Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the TPV thermoplastic elastic material that a kind of antistatic modifier addition is few, processing characteristics keeps well, surface resistivity reduces is provided.
For achieving the above object, the present invention adopts following technical scheme:
A kind of TPV thermoplastic elastic material is comprised of following component and weight percent: polypropylene 15~60%, terpolymer EP rubber 20~60%, polymer bulking agents 0.5~10%, filler 0.1~40%, rubber filling oil 1~60%, properties-correcting agent 0.5~10%, linking agent 0.5~10%, crosslinking coagent 0.1~10%, oxidation inhibitor 0.01~2%, processing aid 0.01~10%; Described properties-correcting agent is carbon nanotube.
Described carbon nanotube be a kind of by hexagon charcoal atomic building by which floor coaxial pipe to tens layers, be the hollow tube-shape structure, drum diameter be zero point several nanometers to tens nanometers, length be tens nanometers to micron order, the carbon nanotube of preferred external diameter 10-20nm, length 0.5-30um.This special hollow structure of carbon nanotube is given its very low tap density, more easily forms continuous conductive network in plastic substrate.
Described polypropylene is a kind of isotactic polyprophlene, it is characterized in that two defectives between the structural chain have the average isotactic block length as statistical average value greater than 70, preferably at least 75, and more preferably 80 average isotactic block length.
Described isotactic polyprophlene weight-average molecular weight (Mw) is 20000~900000g/mol, and more preferably Mw is 40000~800000g/mol.
Described isotactic polyprophlene number-average molecular weight (Mn) is 10000~500000g/mol, and more preferably Mn is 20000~400000g/mol.
Described polyacrylic molecular weight distribution width (MWD) represents with the ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), the polypropylene that the preferred molecular weight Tile Width is lower, and the scope of MWD is 2~5, preferred MWD scope is 2.5~4.
At least 155 ℃ of described polyacrylic fusing points, preferably at least 158 ℃, more preferably more than 160 ℃.
Described terpolymer EP rubber refers to that mooney viscosity is 25~90, contains the terpolymer that unsaturated the 3rd monomer 0.5~10%, ethylene content are 50~75% ethene, propylene and the 3rd monomer, and preferred mooney viscosity is 35~80, unsaturated the 3rd monomer 2~8%, ethylene content are 55~70% terpolymer EP rubber.
Described polymer bulking agents is grafts or the multipolymer of the function monomers such as polypropylene and maleic anhydride, acrylicacidandesters class, glycidyl methacrylate, and perhaps their mixture is described with PP-g-MAH, PP-g-AA, PP-g-GMA respectively.
The percentage of grafting of described polymer bulking agents is not less than 0.5%, and preferred percentage of grafting is greater than 1%; Consumption 0.5~10%, preferred 1~7%.The effect of adding above-mentioned polymer bulking agents is: the functional group in the polymer bulking agents and carbon nanotube generation chemistry or physical action help its dispersion in polypropylene; And the propylene block in the polymer bulking agents and PP have good consistency, make carbon nanotube be enriched in the PP phase, improve the mutually relative content of middle carbon nanotube of PP.Behind the dynamic vulcanization, TPV forms take PP as external phase, crosslinked rubber is " sea-island " structure of disperse phase, thereby in the situation that just can form continuous conductive network than few additive, obtains good antistatic or conductivity.
Described filler can be the mixture of wherein one or more such as talcum powder, barium sulfate, calcium carbonate, wollastonite, kaolin, clay, ceramic fine bead, glass fibre, the mixture of one or more in preferably talc powder, wollastonite, the kaolin.
Described rubber filling oil refers to one or both the mixture in white mineral oil, the naphthenic oil.
Described properties-correcting agent is a kind of carbon nanotube (CNT).
Described linking agent refers to resol (such as SP1045 or SP2045 etc.), superoxide (such as DCP, BIPB, two 25 etc.) etc., the adding of linking agent can cause EPDM produce crosslinked, thereby form the rubber phase of three-dimensional net structure.
Described crosslinking coagent refers to that metal halide is (such as SnCl
2), only when adopting non-halogenated phenols urea formaldehyde to be linking agent, add; And (different) cyanate (TAC, TAIC), divinylbenzene class etc., esters of acrylic acid crosslinking coagent add when adopting superoxide to be linking agent.
Described oxidation inhibitor refers to a kind of in phenolic antioxidant, the phosphite ester kind antioxidant, perhaps multiple composition wherein.Phenolic antioxidant such as BHT, 1010,1076,1790 etc., phosphite ester kind antioxidant is such as 168,626 etc.
Described processing aid is one or more mixtures in stearic acid, stearate, metal oxide, silicone oil or the silicone, can improve processing characteristics in melting mixing or the subsequent forming course of processing.
In addition, as required, the present invention is not precluded within and adds various tinting materials on the basis of said components feature, and the adding of tinting material is to give material certain color, and tinting material comprises the components such as inorganic colourant, organic colorant.
The preparation method of the TPV elastomer material that described electrical property improves is undertaken by melt-blending process, adopts one step of melting mixing equipment to finish dynamic vulcanization all components.
The preparation method of the TPV elastomer material that described electrical property improves can adopt to prepare in advance Preblend (comprising all components except linking agent), then Preblend and linking agent is mixed, and adopts melting mixing equipment to carry out dynamic vulcanization.
The preparation method of the TPV elastomer material that described electrical property improves also can adopt the method described in the Chinese patent 200910193224.8: one step of preparation feedback is expected (all components except vulcanizing agent and vulcanization accelerator), vulcanizing agent rubber master batch, promotor rubber master batch in advance, then above-mentioned three kinds of material mixing is carried out dynamic vulcanization.
Described melting mixing equipment comprises single screw extrusion machine, twin-screw extrusion, Banbury mixer, Double-rotor continuous mixing equipment, and processing condition are 160~250 ℃ of temperature, rotating speed 30~1200rpm.
The TPV elastomer material that the electrical property of foregoing invention is improved adopts the thin slice of heat pressing forming machines mold pressing thickness 2~4mm under 180 ℃ of conditions, adopt the surface resistivity instrument to measure the surface resistivity of thin slice, adopt universal sampling machine to prepare tensile bars, measure tensile strength and the elongation at break of material, the processing flowability of material characterizes by the melt flow index (MI) of measuring under 230 ℃ of temperature, the load 5KG condition.
Compared with prior art, the present invention has following beneficial effect: the present invention is by introducing a kind of novel carbon nanotube antistatic modifier, the special phase structure of utilizing TPV and polymer bulking agents with PP fully compatible and with the crosslinked incomplete compatibility principle of rubber phase, make carbon nanotube be enriched in continuous PP phase, form continuous conductive network structure, obtain desirable antistatic and conductive effect.Surface resistivity is reduced to 10 when adding 0.5%
12, surface resistivity is reduced to 10 when adding 2%
6, can satisfy general anlistatig demand; Surface resistivity is reduced to 10 when adding 5%
2, it is good that processing flowability keeps; Surface resistivity is reduced to 10 when adding 10%
0, reached the performance requriements of electro-conductive material.The TPV elastomer material that the electrical property of the present invention's preparation improves, surface resistivity is well below the graphitized carbon black that adds same component, in the situation that just can reach preferably antistatic effect than few additive (0.5~2%), expanded the application of TPV in antistatic material and electro-conductive material field, be with a wide range of applications.
Embodiment
The present invention is further described below in conjunction with embodiment.
Embodiment 1
By weight with polypropylene 18%, terpolymer EP rubber 32%, expanding material (PP-g-MAH) 1%, SP2045 linking agent 5%, kaolin 12.8%, white mineral oil 25%, carbon nanotube 2%, oxidation inhibitor (1010) 0.2%, polyethylene wax 2%, zinc oxide 1.5%, stearic acid 0.5% mixes, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 500rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
6, tensile strength is that 7.2MPa, elongation at break are 420%, MI is 6.2g/10min.
The carbon nanotube adding proportion of the present embodiment is less, is 2%, and as seen carbon nanotube addition 3% in the comparative example 1, the addition of comparative example 2,3 graphitized carbon black HG-1P the invention has the advantages that and reduced addition to 10~15%.
Embodiment 2
By weight with polypropylene 20%, terpolymer EP rubber 40%, expanding material (PP-g-AA) 1%, wollastonite 9.8%, naphthenic oil 17%, carbon nanotube 3%, crosslinking coagent (SnCl
2) 2%, oxidation inhibitor (1076) 0.1%, oxidation inhibitor (168) 0.1%, polyethylene wax 3%, zinc oxide 0.8%, stearic acid 0.2% mixes, adopt Banbury mixer under the condition of 180~200 ℃ of temperature, rotating speed 30rpm, to carry out melting mixing and prepare Preblend A.
The resol SP1045 of above-mentioned Preblend A and 3% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 500rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
3, tensile strength is that 6.5MPa, elongation at break are 455%, MI is 5.5g/10min.
The carbon nanotube adding proportion 3% of the present embodiment, surface resistivity 10
3Carbon nanotube addition 3% in the comparative example 1, surface resistivity 10
5The addition of comparative example 2 and 3 graphitized carbon black HG-1P is to 10~15%, and the advantage of visible the present embodiment is to have reduced addition.
Embodiment 3
By weight with polypropylene 17%, terpolymer EP rubber 30%, expanding material (PP-g-GMA) 2%, talcum powder 10.8%, naphthenic oil 25%, carbon nanotube 5%, crosslinking coagent (TAIC) 3%, oxidation inhibitor (1010) 0.2%, polyethylene wax 3%, Zinic stearas 2% mix, and adopt Banbury mixer to carry out melting mixing under 180~200 ℃ and prepare Preblend B.
The DCP of above-mentioned Preblend B and 2% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 600rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
1, tensile strength is that 5.2MPa, elongation at break are 386%, MI is 2.6g/10min.
Embodiment 4
By weight with polypropylene 30%, terpolymer EP rubber 42%, expanding material (PP-g-MAH) 0.3%, kaolin 13%, white mineral oil 5%, carbon nanotube 0.5%, crosslinking coagent (SnCl
2) 2%, oxidation inhibitor (1010) 0.2%, polyethylene wax 3%, zinc oxide 0.8%, stearic acid 0.2% mix, and adopt Banbury mixer to carry out melting mixing under 180~200 ℃ and prepare Preblend C.
The resol SP1045 of above-mentioned Preblend C and 3% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 300rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
12, tensile strength is that 8.3MPa, elongation at break are 478%, MI is 6.8g/10min.
The present embodiment only adds 0.5% carbon nanotube, measures very lowly, therefore that surface resistivity seems is high, purpose is to illustrate the scope of protection, from industry through examining, if add 0.5% graphitized carbon black, can not reduce the surface resistivity of PP, be 10
15Above.
Embodiment 5
By weight with polypropylene 8KG, terpolymer EP rubber 13KG, expanding material (PP-g-MAH) 7KG, kaolin 0.8KG, white mineral oil 47KG, carbon nanotube 10KG, oxidation inhibitor (1790) 0.2KG, polyethylene wax 3KG, zinc oxide 0.8KG, stearic acid 0.2KG mix, and adopt Banbury mixer to carry out one step of melting mixing preparation feedback material D1 under 180~200 ℃.
With terpolymer EP rubber 2KG and crosslinking coagent (SnCl
2) 2KG mixes, and adopts melting mixing equipment to prepare promotor rubber master batch D2.
Terpolymer EP rubber 3KG and SP1045 linking agent 3KG are mixed, adopt melting mixing equipment to prepare linking agent rubber master batch D3.
By weight one step of 90% reaction material D1,4% promotor rubber master batch D2 and 6% linking agent rubber master batch D3 are mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 1200rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
0, tensile strength is that 3.8MPa, elongation at break are 340%, MI is 0.8g/10min.
Comparative Examples 1
By weight with polypropylene 20%, terpolymer EP rubber 40%, wollastonite 10.8%, naphthenic oil 17%, carbon nanotube 3%, crosslinking coagent (SnCl
2) 2%, oxidation inhibitor (1076) 0.1%, oxidation inhibitor (168) 0.1%, polyethylene wax 3%, zinc oxide 0.8%, stearic acid 0.2% mixes, adopt Banbury mixer under 180~200 ℃, to carry out melting mixing and prepare Preblend E.
The resol SP1045 of above-mentioned Preblend E and 3% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ (order is from feed opening to head), rotating speed 500rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
5, tensile strength is that 6.3MPa, elongation at break are 438%, MI is 5.6g/10min.
Surface resistivity has increased 2 orders of magnitude than the surface resistivity of embodiment 2, illustrates that the adding of polymer bulking agents is favourable to reducing surface resistivity.
Comparative Examples 2
By weight with polypropylene 20%, terpolymer EP rubber 32%, kaolin 3.8%, white mineral oil 25%, graphitized carbon black (HG-1P) 10%, crosslinking coagent (SnCl
2) 2%, oxidation inhibitor (1010) 0.2%, polyethylene wax 3%, zinc oxide 0.8%, stearic acid 0.2% mixes, adopt Banbury mixer under 180~200 ℃, to carry out melting mixing and prepare Preblend F.
The resol SP1045 of above-mentioned Preblend F and 3% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, (order for from feed opening to head), and rotating speed 500rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
5, tensile strength is that 9.1MPa, elongation at break are 275%, MI is 0.2g/10min.
Comparative Examples 3
By weight with polypropylene 20%, terpolymer EP rubber 32%, kaolin 0.8%, white mineral oil 23%, graphitized carbon black (HG-1P) 15%, crosslinking coagent (SnCl
2) 2%, oxidation inhibitor (1010) 0.2%, polyethylene wax 3%, zinc oxide 0.8%, stearic acid 0.2% mixes, adopt Banbury mixer under 180~200 ℃, to carry out melting mixing and prepare Preblend G.
The resol SP1045 of above-mentioned Preblend G and 3% is mixed, adopt twin-screw extrusion to carry out dynamic vulcanization and prepare the TPV elastomer material that electrical property improves, the Temperature Setting of twin screw extruder heating zone is: 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, (order for from feed opening to head), and rotating speed 500rpm.
Above-mentioned materials adopts heat pressing forming machines under 180 ℃ of conditions, the thin slice of mold pressing thickness 2mm, and the surface resistivity of material is 10
3, tensile strength is that 10.8MPa, elongation at break are 156%, MI is 0.05g/10min.