CN104017346B - A kind of melt blending prepares the method for high-ductility blend polymer alloy - Google Patents
A kind of melt blending prepares the method for high-ductility blend polymer alloy Download PDFInfo
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- CN104017346B CN104017346B CN201410249998.9A CN201410249998A CN104017346B CN 104017346 B CN104017346 B CN 104017346B CN 201410249998 A CN201410249998 A CN 201410249998A CN 104017346 B CN104017346 B CN 104017346B
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Abstract
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include: A, master batch processing: by the mass ratio of 1-20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepares masterbatch after cooling curing；B, reasonable offer: bisphenol A polycarbonate, polymer-modified, bulking agent and masterbatch are pressed the mass ratio melt blending of 40-75:15-45:1-10:1-5, both obtain after cooling curing；Wherein said is polymer-modified for the one in ABS engineering plastics, polylactic acid, polyolefin polymers；Bulking agent is the bulking agent that can promote bisphenol A polycarbonate and polymer-modified combination。The high-ductility blend polymer alloy that the method prepares notch shock performance under low temperature and room temperature is good, and toughness is strong, and tensile property is good。
Description
Technical field
The invention belongs to the preparing technical field of high-ductility blend polymer alloy。
Background technology
Merlon (Polycarbonate, PC) is the polymer in a kind of strand containing carbonate group, including aliphatic, aliphatic-aromatic and aromatic series PC material。And the bisphenol A polycarbonate in aromatic copolycarbonate is owing to having good mechanical performance, high heat distortion temperature, good creep resistance, dimensional stability and good electrical insulation capability, it is widely used in engineering material field。But owing to bisphenol A polycarbonate itself is more sensitive to breach, notch impact strength is low；Although can improving its shortcoming by modifiying, but when bisphenol A polycarbonate and other polyblends, the compatibility being poor, therefore its application is restricted。Therefore the impact property of bisphenol A polycarbonate material, the toughness improving material is current urgent problem。
At present, method of modifying is broadly divided into two kinds, and a kind of change being dependent on macromolecular main chain, side chain or side-chain structure realizes modified, although chemically modified PC modified effect is better, but modifying process operability is little, and relatively costly, therefore apply relatively fewer。Secondly may utilize the metamorphosis of the physical action between different component (such as effects such as absorption, complexation or hydrogen bonds) and whole component itself and reach modified purpose。The physical modification method of bisphenol A polycarbonate is mainly included, filling-modified and blend polymer two kinds。In order to improve bisphenol A polycarbonate performance in a certain respect or reduce its production cost, in most cases can be modified to the filler such as inorganic particle or fiber that adding proportion in bisphenol A polycarbonate is different, being wherein most widely used of glass fibre。Compared with pure bisphenol A polycarbonate, glass fiber reinforcement bisphenol A polycarbonate has intensity height, and rigidity is big, stress cracking resistance is good, the advantages such as thermostability height and good electrical property, but glass fiber reinforcement bisphenol A polycarbonate is while rigidity, intensity improve, and impact strength is remarkably decreased。On the other hand, along with the development of nanotechnology, nanometer composite technology has become as the new modified method of bisphenol A polycarbonate。In order to improve the performance of bisphenol A polycarbonate, can by itself and some inorganic fillers, compound is carried out such as silicon dioxide, zinc oxide, montmorillonite, CNT, white carbon black, clay etc., so that mechanical performance, electric property, hot property etc. improve, but this tend to rely on Nano filling dispersion and and matrix between interaction, therefore the improvement of impact strength is relatively limited。Also it is the advantageous methods improving bisphenol A polycarbonate impact flexibility with another kind of polyblend, it is possible to improve the shock resistance of material；But simple blend material physical and mechanical properties is unstable, and being separated easily occur in goods, and low-temperature impact resistance is poor。
Summary of the invention
It is an object of the invention to provide a kind of method that melt blending prepares high-ductility blend polymer alloy, the high-ductility blend polymer alloy that the method prepares notch shock performance under low temperature and room temperature is good, and toughness is strong, and tensile property is good。
The present invention realizes its goal of the invention and be employed technical scheme comprise that, a kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 1-20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
B, reasonable offer: bisphenol A polycarbonate, polymer-modified, bulking agent and masterbatch are pressed the mass ratio melt blending of 40-75:15-45:1-10:1-5, both obtain after cooling curing；Wherein said is polymer-modified for the one in ABS engineering plastics, polylactic acid, polyolefin polymers；Bulking agent is the bulking agent that can promote bisphenol A polycarbonate and polymer-modified combination。
Compared with prior art, the invention has the beneficial effects as follows:
One, owing to CNT intensity is high, the π-π between CNT and bisphenol A polycarbonate interacts, and is conducive to putting forward heavy alloyed stretch-proof performance。Meanwhile, CNT is optionally dispersed in bisphenol A polycarbonate matrix changes bisphenol A polycarbonate phase domain size, increases bisphenol A polycarbonate phase phase domain, is also beneficial to the improvement of the impact property of alloy。Secondly by bulking agent to incompatible bisphenol A polycarbonate and polymer-modified compatibilization, make polymer-modified and bisphenol A polycarbonate combination enhancing, again improve toughness and the stretch-proof performance of material。Thus incompatible blend is served the effect of coordination plasticizing by CNT and bulking agent, prepared blend polymer Alloy Anti impact property is strong, good toughness, and stretch-proof performance is high。Not only the high tenacity under room temperature is good, also has good toughness at low temperatures, and after experiment proves to add CNT and bulking agent at the same time, under the room temperature of the mixed thing alloy of bisphenol A polycarbonate/polylactic acid, impact strength is from 13.4kJ/m2Amplitude peak can increase to 87.1kJ/m2, and the impact strength under low temperature (0 DEG C) can from 7.5kJ/m2Increase to 40.0kJ/m2. its tensile strength then amplitude of variation is little。
Two, the optional different qualities of the present invention is polymer-modified, alloy is made to have corresponding characteristic, such as polylactic acid and bisphenol A polycarbonate are carried out blended, polylactic acid is as a kind of degradable biological material, the hydrolysis property of high-ductility bisphenol A polycarbonate base alloy material can be improved, therefore, alloy combination property has controllability。
Above-mentioned CNT is diameter is 5-200nm, and length is SWCN or the multi-walled carbon nano-tubes of 100nm-50 μm。
The CNT of this caliber and length can be dispersed in bisphenol A polycarbonate, and combines better with bisphenol A polycarbonate, can well improve toughness and the tensile strength of alloy。
The process conditions of the above-mentioned melt blending in master batch processing are: temperature is 260-280 DEG C, and the blended time is 5-20min。
The temperature of melt blending is 260-280 DEG C exceeds the melt temperature (240 DEG C) 20-40 DEG C of bisphenol A polycarbonate, can guarantee that bisphenol A polycarbonate is fully melted；The blended time coordinating 5-20min again can make bisphenol A polycarbonate and CNT well be mixed to form masterbatch。
The process conditions of melt blending during above-mentioned reasonable offer are: temperature is 260-280 DEG C, and the blended time is 5-20min。
In bisphenol A polycarbonate, polymer-modified, bulking agent and four kinds of materials of masterbatch, the melt temperature of bisphenol A polycarbonate is up to 240 DEG C。Melt temperature during reasonable offer is 260-280 DEG C, exceeds most high melting temperature 20-40 DEG C of four kinds of materials, can guarantee that four kinds of materials are fully melted；Coordinate the blended time coordinating 5-20min more again, the better melt blending of masterbatch, polymer-modified, bisphenol A polycarbonate and bulking agent can be made to form polyblend 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 comparative example prepares。
Fig. 1 b is the TEM picture of the blend polymer alloy that embodiment one prepares。
Fig. 2 a is the room temperature impact property block diagram of the polyblend alloy that embodiment one, two, three and comparative example prepare。
Fig. 2 b is low temperature (0 DEG C) the impact property block diagram of the polyblend alloy that embodiment one, two, three and comparative example prepare。
Detailed description of the invention
Embodiment one
A kind of melt blending prepares the method for the method of high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 20min。
The CNT of this example is diameter is 50nm, and length is the SWCN of 100nm。
B, reasonable offer: bisphenol A polycarbonate, polylactic acid, maleic anhydride grafted ethene-octene copolymer (bulking agent) and masterbatch are pressed the mass ratio melt blending of 75:15:7.5:2.5, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 10min。
In order to prove CNT and the bulking agent coordination plasticizing effect to bisphenol A polycarbonate base alloy, the present inventor is without CNT and bulking agent, all the other operations are identical with embodiment one, are prepared for bisphenol A polycarbonate base/polylactic acid alloy material, see comparative example。
Comparative example
Bisphenol A polycarbonate and polylactic acid are pressed the mass ratio melt blending of 75:15, both obtains after cooling curing。
The process conditions of the process conditions melt blending of melt blending are: temperature is 260 DEG C, and the blended time is 10min。
Fig. 1 a is the scanning electron microscopic picture of the bisphenol A polycarbonate base alloy material that comparative example prepares, and Fig. 1 b is the scanning electron microscopic picture of the blend polymer alloy that embodiment one prepares。Fig. 1 a can be seen that, spherical polylactic acid is dispersed in bisphenol A polycarbonate matrix, the average-size of polylactic acid phase is at 0.36 μm, Fig. 1 b can be seen that, after adding CNT and bulking agent, polylactic acid domain size is reduced to 0.24 μm, and bisphenol A polycarbonate phase domain increases accordingly, and CNT is evenly distributed in bisphenol A polycarbonate。
Embodiment two
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 20min。
The CNT of this example is diameter is 50nm, and length is the SWCN of 100nm。
B, reasonable offer: bisphenol A polycarbonate, polylactic acid, maleic anhydride grafted ethene-octene copolymer (bulking agent) and masterbatch are pressed the mass ratio melt blending of 75:15:5:5, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 10min。
Embodiment three
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 1:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 20min。
The CNT of this example is diameter is 0.5nm, and length is the SWCN of 100nm。
B, reasonable offer: bisphenol A polycarbonate, polylactic acid, maleic anhydride grafted ethene-octene copolymer (bulking agent) and masterbatch are pressed the mass ratio melt blending of 75:15:5:3, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 260 DEG C, and the blended time is 10min。
Fig. 2 a is the room temperature impact property block diagram of the polyblend alloy that embodiment one, two, three and comparative example prepare。It can be seen that the room temperature impact property that the addition of bulking agent and CNT makes blend is all significantly improved from Fig. 2 a。The room temperature impact strength of such as embodiment one to three is 87.1,74.3 and 64.3kJ/m respectively2, and the impact strength of comparative example (bisphenol A polycarbonate/polylactic acid) is only 13.4kJ/m2, the impact strength of pure bisphenol A polycarbonate is 13.1kJ/m2；
Fig. 2 b is low temperature (0 DEG C) the impact property block diagram of the polyblend alloy that embodiment one, two, three and comparative example prepare。It can be seen that the low temperature impact properties that the addition of bulking agent and CNT makes blend is all significantly improved from Fig. 2 b。The low temperature impact strength of such as embodiment one to three is 32.0,35.3 and 41.6kJ/m2, and the low temperature impact strength of comparative example is only 7.5kJ/m2。
Table 1 is the stretch-proof performance data of embodiment one, two and three and comparative example, and as can be seen from the table, the stretch-proof performance of embodiment one to three is 64.2MPa, 59.7MPa, 58.1MPa, and the stretch-proof performance of comparative example is 62.1MPa。
| Comparative example | Embodiment one | Embodiment two | Embodiment three | |
| Hot strength | 62.1MPa | 64.2MPa | 59.7MPa | 58.1MPa |
Embodiment four
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 270 DEG C, and the blended time is 5min。
The CNT of this example is diameter is 20nm, and length is the multi-walled carbon nano-tubes of 50 μm。
B, reasonable offer: by bisphenol A polycarbonate, ABS engineering plastics (acrylonitrile-butadiene-styrene (ABS) (acrylonitrile-butadiene-styrene, ABS), ABS grafted maleic anhydride (ABSgraftedmaleicanhydride, ABS-g-MA) the mass ratio melt blending of 75:15:5:3 pressed by (bulking agent) and masterbatch, both obtains after cooling curing。
The process conditions of melt blending are: temperature is 270 DEG C, and the blended time is 5min。
Embodiment five
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 280 DEG C, and the blended time is 20min。
The CNT of this example is diameter is 200nm, and length is the SWCN of 50 μm。
B, reasonable offer: bisphenol A polycarbonate, polyethylene, Research of Grafting Malaic Anhydride Onto Polyethylene (bulking agent) and masterbatch are pressed the mass ratio melt blending of 45:30:1:4, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 280 DEG C, and the blended time is 5min。
Embodiment six
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 10:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 280 DEG C, and the blended time is 20min。
The CNT of this example is diameter is 200nm, and length is the SWCN of 50 μm。
B, reasonable offer: bisphenol A polycarbonate, polypropylene, polypropylene grafted maleic anhydride (bulking agent) and masterbatch are pressed the mass ratio melt blending of 40:45:1:1, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 280 DEG C, and the blended time is 20min。
Embodiment seven
A kind of melt blending prepares the method for high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；
The process conditions of melt blending are: temperature is 270 DEG C, and the blended time is 10min。
The CNT of this example is diameter is 5nm, and length is the multi-walled carbon nano-tubes of 100nm。
B, reasonable offer: bisphenol A polycarbonate, polypropylene, polypropylene grafted maleic anhydride (bulking agent) and masterbatch are pressed the mass ratio melt blending of 60:20:10:5, both obtain after cooling curing。
The process conditions of melt blending are: temperature is 280 DEG C, and the blended time is 20min。
Claims (1)
1. the method that melt blending prepares high-ductility blend polymer alloy, the steps include:
A, master batch processing: by the mass ratio of 1-20:100, CNT and bisphenol A polycarbonate are carried out melt blending, prepare masterbatch after cooling curing；The process conditions of described melt blending are: temperature is bisphenol A-type 260-280 DEG C, and the blended time is 5-20min；Described CNT is diameter is 0.5-200nm, and length is SWCN or the multi-walled carbon nano-tubes of 100nm-50 μm；
B, reasonable offer: bisphenol A polycarbonate, polymer-modified, bulking agent and masterbatch are pressed the mass ratio melt blending of 40-75:15-45:1-10:1-5, both obtain after cooling curing；
Wherein said is polymer-modified for the one in ABS engineering plastics, polylactic acid, polyolefin polymers；Bulking agent is the bulking agent that can promote bisphenol A polycarbonate and polymer-modified combination；The process conditions of described melt blending are: temperature is 260-280 DEG C, and the blended time is 5-20min。
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| CN106147011A (en) * | 2015-04-17 | 2016-11-23 | 普立万聚合体（上海）有限公司 | A kind of carbon nanotubes is as the master batch of 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 |
| 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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