CN105037598A - Multi-walled carbon nano-tube reinforced polypropylene resin for automobile parts, and preparation method for multi-walled carbon nano-tube reinforced polypropylene resin - Google Patents

Abstract

A multi-walled carbon nano-tube reinforced polypropylene resin for automobile parts is prepared from the following raw materials in parts by weight: 400-420 parts of liquid propylene, 2.5-3.5 parts of a multi-walled carbon nano-tube-supported Ti-Zr catalyst, 70-80 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, 10-15 parts of 1-nonene, 1.5-1.8 parts of nanometer aluminium oxide, 0.1-0.2 part of polyvinyl pyrrolidone and 8-12 parts of water. Through the adoption of the nanometer aluminium oxide, the thermal conductivity and the antistatic property of polypropylene are improved; through the modification of the multi-walled carbon nano-tube-supported Ti-Zr catalyst, 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; the polypropylene resin is suitable for the production of the automobile parts, durable in use and good in security.

Description

A kind of auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin and preparation method thereof

Technical field

The present invention relates to polypropylene production technical field, particularly relate to a kind of auto parts multi-walled carbon nano-tubes 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 auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin, this resin has good thermal conductivity and antistatic property, is applicable to make automobile component, durable in use and security good.

Technical scheme of the present invention is as follows:

A kind of auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin, is characterized in that being made up of the raw material of following weight part: propylene liquid 400-420, carbon multi-wall nano tube loaded Ti-Zr catalyzer 2.5-3.5, liquid ethylene 70-80, triethyl aluminum 7-9, dimethoxydiphenylsilane 5.4-6.2, normal heptane 50-60, hydrogen are appropriate, ammonium hexafluorosilicate 0.1-0.2,1-octene 10-15, nano-aluminium oxide 1.5-1.8, Polyvinylpyrolidone (PVP) 0.1-0.2, water 8-12.

Described auto parts multi-walled carbon nano-tubes 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 described auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin, is characterized in that:

(1) ammonium hexafluorosilicate, Polyvinylpyrolidone (PVP) are added to the water, add carbon multi-wall nano tube loaded Ti-Zr catalyzer, nano-aluminium oxide again, 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, carry out slurry polymerization 7-9 hour under 2-3MPa condition, then the liquid ethylene adding 1/5 continues reaction 7-9 hour, obtains 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 using nano-aluminium oxide, improves polyacrylic thermal conductivity and antistatic property; By carrying out modification to carbon multi-wall nano tube loaded Ti-Zr catalyzer, improve the activity of catalyzer, reducing polarity difference, add the bonding force between multi-walled carbon nano-tubes and polymer.Production technique of the present invention achieves effective dispersion of nanoparticle and effective control of morphology, this resin is made to have higher impelling strength, keep good intensity and rigidity simultaneously, it is the nano composite material with good industrial prospect, be applicable to make automobile component, durable in use and security good.

Embodiment

A kind of auto parts multi-walled carbon nano-tubes 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 75, triethyl aluminum 8, dimethoxydiphenylsilane 5.9, normal heptane 55, hydrogen are appropriate, ammonium hexafluorosilicate 0.1,1-octene 13, nano-aluminium oxide 1.6, Polyvinylpyrolidone (PVP) 0.1, water 10.

Described auto parts multi-walled carbon nano-tubes 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 described auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin, is characterized in that:

(1) ammonium hexafluorosilicate, Polyvinylpyrolidone (PVP) are added to the water, add carbon multi-wall nano tube loaded Ti-Zr catalyzer, nano-aluminium oxide again, be heated to 65 DEG C, stirring reaction 25 minutes, 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 0.05% of propylene liquid quality again, at 60 DEG C, carry out slurry polymerization 8 hours under 3MPa condition, then the liquid ethylene adding 1/5 continues reaction 9 hours, obtains 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 2MPa, reacts 7 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 60 DEG C, pressure rises to 2MPa, 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 38.8MPa, and elongation at break is 850%, and under normal temperature, notched Izod impact strength reaches 37kJ/ ㎡, and modulus in flexure is 698Mpa.

Claims (3)

1. an auto parts multi-walled carbon nano-tubes Reinforced Polypropylene resin, is characterized in that being made up of the raw material of following weight part: propylene liquid 400-420, carbon multi-wall nano tube loaded Ti-Zr catalyzer 2.5-3.5, liquid ethylene 70-80, triethyl aluminum 7-9, dimethoxydiphenylsilane 5.4-6.2, normal heptane 50-60, hydrogen are appropriate, ammonium hexafluorosilicate 0.1-0.2,1-octene 10-15, nano-aluminium oxide 1.5-1.8, Polyvinylpyrolidone (PVP) 0.1-0.2, water 8-12.

2. auto parts multi-walled carbon nano-tubes 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 auto parts production method of multi-walled carbon nano-tubes Reinforced Polypropylene resin according to claim 1 and 2, is characterized in that:

(1) ammonium hexafluorosilicate, Polyvinylpyrolidone (PVP) are added to the water, add carbon multi-wall nano tube loaded Ti-Zr catalyzer, nano-aluminium oxide again, 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, carry out slurry polymerization 7-9 hour under 2-3MPa condition, then the liquid ethylene adding 1/5 continues reaction 7-9 hour, obtains 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.