CN108384204A - A kind of 3D printing porous material and preparation method thereof of expansion drilling - Google Patents
A kind of 3D printing porous material and preparation method thereof of expansion drilling Download PDFInfo
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- CN108384204A CN108384204A CN201810196685.XA CN201810196685A CN108384204A CN 108384204 A CN108384204 A CN 108384204A CN 201810196685 A CN201810196685 A CN 201810196685A CN 108384204 A CN108384204 A CN 108384204A
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
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Abstract
The present invention disclose it is a kind of expansion drilling 3D printing porous material and preparation method thereof, 1, technical scheme of the present invention formula it is as follows：It is PBSA48 90, PCL5 45, compatilizer 18, reinforcing agent 0.01 5, the nucleating agent 0.05 5 of poly-dopamine cladding according to percentage of weight formula.2, preparation method is：Poly-dopamine coats nucleating agent；It is dry；Weighing；High-speed kneading；Melt pelletization；Melting extrusion；Cooling traction；Volume bundle.The present invention finishes the high molecular material of full-degradable biological material succinic acid-butanediol ester tetramethylene adipate copolymer (PBSA) and polycaprolactone (PCL) preparation suitable for 3D printing using two, since poly-dopamine coats the addition of nucleating agent, caking property between improving traditional 3D printing product layer by layer, with lower print temperature, higher mechanical property and be a kind of green material of fully biodegradable.
Description
Technical field
The PBSA/PCL materials and preparation method thereof that the invention belongs to a kind of for 3D printing.
Background technology
With the fast development of modern processing and the diversification of the market demand, manufacture already from simple tradition
Manufacturing industry changes to green, the intelligent advanced manufacturing industry of global age, forms the interaction of innovation and market, fast accurate
3D printing technique is also just come into being.For wherein Fused Deposition Modeling (FDM) by its is easy to operate, it is many excellent that shaping speed is fast etc.
Point becomes the 3D printing technique being most widely used.Occur a variety of 3D materials, such as PLA, ABS, PETG currently on the market
With ASA etc., but since the caking property of printing product between layers is insufficient, lead to mechanical properties decrease and the higher limit of print temperature
It has been made to popularize in an all-round way in the market.
The lipoid that poly butylene succinate-poly adipate succinic acid ester copolymer (PBSA) the 1990s develops
Fat adoption ester, it is at low cost, mechanical property is good, and processing performance is excellent the advantages that, be widely used in weaving, plastic injection product etc..
Meanwhile containing the adipic acid segment that methylene is more in the strand of PBSA, therefore also there is preferable flexibility, extension at break
Rate and notch impact strength.In addition, the crystallinity of PBSA is relatively low, segment is submissive, therefore also has good biodegradability.
Polycaprolactone (PCL) is a kind of biodegradation material with the strain of higher tension failure, is equally had good
Biocompatibility, but the defect of melting temperature low (53-63 DEG C) limits its application field.Currently, PCL often with other macromolecules
Material is blended, and heat resistance, degradability and processing performance can be improved.Two kinds of aliphatic polyesters of PBSA and PCL are carried out
Melt blending prepares the 3D printing material of low temperature, has complementary advantages, and introduces poly-dopamine and coats nucleating agent so that particle has rigidity
The enhancement effect of particle improves the dispersibility and binding force of particle in the material, and being expected to obtain excellent combination property can be complete
The green material of degradation.
Invention content
For above-mentioned background and problem, the purpose of the present invention aims to solve the problem that existing 3D printing materials processing temperature is high and asks
Topic, provides a kind of PBSA/PCL cryogenic materials and preparation method thereof for 3D printing.The present invention uses fully biodegradable
PBSA and PCL, introduce poly-dopamine cladding nucleating agent and prepare environmentally protective 3D printing cryogenic material, print procedure safety
Nontoxic, printed product is had excellent performance, and subsequent processing is convenient, realizes the objective of safe green environmental protection.
The purpose of the present invention is what is be achieved through the following technical solutions：
1. a kind of PBSA/PCL materials and preparation method thereof for 3D printing are made of the component of following weight percent:
PBSA 48-90
PCL 5-45
Compatilizer 1-8
Reinforcing agent 0.01-5
The nucleating agent 0.05-5 of poly-dopamine cladding.
A kind of PBSA/PCL materials for 3D printing described in 2., which is characterized in that the poly-dopamine cladding
Nucleating agent is prepared by following step：
It is 1 according to the mass ratio of nucleating agent and buffer solution:Nucleating agent is added in buffer solution and 1h is stirred by ultrasonic by 100 ratio,
It is later 8-10 according to the mass ratio of nucleating agent and dopamine:Dopamine is added in buffer solution 1-5, and at room temperature, magnetic force stirs
It mixes for 24 hours, reaction terminates buffer by centrifugation detaching 20min, is cleaned 3 times with ethanol solution, removes unreacted monomer, consolidate
Body is put into 100-180 DEG C of vacuum drying chamber and does 12h, obtains the nucleating agent of poly-dopamine cladding；
3. compatilizer described in is at least a kind of selected from ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), peroxidating
Diisopropylbenzene (DIPB), the terpolymer of GMA- ethylene-methyl acrylates or ethylene-methyl acrylate-ethylene oxidic ester.
4. reinforcing agent described in is at least a kind of selected from single-walled carbon nanotube, hydroxylating single-walled carbon nanotube, carboxylated list
Wall carbon nano tube, amination single-walled carbon nanotube, multi-walled carbon nanotube, hydroxylated multi-walled carbon nanotubes, carboxylated multi wall carbon are received
Mitron, amino multi-wall carbon nanotube, graphitization hydroxylated multi-walled carbon nanotubes or carbon fiber.
5. nucleating agent described in is at least a kind of brilliant selected from kaolin, calcium carbonate, hydrotalcite, mica, talcum powder, calcium sulfate
Palpus, montmorillonite, silica, titanium dioxide, Lanthanum Benzoate or polyvinyl butyral.
Buffer solution described in 6. use ph for 8.5 Tris hydrochloride buffers.
7. a kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, compatilizer, reinforcing agent and PCL are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PBSA, PCL, compatilizer, reinforcing agent and poly-dopamine cladding at
Core agent；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 1000-6000rpm/min, high-speed stirred 3-
20min；
D. it is sufficiently mixed uniform raw material by above-mentioned and puts into screw extruder, heated by 90-130 DEG C of temperature, in screw rod
Molten intracavitary fusion plastification simultaneously squeezes out raw material with rotating speed for 10-280rpm；It is sent into pelleter through cooling from the raw material of Screw Extrusion
Cut into particle；
E. the pellet after cutting is put into screw extruder, is heated by 80-130 DEG C of temperature, melt intracavitary melting in screw rod
It is plasticized and is that 10-280rpm squeezes out lines from stainless steel mouth mold with rotating speed；
F. lines are fully cooled molding through three-stage cooling sink, and the wire rod of fixed size diameter is then distracted into through dragger；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 5-40HZ.
8. extruder described in is one kind in single screw extrusion machine, double screw extruder, three-screw extruder.
9. the first bosh water temperature described in is 25 DEG C -40 DEG C；Second bosh water temperature is 5 DEG C -20 DEG C；Third is cold
But sink is 0 DEG C of mixture of ice and water.
The features and advantages of the invention are：The present invention uses resin PBSA and the PCL preparation process of two kinds of complete biodegradables
Safety approximately, meets environmentally protective material preparation objective；The fusing point of two kinds of resins of PBSA and PCL is relatively low, is low temperature 3D printing
Open new path；It introduces poly-dopamine and coats nucleating agent, give full play to poly-dopamine auto polymerization effect, improve particle in material
Dispersibility in material and caking property so that particle possesses the enhancement effect of rigid particles, improves material mechanical performance energetically；With
CNTs is combined, the particularly preferably CNTs Jing Guo functionalization, using its surface reactable functional group, raising CNTs PBS,
Dispersion in PBC polymeric matrixs generates synergistic effect with the nucleating agent of poly-dopamine cladding, strong to improve the comprehensive of material
Energy.
Specific implementation mode
With reference to specific embodiment to being described in further details to the present invention, but this should not be interpreted as to the present invention
Range be only limitted to following instance.
Embodiment 1
A kind of PBSA/PCL materials and preparation method thereof for 3D printing, which is characterized in that by following weight percent
Component is made:
PBSA 70
PCL 20
Ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) 7
Hydroxylating single-walled carbon nanotube 2
The nucleating agent 1 of poly-dopamine cladding
1）The nucleating agent preparation method of poly-dopamine cladding, includes the following steps:
It is 1 according to mass ratio:30g silica is added in the Tris hydrochloride buffers that ph is 8.5 and is stirred by ultrasonic by 100 ratio
1h, later according to nucleating agent and dopamine mass ratio 8:1 ratio 3.75g dopamines is added above-mentioned added with silica
In Tris hydrochloric acid buffer solutions, at room temperature, for 24 hours, reaction terminates buffer by centrifugation detaching 20min magnetic agitation, molten with ethyl alcohol
Liquid cleans 3 times, removes unreacted monomer, obtains solid and is put into 150 DEG C of vacuum drying chamber drying 12h, obtains poly-dopamine packet
The nucleating agent covered.
2）A kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and hydroxylating single-walled carbon nanotube are put into 60
DEG C vacuum drying 12h, PCL be put into 60 DEG C vacuum drying 12h；
B. according to percentage of weight formula, PBSA (1400g), PCL (400g), ethylene-octene copolymer grafting after drying are weighed
The nucleating agent (20g) of maleic anhydride (POE-g-MAH) (140g), hydroxylating single-walled carbon nanotube (40g) and poly-dopamine cladding；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 1000rpm/min, high-speed stirred 10min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature is set as 80,90,95,100,
105, it 105,105,100,95,85 DEG C, melts intracavitary fusion plastification and with rotating speed for 150rpm/min in twin-screw, squeezes out raw material；
From the raw material of twin-screw extrusion particle is cut into through cooling be sent into pelleter；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter is：One 85 DEG C of area, two areas 95
DEG C, three 102 DEG C of areas, four 102 DEG C of areas, five 95 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with rotating speed
80rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and bosh water temperature is respectively：It 25 DEG C, 20 DEG C and 0 DEG C, then passes through
Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 5HZ.
Embodiment 2
A kind of PBSA/PCL materials and preparation method thereof for 3D printing, which is characterized in that by following weight percent
Component is made:
PBSA 74
PCL 15
The terpolymer 6 of GMA- ethylene-methyl acrylates
Amination single-walled carbon nanotube 3
The nucleating agent 2 of poly-dopamine cladding
1）The nucleating agent preparation method of poly-dopamine cladding, includes the following steps:
It is 1 according to mass ratio:It is to be stirred by ultrasonic in 8.5Tris hydrochloride buffers that ph, which is added, in 43.2g titanium dioxide by 100 ratio
1h, later according to nucleating agent and dopamine mass ratio 9:2 ratio 9.6g dopamines is added above-mentioned added with titanium dioxide
In Tris hydrochloric acid buffer solutions, at room temperature, for 24 hours, reaction terminates buffer by centrifugation detaching 20min magnetic agitation, molten with ethyl alcohol
Liquid cleans 3 times, removes unreacted monomer, obtains solid and is put into 130 DEG C of vacuum drying chamber drying 12h, obtains poly-dopamine packet
The nucleating agent covered.
2）A kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and hydroxylating single-walled carbon nanotube are put into 60
DEG C vacuum drying 12h, PCL be put into 60 DEG C vacuum drying 12h；
B. according to percentage of weight formula, PBSA (1480g), PCL (300g), GMA- ethylene-methyl acrylates after drying are weighed
Terpolymer (120g), amination single-walled carbon nanotube (60g) and poly-dopamine cladding titanium dioxide (40g)；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 2000rpm/min, high-speed stirred 12min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature is set as 82,88,96,100,
103, it 108,118,115,95,95 DEG C, melts intracavitary fusion plastification and with rotating speed for 160rpm/min in single screw rod, squeezes out raw material；
From the raw material of Single screw extrusion particle is cut into through cooling be sent into pelleter；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter is：One 85 DEG C of area, two areas 95
DEG C, three 105 DEG C of areas, four 105 DEG C of areas, five 95 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with rotating speed
90rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and bosh water temperature is respectively：It 26 DEG C, 18 DEG C and 0 DEG C, then passes through
Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 8HZ.
Embodiment 3
A kind of PBSA/PCL materials and preparation method thereof for 3D printing, which is characterized in that by following weight percent
Component is made:
PBSA 80
PCL 12
Cumyl peroxide 4
Multi-walled carbon nanotube 1
The nucleating agent 3 of poly-dopamine cladding
1）The nucleating agent preparation method of poly-dopamine cladding, includes the following steps:
According to mass ratio 1:It is that 1h is stirred by ultrasonic in 8.5Tris hydrochloride buffers that ph, which is added, in 60g calcium carbonate by 100 ratio, it
Afterwards according to nucleating agent and dopamine mass ratio 8:The above-mentioned Tris hydrochloric acid added with calcium carbonate is added in 22.5g dopamines by 3 ratio
In buffer solution, at room temperature, for 24 hours, reaction terminates buffer by centrifugation detaching 20min magnetic agitation, and 3 are cleaned with ethanol solution
It is secondary, unreacted monomer is removed, solid is obtained and is put into 160 DEG C of vacuum drying chamber drying 12h, obtain the nucleation of poly-dopamine cladding
Agent.
2）A kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and hydroxylating single-walled carbon nanotube are put into 60
DEG C vacuum drying 12h, PCL be put into 60 DEG C vacuum drying 12h；
B. according to percentage of weight formula, weigh it is dry after PBSA (1600), PCL (240g), cumyl peroxide (80g),
The calcium carbonate (60g) of multi-walled carbon nanotube (20g) and poly-dopamine cladding；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 2500rpm/min, high-speed stirred 12min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into three-screw extruder, extrusion temperature is set as 85,88,98,105,
110, it 115,115,115,100,95 DEG C, melts intracavitary fusion plastification and with rotating speed for 180rpm/min in screw rod, squeezes out raw material；
From the raw material of Tri-screw Extrusion particle is cut into through cooling be sent into pelleter；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter is：One 90 DEG C of area, two areas 100
DEG C, three 110 DEG C of areas, four 110 DEG C of areas, five 105 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with rotating speed
95rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and bosh water temperature is respectively：It 27 DEG C, 17 DEG C and 0 DEG C, then passes through
Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 9HZ.
Embodiment 4
A kind of PBSA/PCL materials and preparation method thereof for 3D printing, which is characterized in that by following weight percent
Component is made:
PBSA 68
PCL 25
Ethylene-methyl acrylate-ethylene oxidic ester 2.5
Functionalized multi-wall carbonnanotubes 2
The nucleating agent 2.5 of poly-dopamine cladding
1）The nucleating agent preparation method of poly-dopamine cladding, includes the following steps:
According to mass ratio 1:It is that 1h is stirred by ultrasonic in 8.5Tris hydrochloride buffers that ph, which is added, in 60g micas by 100 ratio, later
According to nucleating agent and dopamine mass ratio 10:It is molten that the above-mentioned Tris hydrochloride buffers added with mica are added in 18g dopamines by 3 ratio
In liquid, at room temperature, for 24 hours, reaction terminates buffer by centrifugation detaching 20min magnetic agitation, is cleaned 3 times with ethanol solution, removes
Unreacted monomer obtains solid and is put into 170 DEG C of vacuum drying chamber drying 12h, obtains the nucleating agent of poly-dopamine cladding.
2）A kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and hydroxylating single-walled carbon nanotube are put into 60
DEG C vacuum drying 12h, PCL be put into 60 DEG C vacuum drying 12h；
B. according to percentage of weight formula, PBSA (1360), PCL (500g), ethylene-methyl acrylate-contracting after drying are weighed
The mica (50g) of water glyceride (50g), functionalized multi-wall carbonnanotubes (40g) and poly-dopamine cladding；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 3000rpm/min, high-speed stirred 13min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature is set as 80,85,90,95,
100, it 108,108,105,90,85 DEG C, melts intracavitary fusion plastification and with rotating speed for 160rpm/min in screw rod, squeezes out raw material；From
The raw material of twin-screw extrusion cuts into particle through cooling be sent into pelleter；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter is：One 85 DEG C of area, two areas 95
DEG C, three 102 DEG C of areas, four 102 DEG C of areas, five 95 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with rotating speed
96rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and bosh water temperature is respectively：It 26 DEG C, 18 DEG C and 0 DEG C, then passes through
Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 10HZ.
Embodiment 5
A kind of PBSA/PCL materials and preparation method thereof for 3D printing, which is characterized in that by following weight percent
Component is made:
PBSA 85
PCL 10
Ethylene-methyl acrylate-ethylene oxidic ester 3
Hydroxylated multi-walled carbon nanotubes 1
The nucleating agent 1 of poly-dopamine cladding
1）The nucleating agent preparation method of poly-dopamine cladding, includes the following steps:
According to mass ratio 1:It is that 1h is stirred by ultrasonic in 8.5Tris hydrochloride buffers that ph, which is added, in 30g hydrotalcites by 100 ratio, it
Afterwards according to nucleating agent and dopamine mass ratio 10:6g dopamines are added the above-mentioned Tris hydrochloric acid added with hydrotalcite and delayed by 2 ratio
It rushes in solution, at room temperature, for 24 hours, reaction terminates buffer by centrifugation detaching 20min magnetic agitation, is cleaned 3 times with ethanol solution,
Unreacted monomer is removed, solid is obtained and is put into 155 DEG C of vacuum drying chamber drying 12h, obtain the nucleating agent of poly-dopamine cladding.
2）A kind of preparation method of PBSA/PCL materials for 3D printing, includes the following steps：
A. PBSA, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and hydroxylating single-walled carbon nanotube are put into 60
DEG C vacuum drying 12h, PCL be put into 60 DEG C vacuum drying 12h；
B. according to percentage of weight formula, PBSA (1700), PCL (200g), ethylene-methyl acrylate-contracting after drying are weighed
The mica (20g) of water glyceride (60g), functionalized multi-wall carbonnanotubes (20g) and poly-dopamine cladding；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 2600rpm/min, high-speed stirred 12min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature is set as 80,88,92,98,
103, it 113,113,100,92,85 DEG C, melts intracavitary fusion plastification and with rotating speed for 150rpm/min in screw rod, squeezes out raw material；From
The raw material of twin-screw extrusion cuts into particle through cooling be sent into pelleter；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter is：One 85 DEG C of area, two areas 89
DEG C, three 105 DEG C of areas, four 105 DEG C of areas, five 95 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with rotating speed
88rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and bosh water temperature is respectively：It 25 DEG C, 19 DEG C and 0 DEG C, then passes through
Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 8HZ.
The modification PBSA/PCL the performance test results of the various embodiments described above are shown in Table 1.
Table 1 is modified PBSA/PCL the performance test results
| Sample | Tensile strength（MPa） | Bending strength（MPa） | Bending modulus（MPa） | Impact strength（kJ/m2） |
| Embodiment 1 | 42.5 | 36.4 | 612 | 21.7 |
| Embodiment 2 | 40.3 | 30.2 | 636 | 17.3 |
| Embodiment 3 | 39.6 | 35.8 | 623 | 18.4 |
| Embodiment 4 | 44.8 | 33.5 | 657 | 23.5 |
| Embodiment 5 | 40.2 | 28.8 | 668 | 20.3 |
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to the present patent application range with repair
Decorations should all belong to the covering scope of the present invention.
Claims (9)
1. a kind of 3D printing porous material of expansion drilling, which is characterized in that be made of the component of following weight percent:
PBSA 48-90
PCL 5-45
Compatilizer 1-8
Reinforcing agent 0.01-5
The nucleating agent 0.05-5 of poly-dopamine cladding.
2. a kind of 3D printing porous material of expansion drilling according to claim 1, which is characterized in that the poly- DOPA
What the nucleating agent of amine cladding was prepared by following step：
It is 1 according to the mass ratio of nucleating agent and buffer solution:Nucleating agent is added in buffer solution and 1h is stirred by ultrasonic by 100 ratio,
It is later 8-10 according to the mass ratio of nucleating agent and dopamine:Dopamine is added in above-mentioned buffer solution 1-5, at room temperature, magnetic
Power stirs for 24 hours, and reaction terminates buffer by centrifugation detaching 20min, is cleaned 3 times with ethanol solution, removes unreacted monomer, obtain
It is put into 100-180 DEG C of vacuum drying chamber to solid and dries 12h, obtains the nucleating agent of poly-dopamine cladding.
3. a kind of 3D printing porous material of expansion drilling according to claim 1 or 2, which is characterized in that the phase
It is at least a kind of selected from ethylene-octene copolymer grafted maleic anhydride to hold agent（POE-g-MAH）, cumyl peroxide, GMA-
The terpolymer or ethylene-methyl acrylate-ethylene oxidic ester of ethylene-methyl acrylate.
4. a kind of 3D printing porous material of expansion drilling according to claim 1 or 2, which is characterized in that the increasing
Strong agent is at least a kind of to be selected from single-walled carbon nanotube, hydroxylating single-walled carbon nanotube, carboxylated single-walled carbon nanotube, amination list
Wall carbon nano tube, multi-walled carbon nanotube, hydroxylated multi-walled carbon nanotubes, functionalized multi-wall carbonnanotubes, amination multi wall carbon are received
Mitron, graphitization hydroxylated multi-walled carbon nanotubes or carbon fiber.
5. a kind of 3D printing porous material of expansion drilling according to claim 2, which is characterized in that the nucleating agent
It is at least a kind of selected from kaolin, calcium carbonate, hydrotalcite, mica, talcum powder, calcium sulfate crystal whiskers, montmorillonite, silica, two
Titanium oxide or polyvinyl butyral.
6. a kind of 3D printing porous material of expansion drilling according to claim 2, which is characterized in that buffer solution uses
The Tris hydrochloride buffers that ph is 8.5.
7. a kind of preparation method of the 3D printing porous material of any expansion drilling of claim 1 to 6, feature exist
In including the following steps：
A. PBSA, compatilizer, reinforcing agent and PCL are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PBSA, PCL, compatilizer, reinforcing agent and poly-dopamine cladding at
Core agent；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 1000-6000rpm/min, high-speed stirred 3-
20min；
D. it is sufficiently mixed uniform raw material by above-mentioned and puts into screw extruder, heated by 90-130 DEG C of temperature, in screw rod
Molten intracavitary fusion plastification simultaneously squeezes out raw material with rotating speed for 10-280rpm；It is sent into pelleter through cooling from the raw material of Screw Extrusion
Cut into particle；
E. the pellet after cutting is put into screw extruder, is heated by 80-130 DEG C of temperature, melt intracavitary melting in screw rod
It is plasticized and is that 10-280rpm squeezes out lines from stainless steel mouth mold with rotating speed；
F. lines are fully cooled molding through three-stage cooling sink, and the wire rod of fixed size diameter is then distracted into through dragger；
G. the wire rod after shaping enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected
The frequency of dragger is 5-40HZ.
8. a kind of 3D printing porous material of expansion drilling according to claim 6, which is characterized in that the extruder
For one kind in single screw extrusion machine, double screw extruder, three-screw extruder.
9. a kind of 3D printing porous material of expansion drilling according to claim 6, which is characterized in that described first is cold
But sink water temperature is 25 DEG C -40 DEG C；Second bosh water temperature is 5 DEG C -20 DEG C；Third bosh is 0 DEG C of mixture of ice and water.
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| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
| CN113861943A (en) * | 2021-10-19 | 2021-12-31 | 佛山市顺德区美的洗涤电器制造有限公司 | Phase-change material composition, phase-change material, and preparation method and application thereof |
| CN113861944A (en) * | 2021-10-19 | 2021-12-31 | 佛山市顺德区美的洗涤电器制造有限公司 | Inorganic hydrated salt phase-change material composition, inorganic hydrated salt phase-change material, and preparation method and application thereof |
| CN115008800A (en) * | 2022-06-08 | 2022-09-06 | 江西千通管业有限公司 | Method for improving high-pressure-resistant strength of HDPE steel wire mesh framework polyethylene composite pipe |
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| CN109485768B (en) * | 2018-11-18 | 2021-03-16 | 长春工业大学 | Acrylic ester polymer coated carbon nanotube and preparation method thereof |
| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
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| CN113861944A (en) * | 2021-10-19 | 2021-12-31 | 佛山市顺德区美的洗涤电器制造有限公司 | Inorganic hydrated salt phase-change material composition, inorganic hydrated salt phase-change material, and preparation method and application thereof |
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