CN105199340A - PBS (poly butylenes succinate)/halloysite nanotubes composite wire for 3D printing and preparation method of PBS/halloysite nanotubes composite wire - Google Patents

Abstract

The invention discloses a preparation method of a PBS (poly butylenes succinate)/halloysite nanotubes composite wire for 3D printing. The technical scheme is that the halloysite nanotubes composite wire is prepared from the following raw materials by weight percent: 70-95 percent of PBS, 0.1-20 percent of halloysite nanotubes, 0.1-10 percent of a coupling agent, 0.1-2 percent of a nucleating agent, 0.1-1 percent of a chain extendor, 0.1-1 percent of a cross-linking agent, 0.2-1 percent of an anti-oxidant and 0.2-1.2 percent of a lubricant. The preparation method comprises the following steps: (1) drying, (2) material weighing, (3) high-speed kneading, (4) melt extrusion, (5) cooling and drawing, and (6) winding and bundling. According to the preparation method, the two completely biodegradable materials, PBS and the halloysite nanotubes, are adopted to prepare a polymer material suitable for 3D printing, and compared with a traditional polylactic acid (PLA) wire, the PBS/halloysite nanotubes composite wire is relatively low in printing temperature and relatively good in tensile strength and flexibility.

Description

A kind of PBS/ halloysite nanotubes composite wire for 3D printing and preparation method thereof

Technical field

The invention belongs to a kind of PBS/ halloysite nanotubes composite wire for 3D printing and preparation method thereof.

Background technology

3D printing technique, namely increases material manufacturing technology, is called as the gordian technique promoting the third time Industrial Revolution together with robot technology, artificial intelligence technology.3D printing technique a kind ofly piles up material generate the quick increasing material manufacturing technology of 3D solid by successively increasing, and it subtracts compared with material manufacturing technology with traditional, has that loss is low, product manufacturing is intelligent, precision and a feature efficiently.Relate in particular to the high-end manufacture field of complicated shape, 3D printing technique shows huge superiority.

According to the difference of printing technique principle and institute's suitable material, 3D printing technique can be divided into laser fusing-covering forming technique (LCF), thaw collapse amasss rapid shaping technique (FDM), Selective Laser Sintering (SLS), Stereo Lithography technology (SLA), molded through three-dimensional printing (3DP) etc.FDM is a kind of quick, safe, cheap quick shaping process, and it easily operates, and equipment used cost is low, concise in technology, and available materials kind is many, comparatively cheap and utilization ratio is high, is applicable to office environment and uses.Current FDM system accounts for 30% in the mounted rapid prototyping system in the whole world, is the mainstream technology that desktop 3D printer popular at present adopts.

Poly(lactic acid) (PLA) to be FDM technology the be most widely used macromolecular material with biological degradability and biocompatibility at present, but nozzle temperature is generally at about 230 DEG C when PLA prints for 3D, energy consumption is higher, easily cause operator to scald, be not suitable for children and use 3D printer.Therefore develop and both the same with PLA there is biological degradability and biocompatibility, the focus of research can be become by the novel 3D printed material that prints of lesser temps again.

Poly butylene succinate (PBS), also claim polybutylene succinate or poly-succsinic acid fourth diester, its fusing point is 105 DEG C, Tc is at about 61 DEG C, relative crystallinity is 40-60%, is a kind of hemicrystalline resin with complete biodegradable ability, has good processing characteristics.At present, can be applicable to the aspects such as table ware, various household supplies articles for use, agricultural materials, biological medical polymer material, food and medicine wrapping material, but the PBS material being directly used in 3D printing is not yet seen in report.

Pure PBS directly applies to 3D and prints the problem that there is thermal contraction, and adding PBS main chain is aliphatic carbon oxygen chain composition, and toughness and tensile strength need to be improved further.Halloysite is a kind of natural aluminosilicate clays, and form by kaolinic lamella is curling under natural condition, mainly there is occurring in nature with the form that many walls are nanotube-shaped, pipe range is 500-1000nm, and internal diameter is 10-20nm, and external diameter is 20-40nm.The lamella of halloysite nanotubes is formed by the alumina octahedral regular array of outer field silicon-oxy tetrahedron and internal layer, and outside surface is Si-O-Si key and a small amount of silicone hydroxyl composition mainly, and inwall is mainly aluminium hydroxyl.Special surface charge distribution, larger length-to-diameter ratio, make halloysite nanotubes be easier to dispersion, is less likely to occur to reunite.In addition, halloysite nanotubes is cheap, wide advantage of originating, and makes it day by day be subject to the attention of investigator as filling or material modified application in polymer composite.

(the plastics such as Cao Xianwu, 42 volumes the 2nd phase in 2013) have studied the fabrication & properties of PBS/ halloysite nanotubes matrix material, but this article does not carry out coupling processing to halloysite nanotubes surface, the tensile strength making the halloysite nanotubes of interpolation 10 parts is 37.74MPa, and shock strength is studied.And this article is only limitted to preparation PBS/ halloysite nanotubes matrix material, is not applied to 3D and prints field.

Summary of the invention

Based on above-mentioned background and problem, the object of the present invention is to provide a kind of PBS/ halloysite nanotubes composite wire for 3D printing and preparation method thereof.The present invention adopts the degradable biomaterial poly butylene succinate (PBS) of energy and halloysite nanotubes preparation to be applicable to the macromolecular material of 3D printing, compared with traditional poly(lactic acid) (PLA) wire rod, there is lower print temperature, good tensile strength and snappiness, be applicable to multiple 3D forming technique, print field at 3D and have broad application prospects.

The object of the invention is to be achieved through the following technical solutions:

A kind of PBS/ halloysite nanotubes composite wire printed for 3D of the present invention, is characterized in that: according to weight percent formula:

PBS70-95

Halloysite nanotubes 0.1-20

Coupling agent 0.1-10

Nucleator 0.1-2

Chainextender 0.1-1

Linking agent 0.1-1

Oxidation inhibitor 0.2-1

Lubricant 0.2-2.

Described coupling agent is the mixture of one or more arbitrary proportions in γ-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxy third oxygen) propyl group three TMOS (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), two-[γ-(triethoxysilicane) propyl group] tetrasulfide (Si-69), 3-r-chloropropyl trimethoxyl silane, dodecyl Trimethoxy silane.

Described nucleator is the mixture of one or more arbitrary proportions in kaolin, calcium carbonate, hydrotalcite, attapulgite, mica, talcum powder, calcium sulfate crystal whiskers, polynite, silicon-dioxide, titanium dioxide, Lanthanum Benzoate, cyclic phosphoric acid lanthanum, polyvinyl butyral acetal.

Described chainextender is the mixture of one or more arbitrary proportions of Tetra hydro Phthalic anhydride, Succinic anhydried, pyromellitic dianhydride, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate.

Described linking agent is the mixture of trihydroxy methyl propane trimethyl acrylic ester, one or both arbitrary proportions of trihydroxy methyl propane triacrylate.

Described oxidation inhibitor is the mixture of one or more arbitrary proportions in tea-polyphenol, phytic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (168), dipentaerythritol diphosphites (626).

Described lubricant is the mixture of one or more arbitrary proportions in stearic acid, N, N'-ethylene bis stearamide (EBS), oxidized polyethlene wax, magnesium stearate, white oil.

Another object of the present invention is to provide a kind of preparation method of the PBS/ halloysite nanotubes composite wire for 3D printing, comprises the steps:

A. by PBS vacuum-drying, most preferably dry 12h in 80 DEG C of vacuum drying ovens;

B. according to weight percent formula, dried PBS, halloysite nanotubes, coupling agent, nucleator, chainextender, linking agent, oxidation inhibitor, lubricant is taken;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 1000-6000rpm/min, high-speed stirring 5-30min;

D. the PBS mixed, halloysite nanotubes, coupling agent, nucleator, chainextender, linking agent, oxidation inhibitor, lubricant are joined screw extrusion press charging opening, screw extrusion press parameter is: a district 75-130 DEG C, two district 90-150 DEG C, three district 90-160 DEG C, four district 80-150 DEG C, five district 100-160 DEG C, rotating speed is 10-150rpm/min, extruding pelletization;

E. be processed into filament by extruding with screw extrusion press after the sub-drying of institute's granulation in step D, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

9, described forcing machine is the one in single screw extrusion machine, twin screw extruder, three-screw extruder.

Advantage and disadvantage of the present invention is: the present invention adopts the degradable biomaterial poly butylene succinate (PBS) of energy and halloysite nanotubes preparation to be applicable to the macromolecular material of 3D printing.Halloysite nanotubes has higher length-to-diameter ratio and unique surface chemical property, it can be linked into inorganic network by hydrogen bond action or Charger transfer, there is between halloysite nanotubes and PBS matrix stronger interface cohesion effect, make load be delivered to halloysite nanotubes smoothly by matrix, thus play the effect of enhancing.The wire rod of preparation, compared with traditional poly(lactic acid) (PLA) wire rod, has lower print temperature, good tensile strength and snappiness, is applicable to multiple 3D forming technique, prints field have broad application prospects at 3D.

Chinese patent application publication number CN104530669A discloses a kind of polydactyl acid PLA material and preparation method thereof that can be used for 3D and print, the method utilizes poly butylene succinate to carry out toughening modifying as toughner to PLA, although the method can improve the toughness of PLA, but because modified wire rod is PLA and PBS two-phase system, the tensile strength of modification PLA is not high, and easily cause in print procedure and be separated, make printing effect poor, the wire rod of extruding of 1.75 ± 0.05mm that the present invention obtains carries out 3D printing test, print temperature 140 DEG C, print procedure is smooth, print product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

Embodiment

Below in conjunction with specific embodiment, the present invention is described in further details, but this should be interpreted as scope of the present invention is only limitted to following instance.

embodiment 1

1, for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: according to weight percent formula:

PBS75

Halloysite nanotubes 15

KH5607

Silica 1

Tetra hydro Phthalic anhydride 0.4

Trihydroxy methyl propane trimethyl acrylic ester 0.6

Tea-polyphenol 0.5

White oil 0.5.

2, for a preparation method for the PBS/ halloysite nanotubes composite wire of 3D printing, comprise the steps:

A. by PBS dry 12h in 80 DEG C of vacuum drying ovens;

B. according to the formula of step 1, dried PBS, halloysite nanotubes, KH560, silicon-dioxide, Tetra hydro Phthalic anhydride, trihydroxy methyl propane trimethyl acrylic ester, tea-polyphenol, white oil is taken;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 3000rpm/min, high-speed stirring 25min;

D. the PBS mixed, halloysite nanotubes, KH560, silicon-dioxide, Tetra hydro Phthalic anhydride, trihydroxy methyl propane trimethyl acrylic ester, tea-polyphenol, white oil are joined twin screw extruder charging opening, twin screw extruder parameter is: 100 DEG C, a district, two 125 DEG C, districts, three 135 DEG C, districts, four 135 DEG C, districts, five 130 DEG C, districts, rotating speed is 100rpm/min, extruding pelletization;

E. be processed into filament by extruding with single screw extrusion machine after the sub-drying of institute's granulation in step D, extruder temperature is set as 90 DEG C, a district, two 110 DEG C, districts, three 130 DEG C, districts, and four 120 DEG C, districts, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

F. the wire rod of extruding of the 1.75 ± 0.05mm obtained in E step is carried out 3D printing test, print temperature 145 DEG C, print procedure is smooth, prints product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

G. by injection moulding after the particle drying that obtains in D step, injection moulding batten carries out tensile property test (GB/T1040.2-2006), flexural strength (GB/T1446-2006) and impact property test (GB/T1943-2008) respectively, and test result is in table 1.

embodiment 2

1, for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: according to weight percent formula:

PBS82.6

Halloysite nanotubes 9

KH5705

Calcium carbonate 1

Tolylene diisocyanate 0.5

Trihydroxy methyl propane triacrylate 0.4

10100.5

Stearic acid 1.

2, for a preparation method for the PBS/ halloysite nanotubes composite wire of 3D printing, comprise the steps:

A. by PBS dry 12h in 80 DEG C of vacuum drying ovens;

B. according to the formula of step 1, take dried PBS, halloysite nanotubes, KH570, calcium carbonate, tolylene diisocyanate, trihydroxy methyl propane triacrylate, 1010, stearic acid;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 5000rpm/min, high-speed stirring 20min;

D. by the PBS mixed, halloysite nanotubes, KH570, calcium carbonate, tolylene diisocyanate, trihydroxy methyl propane triacrylate, 1010, stearic acid joins three-screw extruder charging opening, three-screw extruder parameter is: 110 DEG C, a district, two 122 DEG C, districts, three 130 DEG C, districts, four 130 DEG C, districts, five 125 DEG C, districts, rotating speed is 80rpm/min, extruding pelletization;

E. be processed into filament by extruding with single screw extrusion machine after the sub-drying of institute's granulation in step D, extruder temperature is set as 95 DEG C, a district, two 110 DEG C, districts, three 130 DEG C, districts, and four 125 DEG C, districts, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

F. the wire rod of extruding of the 1.75 ± 0.05mm obtained in E step is carried out 3D printing test, print temperature 135 DEG C, print procedure is smooth, prints product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

G. by injection moulding after the particle drying that obtains in D step, injection moulding batten carries out tensile property test (GB/T1040.2-2006), flexural strength (GB/T1446-2006) and impact property test (GB/T1943-2008) respectively, and test result is in table 1.

embodiment 3

1, for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: according to weight percent formula:

PBS84

Halloysite nanotubes 11

Si-693

Mica 0.8

Pyromellitic dianhydride 0.2

Trihydroxy methyl propane triacrylate 0.3

1680.3

EBS0.4。

2, for a preparation method for the PBS/ halloysite nanotubes composite wire of 3D printing, comprise the steps:

A. by PBS dry 12h in 80 DEG C of vacuum drying ovens;

B. according to the formula of step 1, take dried PBS, halloysite nanotubes, Si-69, mica, pyromellitic dianhydride, trihydroxy methyl propane triacrylate, 168, EBS;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 5500rpm/min, high-speed stirring 10min;

D. by the PBS mixed, halloysite nanotubes, Si-69, mica, pyromellitic dianhydride, trihydroxy methyl propane triacrylate, 168, EBS joins three-screw extruder charging opening, three-screw extruder parameter is: 100 DEG C, a district, two 120 DEG C, districts, three 130 DEG C, districts, four 135 DEG C, districts, five 130 DEG C, districts, rotating speed is 80rpm/min, extruding pelletization;

E. be processed into filament by extruding with twin screw extruder after the sub-drying of institute's granulation in step D, extruder temperature is set as 90 DEG C, a district, two 115 DEG C, districts, three 120 DEG C, districts, four 130 DEG C, districts, and five 125 DEG C, districts, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

F. the wire rod of extruding of the 1.75 ± 0.05mm obtained in E step is carried out 3D printing test, print temperature 140 DEG C, print procedure is smooth, prints product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

G. by injection moulding after the particle drying that obtains in D step, injection moulding batten carries out tensile property test (GB/T1040.2-2006), flexural strength (GB/T1446-2006) and impact property test (GB/T1943-2008) respectively, and test result is in table 1.

embodiment 4

1, for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: according to weight percent formula:

PBS89

Halloysite nanotubes 3

Dodecyl Trimethoxy silane 5

Hydrotalcite 0.5

Hexamethylene diisocyanate 0.5

Trihydroxy methyl propane trimethyl acrylic ester 0.4

6260.8

White oil 0.8.

2, for a preparation method for the PBS/ halloysite nanotubes composite wire of 3D printing, comprise the steps:

A. by PBS dry 12h in 80 DEG C of vacuum drying ovens;

B. according to the formula of step 1, take dried PBS, halloysite nanotubes, dodecyl Trimethoxy silane, hydrotalcite, hexamethylene diisocyanate, trihydroxy methyl propane trimethyl acrylic ester, 626, white oil;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 4000rpm/min, high-speed stirring 15min;

D. by the PBS mixed, halloysite nanotubes, dodecyl Trimethoxy silane, hydrotalcite, hexamethylene diisocyanate, trihydroxy methyl propane trimethyl acrylic ester, 626, white oil joins twin screw extruder charging opening, twin screw extruder parameter is: 90 DEG C, a district, two 110 DEG C, districts, three 125 DEG C, districts, four 130 DEG C, districts, five 125 DEG C, districts, rotating speed is 90rpm/min, extruding pelletization;

E. be processed into filament by extruding with single screw extrusion machine after the sub-drying of institute's granulation in step D, extruder temperature is set as 90 DEG C, a district, two 114 DEG C, districts, three 130 DEG C, districts, and four 123 DEG C, districts, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

F. the wire rod of extruding of the 1.75 ± 0.05mm obtained in E step is carried out 3D printing test, print temperature 145 DEG C, print procedure is smooth, prints product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

G. by injection moulding after the particle drying that obtains in D step, injection moulding batten carries out tensile property test (GB/T1040.2-2006), flexural strength (GB/T1446-2006) and impact property test (GB/T1943-2008) respectively, and test result is in table 1.

embodiment 5

1, for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: according to weight percent formula:

PBS91.5

Halloysite nanotubes 5

KH5501.5

Kaolin 0.5

Pyromellitic dianhydride 0.2

Trihydroxy methyl propane trimethyl acrylic ester 0.5

10100.3

Stearic acid 0.3.

2, for a preparation method for the PBS/ halloysite nanotubes composite wire of 3D printing, comprise the steps:

A. by PBS dry 12h in 80 DEG C of vacuum drying ovens;

B. according to the formula of step 1, take dried PBS, halloysite nanotubes, KH550, kaolin, pyromellitic dianhydride, trihydroxy methyl propane trimethyl acrylic ester, 1010, stearic acid;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 4500rpm/min, high-speed stirring 20min;

D. by the PBS mixed, halloysite nanotubes, KH550, kaolin, pyromellitic dianhydride, two hydroxymethyl propane trimethacrylate, 1010, stearic acid joins twin screw extruder charging opening, three-screw extruder parameter is: 100 DEG C, a district, two 115 DEG C, districts, three 124 DEG C, districts, four 138 DEG C, districts, five 130 DEG C, districts, rotating speed is 60rpm/min, extruding pelletization;

E. be processed into filament by extruding with single screw extrusion machine after the sub-drying of institute's granulation in step D, extruder temperature is set as 90 DEG C, a district, two 115 DEG C, districts, three 130 DEG C, districts, and four 125 DEG C, districts, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

F. the wire rod of extruding of the 1.75 ± 0.05mm obtained in E step is carried out 3D printing test, print temperature 140 DEG C, print procedure is smooth, prints product surface smooth well-balanced, appearance looks elegant, dimensional stabilizing.

G. by injection moulding after the particle drying that obtains in D step, injection moulding batten carries out tensile property test (GB/T1040.2-2006), flexural strength (GB/T1446-2006) and impact property test (GB/T1943-2008) respectively, and test result is in table 1.

Table 1.PBS/ halloysite nanotubes composite property test result

Sample	Tensile strength (MPa)	Flexural strength (MPa)	Modulus in flexure (MPa)	Shock strength (kJ/m 2)
					Example 1	35.4	39.6	621	10.9
Example 2	42.2	55.3	593	16.5
					Example 3	38.7	48.4	636	15.4
Example 4	34.3	45.2	551	9.2
					Example 5	37.4	47.7	540	12.7

Claims (9)

1., for the PBS/ halloysite nanotubes composite wire that 3D prints, it is characterized in that: weight percent formula is as follows:

PBS70-95

Halloysite nanotubes 0.1-20

Coupling agent 0.1-10

Nucleator 0.1-2

Chainextender 0.1-1

Linking agent 0.1-1

Oxidation inhibitor 0.2-1

Lubricant 0.2-2.

2. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1, it is characterized in that: described coupling agent has at least one to be selected from γ-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxy third oxygen) propyl group three TMOS (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), two-[γ-(triethoxysilicane) propyl group] tetrasulfide (Si-69), 3-r-chloropropyl trimethoxyl silane or dodecyl Trimethoxy silane.

3. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1, is characterized in that: described nucleator has at least one to be selected from kaolin, calcium carbonate, hydrotalcite, attapulgite, mica, talcum powder, calcium sulfate crystal whiskers, polynite, silicon-dioxide, titanium dioxide, Lanthanum Benzoate, cyclic phosphoric acid lanthanum or polyvinyl butyral acetal.

4. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1, is characterized in that: described chainextender has at least one to be selected from Tetra hydro Phthalic anhydride, Succinic anhydried, pyromellitic dianhydride, tolylene diisocyanate, diphenylmethanediisocyanate or hexamethylene diisocyanate.

5. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1, is characterized in that: described linking agent has at least one to be selected from trihydroxy methyl propane trimethyl acrylic ester or trihydroxy methyl propane triacrylate.

6. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1, it is characterized in that: described oxidation inhibitor has at least one to be selected from tea-polyphenol, phytic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (168) or dipentaerythritol diphosphites (626).

7. a kind of PBS/ halloysite nanotubes composite wire printed for 3D according to claim 1 or 2 or 3 or 4 or 5 or 6, it is characterized in that: described lubricant has at least one to be selected from stearic acid, N, N'-ethylene bis stearamide (EBS), oxidized polyethlene wax, magnesium stearate or white oil.

8. the preparation method of the arbitrary described a kind of PBS/ halloysite nanotubes composite wire for 3D printing of claim 1-7, comprises the steps:

A. by PBS vacuum-drying;

B. according to formula, dried PBS, halloysite nanotubes, coupling agent, nucleator, chainextender, linking agent, oxidation inhibitor, lubricant is taken;

C. each component after taking is placed in high-speed kneading machine, keeps rotating speed 1000-6000rpm/min, high-speed stirring 5-30min;

D. the PBS mixed, halloysite nanotubes, coupling agent, nucleator, chainextender, linking agent, oxidation inhibitor, lubricant are joined screw extrusion press charging opening, screw extrusion press parameter is: a district 75-130 DEG C, two district 90-150 DEG C, three district 90-160 DEG C, four district 80-150 DEG C, five district 100-160 DEG C, rotating speed is 10-150rpm/min, extruding pelletization;

E. be processed into filament by extruding with screw extrusion press after the sub-drying of institute's granulation in step D, what obtain 1.75 ± 0.05mm or 3 ± 0.05mm extrudes wire rod.

9. the preparation method of a kind of PBS/ halloysite nanotubes composite wire for 3D printing according to claim 8, is characterized in that: described forcing machine is the one in single screw extrusion machine, twin screw extruder, three-screw extruder.