CN106009569A - Modified polylactic acid 3D printing material based on ABS recycled materials - Google Patents
Modified polylactic acid 3D printing material based on ABS recycled materials Download PDFInfo
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- CN106009569A CN106009569A CN201610536474.7A CN201610536474A CN106009569A CN 106009569 A CN106009569 A CN 106009569A CN 201610536474 A CN201610536474 A CN 201610536474A CN 106009569 A CN106009569 A CN 106009569A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention relates to a modified polylactic acid 3D printing material based on ABS recycled materials. The material is a composition material formed by melt-blending 40-70 parts of polylactic resin, 20-40 parts of ABS recycled materials, 7-13 parts of flexibilizer and 3-7 parts of compatilizer. ABS recycled materials and polylactic acid are combined to serve as 3D printing materials, on one hand, waste ABS plastic is recycled and pollution and damage to the ecological environment are reduced; on the other hand, the 3D printing materials are used in cooperation with thermoplastic elastomer and compatilizer, so the shock strength and elongation at break of polylactic acid are improved, production cost of products is reduced, and the application range of polylactic acid as the 3D printing material is widened.
Description
Technical field
The invention belongs to the recovery and reuse technology field of macromolecular material, relate to a kind of polydactyl acid 3D printed material based on recycling ABS material and preparation method thereof.
Background technology
3D prints also known as rapid prototyping technique, the developing history of existing 30 years, is that one based on buildup of material method reprints technology without mould, according to Computerized three-dimensional graph data, control 3D printer by software, polymer, metal or pottery etc. can be successively piled into physical prototypes by jointing material.3D printing has the most finely, can reproduce 3-D effect completely and realize the feature of integrated manufacturing system (IMS), achieved with relatively broad application in the fields such as medical treatment, industrial modeling, scientific research archaeology, architectural design, electronic device and the vehicles.
3D prints main selective laser sintered, the stereolithography apparatus of the technology used, fusion sediment moulding and layer separated growth etc..Wherein, fusion sediment moulding is by thermoplastic silk material is added heat fusing, make it successively pile up and cool and solidify and constitute three-dimensional objects, due to not against laser as the molding energy, thus it is the simplest to equipment requirements, print cost minimum, be to apply the most universal a kind of 3D printing type at present.
The most frequently used two kinds of 3D printed materials of fusion sediment moulding are polylactic acid (PLA) and ABS.PLA is a kind of environmentally friendly bioabsorbable polymer material, its mechanical strength/modulus height, good processability, molding shrinkage are little, derive from Renewable resource, can be degradable for carbon dioxide with water, but the shock resistance of PLA is poor, price is of a relatively high, thus limit its popularization and application printing field at 3D.ABS is acrylonitrile, butadiene and cinnamic terpolymer, it is a kind of intensity height, impact resistance, chemical-resistant resistance, surface gloss is high, electric property is good, easily processed into type petroleum base non-degradable type macromolecular material, but as 3D printing consumables, ABS is irritant abnormal smells from the patient in print procedure, and the shrinkage factor printing goods each dimension after the cooling period is relatively large.
Be used alone PLA or ABS and all there is obvious defect as 3D printing consumables, and if the two is combined and uses as compositions, then can play respective advantage, it has also become a focus of at present 3D printed material research.CN 104945837A discloses a kind of ABS/PLA alloy resin composition for 3D printing and preparation method thereof, the method being blended by interpolation peroxide cross-linking agent and reactive extrursion, improve the compatibility of ABS and PLA, prepare the 3D printing ABS/PLA alloy resin with high intensity, high tenacity, high-dimensional stability and low-carbon environment-friendly.CN 105419265A discloses a kind of polylactic acid alloy and preparation method thereof, 3D printed material, ABS resin and the surfactant such as VTES, aminopropyl trimethoxysilane is used to carry out polydactyl acid, it is thus achieved that the 3D than single polylactic acid with more preferable glossiness and impact flexibility prints alloy material.CN 105001586A discloses a kind of 3D and prints wire conduction ABS/PLA composite and its preparation method and application, arranged in pairs or groups by the optimization of metal nickel powder, graphene microchip and CNT, and being used in mixed way of different-grain diameter ABS, prepare the 3D printing ABS/PLA composite of high tenacity, high connductivity.
ABS material is widely used at aspects such as machinery, building materials, automotive trim and instrument appliances, every annual meeting produces substantial amounts of ABS waste products, use the modes such as landfill or burning to process, not only can bring pollution to ecological environment, also result in the serious waste of resource.But the performance of the ABS reworked material owing to reclaiming decreases relative to virgin material, particularly toughness declines substantially, therefore, how to realize the recycling of discarded ABS, it has also become a problem demanding prompt solution.
Summary of the invention
It is an object of the invention to problem and the defect of polylactic resin pliability difference simultaneously overcoming ABS reclaiming material toughness to reduce, it is provided that the polydactyl acid 3D printed material based on ABS reclaiming material that a kind of impact strength and elongation at break are all improved.
The present invention also aims to provide a kind of preparation method of described 3D printed material.
Polydactyl acid 3D printed material based on ABS reclaiming material of the present invention is blended the compositions made by the raw materials melt of following weight parts: polylactic resin 40～70 parts, ABS reclaiming material 20～40 parts, toughener 7～13 parts, compatilizer 3～7 parts.
The present invention adds toughener in described polydactyl acid 3D printed material, in order to improve polylactic resin and the toughness of ABS reclaiming material.Described toughener is the one in ABS high glue powder, styrene butadiene styrene block copolymer (SBS) (SBS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS).
Then, the present invention is also added with suitable compatilizer in described polydactyl acid 3D printed material, is used for improving polylactic resin, the compatibility between ABS reclaiming material and toughener three.Described compatilizer includes the one in the SEBS (SEBS-g-MAH or SEBS-g-GMA) of SBS (SBS-g-MAH or SBS-g-GMA), maleic anhydride or the glycidyl methacrylate graft of ABS (ABS-g-MAH or ABS-g-GMA), maleic anhydride or the glycidyl methacrylate graft of maleic anhydride or glycidyl methacrylate graft.Wherein, the percent grafting of maleic anhydride or glycidyl methacrylate is 1～5%.
Preferably, the present invention, should be corresponding to the toughener with type when selecting compatilizer.Such as, when selecting SBS as toughener, should preferably be such that with SBS-g-MAH or SBS-g-GMA as compatilizer.
ABS reclaiming material used in the present invention be discarded ABS goods pulverize through disintegrating machine, clean, dry after the powder, pellet or the sheet stock that obtain.
Polylactic resin of the present invention is preferably used weight average molecular weight more than 100,000 g/mol, the polylactic resin of melt index 5～20g/10min (2.16kg, 210 DEG C).
And then, present invention also offers a kind of preparation method of above-mentioned polydactyl acid 3D printed material based on ABS reclaiming material, it is by polylactic resin, ABS reclaiming material, toughener and compatilizer melt blending pelletize, the particle fusion extrusion that will obtain again, 3D printed material silk material is made in traction wire drawing.
3D printed material silk material diameter 1.75mm or 3mm prepared by the present invention, diameter error is within ± 2%, for fusion sediment 3D printer, print temperature scope 200～230 DEG C.
In the above-mentioned preparation method of the present invention, after various raw materials the most first carry out dried, then carry out melt blending.Present invention preferably employs vacuum drying, general control vacuum drying temperature is 60～80 DEG C, drying time 6～12h.After drying, moisture is less than 0.025% to various raw materials.
In order to realize ABS reclaiming material, toughener and compatilizer fine dispersion in polylactic acid matrix, and improve alignment degree and the homogeneity of diameter in 3D printing silk material cross section, present invention employs first double screw extruder melting mixing, the process of rear Single screw extrusion machine travel wire drawing.Wherein, double screw extruder is disposed as 40～120rpm with the screw speed of single screw extrusion machine, and the heating temperature range of head and each section of machine barrel is 170～220 DEG C.
It is pointed out that in order to avoid ABS reclaiming material and polylactic resin occur thermal-oxidative degradation and hydrolysis during melt blending, it is also possible in composition material, add antioxidant and the hydrolysis inhibitor of 0.2～0.6 part.Wherein, described antioxidant includes Hinered phenols and phosphorous acid esters composite antioxidant, and hydrolysis inhibitor is carbodiimide compound.
The 3D printed material of the present invention have employed ABS reclaiming material, efficiently solve environmental pollution and problem of resource waste that discarded ABS plastic is brought, it is achieved that the recycling of resource, improve the economic worth of regeneration ABS, there is environment and economical effects.
The present invention by ABS reclaiming material and thermoplastic elastomer (TPE) and compatilizer with the use of, improve impact strength and the elongation at break of polylactic acid, and reduce product cost, widened the polylactic acid range of application as 3D printed material.
The present invention uses the preparation method of screw extruder melt blending, and operating process is easy, and technological parameter is easily controllable, and production cost is low, is suitable for popularization and application.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with specific embodiment and comparative example, the preferred embodiment of the invention is described in detail.It is to be understood that, following example are merely to illustrate the present invention, rather than limit the scope of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment that the inventive method, step or condition are made or replacement, belong to the scope of the present invention.
If not specializing, the technological means employed in embodiment is conventional means well known to those skilled in the art.
In following embodiment and comparative example, the weight average molecular weight of polylactic resin is 210,000 g/mol, melt index 7g/10min (2.16kg, 210 DEG C)；ABS reclaiming material be discarded ABS goods pulverize through disintegrating machine, clean, dry after the powder that obtains.Erichsen test performs with reference to GB/T 1040-2006 standard, draw speed 2mm/min；Izod nick break test performs with reference to GB/T 1843-2008 standard.
Embodiment 1.
In terms of mass parts; weigh the polylactic resin 55 parts after being dried 10h in vacuum drying oven at 70 DEG C, 30 parts of ABS reclaiming material, ABS high glue powder (glue content 60%) 10 parts; ABS (the ABS-g-MAH of maleic anhydride grafting; MAH percent grafting 3%) 5 parts; after high speed mixer premixes 6min with the rotating speed of 1000rpm; pre-composition is used double screw extruder melting mixing, and the lines of extrusion, after tank cools down, are obtained composition grain by pelleter pelletizing.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 170,185,195,205,210 DEG C, and head temperature is set as 215 DEG C, and screw speed is 100rpm.
After vacuum dried for the composition grain that obtains, melt extruding with single screw extrusion machine, traction wire drawing is shaped into the 3D of a diameter of 1.75mm and prints silk material.Five sections of heating-up temperatures of extruder cylinder of single screw extruder are respectively set as 175,185,195,200,205 DEG C, and head temperature is set as 210 DEG C, and screw speed is 60rpm.
Above-mentioned 3D printing silk material desktop level 3D printer is printed as the standard batten needed for tensile and impact properties test, and print temperature 220 DEG C, marker's station temperature 60 C, test result is shown in Table 1.
Embodiment 2.
In terms of mass parts; weigh the polylactic resin 45 parts after being dried 12h in vacuum drying oven at 60 DEG C, 35 parts of ABS reclaiming material, SBS 13 parts; SBS (the SBS-g-MAH of maleic anhydride grafting; MAH percent grafting 4%) 7 parts; after high speed mixer premixes 8min with the rotating speed of 800rpm; pre-composition is used double screw extruder melting mixing, and the lines of extrusion, after tank cools down, are obtained composition grain by pelleter pelletizing.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 175,190,200,210,215 DEG C, and head temperature is set as 220 DEG C, and screw speed is 80rpm.
After vacuum dried for the composition grain that obtains, melt extruding with single screw extrusion machine, traction wire drawing is shaped into the 3D of a diameter of 1.75mm and prints silk material.Five sections of heating-up temperatures of extruder cylinder of single screw extruder are respectively set as 180,190,200,205,210 DEG C, and head temperature is set as 215 DEG C, and screw speed is 80rpm.
Above-mentioned 3D printing silk material desktop level 3D printer is printed as the standard batten needed for tensile and impact properties test, and print temperature 230 DEG C, marker's station temperature 70 C, test result is shown in Table 1.
Embodiment 3.
In terms of mass parts; weigh the polylactic resin 65 parts after being dried 8h in vacuum drying oven at 80 DEG C, 25 parts of ABS reclaiming material, SEBS 7 parts; SEBS (the SEBS-g-GMA of glycidyl methacrylate graft; GMA percent grafting 2%) 3 parts; after high speed mixer premixes 10min with the rotating speed of 600rpm; pre-composition is used double screw extruder melting mixing, and the lines of extrusion, after tank cools down, are obtained composition grain by pelleter pelletizing.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 170,180,190,200,205 DEG C, and head temperature is set as 210 DEG C, and screw speed is 60rpm.
After vacuum dried for the composition grain that obtains, melt extruding with single screw extrusion machine, traction wire drawing is shaped into the 3D of a diameter of 1.75mm and prints silk material.Five sections of heating-up temperatures of extruder cylinder of single screw extruder are respectively set as 170,180,190,195,200 DEG C, and head temperature is set as 205 DEG C, and screw speed is 100rpm.
Above-mentioned 3D printing silk material desktop level 3D printer is printed as the standard batten needed for tensile and impact properties test, and print temperature 210 DEG C, marker's station temperature 50 C, test result is shown in Table 1.
Comparative example.
In terms of mass parts; weigh the polylactic resin 65 parts after being dried 10h in vacuum drying oven at 70 DEG C, 35 parts of ABS reclaiming material; after high speed mixer premixes 6min with the rotating speed of 1000rpm; pre-composition is used double screw extruder melting mixing; the lines of extrusion, after tank cools down, are obtained composition grain by pelleter pelletizing.Five sections of heating-up temperatures of double screw extruder machine barrel are respectively set as 170,185,195,205,210 DEG C, and head temperature is set as 215 DEG C, and screw speed is 100rpm.
After vacuum dried for the composition grain that obtains, melt extruding with single screw extrusion machine, traction wire drawing is shaped into the 3D of a diameter of 1.75mm and prints silk material.Five sections of heating-up temperatures of extruder cylinder of single screw extruder are respectively set as 175,185,195,200,205 DEG C, and head temperature is set as 210 DEG C, and screw speed is 60rpm.
With desktop level 3D printer, 3D being printed silk material and be printed as the standard batten needed for tensile and impact properties test, print temperature 220 DEG C, marker's station temperature 60 C, test result is shown in Table 1.
As can be seen from Table 1, after adding toughener and compatilizer in the mixture of polylactic resin and ABS reclaiming material, the hot strength of compositions and Young's modulus have reduction slightly, but elongation at break and impact strength are obtained for and are greatly improved, illustrate that preparation-obtained modified polylactic acid material has excellent comprehensive mechanical property, it is possible to achieve ABS reclaiming material recycling in terms of 3D printed material.
Claims (10)
1. a polydactyl acid 3D printed material based on ABS reclaiming material, is blended the compositions made by the raw materials melt of following weight parts: polylactic resin 40～70 parts, ABS reclaiming material 20～40 parts, toughener 7～13 parts, compatilizer 3～7 parts.
Polydactyl acid 3D printed material the most according to claim 1, is characterized in that described toughener is the one in ABS high glue powder, styrene butadiene styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymers.
Polydactyl acid 3D printed material the most according to claim 1, is characterized in that described compatilizer is the one in the SEBS of maleic anhydride or the SBS of the ABS of glycidyl methacrylate graft, maleic anhydride or glycidyl methacrylate graft, maleic anhydride or glycidyl methacrylate graft.
Polydactyl acid 3D printed material the most according to claim 3, is characterized in that the percent grafting of described maleic anhydride or glycidyl methacrylate is 1～5%.
Polydactyl acid 3D printed material the most according to claim 1, it is characterized in that described ABS reclaiming material be discarded ABS goods pulverize through disintegrating machine, clean, dry after the powder, pellet or the sheet stock that obtain.
6. the preparation method of polydactyl acid 3D printed material described in claim 1, is by polylactic resin, ABS reclaiming material, toughener and compatilizer melt blending pelletize, then the particle fusion extrusion that will obtain, and 3D printed material silk material is made in traction wire drawing.
The preparation method of polydactyl acid 3D printed material the most according to claim 6, remelted blended after it is characterized in that processing various raw material dryings.
The preparation method of polydactyl acid 3D printed material the most according to claim 7, is characterized in that described dried uses vacuum drying, baking temperature 60～80 DEG C, drying time 6～12h.
The preparation method of polydactyl acid 3D printed material the most according to claim 6, is characterized in that adding in the feed antioxidant and the hydrolysis inhibitor of 0.2～0.6 part.
The preparation method of polydactyl acid 3D printed material the most according to claim 9, is characterized in that described antioxidant is Hinered phenols and phosphorous acid esters composite antioxidant, and hydrolysis inhibitor is carbodiimide compound.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735072A (en) * | 2018-12-28 | 2019-05-10 | 青岛科凯达橡塑有限公司 | A kind of biology base rubber and plastic alloy modifying agent and its preparation method and application, asphalt |
| CN115651351A (en) * | 2022-12-29 | 2023-01-31 | 广州市威柏乐器制造有限公司 | ABS composite material for 3D printing of guitar and preparation method thereof |
Citations (3)
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| WO2015108768A1 (en) * | 2014-01-16 | 2015-07-23 | Dow Global Technologies Llc | Support materials for 3d printing |
| CN104945837A (en) * | 2015-07-15 | 2015-09-30 | 上海锦湖日丽塑料有限公司 | ABS/PLA alloy resin combination for 3D printing and preparation method thereof |
| CN105647138A (en) * | 2014-11-30 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Method for preparing high-toughness ABS/PLA based alloy |
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- 2016-07-08 CN CN201610536474.7A patent/CN106009569B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015108768A1 (en) * | 2014-01-16 | 2015-07-23 | Dow Global Technologies Llc | Support materials for 3d printing |
| CN105647138A (en) * | 2014-11-30 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Method for preparing high-toughness ABS/PLA based alloy |
| CN104945837A (en) * | 2015-07-15 | 2015-09-30 | 上海锦湖日丽塑料有限公司 | ABS/PLA alloy resin combination for 3D printing and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735072A (en) * | 2018-12-28 | 2019-05-10 | 青岛科凯达橡塑有限公司 | A kind of biology base rubber and plastic alloy modifying agent and its preparation method and application, asphalt |
| CN115651351A (en) * | 2022-12-29 | 2023-01-31 | 广州市威柏乐器制造有限公司 | ABS composite material for 3D printing of guitar and preparation method thereof |
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