CN105017734A - Polymeric material for 3D printing and preparation method of polymeric material - Google Patents
Polymeric material for 3D printing and preparation method of polymeric material Download PDFInfo
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Abstract
The invention relates to a polymeric material for 3D printing. The raw materials of the polymeric material comprise the following components in parts by weight: 20-100 parts of polybuthylenesuccinate and 0.1-80 parts of a modifying agent, wherein the modifying agent is selected from one kind or more than two kinds of polylactic acid, a reinforcing filler and a nucleator. Polymer resins which can be used for 3D printing, disclosed by the invention, not only have high toughness, but also have high mechanical strength and high heat resistance, so that the polymeric resins have a wide application prospect in 3D printing materials.
Description
Technical field
The present invention relates to a kind of polymer materials for 3D printing and preparation method thereof, be specifically related to a kind of polymer materials based on PBS.
Background technology
In recent years, 3D prints and is subject to paying close attention to more and more widely because of the forming process advantage of its uniqueness.3D prints, and also known as increasing material manufacturing technology, generally refers to and utilizes digitized model file, by time variable control printing head, go out the technology of 3D solid with the mode straight forming successively accumulated.Compared with traditional forming method, 3D prints does not need complicated mould and operating procedure, and the course of processing is controlled by computer program, handy and safe, substantially reduces the forming process cycle, and the baroque part of rapid shaping, can realize personalized customization.Along with going deep into of research, 3D prints has more and more wide application in fields such as medical science, aviation, building, automobiles gradually.
Material strand melt extrusion technology, also known as fused glass pellet technology, it is one of most widely used technology in 3D printing technique, its principle is by more than oven heats to its fusing point by the wire rod of certain specification, be expressed on platform by a nozzle after making material be in certain flow state, be deposited as 3D solid layer by layer.
At present, the fertile material of marketization melting deposition modeling used whether is biodegradablely divided into two large classes by it, is with acrylonitrile-butadiene-styrene copolymer (ABS) the not Biodegradable material that is representative and the Biodegradable material that is representative with poly(lactic acid) (PLA) respectively.ABS has fabulous shock strength, the product good stability of the dimension printed, and wear-resisting, dyeability is good, heat resisting temperature nearly 100 DEG C, but its not biodegradable can not meet the environmental requirement that people strengthen day by day.PLA has lower shrinking percentage and lower melt strength, does not need heating platform during printing, substantially warping phenomenon can not occur, but its resistance toheat is poor, and heat-drawn wire is only about 60 DEG C.The thermostability of poly-succinic fourth diester (PBS), toughness and crystal property are obviously better than PLA, are expected to the 3D printed material becoming a new generation.But PBS degree of crystallinity is higher, molding shrinkage is comparatively large, and Young's modulus is lower, easy buckling deformation when 3D prints.These shortcomings significantly limit its application as 3D printed material.
Although 3D printing technique has boundless application prospect, but be also faced with huge challenge at present.One of the principal element limiting its development be can the kind of 3D printed material few, limited capacity.China Patent Publication No. CN103467950A discloses a kind of 3D and prints modified polylactic acid material and preparation method thereof, this invention utilizes pulverize at low temperature hybrid reaction technology, carry out modification to poly(lactic acid), prepared poly(lactic acid) all has significant improvement in toughness, shock strength and heat-drawn wire etc.But pulverize at low temperature hybrid reaction technology is suitable for small serial production, and heavy industrialization has difficulties.China Patent Publication No. CN103992628A disclose a kind of can the 3D printed material of ultraviolet light cross-linking, carry out modifiedly preparing 3D printed material with other polymerization to PBS, but this material is mainly used in UV-light 3D to be printed.
Summary of the invention
(1) technical problem that will solve
Directly apply to molding shrinkage in 3D printing for PBS in prior art large, the defect that Young's modulus is lower, the invention provides a kind of polymer materials based on PBS.
(2) technical scheme
Polymer materials of the present invention, its raw material comprises the component of following weight part: poly-succinic fourth diester 20 ~ 100 parts; Properties-correcting agent 2 ~ 80 parts; Wherein, described properties-correcting agent is selected from one or more in poly(lactic acid), reinforcing filler, nucleator.
Polymer materials of the present invention, its raw material comprises the component of following weight part: poly-succinic fourth diester 20 ~ 90 parts; Poly(lactic acid) 10 ~ 80 parts, the two total amount is 100 parts.
Polymer materials of the present invention, its raw material preferably includes the component of following weight part: poly-succinic fourth diester 20 ~ 80 parts; Poly(lactic acid) 20 ~ 80 parts, the two total amount is 100 parts.
Polymer materials of the present invention, its raw material comprises following component: poly-succinic fourth diester 100 parts; Reinforcing filler 5 ~ 10 parts.
Polymer materials of the present invention, its raw material comprises following component: poly-succinic fourth diester 100 parts; Nucleator 0.1 ~ 5 part.
Polymer materials of the present invention, its raw material comprises following component: poly-succinic fourth diester 20 ~ 90 parts; Poly(lactic acid) 10-80 part; Reinforcing filler 2-10 part, the total amount of described poly-succinic fourth diester and poly(lactic acid) is 100 parts.
Polymer materials of the present invention, its raw material also comprises the colour batch of 1 ~ 5 weight part and the blended used additives being suitable for 3D printing of 1 ~ 5 weight part.
In the present invention, described colour batch comprises mineral dye and pigment dyestuff; Described mineral dye chromic salt, the one in titanium dioxide, carbon black, iron pigment; Described pigment dyestuff is selected from phthalocyanine pigment or forever consolidates class pigment.
In the present invention, described in be suitable for the blended used additives that 3D prints and can be polyethylene low-molecular-weight wax, or other any other reagent playing phase same-action.
Polymer materials of the present invention, the molecular weight of described poly-succinic fourth diester is 2-20 ten thousand, and degree of crystallinity is 25-65%; The molecular weight of described poly(lactic acid) is 2 ~ 200,000, and degree of crystallinity is 0-40%; Described reinforcing filler comprises one or more of titanium dioxide, attapulgite, boron nitride, calcium carbonate, talcum powder and potter's clay; Described nucleator comprise in boron nitride, TMC300, TMC306 and poly-fumaric acid fourth diester one or more.By adding reinforcing filler, the Young's modulus of material can be improved, thus improve the ability of material repels distortion.By adding nucleator, can solidification rate be improved, thus accelerate 3D print speed.
Polymer materials of the present invention, the preferred 6-15 ten thousand of molecular weight of described poly-succinic fourth diester.The molecular weight of described poly(lactic acid) is preferably 4-10 ten thousand; The preferred 0-30% of degree of crystallinity of poly(lactic acid).The poly(lactic acid) of this scope, existing good mechanical property, also has good melt-processable.
Another object of the present invention is to provide the preparation method of polymer materials of the present invention, comprises the steps:
1) by premix after the raw material drying of polymer materials, add in twin screw extruder blended evenly after extrude pelletizing, obtain lay-by material; The temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C; Engine speed is 40 ~ 200rpm;
2) described lay-by material is joined in single screw extrusion machine, extrude rear tractor drawing-off, make the wire rod printed for 3D; The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C; Screw speed is 10 ~ 30rpm, and the ratio of drawing of tractor is 1.1 ~ 3.2.
Last object of the present invention is to provide the method utilizing material of the present invention to carry out 3D printing, is specially, and adopts fusion sediment technology to print, control print speed 20 ~ 42mm/s, print temperature 170 ~ 215 DEG C, prints floor height 0.05 ~ 0.15mm, gauge or diameter of wire 1.6 ~ 2.0mm.
(3) beneficial effect
Material of the present invention has following beneficial effect:
1) of the present invention based on the polymer materials that can be used for 3D printing of poly-succinic fourth diester: to effectively improve the defect that molding shrinkage is large, Young's modulus is low existed when directly using poly-succinic fourth diester to print for 3D, the material of preparation has higher tensile strength and tensile modulus, and remaining the good toughness of former PBS, its performance index such as elongation at break and shock strength are good.
2) poly-succinic fourth diester class intermingling material with existing can compared with the polymer materials that prints of 3D, not only have quite high toughness, also have higher thermotolerance, its vicat softening point temperature is higher than 80 DEG C;
3) the poly-succinic fourth diester prepared and polylactic acid blend material bright color, its L value is greater than 90, a and b value is all less than 5, has good biodegradable performance;
4) the present invention is by changing the parts by weight of reinforcing filler and pigment and the poly(lactic acid) of adding, and can obtain different colours, the product of different mechanical properties.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The present embodiment relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 60 weight parts, the poly(lactic acid) of 40 weight parts and the iron oxide yellow of 1 weight part.
Embodiment 2
The present embodiment relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 20 weight parts, the poly(lactic acid) of 80 weight parts and the iron oxide yellow of 1 weight part.
Embodiment 3
The present embodiment relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 100 weight parts, the attapulgite of 5 weight parts and the phthalocyanine blue of 1 weight part.
Embodiment 4
The present embodiment relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 100 weight parts, the poly-fumaric acid fourth diester of 2 weight parts, the permanent violet of 1 weight part.
Embodiment 5
The present embodiment relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 80 weight parts, the poly(lactic acid) of 20 weight parts and the attapulgite of 2 weight parts.
Embodiment 6
This enforcement relate to a kind of utilize the raw material described in embodiment 1 to print for the preparation of 3D polymer materials and print the example of hollow out rabbit, its step is as follows:
1) by described poly-succinic fourth diester, poly(lactic acid) and iron oxide yellow dry 2h at 80 DEG C.
2) the poly-succinic fourth diester of dried 60 weight parts is taken, the poly(lactic acid) of 40 weight parts, after the iron oxide yellow premix of 1 part, extrude pelletizing with twin screw extruder, obtain lay-by material, the temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 DEG C ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, engine speed is 60rpm.
3) with single screw extrusion machine described lay-by material extruded and be processed into the silk that diameter is 1.75 ± 0.05mm.The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 10rpm, and ratio of drawing is 1.1 ~ 2.4.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has then laid one deck.Utilize the viscosity flow characteristic of material itself, in layer pile up shaping, form goods hollow out rabbit.Optimum configurations during printing is as table 1.
Optimum configurations when table 1.PBS60/PLA40 prints
To step 2) in the material that obtains carry out performance characterization, characterization result is as table 2.
The performance perameter of table 2.PBS60/PLA40
| Tensile strength/MPa | 45.6 |
| Tensile modulus/MPa | 1545.9 |
| Elongation at break/% | 297 |
| Shock strength/kJm-2 | 14.7 |
| Zero shear viscosity/Pas | 1697 |
In above-mentioned test, tensile property is pressed ASTM D638 and is measured, and selects II type batten, and during test, draw speed is 50mm/min.
In above-mentioned test, shock strength is pressed ASTM D648 and is measured.
In above-mentioned test, melt viscosity is at 160 DEG C, and strain is that 1% time frequency of utilization scanning 0.01 ~ 100Hz measures.
Embodiment 7
This enforcement relates to and a kind ofly utilizes the raw material described in embodiment 2 to prepare polymer materials and print further the example of hollow out rabbit, and its step is as follows:
1) by the mixture of poly-succinic fourth diester, poly(lactic acid) and iron oxide yellow vacuum-drying 12h under the condition of 60 DEG C.
2) by the poly-succinic fourth diester of 20 weight parts, the poly(lactic acid) of 80 heavy parts, after the iron oxide yellow mixing of 1 part, extrudes pelletizing with twin screw extruder, obtains lay-by material.The temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 DEG C ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, and engine speed is 60rpm.
3) described lay-by material single screw extrusion machine is extruded be processed into the silk that diameter is 1.75 ± 0.05mm.The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 10rpm, and ratio of drawing is 1.1 ~ 2.4.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has then laid one deck.Utilize the viscosity flow characteristic of material itself, in layer pile up shaping, form hollow out rabbit.Optimum configurations during printing is as table 3.
Optimum configurations when table 3.PBS20/PLA80 prints
To step 2) in the material that obtains carry out performance characterization, characterization result is as table 4
The performance perameter of table 4.PBS20/PLA80
| Tensile strength/MPa | 55.6 |
| Tensile modulus/MPa | 2150 |
| Elongation at break/% | 93 |
| Shock strength/kJm -2 | 12.9 |
| Zero shear viscosity/Pas | 4837 |
In above-mentioned test, tensile property is pressed ASTM D638 and is measured, and selects II type batten, and during test, draw speed is 50mm/min.
In above-mentioned test, shock strength is pressed ASTM D648 and is measured.
In above-mentioned test, melt viscosity is at 160 DEG C, and strain is that 1% time frequency of utilization scanning 0.01 ~ 100Hz measures.
Embodiment 8
This enforcement relates to and a kind ofly utilizes the raw material described in embodiment 3 to prepare polymer materials and print further the example of cards folder, and its step is as follows:
1) the vacuum-drying 12h under the condition of 60 DEG C by poly-succinic fourth diester and attapulgite.
2) by the poly-succinic fourth diester of 100 weight parts, the attapulgite of 5 weight parts, after the phthalocyanine blue premix of 1 part, extrude pelletizing with twin screw extruder, obtain lay-by material, the temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, engine speed is 60rpm.
3) lay-by material single screw extrusion machine is extruded be processed into the filament that diameter is 1.75 ± 0.05mm.The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 30rpm, and ratio of drawing is 1.1-2.4.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has then laid one deck.Utilize the viscosity flow characteristic of material itself, in layer pile up shaping, form cards folder.Optimum configurations during printing is as table 5.
Optimum configurations when table 5.PBS/Att nano composite material prints
To step 2) in the material that obtains carry out performance characterization, characterization result is as table 6.
The performance perameter of table 6.PBS/Att nano composite material
| Tensile strength/MPa | 34.3 |
| Tensile modulus/MPa | 706.6 |
| Elongation at break/% | 134 |
In above-mentioned test, tensile property is pressed ASTM D638 and is measured, and selects II type batten, and during test, draw speed is 50mm/min.
Embodiment 9
This enforcement relates to and a kind ofly utilizes the raw material described in embodiment 4 to prepare polymer materials and print further the example of mobile phone shell, and its step is as follows:
1) by poly-succinic fourth diester, poly-fumaric acid butanediol ester and permanent violet vacuum-drying 12h under the condition of 60 DEG C.
2) by the poly-succinic fourth diester of 100 weight parts, the poly-fumaric acid fourth diester of 2 weight parts, after the permanent violet premix of 1 part, extrude pelletizing with twin screw extruder and obtain lay-by material, the temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, engine speed is 40rpm.
3) described lay-by material single-screw machine is extruded be processed into the filament that diameter is 1.75 ± 0.05mm.The temperature of forcing machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 10rpm, and ratio of drawing is 2.1-3.2.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has then laid one deck.Utilize the viscosity flow characteristic of material itself, in layer pile up shaping, form mobile phone shell.Optimum configurations during printing is as table 7.
Optimum configurations when table 7.PBS/PBF intermingling material prints
Described goods E purple, sample crystallinity 52%, tensile break strength 35MPa.
Embodiment 10
This enforcement relates to and a kind ofly utilizes the raw material described in embodiment 5 to prepare polymer materials and print further the example of mobile phone shell, and its step is as follows:
1) by poly-succinic fourth diester, poly(lactic acid) and attapulgite vacuum-drying 12h. under the condition of 60 DEG C
2) by the poly-succinic fourth diester of 80 weight parts, after the poly(lactic acid) of 20 weight parts and the attapulgite premix of 2 weight parts, extrude pelletizing with twin screw extruder and obtain lay-by material, the temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, engine speed is 200rpm.
3) described lay-by material single-screw machine is extruded be processed into the filament that diameter is 1.75 ± 0.05mm.The temperature of forcing machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 10rpm, and ratio of drawing is 2.1-3.2.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has then laid one deck.Utilize the viscosity flow characteristic of material itself, in layer pile up shaping, form mobile phone shell.Optimum configurations during printing is as table 8.
Optimum configurations when table 8.PBS/PLA/Att intermingling material prints
To step 2) in the material that obtains carry out performance characterization, characterization result is as table 9.
The performance perameter of table 9.PBS/PLA/Att nano composite material
| Tensile strength/MPa | 36.3 |
| Tensile modulus/MPa | 682 |
| Elongation at break/% | 267 |
Comparative example 1
This comparative example relates to a kind of polymer materials printed for 3D, and its raw material consists of the poly-succinic fourth diester of 100 weight parts and the titanium dioxide of 1 weight part.
Comparative example 2
This comparative example relates to the polymer materials that utilizes the feed composition described in comparative example 1 to print for the preparation of 3D and prints the example of Geko, and its step is as follows:
1) by poly-succinic fourth diester dry 12h at 60 DEG C;
2) by the poly-succinic fourth diester of 100 weight parts, after the titanium dioxide premix of 1 part, after extruding pelletizing with twin screw extruder, lay-by material is obtained; The temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C, and engine speed is 40rpm.
3) described lay-by material is joined in single screw extrusion machine, extrude rear tractor drawing-off, be processed into the filament that diameter is 1.75 ± 0.05mm, the temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C.Screw speed is 20rpm, and ratio of drawing is 1.0 ~ 2.0.
4) by step 3) in obtain filament harvest volume, send heating chamber to, in heating chamber after heating and melting by the gear before Aod printer nozzle.Nozzle is according to the 3D printer model Sequence motion arranged in advance, and the material simultaneously melted is expressed into a glass platform under the propelling movement of wire rod.The material extruded is cooling curing on platform gradually, has printed the decline of one deck rear platform and has laid one deck again.Utilize the viscosity flow characteristic of material itself, pile up shaping layer by layer, form goods Geko.Optimum configurations during printing is as table 10.
Optimum configurations when the pure PBS of table 10. prints
To step 12) in the material that obtains carry out performance characterization, characterization result is as table 11.
The performance perameter of the pure PBS of table 11.
| Tensile strength/MPa | 31.5 |
| Tensile modulus/MPa | 554 |
| Elongation at break/% | 324 |
| Shock strength/kJm-2 | 7.2 |
| Zero shear viscosity/Pas | 678 |
In above-mentioned test, tensile property is pressed ASTM D638 and is measured, and selects II type batten, and during test, draw speed is 50mm/min.
In above-mentioned test, shock strength is pressed ASTM D648 and is measured.
In above-mentioned test, melt viscosity is at 160 DEG C, and strain is that 1% time frequency of utilization scanning 0.01 ~ 100Hz measures.
Can be found out by the present embodiment only uses PBS as 3D printed material, the performances such as its tensile modulus, shock strength, Zero shear viscosity are obviously not as with the addition of the excellence after the auxiliary materials such as poly(lactic acid), therefore mixing material of the present invention is compared with pure PBS material, its tensile strength, tensile modulus and shock strength can be improved significantly, 3D prints goods buckling deformation significantly to be improved, and dimensional precision improves.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1., for the polymer materials that 3D prints, it is characterized in that, its raw material comprises the component of following weight part: poly-succinic fourth diester 20 ~ 100 parts; Properties-correcting agent 0.1 ~ 80 part; Wherein, described properties-correcting agent is selected from one or more in poly(lactic acid), reinforcing filler, nucleator.
2. polymer materials according to claim 1, is characterized in that, its raw material comprises the component of following weight part: poly-succinic fourth diester 20 ~ 90 parts; Poly(lactic acid) 10 ~ 80 parts, the two total amount is 100 parts.
3. polymer materials according to claim 1, is characterized in that, its raw material comprises the component of following weight part: poly-succinic fourth diester 100 parts; Reinforcing filler 5 ~ 10 parts.
4. polymer materials according to claim 1, is characterized in that, its raw material comprises the component of following weight part: poly-succinic fourth diester 100 parts; Nucleator 0.1 ~ 5 part.
5. polymer materials according to claim 1, is characterized in that, its raw material comprises the component of following weight part: poly-succinic fourth diester 20 ~ 90 parts; Poly(lactic acid) 10-80 part; Reinforcing filler 2-10 part, the total amount of described poly-succinic fourth diester and poly(lactic acid) is 100 parts.
6. according to the arbitrary described polymer materials of claim 1-5, it is characterized in that, described raw material also comprises the colour batch of 1 ~ 5 weight part and the blended used additives being suitable for 3D printing of 1 ~ 5 weight part.
7. the polymer materials according to any one of Claims 1 to 5, is characterized in that, the molecular weight of described poly-succinic fourth diester is 2-20 ten thousand, and degree of crystallinity is 25-65%;
The molecular weight of described poly(lactic acid) is 2 ~ 200,000, and degree of crystallinity is 0-40%;
Described reinforcing filler comprise in titanium dioxide, attapulgite, boron nitride, calcium carbonate, talcum powder and potter's clay one or more;
Described nucleator comprise in boron nitride, TMC300, TMC306 and poly-fumaric acid fourth diester one or more.
8. the preparation method of polymer materials described in any one of claim 1 ~ 7, is characterized in that, comprise the steps:
1) by premix after the raw material drying of the polymer materials described in claim 1 ~ 7, add in twin screw extruder blended evenly after extrude pelletizing, obtain lay-by material;
The temperature of twin screw extruder one district, 2nd district, 3rd district and die head is respectively 140 ~ 150 DEG C, 165 ~ 170 DEG C, 180 ~ 185 DEG C, 180 ~ 185 DEG C; Engine speed is 40 ~ 200rpm;
2) described lay-by material is joined in single screw extrusion machine, extrude rear tractor drawing-off, make the wire rod printed for 3D;
The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 130 ~ 135 DEG C, 150 ~ 155 DEG C, 160 ~ 165 DEG C, 150 ~ 155 DEG C; Screw speed is 10 ~ 30rpm, and the ratio of drawing of tractor is 1.1 ~ 3.2.
9. utilize the arbitrary described polymer materials of right 1 ~ 7 to carry out the method for fusion stacking 3D printing, it is characterized in that, control print speed 20 ~ 42mm/s, print temperature 170 ~ 215 DEG C, print floor height 0.05 ~ 0.15mm, gauge or diameter of wire 1.6 ~ 2.0mm.
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| CN106380805A (en) * | 2016-09-26 | 2017-02-08 | 桂林理工大学 | Preparation method of PBS/PLA (Poly Butylenes Succinate/Poly Lactic Acid) conductive 3D (three-dimensional) printing supplies |
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| CN106674918A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
| CN106699110A (en) * | 2016-11-28 | 2017-05-24 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Boron nitride ceramic material for 3D (Three Dimensional) printing and preparation method thereof |
| CN107652635A (en) * | 2017-09-20 | 2018-02-02 | 福建师范大学 | A kind of high inorganic fill PBS wire rods for 3D printing and preparation method thereof |
| CN108250693A (en) * | 2016-12-28 | 2018-07-06 | 上海邦中高分子材料有限公司 | A kind of 3D printing material |
| CN108699198A (en) * | 2016-01-21 | 2018-10-23 | 3M创新有限公司 | Fluoropolymer-containing increasing material processing |
| CN112266592A (en) * | 2020-11-04 | 2021-01-26 | 中国矿业大学 | High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992628A (en) * | 2014-04-30 | 2014-08-20 | 中国科学院化学研究所 | Material capable of realizing ultraviolet-light crosslinking and application thereof to 3D printing material |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
-
2015
- 2015-07-10 CN CN201510406096.6A patent/CN105017734A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992628A (en) * | 2014-04-30 | 2014-08-20 | 中国科学院化学研究所 | Material capable of realizing ultraviolet-light crosslinking and application thereof to 3D printing material |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
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| CN106674917A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Preparation method of nanotube composite wire containing PBC (Poly Butylene carbonate) |
| CN106674918A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
| US11179886B2 (en) | 2016-01-21 | 2021-11-23 | 3M Innovative Properties Company | Additive processing of fluoropolymers |
| CN108699198A (en) * | 2016-01-21 | 2018-10-23 | 3M创新有限公司 | Fluoropolymer-containing increasing material processing |
| US11230053B2 (en) | 2016-01-21 | 2022-01-25 | 3M Innovative Properties Company | Additive processing of fluoropolymers |
| CN108699198B (en) * | 2016-01-21 | 2021-06-08 | 3M创新有限公司 | Additive treatment of fluoropolymers |
| US11148361B2 (en) | 2016-01-21 | 2021-10-19 | 3M Innovative Properties Company | Additive processing of fluoroelastomers |
| CN106147279A (en) * | 2016-07-12 | 2016-11-23 | 广西南宁桂尔创环保科技有限公司 | A kind of novel 3D printing material |
| CN105925003A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Environment-friendly 3D printing material |
| CN106380805A (en) * | 2016-09-26 | 2017-02-08 | 桂林理工大学 | Preparation method of PBS/PLA (Poly Butylenes Succinate/Poly Lactic Acid) conductive 3D (three-dimensional) printing supplies |
| CN106699110A (en) * | 2016-11-28 | 2017-05-24 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Boron nitride ceramic material for 3D (Three Dimensional) printing and preparation method thereof |
| CN108250693A (en) * | 2016-12-28 | 2018-07-06 | 上海邦中高分子材料有限公司 | A kind of 3D printing material |
| CN107652635A (en) * | 2017-09-20 | 2018-02-02 | 福建师范大学 | A kind of high inorganic fill PBS wire rods for 3D printing and preparation method thereof |
| CN112266592B (en) * | 2020-11-04 | 2021-11-30 | 中国矿业大学 | High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof |
| CN112266592A (en) * | 2020-11-04 | 2021-01-26 | 中国矿业大学 | High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof |
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