CN103980590A - Toughened high density polyethylene 3D printing moulding material and preparation method thereof - Google Patents
Toughened high density polyethylene 3D printing moulding material and preparation method thereof Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The invention relates to a toughened high density polyethylene which includes high density polyethylene and a toughening master batch. The toughening master batch is prepared from an ethylene-propylene elastomer, butylbenzene elastomer, a diluent, an anti-crosslinking agent and a free radical polymerization initiator. The invention also relates to a preparation method of the toughened high density polyethylene, the toughening master batch, a preparation method of the toughening master batch, an application of the toughening master batch in the toughened high density polyethylene, an application of the toughened high density polyethylene in 3D printing and a 3D printing method. High density polyethylene is toughened with the self-made synthesized toughening master batch. The toughened high density polyethylene is good in heat resistance, has high rigidity and toughness, and is also good in environment stress cracking resistance. An obtained blend, which is formed by blending the toughened high density polyethylene with elastomers, has not only original characteristics but also a relative high rigidity conservation rate when toughness of the obtained blend is significantly increased, so that the blend is suitable for 3D printing.
Description
Technical field
The present invention relates to a kind of 3D printing shaping material, be specifically related to a kind of toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material and preparation method thereof.
Background technology
3D printing technique (Three Dimensions Printing, three-dimensional printing technology, 3DP), lamination manufacture (Additive Manufacturing, AM) a kind of form of technology, it is that one designs a model as source taking Computerized three-dimensional, discrete and the numerical control molding system by software hierarchy, utilize the mode such as laser beam, hot melt nozzle that the exotic materialss such as metal-powder, ceramic powder, plastics, cell tissue are successively piled up to bonding, final stack moulding, produces entity products.Lamination manufacturing technology is the earliest by ASTM International Standards Organization (predecessor is U.S.'s test and materials association) stdn.Lamination manufacturing technology has 3 kinds of different terms: stereolithography (Stereolithography), and 3-D stacks manufacture (3-D layering) and 3D print; Wherein 3D prints becomes the most frequently used term gradually due to the most applicable description lamination manufacturing technology and products thereof.
3D printing technique came out in the U.S. first in 1986, and was paid close attention to gradually the nineties in 20th century.Enter after 21 century, 3D printing technique obtains rapidly widespread use.3D printing technique obtains very large development in industries such as automobile, medical treatment, commercial and industrial equipment, education, building and the consumer's goods.3D printing technique has been realized the leap from orthographic plan to entity, and a series of digital applications technology taking it as representative are even known as the Industrial Revolution for the third time.But 3D printing technique faces at present the most serious problem and challenge are that 3D printing shaping material is very rare.Current 3D printing shaping material is mainly the thermoplastic materials such as nylon, polyethylene terephthalate, polybutylene terephthalate and ABS (acrylonitrile-butadiene-styrene (ABS)).These materials not only hardness are higher, and the parts that print are more crisp frangible, and high to printing conditional request, and usually cannot be by small structure high-resolution ground printing shaping.
High density polyethylene(HDPE) (HDPE) has good thermotolerance and winter hardiness, chemical stability is good, also there is higher rigidity and toughness, physical strength is good, barrier property, dielectric properties and environmental stress crack resistance are also better, are widely used in the fields such as blow-molded article, film and board product, injection-molded item, tubing goods, fiber, electric wire.As the current the third-largest general purpose material of usage quantity in the world, HDPE is a kind of synthesized polymer material that concerns national economy.But because its homopolymer shock strength is low, be difficult to meet the demand of some engineering fields to performance.In order to improve the using value of HDPE, expand its Application Areas, it is carried out to toughening modifying so that this large kind general purpose material is used as engineering materials, be one of focus of domestic and international polymer material science and engineering research always.Both at home and abroad HDPE is carried out to the research work of toughening modifying a lot.Can but make, how to make, toughness significantly improves and the higher elastomerics toughness HDPE of while rigidity conservation rate, has important scientific and technical meaning and application prospect.In the time that 3D prints, conventional high density polyethylene(HDPE) exists easily aging, and easily embrittlement shortcoming, is therefore difficult to meet the demand of some association areas to its correlated performance.
CN1433443A relates to a kind of method that embeds the complex body of nanofiber in polymeric matrix that is formed on, the method is included in sneaks into nanofiber to form coacervate in plastic substrate, and by diplomatic corps's aggressiveness under hydrodynamic force stress and the nanofiber that distributes equably; Described hydrodynamic force stress splits off described coacervate, flows and can be used to realize minor diameter and arrangement in conjunction with carrying out extra extension.Gained complex body can deposit with consolidation (FDM) moulding, and the polymkeric substance wherein a volume nanofiber being strengthened is as the wire raw material of FDM technique.In this process, nanofiber complex line (diameter is about 2 millimeters) is extruded through the die head of mm size, produces complex line in a row and makes sheet material and 3D parts.In this patent, raw material used is the polymkeric substance wire rod that nanofiber strengthens.Its shortcoming is: the FDM of nanofiber complex line is very complicated, is difficult for processing.
CN1812878A relates to a kind of powder of the 3D of being suitable for printing, this powder comprises the blend of thermoplastic granulates thing and adhesive particle thing, wherein said thermoplastic granulates thing is optional from polyolefine, and adhesive particle thing is only suitable in the time that fluid activates this adhesive particle thing, adhesion heat plastic particle thing.The powder of this patent, in the time printing for 3D, need to use solvent as fluid, and must on the layer having printed, apply at least one in UV-light, visible ray, heat and electron beam, induces non-aqueous fluid to solidify.Therefore, the 3D printing system of CN1812878A is liquid composition, and its shortcoming is to need to use in many cases to the mankind and harmful solvent or the dispersion agent of environment, and complicated operation, is difficult for dispersed or dissolves.
CN102093646A relates to a kind of material of printing rapid shaping for 3D and preparation method thereof, rapid prototyping material comprises modified powder materials A and binding agent B, wherein: the preparation of modified powder materials A: powdered material and the first solvent are joined to ball mill or grinding machine for grinding, obtain powdered material pre-treatment material; By tensio-active agent, lubricant, organic resin successively joins in the second solvent, and dispersed with stirring 2-3h, obtains modification liquid; Powdered material pre-treatment material is mixed with modification liquid, put into shredder, normal temperature mixed grinding, dry, grind, obtain modified powder materials A; When use, 1 part of modified powder materials A and 0.01-0.07 part binding agent B adapted.This patent 3D formed body used is solution system, and its shortcoming is to be not easy to dispersed, the special bonding degree that must note material, and need to grind and modification to material complicated operation.
US2004/0232583A1 relates to a kind of method of manufacturing three-dimensional body, and it comprises: a powdered substrate layer a) is provided; B) on one or more regions of described base material, selectivity applies at least one microwave absorbing first sensitive materials; C) with layer described in microwave radiation processing at least one times.Wherein loosely mention and can use the polymkeric substance that is selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, PMMI, PMMA, ionomer, polymeric amide, copolyesters, copolyamide, terpolymer, ABS or its mixture.US2004/0232583A1 does not mention polyethylene is carried out to modification, so that it is suitable for 3D printing.
Summary of the invention
The object of the invention is to overcome above-mentioned prior art shortcoming, a kind of toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material is provided, the solid material cohesive strength and the firmness that print with it are higher, and snappiness is good.
Described object realizes by a kind of toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, and it comprises: high density polyethylene(HDPE) and toughened master batch.
Described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping materials'use high density polyethylene(HDPE) is as matrix.The commercially available acquisition of described high density polyethylene(HDPE), for example 2200J type or 5000S type.
Described toughened master batch is by making Ethylene-propylene Elastomer and/or butadiene-styrene elastomer, thinner, and resistance linking agent and radical polymerization initiator react and prepare.
The commercially available acquisition of described Ethylene-propylene Elastomer and butadiene-styrene elastomer.
Described thinner can be xylene solvent.
Described resistance linking agent can be dimethyl sulfoxide (DMSO) (DMSO).
Described radical polymerization initiator can be dibenzoyl peroxide (BPO).
Described toughened master batch can be prepared by the following method: Ethylene-propylene Elastomer, butadiene-styrene elastomer, xylene solvent, resistance linking agent and initiator are reacted in reactor at 120-130 DEG C and prepare.Preferably, described method comprises: thus Ethylene-propylene Elastomer, butadiene-styrene elastomer, xylene solvent and resistance linking agent are mixed and make mixture, initiator is dissolved in xylene solvent to obtain initiator solution, described initiator solution is slowly dropped in described mixture, reaction at 120-130 DEG C, reaction finishes rear separation and removes xylene solvent, washing, dry, makes toughened master batch.
The consumption of the Ethylene-propylene Elastomer in described toughened master batch can be 0-200 weight part, is preferably 0-100 weight part, more preferably 20-80 weight part; The consumption of the butadiene-styrene elastomer in described toughened master batch can be 0-200 weight part, is preferably 0-100 weight part, more preferably 20-80 weight part; Wherein the consumption sum of Ethylene-propylene Elastomer and butadiene-styrene elastomer is at least 10 weight parts, is preferably at least 20 weight parts, more preferably at least 30 weight parts, also preferred at least 40 weight parts.
The consumption of the thinner in described toughened master batch can be 500-2000 weight part, is preferably 800-1500 weight part, more preferably 1000-1200 weight part.
The consumption of the resistance linking agent in described toughened master batch can be 0-10 weight part, is preferably 1-5 weight part, more preferably 3-4 weight part.
The consumption of the initiator in described toughened master batch can be 0.1-0.5 weight part, is preferably 0.2-0.4 weight part, more preferably 0.25 weight part.
Described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material comprises 40-80 weight part, preferably 52-80 weight part, the more preferably high density polyethylene(HDPE) of 52-64 weight part.
Described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material comprises 20-60 weight part, preferably 20-48 weight part, the more preferably toughened master batch of 36-48 weight part.
In preferred embodiments, described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material comprises carbon nanotube, and this makes described bill of material reveal better hardness, elasticity, fatigue resistance and better processibility.Described carbon nanotube can be various carbon nanotubes, for example Single Walled Carbon Nanotube, multi-walled carbon nano-tubes.
In another preferred embodiment, described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material can further comprise oxidation inhibitor.Described oxidation inhibitor can be for example three [2.4-di-tert-butyl-phenyl] phosphorous acid ester; Or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Or (N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine) and phosphite ester kind antioxidant interworking thing etc.
Carbon nanotube consumption in described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material can be 0-30 weight part, is preferably 10-20 weight part, more preferably 15 weight parts.
Oxidation inhibitor consumption in described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material can be 0-0.5 weight part, is preferably 0.1-0.3 weight part, more preferably 0.2 weight part.
Certainly, described toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material also can comprise optional auxiliary agent, as rheology control agent, fire retardant, filler, pigment etc.
In the present invention, except as otherwise noted, otherwise all " part " all refers to weight part.
The method that the invention still further relates to the toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material of a kind of the present invention of preparation, it comprises:
1) thus by Ethylene-propylene Elastomer, butadiene-styrene elastomer, dimethylbenzene mix with resistance linking agent obtain mixture, initiator is dissolved in dimethylbenzene to obtain initiator solution, described initiator solution is dropped in described mixture, react to make toughened master batch;
2) by described toughened master batch and high density polyethylene(HDPE) extruding pelletization.
Step 1) in temperature of reaction be 120-130 DEG C; Reaction times can be 10 minutes to 12 hours, is preferably 30 minutes to 10 hours, more preferably 1-8 hour, and more preferably 2-6 hour, for example, be 3-5 hour.
Step 2) in extruding pelletization can in single screw extrusion machine or twin screw extruder, carry out, preferably in twin screw extruder, carry out.In the situation that using twin screw extruder, be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
In another aspect of this invention, the present invention relates to the purposes of toughness reinforcing high density polyethylene(HDPE) of the present invention in 3D prints.
In still another aspect of the invention, the present invention relates to a kind of 3D Method of printing, it is characterized in that using toughness reinforcing high density polyethylene(HDPE) of the present invention.
The outstanding feature of the present invention is:
L. adopt the toughened master batch of the synthetic different ingredients of self-control and high density polyethylene(HDPE), carbon nanotube, oxidation inhibitor blend, prepared the elastomeric blend containing different mass mark.High density polyethylene(HDPE) possesses good thermotolerance, also has higher rigidity and toughness, and environmental stress cracking resistance is also relatively good.With elastomer blended after, the blend obtaining not only has original characteristic, and when toughness increases substantially, rigidity conservation rate is also higher, thus be suitable for 3D print.
2. production cost of the present invention is low, and production process is simple.
Embodiment
By specific embodiment, the present invention is described in further detail below, but this should be interpreted as to scope of the present invention is limited to following embodiment.In the situation that not departing from aforesaid method thought of the present invention, various replacements or the change made according to ordinary skill knowledge and customary means, all should be within the scope of the present invention.
In the context of the invention, except as otherwise noted, otherwise all umbers and percentage ratio are all based on weight.
2200J type high density polyethylene(HDPE) used in embodiment is available from PetroChina Company Limited.'s Daqing petrochemical company, and molecular weight is 40000～300000.
5000S type high density polyethylene(HDPE) used in embodiment is available from PetroChina Company Limited.'s Daqing petrochemical company, and molecular weight is 400,000 to 600,000.
Ethylene-propylene Elastomer used in embodiment is available from Jilin Petrochemical company, and commodity are called EPDM2070, and weight-average molecular weight is 200,000 to 400,000.
Butadiene-styrene elastomer used in embodiment is available from Ba Ling petrochemical complex responsibility company limited, and commodity are called YH-815, and weight-average molecular weight is 200,000 to 300,000.
Other products are commercially available.
Embodiment 1
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
Described masterbatch is by 100 parts of Ethylene-propylene Elastomers, 1000 parts of dimethylbenzene thinners, 0.25 part of BPO and 4.0 parts of DMSO are added agitator is housed, reflux condensing tube, and in the reactor of thermometer, stirring heating is warming up to 125 DEG C, reacts 3 hours, makes toughened master batch.By the 2200J type high density polyethylene(HDPE) of 68 parts, antioxidant three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 10 parts and 0.2 part mixes with the toughened master batch of 32 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
Embodiment 2
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
80 parts of Ethylene-propylene Elastomers, 20 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO, 4.0 parts of DMSO are added agitator is housed, reflux condensing tube, in the reactor of thermometer, stirring heating is warming up to 125 DEG C, reacts 3 hours, makes toughened master batch.By the 2200J type high density polyethylene(HDPE) of 64 parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 20 parts and 0.2 part mixes with the toughened master batch of 36 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
Embodiment 3
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
60 parts of Ethylene-propylene Elastomers, 40 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO and 4.0 parts of DMSO are added in the reactor that agitator, reflux condensing tube and thermometer are housed, stirring heating is warming up to 125 DEG C, the toughened master batch that reaction makes under this formula for 3 hours.By the 2200J type high density polyethylene(HDPE) of 60 parts, antioxidant three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 15 parts and 0.1 part mixes with the toughened master batch of 40 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.Embodiment 4
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
40 parts of Ethylene-propylene Elastomers, 60 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO and 4.0 parts of DMSO are added in the reactor that agitator, reflux condensing tube and thermometer are housed, stirring heating is warming up to 125 DEG C, react 3 hours, make the toughened master batch under this formula.By the 2200J type high density polyethylene(HDPE) of 56 parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 15 parts and 0.2 part mixes with the toughened master batch of 44 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
Embodiment 5
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
20 parts of Ethylene-propylene Elastomers, 80 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO and 4.0 parts of DMSO are added in the reactor that agitator, reflux condensing tube and thermometer are housed, stirring heating is warming up to 125 DEG C, react 3 hours, make the toughened master batch under this formula.By the 2200J type high density polyethylene(HDPE) of 52 parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 15 parts and 0.2 part mixes with the toughened master batch of 48 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
Embodiment 6
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
By 100 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO and 4.0 parts of DMSO add in the reactor that agitator, reflux condensing tube and thermometer are housed, and stirring heating is warming up to 125 DEG C, reacts 3 hours, makes the toughened master batch under this formula.By the 2200J type high density polyethylene(HDPE) of 68 parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 15 parts and 0.2 part mixes with the toughened master batch of 32 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
Embodiment 7
A toughness reinforcing high density polyethylene(HDPE) 3D printing shaping material, its formula is as follows:
By 100 parts of butadiene-styrene elastomers, 1000 parts of xylene solvents, 0.25 part of BPO and 4.0 parts of DMSO add in the reactor that agitator, reflux condensing tube and thermometer are housed, and stirring heating is warming up to 125 DEG C, reacts 3 hours, makes the toughened master batch under this formula.By the 2200J type high density polyethylene(HDPE) of 56 parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of the carbon nanotube of 15 parts and 0.2 part mixes with the toughened master batch of 44 parts, and extruding pelletization on twin screw extruder, prepares blend.Be followed successively by 130,135,155,165,185,180 DEG C from feeding section to machine head port mould temperature; Driving screw rotating speed is 90r/min.
The toughened HDPE performance test results of preparing in above-mentioned each example is as shown in table 1:
Table 1
| ? | Melt flow rate (MFR) | Shock strength | Tensile yield | The elasticity of flexure |
| ? | /g·(10min) -1 | /kJ·m -2 | Stress/Mpa | Modulus/Mpa |
| 2200J?HDPE | 5.40 | 4.40 | 30.58 | 1290.1 |
| Embodiment 1 | 2.70 | 19.94 | 27.61 | 1012.1 |
| Embodiment 2 | 2.77 | 25.68 | 27.43 | 999.7 |
| Embodiment 3 | 3.10 | 21.92 | 27.48 | 1006.5 |
| Embodiment 4 | 3.17 | 28.12 | 27.36 | 996.3 |
| Embodiment 5 | 3.40 | 25.12 | 27.34 | 1000.9 |
| Embodiment 6 | 3.43 | 21.87 | 26.72 | 926.6 |
| Embodiment 7 | 2.78 | 37.17 | 27.02 | 873.4 |
Melt flow rate (MFR) is pressed GB/T3682-2000 test; Stretching yield stress is pressed GB/T1042-1992 test, and draw speed is 100mm/min; Bending elastic modulus is pressed GB/T9341-2008 test, and speed is 2mm/min; Socle girder notched Izod impact strength is pressed GB/T1843-2008 test.
From the performance test results of table 3, by the high-density polyethylene material of toughening modifying, when toughness increases substantially, rigidity conservation rate is higher.The toughened HDPE material of being produced by the technology of the present invention can be used as the shaping raw material of 3D printing technique completely, can produce plastic components and the high precision part of various types of light weight high-ductilities on 3D printer, has very high technology application prospect.
Claims (10)
1. a toughened HDPE, it comprises: high density polyethylene(HDPE) and toughened master batch.
2. according to the toughened HDPE of claim 1, it is characterized in that described toughened master batch is by making Ethylene-propylene Elastomer and/or butadiene-styrene elastomer, thinner, resistance linking agent and radical polymerization initiator react and prepare at 120-130 DEG C.
Preferably, described thinner can be dimethylbenzene; Described resistance linking agent is dimethyl sulfoxide (DMSO).
3. according to the toughened HDPE of any one in claim 1-2, it also comprises carbon nanotube.
Preferably, the amount of carbon nanotube is 0-30 weight part, is preferably 10-20 weight part, more preferably 15 weight parts.
4. according to the toughened HDPE of any one in claim 1-3, the consumption that it is characterized in that high density polyethylene(HDPE) is 40-80 weight part, preferably 52-80 weight part, more preferably 52-64 weight part.
Preferably, the consumption of toughened master batch is 20-60 weight part, preferably 20-48 weight part, more preferably 36-48 weight part.
5. prepare according to a toughened HDPE method for any one in claim 1-4, comprise each component extruding pelletization.
6. a toughened master batch, it is by Ethylene-propylene Elastomer, butadiene-styrene elastomer, thinner, and resistance linking agent and radical polymerization initiator are made.
7. prepare according to a method for the toughened master batch of claim 6, it comprises and is incorporated in reaction at 120-130 DEG C by mixed to Ethylene-propylene Elastomer and/or butadiene-styrene elastomer, xylene solvent, initiator and resistance linking agent.
8. the toughened master batch according to Claim 8 purposes in toughened HDPE.
9. the purposes in 3D prints according to the toughened HDPE of any one in claim 1-4.
10. a 3D Method of printing, is characterized in that using according to the toughened HDPE of any one in claim 1-4 the purposes in 3D prints.
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