiment 5
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 8 parts of kevlar chopped strands, 10 parts of wollastonite, 0.2 part of coupling agent, 3 parts of toughener, over-expense
Change 0.7 part of resin, 0.7 part of antioxidant；The kevlar chopped strands length be 1mm, a diameter of 10 μm；The wollastonite is needle-shaped
The draw ratio of fiber is more than 15；The long-chain nylon is PA11；The coupling agent is silane coupling agent, and structural formula isThe toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched tree
Fat is Hyper H403；The antioxidant is antioxidant 2246.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent water is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 200r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 5 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2.5 hours at 120 DEG C, is cooled to often
Temperature is to get coupling agent modified wollastonite；
Long-chain nylon, toughener, hyperbranched resin, antioxidant are mixed into 15 minutes to obtain mixture with the speed of 200r/min
Kevlar chopped strands and coupling agent modified wollastonite are stirred 15 minutes to obtain mixture by M1 with the speed of 200r/min
M2；
The mixture M 1 of gained is added in from twin-screw extrusion owner charge door, mixture M 2 is added in from side loading mouth, double
Screw extruder extruding pelletization obtains modified particle, and each section of temperature setting of double screw extruder is：One 180 DEG C of area, 190 DEG C of 2nd area,
Three 196 DEG C of areas, 199 DEG C of 4th area, 195 DEG C of 5th area, 195 DEG C of 6th area, 194 DEG C of 7th area, 194 DEG C of 8th area, 192 DEG C of 9th area, ten areas 192
DEG C, 192 DEG C of 11st area, 196 DEG C of head, engine speed 400r/min, feeding frequency 8r/min；
Modified particle is dried to moisture content no more than 0.05% at 100 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 180 DEG C of an area, two 194 DEG C of areas, three 196 DEG C of areas, 4th area
197 DEG C, five 195 DEG C of areas, six 194 DEG C of areas, 48 DEG C of hot water temperature, 28 DEG C of cold water temperature.
Embodiment 6
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 6 parts of kevlar chopped strands, 10 parts of wollastonite, 0.3 part of coupling agent, 5 parts of toughener, over-expense
Change 0.5 part of resin, 0.2 part of antioxidant；The kevlar chopped strands length be 1.6mm, a diameter of 10 μm；The silicon ash lithostyle
The draw ratio of shape fiber is more than 15；The long-chain nylon is PA11；The coupling agent be silane coupling agent, structural formula NH2
(CH2)3Si(OC2H5)3；The toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched resin is Hyper
C100；The antioxidant is irgasfos 168.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent ethyl alcohol is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 600r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 5 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2.5 hours at 120 DEG C, is cooled to often
Temperature is to get coupling agent modified wollastonite；
Long-chain nylon, toughener, hyperbranched resin, antioxidant are stirred 5 minutes and must be mixed with the speed of 600r/min
Object M1 is closed, kevlar chopped strands and coupling agent modified wollastonite are mixed into 5 minutes to obtain mixture M 2 with the speed of 600r/min；
By mixture M 1, main charge door adds at one area of double screw extruder, and mixture M 2 adds from side loading mouth at 4th area
Enter, double screw extruder extruding pelletization obtains modified particle, and each section of temperature setting of double screw extruder is：One 180 DEG C of area, 2nd area
193 DEG C, 197 DEG C of 3rd area, 198 DEG C of 4th area, 196 DEG C of 5th area, 194 DEG C of 6th area, 194 DEG C of 7th area, 195 DEG C of 8th area, 195 DEG C of 9th area,
Ten 193 DEG C of areas, 193 DEG C of 11st area, 197 DEG C of head, engine speed 400r/min, feeding frequency 8r/min；
Modified particle is dried to moisture content no more than 0.05% at 105 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 185 DEG C of an area, two 196 DEG C of areas, three 200 DEG C of areas, 4th area
200 DEG C, five 196 DEG C of areas, six 195 DEG C of areas, 50 DEG C of hot water temperature, 20 DEG C of cold water temperature.
Embodiment 7
The present embodiment provides a kind of 3D printing long-chain nylon composite materials, include the component of following parts by weight：
100 parts of long-chain nylon, 8 parts of kevlar chopped strands, 10 parts of wollastonite, 0.2 part of coupling agent, 7 parts of toughener, over-expense
Change 0.7 part of resin, 0.7 part of antioxidant；The kevlar chopped strands length be 2mm, a diameter of 10 μm；The wollastonite is needle-shaped
The draw ratio of fiber is more than 15；The long-chain nylon is PA11；The coupling agent be silane coupling agent, structural formula NH2
(CH2)3Si(OC2H5)3；The toughener is grafted ethylene propylene diene rubber for maleic anhydride；The hyperbranched resin is Hyper
H401；The antioxidant is antioxidant 626.
The preparation method of the present embodiment 3D printing long-chain nylon composite material includes the following steps：
Coupling agent water is prepared into coupling agent solution, and its pH value is adjusted between 4-5.5；
The coupling agent solution of atomization is sprayed into while wollastonite is stirred with the speed of 400r/min, it is subsequent to have sprayed coupling agent
Continuous stirring 5 minutes, then wollastonite that the surface of gained is impregnated with to coupling agent dries 2.5 hours at 120 DEG C, is cooled to often
Temperature is to get coupling agent modified wollastonite；
Long-chain nylon, toughener, hyperbranched resin, antioxidant are mixed into 10 minutes to obtain mixture with the speed of 400r/min
Kevlar chopped strands and coupling agent modified wollastonite are stirred 10 minutes to obtain mixture by M1 with the speed of 400r/min
M2；
Mixture M 1 is added in from twin-screw extrusion owner charge door, mixture M 2 is added in from side loading mouth, and twin-screw squeezes
Go out machine extruding pelletization and obtain modified particle, each section of temperature setting of double screw extruder is：One 182 DEG C of area, 193 DEG C of 2nd area, three areas 197
DEG C, 200 DEG C of 4th area, 200 DEG C of 5th area, 197 DEG C of 6th area, 197 DEG C of 7th area, 195 DEG C of 8th area, 195 DEG C of 9th area, 193 DEG C of tenth area, 11
193 DEG C of area, 197 DEG C of head, engine speed 380r/min, feeding frequency 9r/min；
Modified particle is dried to moisture content no more than 0.05% at 100 DEG C, obtains drying pellet, then adds drying pellet
Enter extrusion plastic melt in single screw extrusion machine, gained plastic melt is passed through into hot water treatment, cold water cooling and shaping, is air-dried, is obtained
To wire rod, each heating interval temperature setting of single screw extrusion machine is 185 DEG C of an area, two 198 DEG C of areas, three 200 DEG C of areas, 4th area
202 DEG C, five 198 DEG C of areas, six 197 DEG C of areas, 50 DEG C of hot water temperature, 25 DEG C of cold water temperature.
Comparative example 1
With being different only in that for embodiment 7, the length of kevlar chopped strands is 2mm, a diameter of 16 μm.
Comparative example 2
With being different only in that for embodiment 7, the length of kevlar chopped strands is 2mm, a diameter of 20 μm.
Comparative example 3
With being different only in that for embodiment 7,2 parts of kevlar chopped strands, 16 parts of wollastonite.
Comparative example 4
With being different only in that for embodiment 7,18 parts of kevlar chopped strands, no wollastonite.
Comparative example 5
With being different only in that for embodiment 7, no toughener.
FDM type 3D printer printing test battens are used by embodiment 1-7 and with the wire rod of comparative example 1-4, check printing
Effect and test bars performance, with the tensile strength of 527 test bars of standard ISO, the A pattern items in selection standard；With standard
The bending strength of 178 test bars of ISO, batten size 80mm × 10mm × 4mm；With the thermal change of 75 test bars of standard ISO
Shape temperature, batten size 80mm × 10mm × 4mm, using A methods (bending stress of 1.80MPa)；It is surveyed using standard GB/T 1036
The linear expansion coefficient of testing bar, batten size 50mm × 7mm × 7mm.Acquired results are as shown in table 1 below：
The effect and results of property of the wire rod printed sample of table 1 embodiment 1-7 and comparative example 1-4
Note：Linear expansion coefficient is smaller with shrinking percentage positive correlation, i.e. linear expansion coefficient, and material molding shrinkage is smaller, with temperature
It is more stable to spend varying dimensions.
By the comparison of comparative example 1, comparative example 2 and embodiment 7 as can be seen that constant in kevlar chopped strand length
In the case of, it selects kevlar chopped strand of the diameter no more than 15 μm that can ensure the draw ratio of fiber, can more effectively carry
Tensile strength, bending strength, the heat distortion temperature of high long-chain nylon reduce linear expansion coefficient, and with kevlar chopped strands
The increase of diameter, tensile strength, bending strength and the heat distortion temperature of 3D printing product continuously decrease, and linear expansion coefficient gradually increases
Greatly.
It can be seen that by the comparison of comparative example 3, comparative example 4 and embodiment 7 total in kevlar chopped strands and wollastonite
In the case that content is constant, when kevlar chopped strands are 2 parts, and wollastonite is 16 parts, the tensile strength of 3D printing product,
Bending strength and heat distortion temperature can be substantially reduced, and linear expansion coefficient significantly increases, and it is 18 parts to work as kevlar chopped strands, nothing
During wollastonite, improper 3D printing, it is seen then that kevlar chopped strands and wollastonite must mix ability effectively in certain proportion
Tensile strength, bending strength and the heat distortion temperature of 3D printing product are improved, reduces linear expansion coefficient.
By the comparison of comparative example 5 and embodiment 1-7 as can be seen that Malaysia of the selection with certain polarity and reactivity
Acid anhydrides is grafted ethylene propylene diene rubber or ethylene-acrylate-copolymer-maleic anhydride as toughener, can significantly improve nylon
The tensile strength and bending strength of composite material.
Using above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the content on specification, it is necessary to determine its technical scope according to right.
Claims (8)
1. a kind of 3D printing long-chain nylon composite material, which is characterized in that include the component of following parts by weight：
100 parts of long-chain nylon, 5-10 parts of kevlar chopped strands, 5-15 parts of wollastonite, 0.1-0.3 parts of coupling agent, toughener 3-8
Part, 0.5-1 parts of hyperbranched resin, 0.2-1 parts of antioxidant.
2. 3D printing according to claim 1 long-chain nylon composite material, which is characterized in that include following parts by weight
Component：
100 parts of long-chain nylon, 7-8 parts of kevlar chopped strands, 8-10 parts of wollastonite, 0.2-0.3 parts of coupling agent, toughener 5-7
Part, 0.7-1 parts of hyperbranched resin, 0.4-0.7 parts of antioxidant.
3. 3D printing according to claim 1 or 2 long-chain nylon composite material, which is characterized in that the toughener is
Maleic anhydride is grafted ethylene propylene diene rubber or ethylene-acrylate-copolymer-maleic anhydride.
4. according to claim 1-3 any one of them 3D printing long-chain nylon composite material, which is characterized in that described
The length of kevlar chopped strands is 1-3mm, and diameter is no more than 15 μm.
5. according to claim 1-4 any one of them 3D printing long-chain nylon composite material, which is characterized in that the silicon ash
The draw ratio of stone raphioid fiber is more than 15.
6. according to claim 1-5 any one of them 3D printing long-chain nylon composite material, which is characterized in that the coupling
Agent is silane coupling agent, and the general formula of the silane coupling agent is YSiX3, X is methoxy or ethoxy, and Y contains amino or epoxy
Base.
7. according to claim 1-6 any one of them 3D printing long-chain nylon composite material, which is characterized in that the over-expense
It is polyester or polyamide hyperbranched resin to change resin.
8. according to claim 1-7 any one of them 3D printing long-chain nylon composite material, which is characterized in that the antioxygen
Agent is Hinered phenols antioxidant or phosphite ester kind antioxidant.
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