CN110157101A - A kind of 3D printing modified poly propylene composition and preparation method thereof - Google Patents
A kind of 3D printing modified poly propylene composition and preparation method thereof Download PDFInfo
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- CN110157101A CN110157101A CN201810145046.0A CN201810145046A CN110157101A CN 110157101 A CN110157101 A CN 110157101A CN 201810145046 A CN201810145046 A CN 201810145046A CN 110157101 A CN110157101 A CN 110157101A
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- modified poly
- poly propylene
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- propylene composition
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Abstract
The invention discloses a kind of 3D printing modified poly propylene compositions and preparation method thereof, are prepared by weight by following components: 75-85 parts of atactic copolymerized polypropenes, 0.1-0.3 portions of nucleating agents, 0.3-0.5 parts, 15-25 parts of AS resins of hyper-dispersant, 0.5-1.5 parts of aluminium powders, 2-5 parts of crosslinking agents, 0.5 part of heat stabilizer.3D printing modified poly propylene composition provided by the invention improves the crystallization temperature and crystalline rate of polypropylene material, improves melt strength, allow the material to faster more stable molding by being added to nucleating agent and crosslinking agent into system.Meanwhile the hyper-dispersant system of metal powder and compounding being added into polypropylene matrix, keep metal powder evenly dispersed in the polymer, make material that there is metal-like, improve the aesthetics of printing product, while further improving the melt strength of polypropene composition.
Description
Technical field
The present invention relates to modified material technical field, specifically a kind of 3D printing modified poly propylene composition and its preparation side
Method.
Background technique
3D printing technique is a kind of using photocuring or the rapid molding device of paper lamination techniques, is beaten by computer quasi-
The object of print is modeled, then by the layer-by-layer subregion of the threedimensional model built up, successively prints material object by printer again later.And
By using different moulding materials, 3D printing technique derives many different forming techniques again, such as fusion sediment formula
(FDM), selective laser sintering (SLS), gypsum 3D printing (PP), layer separated growth (LOM), digital light processing (DLP) etc..
Wherein fusion sediment formula forming method is the most important molding mode of 3D printing thermoplastic product.And FDM technology is to thermoplastic
Property material basic demand be: in processing with certain mobility, and can then be rapidly solidificated into type after formation, together
When have good adhesive effect, the thermoplastic articles that can be applied to FDM moulding process at present include: modified ABS material, modification
Makrolon material, polydactyl acid etc..
Polypropylene material is the reality using extremely wide material in current general-purpose plastics, but applied to FDM moulding process
Example is few, main reason is that its process window is relatively narrow, processing temperature is higher and crystallization temperature is lower, leads to its molding rate
It is slack-off.With popularizing for 3D printing technique, the polymer material for being suitable for traditional molding methods is changed into and can be beaten by 3D
The molding material of print technology, it will there is higher demand and broader development space.
Summary of the invention
The purpose of the present invention is to provide a kind of 3D printing modified poly propylene compositions and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of 3D printing modified poly propylene composition, is prepared by weight by following components:
Further scheme, melt mass flow rate (230 DEG C, 2.16kg) >=8g/ of the atactic copolymerized polypropene
10min, tension fracture elongation rate >=50%, notch impact strength >=75J/m.
The nucleating agent is to methyldibenzylidene sorbierite, aluminum benzoate, bis- (4- p t butylbenzoic acid) hydroxy Als, gathers
One of cyclopentene.
The hyper-dispersant presses matter for one of octadecenyl amine potassium acetate, octadecenic acid glyceride and polysilicon acid N-butyl
Measure the compounding than 1:1.
The aluminium powder is superfine aluminium power.
The crosslinking agent is methyl vinyl diethoxysilane, vinyltriethoxysilane, dual-tert-butyl peroxidating
The mixing of one or both of diisopropylbenzene (DIPB), 1,3- bis- (tert-butyl hydroperoxide), 3,3,5- dimethyl cyclohexane.
The heat stabilizer is four [β-(3,5- di-t-butyl 4- hydroxy phenyl) propionic acid] pentaerythritol esters (1010), β-
The positive octadecyl of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid (1076), three-(2,4- di-tert-butyl-phenyl) phosphite esters
(168), at least three kinds in the double octadecyls (DSTDP) of thio-2 acid.
It is another object of the present invention to provide a kind of preparation methods of 3D printing modified poly propylene composition, will be random
75-85 parts of copolymer polypropylene, 0.1-0.3 parts of nucleating agent, 0.3-0.5 parts of hyper-dispersant, 15-25 parts of AS resin, aluminium powder 0.5-1.5
Part, 2-5 parts of crosslinking agent, 0.5 part of heat stabilizer be added to high mixer high speed mixing 5min, then uniformly mixed material is added
Enter and be kneaded, squeezed out in double screw extruder, obtains 3D printing modified poly propylene composition after cooling.
Further scheme, respectively squeezing out the extrusion temperature in section in the double screw extruder is 160-170 DEG C, 165- respectively
175℃、175-185℃、185-195℃、195-205℃、195-205℃、200-210℃、200-210℃、205-215℃、
210-220℃。
Compared with prior art, beneficial effects of the present invention:
3D printing modified poly propylene composition provided by the invention, by being added to nucleating agent and crosslinking agent into system,
The crystallization temperature and crystalline rate for improving polypropylene material, improve melt strength, allow the material to faster more stable
Molding.Meanwhile the hyper-dispersant system of metal powder and compounding being added into polypropylene matrix, keep metal powder equal in the polymer
Even dispersion makes material have metal-like, improves the aesthetics of printing product, while further improving polypropene composition
Melt strength.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below.
Melt mass flow rate (230 DEG C, 2.16kg) >=8g/10min of atactic copolymerized polypropene in following cases,
Tension fracture elongation rate >=50%, notch impact strength >=75J/m.
Nucleating agent in following cases is to methyldibenzylidene sorbierite, aluminum benzoate, bis- (4- p t butylbenzoic acids)
One of hydroxy Al, polycyclic amylene.
Hyper-dispersant in following cases be one of octadecenyl amine potassium acetate, octadecenic acid glyceride with polysilicon acid just
The butyl ester compounding of 1:1 in mass ratio.
Crosslinking agent in following cases is methyl vinyl diethoxysilane, vinyltriethoxysilane, double tertiary fourths
The mixing of one or both of base cumyl peroxide, 1,3- bis- (tert-butyl hydroperoxide), 3,3,5- dimethyl cyclohexane.
Heat stabilizer in following cases is four [β-(3,5- di-t-butyl 4- hydroxy phenyl) propionic acid] pentaerythritol esters
(1010), in the double octadecyls (DSTDP) of three-(2,4- di-tert-butyl-phenyl) phosphite esters (168), thio-2 acid at least
Three kinds.
Embodiment 1
By 75 parts of atactic copolymerized polypropene, 0.1 part of nucleating agent, 0.3 part of hyper-dispersant, 25 parts of AS resin, 0.5 part of aluminium powder,
2 parts of crosslinking agent, 0.5 part of heat stabilizer be added to high mixer high speed mixing 5min, material that then will be uniformly mixed is added double
It is kneaded, squeezed out in screw extruder, obtain 3D printing modified poly propylene composition after cooling.It is wherein each in double screw extruder
The extrusion temperature for squeezing out section is 170 DEG C, 175 DEG C, 185 DEG C, 195 DEG C, 205 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 215 respectively
℃、220℃。
Properties of product such as table 1.
Embodiment 2
By 80 parts of atactic copolymerized polypropene, 0.2 part of nucleating agent, 0.4 part of hyper-dispersant, 20 parts of AS resin, 1.0 parts of aluminium powder,
3.5 parts of crosslinking agent, 0.5 part of heat stabilizer be added to high mixer high speed mixing 5min, material that then will be uniformly mixed is added
It is kneaded, squeezed out in double screw extruder, obtain 3D printing modified poly propylene composition after cooling.Wherein in double screw extruder
Each extrusion temperature for squeezing out section is 165 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 205 DEG C, 205 DEG C, 210 respectively
℃,215℃.Properties of product such as table 1.
Embodiment 3
By 85 parts of atactic copolymerized polypropene, 0.3 part of nucleating agent, 0.5 part of hyper-dispersant, 15 parts of AS resin, 1.5 parts of aluminium powder,
5 parts of crosslinking agent, 0.5 part of heat stabilizer be added to high mixer high speed mixing 5min, material that then will be uniformly mixed is added double
It is kneaded, squeezed out in screw extruder, obtain 3D printing modified poly propylene composition after cooling.It is wherein each in double screw extruder
The extrusion temperature for squeezing out section is 160 DEG C, 165 DEG C, 175 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 200 DEG C, 200 DEG C, 205 respectively
℃、210℃。
Properties of product such as table 1.
Table 1: the 3D printing modified poly propylene composition performance of embodiment 1-3
Comparative example 1
By 85 parts of atactic copolymerized polypropene, 0.3 part of nucleating agent, 0.5 part of hyper-dispersant, 15 parts of AS resin, heat stabilizer 0.5
Part is added to high mixer high speed mixing 5min, then adds twin-screw extrude uniformly mixed material and is kneaded, is squeezed
Out, final products are obtained after cooling.The extrusion temperature that section is wherein respectively squeezed out in double screw extruder is 160 DEG C, 165 respectively
℃,175℃,185℃,195℃,195℃,200℃,200℃,205℃,210℃.Properties of product such as table 2.
Comparative example 2
By 75 parts of atactic copolymerized polypropene, 0.3 part of hyper-dispersant, 25 parts of AS resin, 0.5 part of aluminium powder, 2 parts of crosslinking agent, heat
0.5 part of stabilizer is added to high mixer high speed mixing 5min, then adds twin-screw extrude uniformly mixed material
It is kneaded, squeezed out, obtain final products after cooling.The extrusion temperature that section is wherein respectively squeezed out in double screw extruder is respectively
170℃,175℃,185℃,195℃,205℃,205℃,210℃,210℃,215℃,220℃.Properties of product such as table 2.
Comparative example 3
By 75 parts of atactic copolymerized polypropene, 0.1 part of nucleating agent, 25 parts of AS resin, 2 parts of crosslinking agent, 0.5 part of heat stabilizer plus
Enter to high mixer high speed and mix 5min, then uniformly mixed material is added twin-screw extrude and is kneaded, squeezed out, it is cold
But final products are obtained afterwards.The extrusion temperature that section is wherein respectively squeezed out in double screw extruder is 170 DEG C, 175 DEG C, 185 respectively
℃,195℃,205℃,205℃,210℃,210℃,215℃,220℃.Properties of product such as table 2.
Table 2: the properties of product of embodiment 1 and comparative example 1-3
From embodiment 1-3 and comparative example 1-3 can be seen that nucleating agent addition so that composition polypropylene crystal phase crystallization
Temperature is promoted, and crosslinking agent and the addition of aluminium powder-hyper-dispersant system are so that the intensity of composition melt significantly improves.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementation cases here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (9)
1. a kind of 3D printing modified poly propylene composition, which is characterized in that be prepared by weight by following components:
75-85 parts of atactic copolymerized polypropene
0.1-0.3 parts of nucleating agent
0.3-0.5 parts of hyper-dispersant
15-25 parts of AS resin
0.5-1.5 parts of aluminium powder
2-5 parts of crosslinking agent
0.5 part of heat stabilizer.
2. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the atactic copolymerized polypropene
Melt mass flow rate (230 DEG C, 2.16kg) >=8g/10min, tension fracture elongation rate >=50%, notch impact strength >=
75J/m。
3. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the nucleating agent is to methyl
One of dibenzyl sorbitol, aluminum benzoate, bis- (4- p t butylbenzoic acid) hydroxy Als, polycyclic amylene.
4. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the hyper-dispersant is 18
One of enamine potassium acetate, octadecenic acid glyceride are compounded with polysilicon acid N-butyl 1:1's in mass ratio.
5. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the aluminium powder is ultra-fine aluminium
Powder.
6. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the crosslinking agent is methyl second
Alkenyl diethoxy silane, vinyltriethoxysilane, dual-tert-butyl cumyl peroxide, 1,3-, bis- (t-butyl peroxy
Change) mixing of one or both of 3,3,5- dimethyl cyclohexanes.
7. 3D printing modified poly propylene composition according to claim 1, which is characterized in that the heat stabilizer is four
[β-(3,5- di-t-butyl 4- hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3,5- di-tert-butyl-hydroxy phenyl)
The double octadecyls of the positive octadecyl of propionic acid (1076), three-(2,4- di-tert-butyl-phenyl) phosphite esters (168), thio-2 acid
(DSTDP) at least three kinds in.
8. such as the preparation method of the described in any item 3D printing modified poly propylene compositions of claim 1-9, which is characterized in that will
75-85 parts of atactic copolymerized polypropene, 0.1-0.3 parts of nucleating agent, 0.3-0.5 parts of hyper-dispersant, 15-25 parts of AS resin, aluminium powder
0.5-1.5 parts, 2-5 parts of crosslinking agent, 0.5 part of heat stabilizer be added to high mixer high speed mixing 5min, then will be uniformly mixed
Material add twin-screw extrude and be kneaded, squeezed out, obtain 3D printing modified poly propylene composition after cooling.
9. the preparation method of 3D printing modified poly propylene composition according to claim 8, which is characterized in that double spiral shells
The extrusion temperature that section is respectively squeezed out in bar extruder is 160-170 DEG C respectively, 165-175 DEG C, 175-185 DEG C, 185-195 DEG C,
195-205℃、195-205℃、200-210℃、200-210℃、205-215℃、210-220℃。
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| CN201810145046.0A CN110157101A (en) | 2018-02-12 | 2018-02-12 | A kind of 3D printing modified poly propylene composition and preparation method thereof |
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| CN201810145046.0A CN110157101A (en) | 2018-02-12 | 2018-02-12 | A kind of 3D printing modified poly propylene composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372647A (en) * | 2021-05-14 | 2021-09-10 | 华南理工大学 | Polypropylene compound with high-precision FDM printing performance and preparation method thereof |
| WO2022043552A1 (en) | 2020-08-31 | 2022-03-03 | SETUP Performance SAS | Powder composition for additive process and printed parts thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022043552A1 (en) | 2020-08-31 | 2022-03-03 | SETUP Performance SAS | Powder composition for additive process and printed parts thereof |
| CN113372647A (en) * | 2021-05-14 | 2021-09-10 | 华南理工大学 | Polypropylene compound with high-precision FDM printing performance and preparation method thereof |
| CN113372647B (en) * | 2021-05-14 | 2022-10-25 | 华南理工大学 | Polypropylene compound with high-precision FDM printing performance and preparation method thereof |
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Application publication date: 20190823 |