CN106146966A - A kind of transparency polyolefin composite for melted extrusion modeling and preparation method thereof - Google Patents
A kind of transparency polyolefin composite for melted extrusion modeling and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of composite polyolefine material for melted extrusion modeling and preparation method thereof, it is blended by polyolefin 100 parts, transparent powder 5～45 parts, coupling agent 1～5 parts, antioxidant 0.5～5 parts, heat stabilizer 0.5～5 parts and lubricant 0.5～5 parts, extruding is prepared from.Composite prepared by the present invention has when melted extrusion modeling that shaping speed is fast, hardness big and bending strength high, maintains the transparency of product well simultaneously；In addition the composite material preparation process that the present invention relates to is simple, can directly apply and be extended to melted extrusion modeling field and prepare transparent products.
Description
Technical field
The present invention relates to technical field of macromolecules, be specifically related to a kind of transparency polyolefin composite for melted extrusion modeling and preparation method thereof.
Background technology
Melted extrusion modeling technology, is a kind of with filamentary material as raw material, uses and add the rapid shaping technique that the mode of heat fusing forms the material into.Melted extrusion modeling technology controls heating shower nozzle with computer, moves in horizontal plane according to product cross section structure, and by the heating of thermoplasticity filamentary material and melted, extruding and coat on the table, material is cooled to a thin layer of product.Subsequently by the adjustment of bench height, thin layer is gradually piled up for three dimensional articles.This technical matters is simple, easy to operate, it is adaptable to the modeling work at product design initial stage and partial function test.The thermoplastic being usually used in melted extrusion modeling technology mostly is virgin resin matrix, therefore has that shaping speed is slow, product hardness is low and the deficiency such as poor mechanical property, has some limitations in terms of the making of large volume product or structural member.
Summary of the invention
The deficiency such as the shaping speed that it is an object of the invention to improve melted extrusion modeling technology common used material is slow, hardness is low and mechanical strength is poor, provide the composite of a kind of transparent polyolefin resin for melted extrusion modeling modified by transparent powder, modified composite improves a lot at aspects such as becoming line speed, hardness and mechanical strength, preferably maintains the transparency of product simultaneously.
For achieving the above object, the present invention is by the following technical solutions:
A kind of composite polyolefine material for melted extrusion modeling, is prepared from by weight by following components:
Polyolefin 100 parts,
Transparent powder 5～45 parts,
Coupling agent 1～5 parts,
Antioxidant 0.5～5 parts,
Heat stabilizer 0.5～5 parts,
Lubricant 0.5～5 parts.
Further, described resin matrix is preferably polyethylene (PE) and COPP (PP).
The size of described transparent powder is 5-50 μm.
Transparent powder is a kind of nonmetallic mineral, uses high-quality natural crystal raw material to make through special processing, and its Main Ingredients and Appearance is silicon dioxide and magnesium oxide.Its transparency is high, and whiteness is good, refraction 1.54, density 2.3, and oil suction 25 is nonpoisonous and tasteless, acidproof durable corrosion.There is high transparent: the index of refraction of the index of refraction of inserts itself and most synthetic resin closely, so the amount of filling out of filler does not affect the transparency of finished product；The surface smoothness of product and wear-resisting scratch resistance can be improved；Low oil absorption ferric: loading is big, advantageously reduces the manufacturing cost of product.
Described coupling agent is gamma-aminopropyl-triethoxy-silane or γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.
Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphite esters.
Described heat stabilizer is calcium stearate or barium stearate.
Described lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
Another goal of the invention of the present invention is to provide the preparation method of the above-mentioned composite polyolefine material for melted extrusion modeling, comprises the steps of
(1) by being equipped with than by polyolefin 100 parts, transparent powder 5～45 parts, coupling agent 1～5 parts, antioxidant 0.5～5 parts, heat stabilizer 0.5～5 parts and lubricant 0.5～5 parts, it is placed in high-speed mixer and disperses 10～30 minutes；
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C～180 DEG C, 180 DEG C～190 DEG C, 190 DEG C～200 DEG C, 210 DEG C～220 DEG C, 220 DEG C～230 DEG C, 220 DEG C～230 DEG C and 225 DEG C～235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
Beneficial effects of the present invention has:
1, the present invention selects vistanex to be raw material, and it is material modified for using the transparent powder that the transparency is high and fillibility is good innovatively, is prepared for a kind of composite polyolefine material for melted extrusion modeling.The composite polyolefine material present invention prepared is shaped to required product through melt extrusion processes, for this composite relatively virgin resin material, has that shaping speed is fast, hardness big and bending strength high in melt extrusion processes.
2, the transparent powder that the present invention uses is a kind of based on silicon dioxide with the mineral dust of magnesium oxide, has that hardness is high, easily disperses and stronger chemical stability, has high transparent simultaneously.Due to its index of refraction and vistanex index of refraction closely, so it uses how many all without the transparency affecting composite.So the product that this composite is made has the good transparency, can directly apply and be extended to melted extrusion modeling field and prepare transparent products.
Specific implementation method
Below in conjunction with instantiation, present invention is further detailed; but described embodiment is not the simple restriction to true spirit, any all should belong to scope of the present invention based on the simple change done by true spirit or equivalent within.
The specific embodiment of the present invention is as follows:
Embodiment 1
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Transparent powder 5 parts,
Coupling agent gamma-aminopropyl-triethoxy-silane 1 part,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.2 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.3 part,
Heat stabilizer calcium stearate 0.5 part,
Lubricant ethylidine bis-stearamides 0.5 part,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 2
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Transparent powder 15 parts,
Coupling agent gamma-aminopropyl-triethoxy-silane 2 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.6 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1 part,
Heat stabilizer calcium stearate 2 parts,
Lubricant ethylidine bis-stearamides 2 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 3
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Transparent powder 25 parts,
Coupling agent gamma-aminopropyl-triethoxy-silane 3 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 1.2 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1.8 parts,
Heat stabilizer calcium stearate 3 parts,
Lubricant ethylidine bis-stearamides 3 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 15 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 4
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Transparent powder 35 parts,
Coupling agent gamma-aminopropyl-triethoxy-silane 4 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 1.5 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 2.5 parts,
Heat stabilizer calcium stearate 4 parts,
Lubricant ethylidine bis-stearamides 4 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 15 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 5
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Transparent powder 45 parts,
Coupling agent gamma-aminopropyl-triethoxy-silane 5 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 2 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 3 parts,
Heat stabilizer calcium stearate 5 parts,
Lubricant ethylidine bis-stearamides 5 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 30 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 6
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Transparent powder 5 parts,
Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 1 part,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.2 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.3 part,
Heat stabilizer barium stearate 0.5 part,
Lubricant pentaerythritol stearate 0.5 part,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 7
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Transparent powder 15 parts,
Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 2 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.6 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1 part,
Heat stabilizer barium stearate 2 parts,
Lubricant pentaerythritol stearate 2 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 8
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Transparent powder 25 parts,
Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 3 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 1.2 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1.8 parts,
Heat stabilizer barium stearate 3 parts,
Lubricant pentaerythritol stearate 3 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 15 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 9
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Transparent powder 35 parts,
Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 4 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 1.5 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 2.5 parts,
Heat stabilizer barium stearate 4 parts,
Lubricant pentaerythritol stearate 4 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 15 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Embodiment 1
0
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Transparent powder 45 parts,
Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 5 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 2 parts,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 3 parts,
Heat stabilizer barium stearate 5 parts,
Lubricant pentaerythritol stearate 5 parts,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 30 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
(3) composite in (2) is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Comparative examples 1
(1) raw material it is equipped with in the following proportions:
Polyethylene 100 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.2 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.3 part,
Heat stabilizer calcium stearate 0.5 part,
Lubricant ethylidine bis-stearamides 0.5 part,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 170 DEG C, 180 DEG C, 190 DEG C, 210 DEG C, 220 DEG C, 220 DEG C and 225 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the resin for melted extrusion modeling.
(3) it is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Comparative examples 2
(1) raw material it is equipped with in the following proportions:
COPP 100 parts,
Antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 0.2 part,
Antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.3 part,
Heat stabilizer barium stearate 0.5 part,
Lubricant pentaerythritol stearate 0.5 part,
The raw material being equipped with in above ratio is placed in high-speed mixer disperse 10 minutes.
(2) by the raw material after dispersion by extruder, from feeding to head, each district temperature is respectively 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 230 DEG C and 235 DEG C.Raw material, after melting, plastify, extrude, drawing, prepares the resin for melted extrusion modeling.
(3) it is shaped to required product through melt extrusion processes.
Gained part performance is shown in Table one.
Product prepared by embodiment 1-10 and comparative examples 1-2 23 DEG C, under 50% humidity environment after regulation, be respectively adopted ASTM
The Rockwell hardness of D785 and ASTM D790 detection product and bending strength, record the shaping speed of they melted extrusion modelings simultaneously.
Table one:
| Performance | Shaping speed (cm3/h) | Rockwell hardness (R) | Bending strength (MPa) |
| Embodiment 1 | 23 | 57 | 27 |
| Embodiment 2 | 27 | 66 | 30 |
| Embodiment 3 | 31 | 75 | 31 |
| Embodiment 4 | 34 | 79 | 32 |
| Embodiment 5 | 36 | 81 | 31 |
| Embodiment 6 | 29 | 77 | 42 |
| Embodiment 7 | 34 | 86 | 47 |
| Embodiment 8 | 37 | 93 | 51 |
| Embodiment 9 | 41 | 112 | 53 |
| Embodiment 10 | 42 | 116 | 52 |
| Comparative examples 1 | 20 | 50 | 23 |
| Comparative examples 2 | 25 | 70 | 35 |
Can be seen that from table one, composite polyolefine material prepared by the present invention is when melted extrusion modeling, and it has, and shaping speed is fast, hardness big and mechanical strength advantages of higher.By data in table one, the composite polyethylene material modified through transparent powder prepared by the present invention, its shaping speed is 36cm the soonest3/ h, (case of comparative examples 1) improves 80% more before modified；Rockwell hardness is 81 to the maximum, and (case of comparative examples 1) improves 62% more before modified；Bending strength is 32MPa to the maximum, and (case of comparative examples 1) improves 39% more before modified.
Transparent powder modified copolymer PP composite material prepared by the present invention, shaping speed is 42cm the soonest3/ h, (case of comparative examples 2) improves 68% more before modified；Rockwell hardness is 116 to the maximum, and (case of comparative examples 2) improves 66% more before modified；Bending strength is 53MPa to the maximum, and (case of comparative examples 2) improves 51% more before modified.In addition the composite material preparation process that the present invention relates to is simple, can directly apply and be extended to melted extrusion modeling field and prepare transparent products.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art should be within protection scope of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment.
Claims (8)
1. the transparency polyolefin composite for melted extrusion modeling, it is characterised in that: it is prepared from by weight by following components:
Polyolefin 100 parts,
Transparent powder 5～45 parts,
Coupling agent 1～5 parts,
Antioxidant 0.5～5 parts,
Heat stabilizer 0.5～5 parts,
Lubricant 0.5～5 parts.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterised in that: described polyolefin is polyethylene and COPP.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterised in that: the size of described transparent powder is 5-50 μm.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterised in that: described coupling agent is gamma-aminopropyl-triethoxy-silane or γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterized in that: described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphite esters.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterised in that: described heat stabilizer is calcium stearate or barium stearate.
A kind of composite polyolefine material for melted extrusion modeling the most according to claim 1, it is characterised in that: described lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
A kind of preparation method of the composite polyolefine material for melted extrusion modeling, it is characterised in that: comprise the steps of
(1) in proportion by polyolefin 100 parts, transparent powder 5～45 parts, coupling agent 1～5 parts, antioxidant 0.5～5 parts, heat stabilizer 0.5～5 parts and lubricant 0.5～5 parts, it is placed in high-speed mixer and disperses 10～30 minutes；
(2) raw material after dispersion is passed through extruder, from feeding to head, each district temperature is respectively 170 DEG C～180 DEG C, 180 DEG C～190 DEG C, 190 DEG C～200 DEG C, 210 DEG C～220 DEG C, 220 DEG C～230 DEG C, 220 DEG C～230 DEG C and 225 DEG C～235 DEG C, raw material, after melting, plastify, extrude, drawing, prepares the composite for melted extrusion modeling.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134993A (en) * | 2017-06-16 | 2019-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of wear-resistant polyolefin composite material and preparation method for rapid shaping |
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| CN101367970A (en) * | 2008-10-06 | 2009-02-18 | 山东春潮色母料有限公司 | Novel material special for transparent plastic and method of preparing the same |
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| CN101367970A (en) * | 2008-10-06 | 2009-02-18 | 山东春潮色母料有限公司 | Novel material special for transparent plastic and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134993A (en) * | 2017-06-16 | 2019-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of wear-resistant polyolefin composite material and preparation method for rapid shaping |
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Application publication date: 20161123 |
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