CN106633582B - A kind of polypropene composition and preparation method thereof for 3D printing - Google Patents
A kind of polypropene composition and preparation method thereof for 3D printing Download PDFInfo
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Abstract
The present invention provides a kind of polypropene composition for 3D printing, and raw material includes：Graft polypropylene, recycled PET modifying agent, gas phase nano silica and the first antioxidant, which is characterized in that the recycled PET modifying agent is prepared by recycled PET, nanometer calcium carbonate, chain extender and the second antioxidant；And the preparation method of the polypropene composition is provided, including：Recycled PET, nanometer calcium carbonate, chain extender and the second antioxidant are mixed, obtain uniform mixture, through melting, extrusion, cooling, granulation, obtain recycled PET modifying agent by step 1)；Obtained recycled PET modifying agent is mixed with graft polypropylene, gas phase nano silica and the first antioxidant, obtains uniform mixture, through melting, extrusion, cooling, obtains above-mentioned polypropene composition by step 2).The polypropene composition has the characteristics that low shrinking percentage, high-modulus and high intensity, and the raw material particularly suitable as 3D printing uses.
Description
Technical field
The present invention relates to petrochemical industries.More particularly to a kind of for the polypropene composition of 3D printing and its preparation side
Method.
Background technique
3D printing technique is designed a model with Computerized three-dimensional for source, by the way that software hierarchy is discrete and numerical control molding system
System, in the way of laser beam, hot melt nozzle etc. by the special materials such as metal powder, ceramic powders, plastics, cell tissue carry out by
Layer heap product is cohered, and final superposition molding produces physical product.Pass through the machinings sides such as mold, turnning and milling with traditional manufacture
Formula carries out shaping raw material, cuts with final production finished product difference, and 3D solid is become several two-dimensional surfaces by 3D printing,
It is produced by being superimposed to material processing and successively, greatly reduces the complexity of manufacture.
3D printing technique is mainly the following technique, layer separated growth method (LOM), Stereolithography method (SLA), choosing
The laser sintered method of selecting property (SLS), fusion sediment method (FDM), 3 D-printing method (3DP) etc..Wherein, fusion sediment method has system
The features such as aufbauprinciple and easy to operate, maintenance cost is low, system operational safety, is suitble to Design of Office environment, is more able to satisfy
Demand is tested in final products production and the product development of a small amount of multiplicity, therefore is widely applied.
The printing high molecular material of relatively conventional FDM technique has acrylonitrile-butadiene-styrene (ABS) total currently on the market
Two kinds of polymers (ABS) and polylactic acid (PLA).
ABS belongs to the preferable engineering plastics of mechanical property, and high abrasion resistance, good stability of the dimension, toughness is high, is widely applied
In the other 3D printing of technical grade, there is excellent mechanical property, impact strength is fabulous.The disadvantage is that having slight modeling when printing
Peptization solution taste.Certain research report points out that in animal test, the thermal decomposition substance of ABS has been found equal to rat and mouse
With poisonous effect.Be not suitable for the desktop 3D printer of office environment.In addition, ABS material hygroscopicity is big, drying need to be deposited in
Environment or sealed package.
PLA belongs to transparent, translucent 3D printing material, beautiful in colour, can be made into translucent effect.Printing effect is smooth
Exquisiteness, good fluidity.This 3D printing technique equally exists security risk, only opens two printers that polylactic acid is raw material
When, the ultramicro powder in air will increase three times.When 5 machines work at the same time, ultramicro powder increases nearly 15 times.Ultra-fine grain
It can be deposited on lung, and be directly ingested in blood, when concentration is higher, tuberculosis, blood and nervous system may be caused
Disease results even in death.
Therefore, for security reasons, ABS and PLA is not optimal FDM printed material.And polypropylene is as one
The common general-purpose plastics of kind, excellent in mechanical performance, and safety is had both, there is bigger application value than ABS and PLA.
But polypropylene in 3D printing field due to being limited by printing technology, application is not very extensive, reason it
One is in print procedure that crystallization rate is fast since self structure is regular, and shrinking percentage is high, so that the spinline diameter pulled out is uneven
Even, cross section is not round.Spray head can be blocked when coiled material enters 3D printer feed inlet in this way, caused discharging difficult, made to print
Intermittently, it or even cannot complete.In addition, being also easy to the defects of leading to the warpage of printed product or collapsing.
Summary of the invention
In view of above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of poly- third for 3D printing
Ene compositions and preparation method thereof.Using the modifying agent based on recycling polyethylene terephthalate (PET) preparation to poly- third
Alkene graft is modified, and is cooperated with gas phase nano silica and antioxidant, obtained with higher-security and comprehensive
The polypropene composition of energy, especially has the characteristics that low shrinking percentage, high-modulus and high intensity, the original particularly suitable as 3D printing
Material uses.
An embodiment of the invention is, provides a kind of polypropene composition, and raw material includes：It is polypropylene grafted
Object, recycled PET modifying agent, gas phase nano silica and the first antioxidant.
In a preferred embodiment of the invention, by graft polypropylene be 100 mass parts in terms of, the recycling
The content of PET modifier is 10-40 mass parts, preferably 10-30 mass parts；The content of the gas phase nano silica is
10-30 mass parts, preferably 10-25 mass parts；The content of first antioxidant is 0.1-3 mass parts, preferably 0.2-0.6
Mass parts.
In another preferred embodiment of the invention, the graft polypropylene is poly- third that direct polymerization obtains
Alkene graft product, can be selected from maleic anhydride inoculated polypropylene, styrene-grafted polypropylene and maleic anhydride and vinyl acetate
At least one of ester block copolymer graft polypropylene.
According to the present invention, graft polypropylene is compared with polypropylene, due to acid anhydrides isopolarity group, with recycled PET
The compatibility of modifying agent is more preferable, is conducive to the performance of the modifying function of recycled PET modifying agent, is suitable as to advantageously form
The polypropene composition of the raw material of 3D printing.
In another preferred embodiment of the invention, the recycled PET modifying agent is by recycled PET, nano-sized carbon
Sour calcium, chain extender and the second antioxidant are prepared, by recycled PET be 100 mass parts in terms of, the content of the nanometer calcium carbonate is
10-40 mass parts, preferably 10-30 mass parts；The content of second antioxidant is 0.1-3 mass parts, preferably 0.2-0.6
Mass parts.
According to the present invention, in the recycled PET modifying agent, the recycled PET can specifically be enumerated as waste PET beverage
Bottle, waste PET fiber etc..
According to the present invention, in the recycled PET modifying agent, nanometer calcium carbonate can be used as filler and reinforcing agent, improve
The processing performance of product.Also, supporting material of the nanometer calcium carbonate as white, can reduce or eliminate recycled PET to product
Color bring adverse effect (jaundice, obfuscation etc.).By adding nanometer calcium carbonate in the recycled PET modifying agent, make it
It is fully dispersed in polymer melt, it can make that product surface light is gorgeous, elongation is good, tensile strength is high, and lear energy is strong, bending resistance
Song, crack resistance can be good.
According to the present invention, the chain extender is epoxy resin or ethylene-styrene copolymer, when chain extender is epoxy resin
When, be 100 mass parts by recycled PET in terms of, content is 1-10 mass parts, preferably 2-6 mass parts；When chain extender is ethylene-
When styrol copolymer, be 100 mass parts by recycled PET in terms of, content is 0.1-1 mass parts, preferably 0.1-0.6 mass
Part.
According to the present invention, first antioxidant and the second antioxidant independently selected from antioxidant 1010, antioxidant 1076,
At least one of antioxidant 2246, antioxidant CA, irgasfos 168, antioxidant 626, antioxidant 636 and antioxidant 1098, it is excellent
It is selected as the composition of antioxidant 1098 and irgasfos 168.
Polypropylene is better than ABS and PLA as 3D printing material, safety and comprehensive performance.But in print procedure
Since self structure is regular, crystallization rate is fast, and shrinking percentage is high, is easy to happen warpage or collapsing.Inventor it has been investigated that, be added
Above-mentioned recycled PET modifying agent, can reduce the crystallization rate of the polypropene composition, improve the compatibility and mechanical property of each component
Can, to obtain that shrinking percentage is lower, intensity is higher, the good polypropene composition of the uniformity, it is particularly suitable for application as 3D printing
Material.In addition, the waste PET as waste largely generated every year has also obtained resource utilization, therefore have significant
Economic value and social benefit.
In another preferred embodiment of the invention, the gas phase nano silica is to be prepared by vapor phase method
Hydrophilic nano silica.
According to the present invention, gas phase nano silica also has apparent reinforcing effect, is greatly improved the intensity of material
And mechanical performance；And the peptizaiton to the nanometer calcium carbonate for not being recovered PET cladding in recycled PET modifying agent, make its point
It dissipates for smaller particle or primary partical, avoids it from assembling or flocculation, advantageously form the good polypropene composition of the uniformity.
Another embodiment of the invention is to provide the preparation method of above-mentioned polypropene composition, including：
Step 1) mixes recycled PET, nanometer calcium carbonate, chain extender and the second antioxidant, obtains uniform mixture, passes through
Melting squeezes out, is cooling, being granulated, and obtains recycled PET modifying agent；
Step 2) is by obtained recycled PET modifying agent and graft polypropylene, gas phase nano silica and the first antioxygen
Agent mixing, obtains uniform mixture, through melting, extrusion, cooling, obtains above-mentioned polypropene composition.
According to the present invention, above-mentioned steps 1) and the melting extrusion process of step 2) carried out preferably in double screw extruder.
According to the present invention, in the step 1), nanometer calcium carbonate and recycled PET are evenly dispersed in high speed agitator
Afterwards, cause chain extending reaction under the action of chain extender, recycled PET is made to form the thin polymer film of long-chain on nanometer calcium carbonate surface
Layer, constitutes in one kind hard outer soft " core-film " structure, the polymer film layer of outer layer can be improved the PET modifier with
The affinity of graft polypropylene.
In addition, nano-calcium carbonate particles are mostly cube and graininess, and crystal is easy to reunite or connects into chain, in height
Dispersibility in copolymer matrix is deteriorated, and when by external impacts, easily causes boundary defect, composite materials property is caused to reduce,
To reduce its application effect.The partial size of nano particle is smaller, and when especially less than 100nm, this defect performance is more obvious.
By the way that coveredwith nanometer calcium carbonate in the polymer film layer that recycled PET is formed, can avoid drawbacks described above, to be conducive to more
The filling effect of good performance nanometer calcium carbonate and reinforcing effect.
In a preferred embodiment of the invention, can in step 1) and 2) obtained in uniform mixture plus
Enter paraffin oil.Since the state of each component is different, has plenty of powder, have plenty of pellet, besides sheet stock, is added paraffin oil,
The adhesiveness between each component can be increased.
According to the present invention, in step 1), the high-speed stirred revolving speed is 500-3000 revs/min, mixing time 0.5-5
Minute.
In a preferred embodiment of the invention, in step 1), by double screw extruder from first segment to
Five sections of temperature is controlled respectively in 200-250 DEG C, 200-250 DEG C, 230-270 DEG C, 230-270 DEG C and 230-270 DEG C (head temperature
Degree) carry out melting extrusion.
According to the present invention, in step 2), the high-speed stirred revolving speed is 500-3000 revs/min, mixing time 0.5-5
Minute.
In another preferred embodiment of the invention, in step 2), by double screw extruder from first segment to
5th section of temperature is controlled respectively in 200-230 DEG C, 210-235 DEG C, 210-244 DEG C, 200-240 DEG C and 200-240 DEG C (head
Temperature) carry out melting extrusion.
Yet further embodiment of the invention is to provide application of the above-mentioned polypropene composition in 3D printing.
In a preferred embodiment of the invention, the Filamentous consumptive material of the above-mentioned polypropene composition for 3D printing
Diameter be 1.75 ± 0.05mm.
There is no common in the market FDM printed material ABS and PLA for provided polypropene composition according to the present invention
Toxic effect, safety are preferable.Also, utilize the modifying agent pair based on recycling polyethylene terephthalate (PET) preparation
Graft polypropylene is modified, and is cooperated with gas phase nano silica and antioxidant, obtained with higher-security and comprehensive
The polypropene composition for closing performance, especially has the characteristics that low shrinking percentage, high-modulus and high intensity, particularly suitable as 3D printing
Raw material use.In addition, it is the secure sample printed using polypropene composition of the invention, nontoxic, hygienic, also there is part
Degradation property is applicable to the multiple fields such as medical apparatus, toy for children and food container.
Detailed description of the invention
The Filamentous consumptive material of 3 preparation according to embodiments of the present invention is shown in Fig. 1.
The 3D printing product of 8 preparation according to embodiments of the present invention is shown in Fig. 2.
The 3D printing product that according to the present invention prepared by comparative example 4 is shown in Fig. 3.
Specific embodiment
The present invention is described in detail by the following examples, but protection scope of the present invention is not limited to down state
It is bright.
In the examples below, used experimental raw includes：
Maleic anhydride inoculated polypropylene (PP-g-MAH)：350K is raw purchased from Beijing Chemical Research Institute of company of Basel of Saudi Arabia
It produces；
Styrene-grafted polypropylene (PP-g-St)：PS-35 is purchased from BASF；
Maleic anhydride and vinyl acetate ester block copolymer graft polypropylene (PP-g-VAc)：Purchased from Beijing chemical research
Institute；
Nanometer calcium carbonate：Average grain diameter 20nm is purchased from Beijing Deco Dao Jin Science and Technology Ltd.；
Recycled PET：Purchased from Yuyao City Di Tangyigao plastic molding and processing plant；
Hydrophily gas phase nano silica：The production of partial size 4-50nm, AEROSIL company；
Ethylene-styrene copolymerADR-4368-C：BASF AG's production；
Epoxy resin E56：Purchased from Tianjin synthetic material research institute；
Antioxidant 1098, irgasfos 168：The production of German BASF Ciba, the first and second antioxidant as described below by
Antioxidant 1098 and irgasfos 168 are with mass ratio 1:1 mixes.
In the examples below, used experimental facilities includes：
Double screw extruder：TE-34, the production of Nanjing Ke Ya plastics machinery company；
High speed agitator：SHR-100A, Machinery Manufacturing Co., Ltd. of Weida of Zhangjagang City；
Microcomputer controlled electronic universal tester, GMT-6104, Shenzhen City Xinsansi Metering Technology Co., Ltd production；
Injection moulding machine：HTF110X/1J, Ningbo Haitian Plastics Machinery Group Co., Ltd；
3D printer：UP Plus 2, Beijing Tiertime Technology Co., Ltd..
The preparation of recycled PET modifier A-D
According to proportion preparing experiment raw material as shown in Table 1, appropriate paraffin oil is added, at room temperature, with 1500
Rev/min revolving speed be stirred 1 minute after take out, obtain uniform mixture.
Obtained uniform mixture is added in the hopper of double screw extruder, by double screw extruder from first segment to
Five sections of temperature is controlled respectively at 230 DEG C, 235 DEG C, 244 DEG C, 250 DEG C and 255 DEG C (head temperature), and screw speed is 360 turns/
Point.Uniform mixture after melting extrusion, with cooling water at room temperature carry out it is cooling, be granulated to get.
Raw material proportioning (the unit of 1 recycled PET modifier A-D of table：Mass parts)
Embodiment 1-7 and comparative example 1-3
Raw material proportioning (the unit of table 2 embodiment 1-7 and comparative example 1-3：Mass parts)
The raw material of embodiment 1-7 and comparative example 1-3 are added in high speed agitator respectively, at room temperature, with 1300
Rev/min revolving speed be stirred 2 minutes after take out, be uniformly mixed material.
Obtained uniform mixture is added in the hopper of double screw extruder, by double screw extruder from first segment to
Five sections of temperature is controlled respectively at 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 235 DEG C (head temperature), and screw speed is 360 turns/
Point.Uniform mixture after melting extrusion, with 30 DEG C of cooling water cooled down to get.Filamentous consumptive material prepared by embodiment 3
As shown in Figure 1.
Filiform consumptive material made from embodiment 1-7 and comparative example 1-3 is granulated, injection moulding machine is then added and is infused
Modeling (it is 230 DEG C that injection molding machine temperature of each section, which is injection moulding machine temperature of each section, 230 DEG C, 220 DEG C, and 220 DEG C, 210 DEG C, dwell pressure
50MPa, dwell time 60s, cooling time 10s), injected sample is made, and test its performance, test result is shown in Table 3.
Test foundation：Tensile strength is tested by GB/T1040-2006；Simply supported beam notch impact strength presses GB/T
1043-1993 is tested；Bending modulus is tested by GB_T 9341-2000；Shrinking percentage presses GB/T 17037.4-2003
It is tested.
The performance of the injected sample of table 3 embodiment 1-7 and comparative example 1-3
As shown in Table 3, the polypropene composition of 1-7 of the embodiment of the present invention is compared with the graft polypropylene of comparative example 1-3,
Shrinking percentage significantly reduces, and bending modulus significantly improves, i.e., toughness is improved.Also, it is respectively compared and is grafted with same polypropylene
When the polypropene composition of object preparation, the modified sample of recovered PET modifier, the i.e. sample of the embodiment of the present invention are stretched strong
Degree and impact strength are also obviously improved, thus especially suitable for fused glass pellet technique.
Embodiment 8
3D printer nozzle temperature is warming up to 260 DEG C, after 3D printer is stablized, the filiform that embodiment 3 is obtained consumes
Material is put into 3D printer feed inlet, starts to print, and stamp with the size is 2cm × 2cm × 2cm cube, and print thickness is
0.4mm/ layers.The photo of printed product is as shown in Figure 2.
Comparative example 4
Filiform consumptive material made from comparative example 1 is subjected to 3D printing according to operation same as Example 8.The photograph of printed product
Piece is as shown in Figure 3.
It can be seen from Fig. 2 and 3 compared with comparative example 4, the feelings that deform of product that the embodiment of the present invention 3 prints
Condition has had clear improvement, overcome well printing in due to shrinking percentage it is excessively high caused by deformation, collapsing the problems such as, product quality
It is significantly improved.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (15)
1. a kind of polypropene composition for 3D printing, raw material include：Graft polypropylene, recycled PET modifying agent, gas phase
Nano silica and the first antioxidant, the recycled PET modifying agent are by recycled PET, nanometer calcium carbonate, chain extender and second
Antioxidant is prepared.
2. polypropene composition according to claim 1, which is characterized in that by graft polypropylene be 100 mass parts in terms of,
The content of the recycled PET modifying agent is 10-40 mass parts；The content of the gas phase nano silica is 10-30 mass parts；
The content of first antioxidant is 0.1-3 mass parts.
3. polypropene composition according to claim 2, which is characterized in that by graft polypropylene be 100 mass parts in terms of,
The content of the recycled PET modifying agent is 10-30 mass parts；The content of the gas phase nano silica is 10-25 mass parts；
The content of first antioxidant is 0.2-0.6 mass parts.
4. polypropene composition according to any one of claim 1-3, which is characterized in that with recycled PET for 100 mass
Part meter, the content of the nanometer calcium carbonate are 10-40 mass parts；The content of second antioxidant is 0.1-3 mass parts.
5. polypropene composition according to claim 4, which is characterized in that by recycled PET be 100 mass parts in terms of, it is described
The content of nanometer calcium carbonate is 10-30 mass parts；The content of second antioxidant is 0.2-0.6 mass parts.
6. polypropene composition according to any one of claim 1-3, which is characterized in that the chain extender is asphalt mixtures modified by epoxy resin
Rouge, by recycled PET be 100 mass parts in terms of, content be 1-10 mass parts.
7. polypropene composition according to claim 6, which is characterized in that the chain extender is epoxy resin, with recycling
PET is 100 mass parts meters, and content is 2-6 mass parts.
8. polypropene composition according to any one of claim 1-3, which is characterized in that the chain extender is ethylene-
Styrol copolymer, by recycled PET be 100 mass parts in terms of, content be 0.1-1 mass parts.
9. polypropene composition according to claim 8, which is characterized in that the chain extender is ethylene-stryene copolymerization
Object, by recycled PET be 100 mass parts in terms of, content be 0.1-0.6 mass parts.
10. polypropene composition according to any one of claim 1-3, which is characterized in that the graft polypropylene
It is grafted selected from maleic anhydride inoculated polypropylene, styrene-grafted polypropylene and maleic anhydride and vinyl acetate ester block copolymer
At least one of polypropylene.
11. polypropene composition according to any one of claim 1-3, which is characterized in that the gas phase nano dioxy
SiClx is the hydrophilic nano silica prepared by vapor phase method.
12. polypropene composition according to any one of claim 1-3, which is characterized in that first antioxidant and
Second antioxidant is independently selected from antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, irgasfos 168, antioxygen
At least one of agent 626, antioxidant 636 and antioxidant 1098.
13. polypropene composition according to claim 12, which is characterized in that first antioxidant and the second antioxidant
For the composition of antioxidant 1098 and irgasfos 168.
14. a kind of preparation method of polypropene composition of any of claims 1-13, including：
Recycled PET, nanometer calcium carbonate, chain extender and the second antioxidant are mixed, obtain uniform mixture by step 1), through molten
Melt, squeeze out, cool down, be granulated, obtains recycled PET modifying agent；
Step 2) mixes obtained recycled PET modifying agent and graft polypropylene, gas phase nano silica and the first antioxidant
It closes, obtains uniform mixture, through melting, extrusion, cooling, obtain above-mentioned polypropene composition.
15. a kind of application of polypropene composition of any of claims 1-13 in 3D printing.
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| CN111393809A (en) * | 2020-04-14 | 2020-07-10 | 苏州大学 | 3D printing material and preparation method thereof |
| CN113004622A (en) * | 2020-12-22 | 2021-06-22 | 江苏集萃先进高分子材料研究所有限公司 | Polypropylene powder for selective laser sintering 3D printing and preparation method thereof |
| CN112670879B (en) * | 2020-12-28 | 2023-12-08 | 国网河南省电力公司超高压公司 | SF6 gas plugging process for high-voltage combined electrical apparatus |
| CN114734054B (en) * | 2022-03-30 | 2023-09-12 | 芯体素(杭州)科技发展有限公司 | Embedded substrate and 3D printing method based on substrate |
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| CN102977453A (en) * | 2012-11-14 | 2013-03-20 | 江苏森帝塑业有限公司 | Waste polypropylene and polyethylene glycol terephthalate composite used for weight packaging woven bag and ribbon-like filament preparation method thereof |
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