CN1215114C - Nano powder composite material and its preparation method - Google Patents
Nano powder composite material and its preparation method Download PDFInfo
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- CN1215114C CN1215114C CN 02104084 CN02104084A CN1215114C CN 1215114 C CN1215114 C CN 1215114C CN 02104084 CN02104084 CN 02104084 CN 02104084 A CN02104084 A CN 02104084A CN 1215114 C CN1215114 C CN 1215114C
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Abstract
The present invention relates to nanometer powder composite materials and a preparation method thereof. The surfaces of nanometer particles are firstly coated and modified by macromolecular compounds by the nanometer powder composite materials so that a thin layer of macromolecular layer is absorbed by the surfaces of the nanometer particles. Agglomerating force among the particles is reduced, and a dispersion degree in resin is increased. The modified nanometer powder can be directly mixed with matrix resin according to a certain proportion so as to make a product of the nanometer powder composite materials, and can also be blended with carrier resin firstly so as to make filling master particles of the nanometer powder. The master particles are then mixed with the matrix resin according to a certain proportion so as to make the product of the nanometer powder composite materials. The content of the modified nanometer powder materials is 1 to 10 wt% in the product of the nanometer powder composite materials, and the mechanical properties of tensile strength, bend strength, impact strength, break elongation rate, etc. are increased by more than 30 %. The nanometer powder composite materials prepared by the present invention have the advantages of simple technology, low cost, high strength and good service property.
Description
Invention field
The present invention relates to nano powder composite material and preparation method thereof.
Background technology
Utilizing the filling-modified polymer manufacture high-performance nano of inorganic nano-particle matrix material, is study in the present Materials science more, a field that using value is bigger.
The particle diameter of nanoparticle is generally 1-100nm, is the transitional region that is in atom family and macro object boundary, is that a kind of typical Jie sees system.Because the constitutional features of nanoparticle, make nanoparticle have high surface energy, itself reunites extremely easily, in the process of research and development nano composite material, solve that nanoparticle is reunited and in matrix resin the homodisperse problem, be the key of decision composite property.The traditional coupling agent treatment method of the general employing of people at present come the modified Nano particle, not only effect is bad, has reduced the peculiar surfactivity of nanoparticle on the contrary, loses the due superperformance of nano composite material.The somebody mixes with nanoparticle with the gas phase monomer, adopts radio polymerization or initiator heated polymerizable technology, and nanoparticle is carried out surface coating modification, though this method is more effective than coupling agent method, and complex process, equipment requirements is special, the cost height.
Summary of the invention
The present invention is by selecting suitable organic solvent for use; polymkeric substance is made the polymer dilute solution; in ball mill, nanoparticle is carried out coating modification through grinding to the surface with macromolecular solution; make nanoparticle surface absorption skim macromolecule layer; both protected the nanoparticle high surface energy not suffer a loss; nano-grain is evenly dispersed in the matrix resin with the nanometer state, thereby obtains high performance nano powder composite material.
Macromolecule surface coating modification nano-powder, can be directly with after matrix resin mixes by a certain percentage, prepare various nano-powder filled composite materials goods with common plastics processing units and complete processing.Macromolecule surface coating modification nano-powder can also mix with vector resin, uses the twin screw extruder extruding pelletization, makes the nano-powder filler parent granule.Nano-powder content is 60-80wt% in the master batch.Mix by a certain percentage with matrix resin with the nano-powder filler parent granule,, can make various nano-powder filled composite materials goods equally by common plastics processing units and complete processing.
Adopt in the nano-powder filled composite materials goods of the present invention's preparation, nano-powder content is generally 1-10wt%.Mechanical properties such as the shock strength of goods, flexural strength, tensile strength and elongation at break are than improving more than 30% with the virgin resin goods.
Therefore, according to the present invention, provide a kind of nano powder composite material, it comprises 85-97wt%, preferred 90-97wt% matrix resin; 1-10wt%, preferred 3-5wt% modified Nano material and the various auxiliary agents of 0-5wt%.This matrix material can adopt common device of plastic processing and complete processing to prepare various plastics, as film, tubing, sheet material and various profiled materials etc.
Wherein nano material is including, but not limited to nano-calcium carbonate, nano titanium oxide, nano silicon, nano kaoline etc.These materials can be by art methods, and as vapor phase process, the liquid phase method preparation perhaps can be purchased.
Wherein said modified nano powder is that nanoparticle is carried out surface coating modification with macromolecular compound, makes nanoparticle surface absorption skim macromolecule layer.Nano-powder after the modification can directly mix the back by a certain percentage to be used with matrix resin, also can be earlier and the vector resin blend, make the nano-powder filler parent granule, and mix use by a certain percentage with matrix resin again with master batch.
Wherein said surperficial coated high molecular is compound modified, used macromolecular compound is one or more mixtures in PE, PP, PS, PVC, CPE, CPVC, PA, PET or the relevant multipolymer (for example propylene-ethylene copolymers, acrylate copolymer etc.).Select suitable organic solvent, these macromolecular compounds are mixed with the macromolecular solution that concentration is 2-10%, be about 1 by nano-powder with the macromolecular solution mass ratio again: after 1-1.5 mixes, in ball mill, carry out surface coating modification by grinding.
Described organic solvent is: benzene,toluene,xylene, ethylene dichloride, chloroform, tetracol phenixin, tetrahydrofuran (THF), hexanaphthene, hexane, acetone, pimelinketone, acetates, low mass molecule alcohol class, ethers or sherwood oil etc. are one or more mixed solvents wherein.
Described matrix resin be PE, PP, PS, PVC, CPVC, PA, PET, CPE, EVA, ABS, AS, EVOH, EPR, PC etc. wherein one or both, two or more blend.
Described auxiliary agent is commonly used those in this area, as one or more of stablizer, softening agent, lubricant, fire retardant, tinting material, static inhibitor etc.The example of these auxiliary agents also is that those skilled in the art are familiar with.
Described common plastics processing units is: forcing machine, as single screw extrusion machine, twin screw extruder; Injector; Blow moulding machine; Casting machine or rolling press.Described common process technology is: extrusion moulding, injection molding, curtain coating or calendering formation etc.
Described various goods are that membrane product is as geomembrane, agriculture greenhouse film, packing film etc.; The tubing goods are as industrial tubing, building pipe etc.; Various sheet materials and profiled material are as plastic-steel door and window, decorate with material etc.
According to another aspect of the present invention, the invention provides the preparation method of nano powder composite material, this method may further comprise the steps:
(A) with macromolecular compound, be mixed with the macromolecular solution that concentration is 2-10% as one or more mixtures in PE, PP, PS, PVC, CPE, CPVC, PA, PET or the relevant multipolymer with suitable organic solvent, be about 1 by nano-powder with the macromolecular solution mass ratio again: after 1-1.5 mixes, carry out surface coating modification by grinding;
(B) nano-powder after the modification can directly mix the back by a certain percentage and uses with matrix resin, perhaps can be earlier and the vector resin blend, make the nano-powder filler parent granule, and mix use by a certain percentage with matrix resin again with master batch;
(C) adopt the common plastics processing units to be: forcing machine, as single screw extrusion machine, twin screw extruder; Injector; Blow moulding machine; Casting machine or rolling press etc., and common process technology is: extrusion moulding, injection molding, curtain coating or calendering formation etc. are processed into various materials.
Further specify the present invention below in conjunction with embodiment.It should be understood that these embodiment only are used for illustrative purposes, never constitute any limitation of the invention.
Embodiment 1
Get a certain amount of PE and a certain amount of benzene and toluene mixed solvent, being configured to concentration is the PE solution of 2-4%, the nano-calcium carbonate grain is mixed the back with it again and becomes pasty state, grinds 20-60min in ball mill, after reclaiming solvent, through pulverizing the sub-surface coating modification nano-calcium carbonate that promptly secures satisfactory grades.
The modified nano calcium carbonate that makes is passed through the twin screw extruder extruding pelletization, promptly get nano-calcium carbonate PE filler parent granule, the nano-calcium carbonate calcium contents is 72.5wt% in the master batch.
(1) get 500g nano-calcium carbonate PE filler parent granule and 6kgLDPE, 1.5kgLLDPE mix after, be blow molded into the thick film of 20 μ m with inflation film manufacturing machine, in this nano-calcium carbonate composite membrane, the nano-calcium carbonate calcium contents is 4.5wt%, and its tensile strength, elongation at break and angle tear strength improve 42%, 56% and 44% respectively than the pure LDPE/LLDPE composite membrane of same ratio.
(2) get 500g nano-calcium carbonate PE filler parent granule and 7kgHDPE mix after, be injected into the standard batten with injector, the nano-calcium carbonate calcium contents is 4.8wt% in the batten.Survey its tensile strength, flexural strength and unnotched impact strength, the result improves 34%, 62% and 84% respectively than pure HDPE batten.
Embodiment 2
Get a certain amount of PP and a certain amount of dimethylbenzene and be configured to the PP solution that concentration is 6-10%, press the same method system of example 1, just replace nano-calcium carbonate with nano silicon, sub-coating modification nano silicon secures satisfactory grades.And be vector resin with PP, make nano silicon PP filler parent granule with embodiment 1 same method.The nanometer titanium dioxide silicone content is 75wt% in the master batch.
(1) getting 500g nano silicon PP filler parent granule mixes with 7kgPP, make the thick film of 20 μ m with the unilateral stretching casting technique, the nanometer titanium dioxide silicone content is 5wt% in this film, and its longitudinal tensile strength, elongation at break improve 38% and 46% than pure PP unilateral stretching film respectively.
(2) get 500g nano silicon PP filler parent granule and mix with 7kgPP, be injected into the standard batten with injector, the nanometer titanium dioxide silicone content is 5wt% in the batten.Survey its tensile strength, flexural strength and unnotched impact strength, the result improves 40%, 46% and 72% respectively than pure PP batten.
Embodiment 3
The CPVC solution that to get a certain amount of CPVC and a certain amount of sherwood oil configuration concentration be 4-8% makes macromolecule surface coating modification nano titanium oxide by example 1 with quadrat method.
After getting 500g modified nano-titanium dioxide and 12kgPVC batch mixing (batch mixing is formed: PVC:100 part, stablizer: 5 parts, softening agent: 5 parts, lubricant: 1.5 parts) and in high stirrer, mixing, be divided into 2 parts.
(1) get wherein 1 part and make the thick monodirectional tension film of 20 μ m with the unilateral stretching casting technique, the nanometer titanium dioxide titanium content is 3.8wt% in this film, and its longitudinal tensile strength, elongation at break improve 32% and 40% respectively than simple PVC batch mixing unilateral stretching film.
(2) get wherein 1 part of 10min that on two roll plastic mixing mill, plasticates in addition, the sheet material of making is pulverized, be injected into the standard batten with injector, the nanometer titanium dioxide titanium content is 3.8% in the batten, survey its tensile strength, flexural strength and unnotched impact strength, the result improves 36%, 44% and 68% respectively than simple PVC batch mixing batten.
Claims (9)
1, a kind of nano powder composite material, it comprises 85-97wt% matrix resin, 1-10wt% modified nano powder material and the various auxiliary agents of 0-5wt%,
Described modified Nano material, be by nanoparticle is carried out surface coating modification with macromolecular compound, nanoparticle surface absorption skim macromolecule layer is obtained, nano material after the modification can directly be mixed the back in described ratio and be used with matrix resin, perhaps can be earlier and the vector resin blend, make the nano-powder filler parent granule, mix use by a certain percentage with matrix resin again with master batch, described macromolecular compound is selected from one or more mixtures in PE, PP, PS, PVC, CPE, CPVC, PA, PET or the relevant multipolymer.
2, the nano powder composite material of claim 1, it comprises the 90-97wt% matrix resin, the various auxiliary agents of 3-5wt% modified nano powder material and 0-5wt%.
3, the nano powder composite material of claim 1, described surface coats and is to use macromolecular compound, select suitable organic solvent, these macromolecular compounds are mixed with the macromolecular solution that concentration is 2-10%, again by 1: the nano material of 1-1.5 is with after the macromolecular solution mass ratio mixes, in ball mill, carry out surface coating modification by grinding.
4, the nano powder composite material of claim 3, described organic solvent is: one or more mixed solvents in benzene,toluene,xylene, ethylene dichloride, chloroform, tetracol phenixin, tetrahydrofuran (THF), hexanaphthene, hexane, acetone, pimelinketone, acetates, low mass molecule alcohol class, ethers or the sherwood oil.
5, each nano powder composite material among the claim 1-4, described matrix resin be among PE, PP, PS, PVC, CPVC, PA, PET, CPE, EVA, ABS, AS, EVOH, EPR, the PC one or both, two or more blend.
6, claim 1 or 2 nano powder composite material, described auxiliary agent is one or more in stablizer, softening agent, lubricant, fire retardant, tinting material, the static inhibitor.
7, the preparation method of nano powder composite material, this method may further comprise the steps:
(A) macromolecular compound is mixed with the macromolecular solution that concentration is 2-10% with suitable organic solvent, be 1 by nano material with the macromolecular solution mass ratio again: after 1-1.5 mixes, carry out surface coating modification by grinding, described macromolecular compound is selected from one or more mixtures in PE, PP, PS, PVC, CPE, CPVC, PA, PET or the relevant multipolymer;
(B) nano material after the modification can be directly in 1-10wt% modified nano powder material: the ratio of 85-97wt% matrix resin is mixed the back and is used with matrix resin, perhaps can be earlier and the vector resin blend, make nanomaterial-filled master batch, mix use by a certain percentage with matrix resin again with master batch;
(C) adopt common plastics processing units and common process processes to become various materials.
8, according to the method for claim 7, described matrix resin be PE, PP, PS, PVC, CPVC, PA, PET, CPE, EVA, ABS, AS, EVOH, EPR, PC wherein one or both, two or more blend.
9, claim 1 nano powder composite material is used to prepare membrane product, the purposes of tubing goods and various sheet materials.
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| CN 02104084 CN1215114C (en) | 2002-03-08 | 2002-03-08 | Nano powder composite material and its preparation method |
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