CN104017346A - Method for preparing high-ductility polymer blend alloy by melt blending - Google Patents
Method for preparing high-ductility polymer blend alloy by melt blending Download PDFInfo
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- CN104017346A CN104017346A CN201410249998.9A CN201410249998A CN104017346A CN 104017346 A CN104017346 A CN 104017346A CN 201410249998 A CN201410249998 A CN 201410249998A CN 104017346 A CN104017346 A CN 104017346A
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Abstract
The invention discloses a method for preparing a high-ductility polymer blend alloy by melt blending. The method comprises the following steps: A, preparing master batch, namely carrying out melt blending on a carbon nano tube and bisphenol A polycarbonate according to the mass ratio of (1-20) to 100, cooling and solidifying to obtain the master batch; and B, preparing the alloy, namely carrying out melt blending on the bisphenol A polycarbonate, a modified polymer, a bulking agent and the master batch according to the mass ratio of (40-75) to (15-45) to (1-10) to (1-5), cooling and solidifying to obtain the high-ductility polymer blend alloy, wherein the modified polymer is one of acrylonitrile-butadiene-styrene (ABS) engineering plastics, a polylactic acid and a polyolefin polymer; the bulking agent is the bulking agent capable of promoting bonding of bisphenol A polycarbonate and the modified polymer. The high-ductility polymer blend alloy prepared by the method is good in gap impact property, strong in ductility and good in tensile property at low temperature and normal temperature.
Description
Technical field
The invention belongs to the preparing technical field of high-ductility blend polymer alloy.
Background technology
Polycarbonate (Polycarbonate, PC) is the polymkeric substance that contains carbonate group in a kind of molecular chain, comprises aliphatics, aliphatic-aromatic and aromatic series PC material.And bisphenol A polycarbonate in aromatic copolycarbonate is owing to having good mechanical property, high heat-drawn wire, good creep resistance, dimensional stability and good electrical insulation capability, be widely used in engineering materials field.But because bisphenol A polycarbonate itself is more responsive to breach, notched Izod impact strength is low; Although can improve its shortcoming by modification, when bisphenol A polycarbonate and other polymer blendings, consistency is poor, so its application is restricted.So the impact property of bisphenol A polycarbonate material, the toughness that improves material is current urgent problem.
At present, method of modifying is mainly divided into two kinds, and a kind of is to rely on the variation of macromolecular main chain, side chain or side-chain structure to realize modification, although better through the PC of chemical modification modified effect, but modifying process operability is little, and cost is higher, and therefore application is relatively less.Secondly can utilize physical action (as effects such as absorption, complexing or hydrogen bonds) and the metamorphosis of whole component itself between different components to reach modification object.Physical modification method to bisphenol A polycarbonate mainly comprises, two kinds of filling-modified and blend polymers.In order to improve performance in a certain respect of bisphenol A polycarbonate or to reduce its production cost, in most cases can carry out modification to weighting agents such as the different inorganic powder of adding proportion in bisphenol A polycarbonate or fibers, wherein glass fibre is most widely used.Compare with pure bisphenol A polycarbonate, it is high that glass fibre enhancing bisphenol A polycarbonate has intensity, rigidity is large, stress cracking resistance is good, the advantages such as thermotolerance height and good electrical property, but glass fibre strengthens bisphenol A polycarbonate when rigidity, intensity improve, and shock strength significantly declines.On the other hand, along with the development of nanotechnology, nanometer composite technology has become the new modified method of bisphenol A polycarbonate.In order to improve the performance of bisphenol A polycarbonate, can be by itself and some mineral fillers, as silicon-dioxide, zinc oxide, polynite, carbon nanotube, carbon black, clay etc. carry out compound, thereby the mechanical property of making, electric property, thermal characteristics etc. improve, but this often depend on Nano filling dispersion and and matrix between interaction, so the improvement of shock strength is comparatively limited.With another kind of polymer blending be also the advantageous methods that improves bisphenol A polycarbonate impelling strength, can improve the shock resistance of material; But simple blend material physical and mechanical properties is unstable, and goods are prone to and are separated, and low-temperature impact resistance is poor.
Summary of the invention
The object of this invention is to provide a kind of melt blending and prepare the method for high-ductility blend polymer alloy, the notch shock performance of the high-ductility blend polymer alloy that the method makes under low temperature and normal temperature is good, and toughness is strong, and tensile property is good.
It is that a kind of melt blending is prepared the method for high-ductility blend polymer alloy, the steps include: that the present invention realizes the technical scheme that its goal of the invention adopts
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 1-20:100, after cooling curing, make masterbatch;
B, alloy preparation: bisphenol A polycarbonate, polymer-modified, expanding material and masterbatch press to the mass ratio melt blending of 40-75:15-45:1-10:1-5, both must after cooling curing; Wherein said polymer-modified be a kind of in ABS engineering plastics, poly(lactic acid), polyolefin polymers; Expanding material is for promoting the expanding material of bisphenol A polycarbonate and polymer-modified combination.
Compared with prior art, the invention has the beneficial effects as follows:
One,, because carbon nanotube intensity is high, the π between carbon nanotube and bisphenol A polycarbonate-π interacts, and is conducive to put forward heavy alloyed stretch-proof performance.Meanwhile, carbon nanotube dispersed bisphenol A polycarbonate phase phase region size that changed optionally in bisphenol A polycarbonate matrix, has increased bisphenol A polycarbonate phase phase farmland, is also conducive to the improvement of the impact property of alloy.Secondly by expanding material to incompatible bisphenol A polycarbonate and polymer-modified compatibilization, make polymer-modified and bisphenol A polycarbonate in conjunction with enhancing, again improve toughness and the stretch-proof performance of material.Thereby carbon nanotube and expanding material have played the effect of coordination plasticizing to incompatible blend, the blend polymer Alloy Anti impact property making is strong, good toughness, and stretch-proof performance is high.Not only the high tenacity under normal temperature is good, also has at low temperatures good toughness, experimental results show that and adds at the same time after carbon nanotube and expanding material, and under the normal temperature of the mixed thing alloy of bisphenol A polycarbonate/poly(lactic acid), shock strength is from 13.4kJ/m
2maximum amplitude can be increased to 87.1kJ/m
2, and shock strength under low temperature (0 ℃) can be from 7.5kJ/m
2be increased to 40.0kJ/m
2. its tensile strength rangeability is little.
Two, the present invention can select the polymer-modified of different qualities, make alloy there is corresponding characteristic, for example poly(lactic acid) and bisphenol A polycarbonate are carried out to blend, poly(lactic acid) is as a kind of degradable biological material, can improve the hydrolysis property of high-ductility bisphenol A polycarbonate base alloy material, therefore, alloy over-all properties has controllability.
Above-mentioned carbon nanotube is that diameter is 5-200nm, and length is Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of 100nm-50 μ m.
The carbon nanotube of this caliber and length can be dispersed in bisphenol A polycarbonate, and better with bisphenol A polycarbonate combination, can well improve toughness and the tensile strength of alloy.
The processing condition of the melt blending in above-mentioned masterbatch preparation are: temperature is 260-280 ℃, and the blend time is 5-20min.
The temperature of melt blending is 260-280 ℃ of melt temperature (240 ℃) 20-40 ℃ that exceeds bisphenol A polycarbonate, can guarantee the abundant melting of bisphenol A polycarbonate; Coordinate again the blend time of 5-20min can make bisphenol A polycarbonate and carbon nanotube well be mixed to form masterbatch.
The processing condition of melt blending when prepared by above-mentioned alloy are: temperature is 260-280 ℃, and the blend time is 5-20min.
In bisphenol A polycarbonate, polymer-modified, expanding material and four kinds of materials of masterbatch, the melt temperature of bisphenol A polycarbonate is up to 240 ℃.Melt temperature when prepared by alloy is 260-280 ℃, exceeds the high melting temperature 20-40 ℃ of four kinds of materials, can guarantee four kinds of abundant meltings of material; Coordinate again the blend time coordinate again 5-20min, can make masterbatch, polymer-modified, bisphenol A polycarbonate and the better melt blending of expanding material form polymer blending alloy.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 a is the TEM picture of the blend polymer alloy that makes of comparative example.
Fig. 1 b is the TEM picture of the blend polymer alloy that makes of embodiment mono-.
Fig. 2 a is the normal temperature impact property histogram of the polymer blending alloy that makes of embodiment mono-, two, three and comparative example.
Fig. 2 b is low temperature (0 ℃) the impact property histogram of the polymer blending alloy that makes of embodiment mono-, two, three and comparative example.
Embodiment
Embodiment mono-
Melt blending is prepared a method for the method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 20:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 20min.
This routine carbon nanotube is that diameter is 50nm, the Single Walled Carbon Nanotube that length is 100nm.
B, alloy preparation: bisphenol A polycarbonate, poly(lactic acid), maleic anhydride grafted ethene-octene copolymer (expanding material) and masterbatch are pressed to the mass ratio melt blending of 75:15:7.5:2.5, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 10min.
In order to prove the coordination plasticizing effect to bisphenol A polycarbonate base alloy of carbon nanotube and expanding material, the inventor does not add carbon nanotube and expanding material, all the other operations are identical with embodiment mono-, prepared bisphenol A polycarbonate base/polylactic acid alloy material, see comparative example.
Comparative example
Bisphenol A polycarbonate and poly(lactic acid) are pressed to the mass ratio melt blending of 75:15, after cooling curing both.
The processing condition of the processing condition melt blending of melt blending are: temperature is 260 ℃, and the blend time is 10min.
Fig. 1 a is the scanning electron microscope picture of the bisphenol A polycarbonate base alloy material that makes of comparative example, and Fig. 1 b is the scanning electron microscope picture of the blend polymer alloy that makes of embodiment mono-.Fig. 1 a can find out, spherical poly(lactic acid) is dispersed in bisphenol A polycarbonate matrix, the mean sizes of poly(lactic acid) phase is at 0.36 μ m, Fig. 1 b can find out, add after carbon nanotube and expanding material, poly(lactic acid) phase region size is reduced to 0.24 μ m, the corresponding increase in bisphenol A polycarbonate phase farmland, and even carbon nanotube is distributed in bisphenol A polycarbonate.
Embodiment bis-
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 20:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 20min.
This routine carbon nanotube is that diameter is 50nm, the Single Walled Carbon Nanotube that length is 100nm.
B, alloy preparation: bisphenol A polycarbonate, poly(lactic acid), maleic anhydride grafted ethene-octene copolymer (expanding material) and masterbatch are pressed to the mass ratio melt blending of 75:15:5:5, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 10min.
Embodiment tri-
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 1:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 20min.
This routine carbon nanotube is that diameter is 0.5nm, the Single Walled Carbon Nanotube that length is 100nm.
B, alloy preparation: bisphenol A polycarbonate, poly(lactic acid), maleic anhydride grafted ethene-octene copolymer (expanding material) and masterbatch are pressed to the mass ratio melt blending of 75:15:5:3, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 260 ℃, and the blend time is 10min.
Fig. 2 a is the normal temperature impact property histogram of the polymer blending alloy that makes of embodiment mono-, two, three and comparative example.From Fig. 2 a, can find out, adding of expanding material and carbon nanotube is all significantly improved the normal temperature impact property of blend.Such as the normal temperature shock strength of embodiment mono-to three is respectively 87.1,74.3 and 64.3kJ/m
2, and the shock strength of comparative example (bisphenol A polycarbonate/poly(lactic acid)) is only 13.4kJ/m
2, the shock strength of pure bisphenol A polycarbonate is 13.1kJ/m
2;
Fig. 2 b is low temperature (0 ℃) the impact property histogram of the polymer blending alloy that makes of embodiment mono-, two, three and comparative example.From Fig. 2 b, can find out, adding of expanding material and carbon nanotube is all significantly improved the low temperature impact properties of blend.Such as the low temperature impact strength of embodiment mono-to three is 32.0,35.3 and 41.6kJ/m
2, and the low temperature impact strength of comparative example is only 7.5kJ/m
2.
Table 1 is embodiment mono-, two and three and the stretch-proof performance data of comparative example, and as can be seen from the table, the stretch-proof performance of embodiment mono-to three is 64.2MPa, 59.7MPa, and 58.1MPa, and the stretch-proof performance of comparative example is 62.1MPa.
? | Comparative example | Embodiment mono- | Embodiment bis- | Embodiment tri- |
Tensile strength | 62.1MPa | 64.2MPa | 59.7MPa | 58.1MPa |
Embodiment tetra-
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 20:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 270 ℃, and the blend time is 5min.
This routine carbon nanotube is that diameter is 20nm, and length is the multi-walled carbon nano-tubes of 50 μ m.
B, alloy preparation: by bisphenol A polycarbonate, ABS engineering plastics (acrylonitrile-butadiene-styrene (ABS) (acrylonitrile-butadiene-styrene, ABS), ABS grafted maleic anhydride (ABS grafted maleic anhydride, ABS-g-MA) (expanding material) and masterbatch are pressed the mass ratio melt blending of 75:15:5:3, after cooling curing, both obtain.
The processing condition of melt blending are: temperature is 270 ℃, and the blend time is 5min.
Embodiment five
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 20:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 280 ℃, and the blend time is 20min.
This routine carbon nanotube is that diameter is 200nm, and length is the Single Walled Carbon Nanotube of 50 μ m.
B, alloy preparation: bisphenol A polycarbonate, polyethylene, Research of Grafting Malaic Anhydride Onto Polyethylene (expanding material) and masterbatch are pressed to the mass ratio melt blending of 45:30:1:4, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 280 ℃, and the blend time is 5min.
Embodiment six
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 10:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 280 ℃, and the blend time is 20min.
This routine carbon nanotube is that diameter is 200nm, and length is the Single Walled Carbon Nanotube of 50 μ m.
B, alloy preparation: bisphenol A polycarbonate, polypropylene, polypropylene grafted maleic anhydride (expanding material) and masterbatch are pressed to the mass ratio melt blending of 40:45:1:1, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 280 ℃, and the blend time is 20min.
Embodiment seven
Melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 20:100, after cooling curing, make masterbatch;
The processing condition of melt blending are: temperature is 270 ℃, and the blend time is 10min.
This routine carbon nanotube is that diameter is 5nm, the multi-walled carbon nano-tubes that length is 100nm.
B, alloy preparation: bisphenol A polycarbonate, polypropylene, polypropylene grafted maleic anhydride (expanding material) and masterbatch are pressed to the mass ratio melt blending of 60:20:10:5, after cooling curing, both obtained.
The processing condition of melt blending are: temperature is 280 ℃, and the blend time is 20min.
Claims (4)
1. melt blending is prepared a method for high-ductility blend polymer alloy, the steps include:
A, masterbatch preparation: carbon nanotube and bisphenol A polycarbonate are carried out to melt blending by the mass ratio of 1-20:100, after cooling curing, make masterbatch;
B, alloy preparation: bisphenol A polycarbonate, polymer-modified, expanding material and masterbatch press to the mass ratio melt blending of 40-75:15-45:1-10:1-5, both must after cooling curing; Wherein said polymer-modified be a kind of in ABS engineering plastics, poly(lactic acid), polyolefin polymers; Expanding material is for promoting the expanding material of bisphenol A polycarbonate and polymer-modified combination.
2. melt-blending process according to claim 1 is prepared the method for high-ductility blend polymer alloy, it is characterized in that: described carbon nanotube is that diameter is 0.5-200nm, and length is Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of 100nm-50 μ m.
3. melt blending according to claim 1 is prepared the method for high-ductility blend polymer alloy, it is characterized in that, the processing condition of the melt blending in described masterbatch preparation are: temperature is bisphenol A-type 260-280 ℃, and the blend time is 5-20min.
4. melt blending according to claim 1 is prepared the method for high-ductility blend polymer alloy, it is characterized in that: the processing condition of melt blending when prepared by described alloy are: temperature is 260-280 ℃, and the blend time is 5-20min.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016165638A1 (en) * | 2015-04-17 | 2016-10-20 | Polyone-Shanghai, China | Masterbatch containing carbon nanotubes as black pigment |
CN106167611A (en) * | 2016-06-30 | 2016-11-30 | 嘉兴市高正高分子材料有限公司 | A kind of PC/ carbon nanotube conducting master batch |
CN106751608A (en) * | 2016-12-05 | 2017-05-31 | 西南交通大学 | A kind of preparation method of high-ductility polylactic acid-base composite material |
CN110079071A (en) * | 2019-06-03 | 2019-08-02 | 南京工业职业技术学院 | One kind can be with biodegradable high-impact polycarbonate nano composite material and preparation method thereof |
CN114621574A (en) * | 2022-03-23 | 2022-06-14 | 武汉金发科技有限公司 | Polycarbonate alloy material and preparation method and application thereof |
Citations (1)
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CN101098921A (en) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | Use of carbon nanotubes for the production of a conductive organic composition and applications of one such composition |
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2014
- 2014-06-07 CN CN201410249998.9A patent/CN104017346B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101098921A (en) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | Use of carbon nanotubes for the production of a conductive organic composition and applications of one such composition |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016165638A1 (en) * | 2015-04-17 | 2016-10-20 | Polyone-Shanghai, China | Masterbatch containing carbon nanotubes as black pigment |
CN106167611A (en) * | 2016-06-30 | 2016-11-30 | 嘉兴市高正高分子材料有限公司 | A kind of PC/ carbon nanotube conducting master batch |
CN106751608A (en) * | 2016-12-05 | 2017-05-31 | 西南交通大学 | A kind of preparation method of high-ductility polylactic acid-base composite material |
CN110079071A (en) * | 2019-06-03 | 2019-08-02 | 南京工业职业技术学院 | One kind can be with biodegradable high-impact polycarbonate nano composite material and preparation method thereof |
CN114621574A (en) * | 2022-03-23 | 2022-06-14 | 武汉金发科技有限公司 | Polycarbonate alloy material and preparation method and application thereof |
CN114621574B (en) * | 2022-03-23 | 2023-06-13 | 武汉金发科技有限公司 | Polycarbonate alloy material and preparation method and application thereof |
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