CN105037599A - Ultraviolet-resistant multi-walled carbon nano-tube reinforced polypropylene resin and preparation method thereof - Google Patents
Ultraviolet-resistant multi-walled carbon nano-tube reinforced polypropylene resin and preparation method thereof Download PDFInfo
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Abstract
An ultraviolet-resistant multi-walled carbon nano-tube reinforced polypropylene resin is prepared from the following raw materials in parts by weight: 400-430 parts of liquid propylene, 2.5-3.5 parts of a multi-walled carbon nano-tube-supported Ti-Zr catalyst, 50-60 parts of liquid ethylene, 7-9 parts of triethyl aluminium, 5.4-6.2 parts of dimethoxy diphenyl silane, 50-60 parts of normal heptane, a proper amount of hydrogen, 0.1-0.2 part of ammonium silicofluoride, 20-25 parts of 1-nonene, 0.1-0.2 part of triethavolamine, 1-2 parts of nanometer zinc oxide and 8-12 parts of water. The multi-walled carbon nano-tube-supported Ti-Zr catalyst is modified, so that the activity of the catalyst is improved, the polarity difference is reduced, and the binding force between a multi-walled carbon nano-tube and macromolecules is enhanced; through the addition of nanometer zinc oxide, the ultraviolet resistance of polypropylene is improved, and the strength of polypropylene is improved.
Description
Technical field
The present invention relates to polypropylene production technical field, particularly relate to a kind of multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin and preparation method thereof.
Background technology
In polyolefine, introduce nanoparticle (as polynite, carbon nanotube and graphene oxide) become polyolefin modified and important channel that is high performance.Be scattered in inorganic rigid particle in polyolefin substrate at loading level seldom (being usually less than 5%(w) with nanoscale) just can significantly improve or improve polyolefinic mechanical property, thermal characteristics and resistive energy, and there is functional nanoparticles (as redox graphene etc.) such as extremely strong conductive and heat-conductive also can give polyolefine certain electrical and thermal conductivity.Therefore, getting a promotion further of olefin polymerization nanometer composite material, Application Areas can significantly be expanded.
Preparing in the numerous method of carbon nanotube composite polypropylene, in-situ polymerization technology is considered to one of the most effective method.This technology is the catalytic active center catalyzing propone monomer polymerization reactions by carbon nanotube loaded transition-metal catalyst, avoid the thermodynamic (al) rigors caused by polypropylene and carbon nanotube polarity difference to a certain extent, and then prepare the carbon nanotube Reinforced Polypropylene resin of excellent performance.But carbon nanotube and polypropylene still exist polarity difference, need improving technique, improve the performance of carbon nanotube Reinforced Polypropylene further.Can also assign to improve polyacrylic performance by improving polyacrylic one-tenth.
Summary of the invention
The object of the present invention is to provide a kind of multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, this resin has ultra-violet resistance energy and high intensity
Technical scheme of the present invention is as follows:
A kind of multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that being made up of the raw material of following weight part: propylene liquid 400-430, carbon multi-wall nano tube loaded Ti-Zr catalyzer 2.5-3.5, liquid ethylene 50-60, triethyl aluminum 7-9, dimethoxydiphenylsilane 5.4-6.2, normal heptane 50-60, hydrogen are appropriate, ammonium hexafluorosilicate 0.1-0.2,1-nonene 20-25, trolamine 0.1-0.2, nano zine oxide 1-2, water 8-12.
The described multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that: it be 5%, Zr is 2% that described carbon multi-wall nano tube loaded Ti-Zr catalyzer contains Ti mass percent.
The production method of the described multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that:
(1) ammonium hexafluorosilicate, trolamine are added to the water, nano zine oxide is added after stirring, carbon multi-wall nano tube loaded Ti-Zr catalyzer is added again after stirring, be heated to 60-70 DEG C, stirring reaction 20-30 minute, drying, obtains the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification;
(2) in reactor, add the normal heptane of 4/5, add the propylene liquid of 1/5, the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification, the triethyl aluminum of 1/5, the dimethoxydiphenylsilane of 1/5, mix, pass into the hydrogen of the 0.02-0.08% of propylene liquid quality again, under 50-80 DEG C, 2-3MPa condition, carry out slurry polymerization 7-9 hour, then add the liquid ethylene of 1/5 and the 1-nonene of 1/5, continue reaction 7-9 hour, obtain the polypropylene of loading multi-wall carbon nanotubes;
(3) under normal temperature, normal pressure, autoclave is full of propylene gas, then passes into the hydrogen of 0.02-0.08% of remaining liquid propylene quality, add 1/2 remaining liquid third rare; Remaining triethyl aluminum, dimethoxydiphenylsilane are added in remaining normal heptane and stirs, add in reactor, add the polypropylene of loading multi-wall carbon nanotubes again, add remaining propylene liquid again, be warming up to 50-80 DEG C, pressure rises to 2-3MPa, reaction 5-8 hour, temperature of reaction kettle is down to room temperature, emptying propylene, then passes into reactor by remaining ethene gasification, then adds other remaining component, be warming up to 50-80 DEG C, pressure rises to 2-3MPa, reaction 8-10 hour, emptying gas, vacuum-drying, to obtain final product.
Beneficial effect of the present invention
The present invention, by carrying out modification to carbon multi-wall nano tube loaded Ti-Zr catalyzer, improves the activity of catalyzer, reduces polarity difference, adds the bonding force between multi-walled carbon nano-tubes and polymer; By adding nano zine oxide, adding polyacrylic ultra-violet resistance energy, and polyacrylic intensity can be increased.Production technique of the present invention achieves effective dispersion of nanoparticle and effective control of morphology, makes this resin have higher impelling strength, keeps good intensity and rigidity simultaneously, is the nano composite material with good industrial prospect.
Embodiment
A kind of multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is made up of the raw material of following weight part (kilogram): propylene liquid 410, carbon multi-wall nano tube loaded Ti-Zr catalyzer 3, liquid ethylene 55, triethyl aluminum 8, dimethoxydiphenylsilane 5.8, normal heptane 55, hydrogen are appropriate, ammonium hexafluorosilicate 0.1,1-nonene 23, trolamine 0.2, nano zine oxide 1.5, water 10.
The described multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that: it be 5%, Zr is 2% that described carbon multi-wall nano tube loaded Ti-Zr catalyzer contains Ti mass percent.
The production method of the described multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that:
(1) ammonium hexafluorosilicate, trolamine are added to the water, after stirring, add nano zine oxide, after stirring, add carbon multi-wall nano tube loaded Ti-Zr catalyzer again, be heated to 65 DEG C, stirring reaction 25 minutes, dry, obtain the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification;
(2) in reactor, add the normal heptane of 4/5, add the propylene liquid of 1/5, the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification, the triethyl aluminum of 1/5, the dimethoxydiphenylsilane of 1/5, mix, pass into the hydrogen of 0.06% of propylene liquid quality again, at 60 DEG C, under 2MPa condition, carry out slurry polymerization 8 hours, then add the liquid ethylene of 1/5 and the 1-nonene of 1/5, continue reaction 8 hours, obtain the polypropylene of loading multi-wall carbon nanotubes;
(3) under normal temperature, normal pressure, autoclave is full of propylene gas, then pass into remaining liquid propylene quality 0.06% hydrogen, add 1/2 remaining liquid third rare; Remaining triethyl aluminum, dimethoxydiphenylsilane are added in remaining normal heptane and stirs, add in reactor, add the polypropylene of loading multi-wall carbon nanotubes again, add remaining propylene liquid again, be warming up to 60 DEG C, pressure rises to 2.5MPa, reacts 6 hours, temperature of reaction kettle is down to room temperature, emptying propylene, then passes into reactor by remaining ethene gasification, then adds other remaining component, be warming up to 70 DEG C, pressure rises to 2.6MPa, reacts 9 hours, emptying gas, vacuum-drying, to obtain final product.
Experimental data:
The polypropylene of this embodiment is through extrusion moulding, and after tested, tensile strength is 37MPa, and elongation at break is 845%, and under normal temperature, notched Izod impact strength reaches 36kJ/ ㎡, and modulus in flexure is 675Mpa.
Claims (3)
1. the multi-walled carbon nano-tubes of a resistance to ultraviolet Reinforced Polypropylene resin, is characterized in that being made up of the raw material of following weight part: propylene liquid 400-430, carbon multi-wall nano tube loaded Ti-Zr catalyzer 2.5-3.5, liquid ethylene 50-60, triethyl aluminum 7-9, dimethoxydiphenylsilane 5.4-6.2, normal heptane 50-60, hydrogen are appropriate, ammonium hexafluorosilicate 0.1-0.2,1-nonene 20-25, trolamine 0.1-0.2, nano zine oxide 1-2, water 8-12.
2. the multi-walled carbon nano-tubes of resistance to ultraviolet Reinforced Polypropylene resin according to claim 1, is characterized in that: it be 5%, Zr is 2% that described carbon multi-wall nano tube loaded Ti-Zr catalyzer contains Ti mass percent.
3. the production method of the multi-walled carbon nano-tubes of the resistance to ultraviolet Reinforced Polypropylene resin according to claim 1 and 2, is characterized in that:
(1) ammonium hexafluorosilicate, trolamine are added to the water, nano zine oxide is added after stirring, carbon multi-wall nano tube loaded Ti-Zr catalyzer is added again after stirring, be heated to 60-70 DEG C, stirring reaction 20-30 minute, drying, obtains the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification;
(2) in reactor, add the normal heptane of 4/5, add the propylene liquid of 1/5, the carbon multi-wall nano tube loaded Ti-Zr catalyzer of modification, the triethyl aluminum of 1/5, the dimethoxydiphenylsilane of 1/5, mix, pass into the hydrogen of the 0.02-0.08% of propylene liquid quality again, at 50-80 DEG C, slurry polymerization 7-9 hour is carried out under 2-3MPa condition, add the liquid ethylene of 1/5 and the 1-nonene of 1/5 again, continue reaction 7-9 hour, obtain the polypropylene of loading multi-wall carbon nanotubes;
(3) under normal temperature, normal pressure, autoclave is full of propylene gas, then passes into the hydrogen of 0.02-0.08% of remaining liquid propylene quality, add 1/2 remaining liquid third rare; Remaining triethyl aluminum, dimethoxydiphenylsilane are added in remaining normal heptane and stirs, add in reactor, add the polypropylene of loading multi-wall carbon nanotubes again, add remaining propylene liquid again, be warming up to 50-80 DEG C, pressure rises to 2-3MPa, reaction 5-8 hour, temperature of reaction kettle is down to room temperature, emptying propylene, then passes into reactor by remaining ethene gasification, then adds other remaining component, be warming up to 50-80 DEG C, pressure rises to 2-3MPa, reaction 8-10 hour, emptying gas, vacuum-drying, to obtain final product.
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Citations (4)
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|---|---|---|---|---|
| US6043326A (en) * | 1994-03-24 | 2000-03-28 | Borealis Polymers Oy | Process for copolymerizing ethene and alpha-olefins |
| CN102731693A (en) * | 2011-04-15 | 2012-10-17 | 中国科学院化学研究所 | Polyolefin catalyst adopting carbon nanotubes as carriers and preparation method thereof |
| CN103910930A (en) * | 2012-12-31 | 2014-07-09 | 中国科学院化学研究所 | Polypropylene intra-autoclave alloy having carbon nanotubes, preparation method for the alloy, and applications thereof |
| CN103980609A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Nanoparticle-containing polypropylene inside-kettle alloy capable of being used for 3D printing, and preparation method and application thereof |
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- 2015-06-25 CN CN201510353930.XA patent/CN105037599A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6043326A (en) * | 1994-03-24 | 2000-03-28 | Borealis Polymers Oy | Process for copolymerizing ethene and alpha-olefins |
| CN102731693A (en) * | 2011-04-15 | 2012-10-17 | 中国科学院化学研究所 | Polyolefin catalyst adopting carbon nanotubes as carriers and preparation method thereof |
| CN103910930A (en) * | 2012-12-31 | 2014-07-09 | 中国科学院化学研究所 | Polypropylene intra-autoclave alloy having carbon nanotubes, preparation method for the alloy, and applications thereof |
| CN103980609A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Nanoparticle-containing polypropylene inside-kettle alloy capable of being used for 3D printing, and preparation method and application thereof |
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Application publication date: 20151111 |