CN1254504C - Nano-particle modified small bulk polypropylene material and its preparation method - Google Patents
Nano-particle modified small bulk polypropylene material and its preparation method Download PDFInfo
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- CN1254504C CN1254504C CN 200410012572 CN200410012572A CN1254504C CN 1254504 C CN1254504 C CN 1254504C CN 200410012572 CN200410012572 CN 200410012572 CN 200410012572 A CN200410012572 A CN 200410012572A CN 1254504 C CN1254504 C CN 1254504C
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Abstract
The present invention discloses a modified small bulk polypropylene material with nanometer particles and a preparation method thereof, which relates to a method for preparing modified small bulk polypropylene with nanometer particles. The present invention belongs to the technical field of polymer modification. The method comprises the steps: after being dried and dispersed by ultrasonic waves, nanometer particles are mixed and dispersed with a solution dissolved with unsaturated monomers and an initiator in the presence of ultrasonic waves; after being dried in a vacuum, the mixed and dispersed nanometer particle compound is firstly mixed with small bulk polypropylene; the granulation is carried out in a double-screw extruder, and the modified small bulk polypropylene is obtained. In the extruding process, the unsaturated monomers can not only be grafted with the polypropylene, but also be grafted on the surfaces of the nanometer particles; consequently, the dispersion of the nanometer particles in the polypropylene is enhanced, and the compatibility of the nanometer particles and the polypropylene is increased. Therefore, the mechanical property of the modified polypropylene can be improved. The preparation method simplifies the filling technology of the nanometer particles, and the preparation method is easily implemented.
Description
One, technical field
The invention belongs to the technical field of polymer modification, in particular to a kind of inorganic nano particle modified small-entity polypropylene material and technology of preparing thereof.
Two, background technology
Polypropylene (PP) is to belong to one of five big general-purpose plastics by the thermoplastic resin that propylene monomer is polymerized, because its source is enriched cheaply, synthesis technique is simple, and the physical synthesis performance is good in addition, and becomes the fastest kind of increase in the general-purpose plastics.Yet because it also exists many weak points, product fragility is big, and particularly low-temperature impact resistance is bad, and thermostability is little, and weathering resistance is poor, and high temperature rigid deficiency etc. make its application be subjected to certain restriction.Therefore, polypropylene is carried out modification and become important research direction in recent years.
Adopting the filling-modified polymkeric substance of nanoparticle is the important means that forms the high performance polymer matrix material.It has been generally acknowledged that, the key of optimizing this composite property is to realize that the superfine of nanoparticle in polymkeric substance disperses, therefore present research mainly utilizes special preparation method (as intercalation polymeric and solution blending etc.), improving nanoparticle in the intravital dispersion of polymer-based carbon, but these dispersing method all can not resemble nanoparticle the common widespread use in polymer processing the material of adding.
Utilize conventional melt blending working method directly to add to nanoparticle in the polymkeric substance, be subjected to the control of kinetic factor, have only the nanoparticle of minute quantity may in the resin matrix of viscosity higher, form the dispersion of primary fine particles level, most of nanoparticle will exist with the coacervate form, the structure of these coacervates is comparatively loose, be easy to generate stress concentration and the destruction that takes the lead in when material is stressed, crack growth resistance is little.Therefore, the key of nano modification is to improve dispersion and the compatibility performance of nanoparticle in polymkeric substance.In the prior art, main by to the surface modification of nanoparticle as with means such as coupling agent treatment, surface grafting, interpolation graftomer compatilizers.
When adopting coupling agent treatment, because its molecular weight is low, the many mechanical properties that can influence material of consumption, and that consumption can be handled less is inhomogeneous; And, need generally to make under the higher temperature that nanoparticle mixes with coupling agent, make hybrid technique comparatively complicated; Adopt nanoparticle surface graft process complexity, the particle after the processing needs further to handle, so cost up; Adopt to add macromolecular grafted thing because consumption is few, and the grafts molecular weight is big, is difficult for well and the nanoparticle thorough mixing, make effect also not ideal enough.
Three, summary of the invention
The present invention is a kind of inorganic nano particle modified small-entity polypropylene material and preparation method thereof, and a kind of inorganic nano particle modified small-entity polypropylene material that provides at the deficiencies in the prior art and the method for preparation thereof are provided purpose.Be characterized in earlier nanoparticle drying, ultrasonic dispersing, then with dissolution with solvents the solution of maleic anhydride and initiator under the ultrasonic wave effect, mix, disperse, through disperse, the blended mixture is after drying under the vacuum, mix in kneader or high-speed mixer with small scale bulk pp, in twin screw extruder, carry out melt blending, granulation gets modifying material.
The nanometer particle-modified small-entity polypropylene material of the present invention, it is characterized in that be a kind of with after inorganic nano-particle drying, the ultrasonic dispersing with dissolution with solvents the solution of maleic anhydride and initiator under the ultrasonic wave effect, mix, disperse; Inorganic nano-particle mixture after mixing, disperseing carries out just mixing with small-entity polypropylene, primary antioxidant, auxiliary anti-oxidant, lubricant processing aid after vacuum-drying, melt extrude the inorganic nano particle modified small-entity polypropylene material that the blend granulation forms in twin screw extruder, used each component and quality proportioning thereof are: 100 parts in small-entity polypropylene powder; 1～10 part of inorganic nano-particle; 1～8 part of maleic anhydride; Initiator is 1%～2% of a monomer consumption; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant, its tensile modulus are 1020MPa～1240MPa; Tensile strength is 29.68MPa～35.5MPa; Modulus in flexure is 558MPa～691.8MPa; Flexural strength is 25.49MPa～29.68MPa; Simply supported beam unnotched impact strength under-20 ℃ is 7.3kJ/m
2～8.5kJ/m
2The dimension card is heat-resisting to be 98.2 ℃～103.1 ℃.
Above-mentioned nanometer particle-modified small-entity polypropylene preparation methods is characterized in that a kind ofly will mixing, disperseing under the ultrasonic wave effect with the solution that has dissolved maleic anhydride and initiator after inorganic nano-particle drying, the ultrasonic dispersing; Nano-particle compound after mixing, disperseing carries out just mixing with small-entity polypropylene, primary antioxidant, auxiliary anti-oxidant, lubricant processing aid after vacuum-drying, melt extrudes the method that the blend granulation forms inorganic nano particle modified small-entity polypropylene material in twin screw extruder.
Above-mentioned nanometer particle-modified small-entity polypropylene preparation methods, it is characterized in that used inorganic nano-particle is lime carbonate or silicon-dioxide inorganic nano-particle, its particle diameter is less than 100nm, employed solution is acetone organic solvent or water, employed initiator is a dicumyl peroxide, employed oxidation inhibitor is B215 and 168, and lubricant is a calcium stearate.
Above-mentioned nanometer particle-modified small-entity polypropylene preparation methods, used each component and quality proportioning thereof are: 100 parts in small-entity polypropylene powder; 1～10 part of inorganic nano-particle; 1～8 part of maleic anhydride; Initiator is 1%～2% of a monomer consumption; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
Above-mentioned nanometer particle-modified small-entity polypropylene preparation methods is characterized in that inorganic nano-particle is at first at 100～140 ℃ of down dry 1～5hr; Adopt ultrasonic dispersing 5～20min; With scattered nanoparticle with acetone solution the solution of maleic anhydride and initiator under the ultrasonic wave effect, mix 5～20min, then carry out vacuum-drying.
Above-mentioned nanometer particle-modified small-entity polypropylene preparation methods, it is characterized in that described just be mixed in high-speed mixer or in kneader normal temperature carry out; The temperature of described double-screw melt blending extruding pelletization is carried out under 170～240 ℃.
According to above-mentioned preparation method, be characterized in having adsorbed initiator and maleic anhydride equably in nanoparticle surface, make it in the melt blending process, to form simultaneously polypropylene grafted maleic anhydride, lime carbonate surface grafting maleic anhydride, and in nanoparticle, form homopolymer, can improve the consistency of nanoparticle and polymkeric substance and the dispersiveness in multipolymer thereof, thereby improve polyacrylic performance, simplify preparation technology.
Four, embodiment
Embodiment one
The 50g nano-calcium carbonate behind 120 ℃ of dry 2hr, is used ultrasonic dispersing 15min; With dissolved the 20g maleic anhydride and 0.2g dicumyl peroxide acetone soln mixes, after disperseing 10min under the ultrasonic wave effect, vacuum-drying; With 1.0kg small-entity polypropylene (melting index 3.5), oxidation inhibitor B2153g, oxidation inhibitor 168 2g, calcium stearate 5g mix 1hr in kneader then, in parallel dual-screw extruding machine, react extrude, granulation, temperature is 170～240 ℃.Get the nono calcium carbonate modified material of small scale bulk pp.Its performance sees Table 1.
Embodiment two
The 50g nano-calcium carbonate behind 120 ℃ of dry 2hr, is used ultrasonic dispersing 15min; Mix with the acetone soln that has dissolved 20g maleic anhydride and 0.2g dicumyl peroxide, after disperseing 10min under the ultrasonic wave effect, vacuum-drying; Then with 1.0kg small-entity polypropylene (melting index 7.6), oxidation inhibitor B215 3g, oxidation inhibitor 168 2g, calcium stearate 5g mix 1hr in kneader, in parallel dual-screw extruding machine, react extrude, granulation, extrusion temperature is 170～240 ℃, gets the nono calcium carbonate modified material of small scale bulk PP.Its performance sees Table 1.
Embodiment three
The 20g nano silicon behind 120 ℃ of dry 2hr, is used ultrasonic dispersing 15min; With dissolved the 8g maleic anhydride and 0.16g dicumyl peroxide acetone soln mixes, after disperseing 10min under the ultrasonic wave effect, vacuum-drying; Then with 1.0kg small-entity polypropylene (Shijiazhuang plastic molding and processing plant 070, melting index 7.0), oxidation inhibitor B2153g, oxidation inhibitor 1682g, calcium stearate 5g mix 1hr in kneader, in parallel dual-screw extruding machine, react extrude, granulation, extrusion temperature is 170～240 ℃, gets the nono calcium carbonate modified material of small scale bulk PP.Its performance sees Table 2.
The performance of the nono calcium carbonate modified small-entity polypropylene of table 1
The nano-silicon dioxide modified small-entity polypropylene performance of table 2.
Claims (6)
1. nanometer particle-modified small-entity polypropylene material, it is characterized in that be a kind of with after inorganic nano-particle drying, the ultrasonic dispersing with dissolution with solvents the solution of maleic anhydride and initiator, under the ultrasonic wave effect, mix, disperse; Inorganic nano-particle mixture after mixing, disperseing carries out just mixing with small-entity polypropylene, primary antioxidant, auxiliary anti-oxidant, lubricant processing aid after vacuum-drying, melt extrude the inorganic nano particle modified small-entity polypropylene material that the blend granulation forms in twin screw extruder, used each component and quality proportioning thereof are: 100 parts in small-entity polypropylene powder; 1～10 part of inorganic nano-particle; 1～8 part of maleic anhydride; Initiator is 1%～2% of a monomer consumption; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant, its tensile modulus are 1020MPa～1240MPa; Tensile strength is 29.68MPa～35.5MPa; Modulus in flexure is 558MPa～691.8MPa; Flexural strength is 25.49MPa～29.68MPa; Simply supported beam unnotched impact strength under-20 ℃ is 7.3kJ/m
2～8.5kJ/m
2The dimension card is heat-resisting to be 98.2 ℃～103.1 ℃.
2. the described nanometer particle-modified small-entity polypropylene preparation methods of claim 1, it is characterized in that a kind of with after inorganic nano-particle drying, the ultrasonic dispersing with dissolution with solvents the solution of maleic anhydride and initiator under the ultrasonic wave effect, mix, disperse; Nano-particle compound after mixing, disperseing carries out just mixing with small-entity polypropylene, primary antioxidant, auxiliary anti-oxidant, lubricant processing aid after vacuum-drying, melt extrudes the method that the blend granulation forms inorganic nano particle modified small-entity polypropylene material in twin screw extruder.
3. according to the described nanometer particle-modified small-entity polypropylene preparation methods of claim 2, it is characterized in that used inorganic nano-particle is lime carbonate or silicon-dioxide inorganic nano-particle, its particle diameter is less than 100nm, employed solvent is acetone or water, employed initiator is a dicumyl peroxide, employed oxidation inhibitor is B215 and 168, and lubricant is a calcium stearate.
4. according to the described nanometer particle-modified small-entity polypropylene preparation methods of claim 2, used each component and quality proportioning thereof are: 100 parts in small-entity polypropylene powder; 1～10 part of inorganic nano-particle; 1～8 part of maleic anhydride; Initiator is 1%～2% of a monomer consumption; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
5. according to the described nanometer particle-modified small-entity polypropylene preparation methods of claim 2, it is characterized in that inorganic nano-particle is at first at 100～140 ℃ of down dry 1～5hr; Adopt ultrasonic dispersing 5～20min; With scattered nanoparticle with acetone solution the solution of maleic anhydride and initiator under the ultrasonic wave effect, mix 5～20min, then carry out vacuum-drying.
6.. according to the described nanometer particle-modified small-entity polypropylene preparation methods of claim 2, it is characterized in that described just be mixed in high-speed mixer or in kneader normal temperature carry out; The temperature of described double-screw melt blending extruding pelletization is carried out under 170～240 ℃.
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