CN106398178A - 3D printing composite material with high rebound resilience and preparation method and application thereof - Google Patents
3D printing composite material with high rebound resilience and preparation method and application thereof Download PDFInfo
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- CN106398178A CN106398178A CN201610802841.3A CN201610802841A CN106398178A CN 106398178 A CN106398178 A CN 106398178A CN 201610802841 A CN201610802841 A CN 201610802841A CN 106398178 A CN106398178 A CN 106398178A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a 3D printing composite material which comprises the following components in percentage by mass: 50-80% of TPU, 20-50% of polyolefin and 0.1-5% of a compatilizer. The 3D printing composite material is applicable to 3D printing consumables and is easy to process and smooth in printing, and a printed product is excellent in mechanical property, stable in size and high in surface gloss degree. The invention further provides a method for preparing the 3D printing composite material and application of the 3D printing composite material.
Description
Technical field
The present invention relates to 3D printing consumptive material, 3D printing composite of more particularly, to a kind of high resilience and preparation method thereof
And application.
Background technology
Existing 3D printing consumptive material substantially can be divided into hard material, soft material, water-soluble material.Hard material is main
There are PLA (PLA), ABS (acrylate/butadiene/styrene terpolymer), nylon618, PC (Merlon), HIPS
(polystyrene), PP (polypropylene) etc.；Soft material mainly has PBAT (polyadipate/butylene terephthalate), TPU (heat
Plastic polyurethane) etc.；Water-soluble material is mainly PVA (polyvinyl alcohol).In place of the equal Shortcomings of above-mentioned various material,
PLA is easy to degraded, material is easily deformed more than 55 DEG C；The common engineering plastics of ABS, buying easily but processes smell weight, deformation
Rate is high.PBAT degradable material, material character is similar to LDPE (low density polyethylene (LDPE)) but price is in 45 yuan/more than Kg, and price is relatively
Height limits its range；TPU hardness range extensively, but extrudes processing difficulties, is common in Shooting Technique.PVA water solubility material
It is few that material is mainly used in printing support material consumption, and process PVA and decompose and easily produce toxic gas.Composite is by two kinds
Or two or more resin alloy new material together, this composite in addition to there is respective resin itself,
Some composites are even also equipped with other advantage, and without the limitation of script material, range is extensive, process operation
Window width.
Although composite species is very abundant but there are no high resilience composite and be suitable as 3D printing consumptive material, make
For the main of 3D printing consumptive material or based on the homogenous materials such as PLA, ABS, nylon618, PVA.Accordingly, it is desirable to provide it is a kind of
New 3D printing composite, be suitable for the requirement of 3D printing, possess have corresponding processing conditions, to have 3D printer universal
Applicability, thus increasing printing consumables description of materials, widening the application of 3D printing technique.
Content of the invention
It is an object of the present invention to provide a kind of 3D printing composite of high resilience, there is good pliability
And high resilience.
Further object is that providing a kind of method preparing this 3D printing composite and its application.
For achieving the above object, the present invention provides a kind of 3D printing composite of high resilience, according to mass fraction meter,
Including TPU50%～80%, polyolefin 20%～50% and compatilizer 0.1%～5%.
It is preferred that described 3D printing composite also includes auxiliary agent, described auxiliary agent includes lubricant, nucleator, dispersant
And at least one in thermal oxidation stabilizer.
It is preferred that described polyolefin is at least one in low density polyethylene (LDPE) and polypropylene.
It is preferred that described compatilizer be maleic anhydride grafting polymer, styrene, acrylonitrile, Glycidyl methacrylate sweet
At least one in grease and styrene-acrylonitrile-glycidyl methacrylate copolymer, wherein, maleic anhydride is grafted
Macromolecule includes at least one in maleic anhydride inoculated polypropylene and maleic anhydride grafted ethene-acetate ethylene copolymer.
It is preferred that described lubricant is Tissuemat E, ethylene bis stearic acid amide, zinc stearate, calcium stearate, erucic acid acyl
In amine at least two.
It is preferred that described nucleator is at least one in PW40 and NAV101.
It is preferred that described dispersant be organic silicone, OPE, at least one in stearic acid.
It is preferred that described thermal oxidation stabilizer is 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester) and 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters) at least one,
Wherein, the structural formula of described 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters)
For：
The structural formula of described 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters) is：
The present invention also provides the method preparing described 3D printing composite, according to mass fraction meter, by TPU50%～
80%th, polyolefin 20%～50% and compatilizer 0.1%～5% carry out mixing, to obtain 3D printing after extruding and pelletizing process multiple
Condensation material.
The 3D printing composite prepared described 3D printing composite or by said method is applied to 3D printer
In.
Compared with prior art, beneficial effects of the present invention have：3D printing composite takes full advantage of the high resilience of TPU
Performance, pliability, compensate for the harder shortcoming of polyolefine material quality, make use of simultaneously polyolefinic stablize processability, make up
The extrusion processing of TPU material is unstable, the shortcoming of material bending resistance difference；This 3D printing composite had both improved existing
The feature that flexible material hardness is low, shrinkage is big, viscosity is poor, also makes 3D printing consumptive material be no longer limited to hard material, especially suitable
With needing the exploitation of highly elastic material business models, the 3D printing composite of the present invention is particularly well-suited to print footwear accessory, beats
Bleeding off is smooth, and printed product handling ease, excellent in mechanical performance, dimensionally stable, surface gloss are high.The 3D printing of the present invention is combined
Add compatilizer in material, improve TPU and polyolefin phase interface bonding strength, increase material compatibility, improve this 3D printing multiple
Condensation material comprehensive mechanical property.
Specific embodiment
The present invention several different most preferred embodiment is described below.
Present invention essence is providing 3D printing composite, the preparation method and applications of a kind of high resilience, and this 3D beats
Print composite has good pliability and high resilience.
According to mass fraction meter, TPU50%～80%, polyolefin 20%～50% and compatilizer 0.1%～5% are entered
3D printing composite is obtained after row mixing, extruding and pelletizing process.Hybrid technique can use high-speed mixer, and extruding pelletization can make
Use double screw extruder.
3D printing composite may also include auxiliary agent, and auxiliary agent is included in lubricant, nucleator, dispersant and thermal oxidation stabilizer
At least one.
Polyolefin is at least one in low density polyethylene (LDPE) and polypropylene.
Compatilizer is maleic anhydride grafting polymer, styrene, acrylonitrile, GMA and benzene second
At least one in alkene-acrylonitrile-methacylate glycidyl ester copolymer, wherein, maleic anhydride grafting polymer includes
At least one in maleic anhydride inoculated polypropylene and maleic anhydride grafted ethene-acetate ethylene copolymer.
Lubricant is Tissuemat E, ethylene bis stearic acid amide, zinc stearate, calcium stearate, in erucyl amide at least
Two kinds.
Nucleator is at least one in PW40 and NAV101.
Dispersant is organic silicone, OPE, at least one in stearic acid.
Thermal oxidation stabilizer is 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters) and 168
At least one in (three [2.4- di-tert-butyl-phenyl] phosphite ester),
Wherein, the structural formula of 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters) is：
The structural formula of 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters) is：
This 3D printing composite or the 3D printing composite prepared by said method can be used as 3D printing consumptive material, borrow
Help 3D printer printed product, printed product can be sport footwear accessory.
Embodiment 1
In terms of mass fraction, each constituent content of the 3D printing composite of the present embodiment is respectively：
TPU content 70.2%, polyethylene (PE 5000S) content 28%, PP-g-MAH content 1%, 1010 (four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) content 0.1%, content of polyethylene wax 0.2%, ethylene is double stearic
Amide content 0.5%
Embodiment 2
In terms of mass fraction, each constituent content of the 3D printing composite of the present embodiment is respectively：
TPU content 65.3%, polyethylene (PE 5000S) content 32.9%, PP-g-MAH content 1%, 1010 (four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) content 0.2%, content of polyethylene wax 0.2%, ethylene is double
Stearmide content 0.4%,
Embodiment 3
In terms of mass fraction, each constituent content of the 3D printing composite of the present embodiment is respectively：
TPU content 60.3%, polyethylene (PE 5000S) content 40%, EVA-g-MAH content 1%, 1010 (four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) content 0.1%, content of polyethylene wax 0.2%, ethylene is double stearic
Amide content 0.4%,
Embodiment 4
In terms of mass fraction, each constituent content of the 3D printing composite of the present embodiment is respectively：
TPU content 55.1%, polyethylene (PE 5000S) content 43%, EVA-g-MAH content 1%, 1010 (four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) content 0.1%, content of polyethylene wax 0.2%, ethylene is double stearic
Amide content 0.5%, OPE 0.1%
The performance of the 3D printing composite of test the various embodiments described above, the performance test results ginseng is shown in Table 1.
Table 1
As can be known from Table 1, the 3D printing composite resilience height of the present invention, excellent in mechanical performance.
Compared with prior art, beneficial effects of the present invention have：3D printing composite takes full advantage of the high resilience of TPU
Performance, pliability, compensate for the harder shortcoming of polyolefine material quality, make use of simultaneously polyolefinic stablize processability, make up
The extrusion processing of TPU material is unstable, the shortcoming of material bending resistance difference；This 3D printing composite had both improved existing
The feature that flexible material hardness is low, shrinkage is big, viscosity is poor, also makes 3D printing consumptive material be no longer limited to hard material, especially suitable
With needing the exploitation of highly elastic material business models, the 3D printing composite of the present invention is particularly well-suited to print footwear accessory, beats
Bleeding off is smooth, and printed product handling ease, excellent in mechanical performance, dimensionally stable, surface gloss are high.The 3D printing composite wood of the present invention
Add compatilizer in material, improve TPU and polyolefin phase interface bonding strength, increase material compatibility, improve this 3D printing and be combined
Material comprehensive mechanical property.
Above disclosed be only presently preferred embodiments of the present invention, certainly the right of the present invention can not be limited with this
Scope, the equivalent variations therefore made according to scope of the present invention patent, still belong to the scope that the present invention is covered.
Claims (10)
1. a kind of 3D printing composite of high resilience is it is characterised in that according to mass fraction meter, including：
TPU 50%～80%；
Polyolefin 20%～50%；And
Compatilizer 0.1%～5%.
2. 3D printing composite as claimed in claim 1 it is characterised in that：Also include auxiliary agent, described auxiliary agent includes lubricating
At least one in agent, nucleator, dispersant and thermal oxidation stabilizer.
3. 3D printing composite as claimed in claim 1 it is characterised in that：Described polyolefin is low density polyethylene (LDPE) and gathers
At least one in propylene.
4. 3D printing composite as claimed in claim 1 it is characterised in that：Described compatilizer is grafted high score for maleic anhydride
Son, styrene, acrylonitrile, GMA and styrene-acrylonitrile-GMA copolymerization
At least one in thing, wherein, maleic anhydride grafting polymer includes maleic anhydride inoculated polypropylene and maleic anhydride grafting second
At least one in alkene-acetate ethylene copolymer.
5. 3D printing composite as claimed in claim 2 it is characterised in that：Described lubricant is Tissuemat E, ethylene is double
In stearic amide, zinc stearate, calcium stearate, erucyl amide at least two.
6. 3D printing composite as claimed in claim 2 it is characterised in that：Described nucleator is in PW40 and NAV101
At least one.
7. 3D printing composite as claimed in claim 2 it is characterised in that：Described dispersant is organic silicone, oxidation is poly-
At least one in ethylene waxes, stearic acid.
8. 3D printing composite as claimed in claim 2 it is characterised in that：Described thermal oxidation stabilizer be 1010 (four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters)
In at least one,
Wherein, the structural formula of described 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters) is：
The structural formula of described 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters) is：
.
9. the method for 3D printing composite as described in any one of claim 1～8 for the preparation is it is characterised in that according to quality
Fraction meter, TPU50%～80%, polyolefin 20%～50% and compatilizer 0.1%～5% is carried out mixing, extruding pelletization
3D printing composite is obtained after technique.
10. by the 3D printing composite described in any one of claim 1～8 or the 3D by the method preparation of claim 9
Printing composite material is applied to 3D printer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610802841.3A CN106398178A (en) | 2016-09-05 | 2016-09-05 | 3D printing composite material with high rebound resilience and preparation method and application thereof |
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| CN201610802841.3A CN106398178A (en) | 2016-09-05 | 2016-09-05 | 3D printing composite material with high rebound resilience and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325528A (en) * | 2017-08-14 | 2017-11-07 | 彭波 | A kind of household intelligent robot |
| CN107603121A (en) * | 2017-09-20 | 2018-01-19 | 福建师范大学 | A kind of ABS3D printing wire rods of resistance to warpage crack resistence and preparation method thereof |
| CN109385002A (en) * | 2017-08-09 | 2019-02-26 | 中国石化扬子石油化工有限公司 | A kind of 3D printing self-lubricating polyethylene composition and preparation method thereof |
| CN110240796A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | Soft consumptive material composition of 3D printing and the preparation method and application thereof |
| CN110452522A (en) * | 2019-08-01 | 2019-11-15 | 无锡市井上海绵有限公司 | A kind of effectively insulating insulating sponge |
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| CN104292850A (en) * | 2014-08-20 | 2015-01-21 | 青岛尤尼科技有限公司 | Three dimensional (3D) printing-based flexible material and preparation method thereof |
| CN104497548A (en) * | 2014-12-08 | 2015-04-08 | 东莞市雄林新材料科技股份有限公司 | TPU material for 3D printer and preparation method of TPU material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109385002A (en) * | 2017-08-09 | 2019-02-26 | 中国石化扬子石油化工有限公司 | A kind of 3D printing self-lubricating polyethylene composition and preparation method thereof |
| CN107325528A (en) * | 2017-08-14 | 2017-11-07 | 彭波 | A kind of household intelligent robot |
| CN107603121A (en) * | 2017-09-20 | 2018-01-19 | 福建师范大学 | A kind of ABS3D printing wire rods of resistance to warpage crack resistence and preparation method thereof |
| CN110240796A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | Soft consumptive material composition of 3D printing and the preparation method and application thereof |
| CN110240796B (en) * | 2018-03-09 | 2021-07-27 | 中国石油化工股份有限公司 | 3D printing soft consumable composition and preparation method and application thereof |
| CN110452522A (en) * | 2019-08-01 | 2019-11-15 | 无锡市井上海绵有限公司 | A kind of effectively insulating insulating sponge |
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Application publication date: 20170215 |
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