CN101838414B - Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material - Google Patents
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- 238000000034 method Methods 0.000 title abstract description 22
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- 229920001155 polypropylene Polymers 0.000 claims description 7
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- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
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Abstract
The invention discloses a method for preparing oriented inorganic nanoparticles/a thermoplastic polymer composite material. The method for preparing the oriented inorganic nanoparticles/the thermoplastic polymer composite material of the invention comprises the following steps of: performing chemical crafting modification on inorganic nanoparticles by radiation; then melting, mixing and pressing the modified nanoparticles and the thermoplastic polymer; stretching the nano-composite material at a constant speed and at the temperature of between the glass-transition temperature of the polymer and the melting point; and cooling and crystallizing the material to obtain the oriented inorganic nanoparticles/the thermoplastic polymer composite material. The preparation method of the invention can promote dispersion of the inorganic nanoparticles in the thermoplastic polymer so as to arrange the nanoparticles three-dimensionally in order, so the enhancement effect of the inorganic nanoparticles to the thermoplastic polymer material is brought into full play, and the problem that the inorganic nanoparticles are difficult to be dispersed uniformly in the polymer substrate is solved; and the method of the invention has simple process and low cost and obviously improves both the tensile strength and the modulus of the prepared oriented composite material.
Description
Technical field
The present invention relates to the high-strength polymer composite material field, be specifically related to a kind of preparation method of oriented inorganic nanoparticles/thermoplastic polymer composite material.
Background technology
In recent years, some special dimension such as aircraft industry, national defence sophisticated industry etc. had higher requirement to the performance of matrix material, and such as high strength, high-modulus, lightweight etc., developing of the high-strength polymer of various particular requirements is more and more aobvious urgent.Metal and ceramic actual modular ratio polymkeric substance are high, calculating theoretically the actual intensity that records of intensity that metallic bond obtains and we approaches or equates, and the actual modulus of polymer materials and intensity level do not reach its theoretical value far away, intensity far below C-C in the polymkeric substance and c h bond, this mainly is because the random arrangement of the inner macromolecular chain of polymer materials, makes the high strength of molecular chain itself not be converted into the high strength of goods.Because the intensity overwhelming majority that polymer materials shows in strength trial is to be provided by relatively weak a lot of intermolecular forces (Van der Waals force, hydrogen bond).Simultaneously because polymkeric substance is a kind of viscous-elastic material, its modulus and intensity time, temperature and change, and a certain amount of free volume is arranged in the polymkeric substance, these all cause theoretical strength and actual strength that larger difference is arranged.By utilize consciously in the macromolecular chain with macromole between different reactive forces, stretch as much as possible the macromolecular chain that closes with the C-C bond, cause the upright and outspoken orientation of chain, just might obtain high-modulus, high-intensity polymer materials.The flexible chain polymer if improve to heavens its orientation degree and degree of crystallinity, then upwards can obtain being enough to the modulus and the intensity that are equal to iron and steel in axis of orientation at least.This has just pointed out direction to the mechanical property that we improve polymer materials, namely allow the inner macromole of polymer materials along the stress direction ordered arrangement, in the certain situation of chemical bond energy, the macro strength of material can be greatly improved, the ordered arrangement of molecular chain improves degree of crystallinity simultaneously, thereby the intensity of material is further improved.
The polymer materials that obtains high orientation by special technique is one of focus of present macromolecular material and scientific research, and nano-inorganic particle filled modification provides new approach also for the polymer composites performance.The characteristics such as particle diameter is little, specific surface area is large because having for nanoparticle, surperficial non-matching atom is many, if with the nanoparticle good distribution in polymkeric substance, to form the strong interaction interface of huge amount, thereby under very low loading level, significantly improve mechanical property, thermal characteristics and the barrier property etc. of polymkeric substance.Nanoparticle reinforced plastics effect quality and nanoparticle in matrix degree of scatter and the interface between filler and matrix in conjunction with relevant.If adopt specific means that matrix material is applied stretching action, as long as between nanoparticle and matrix enough interface interactions are arranged, the nanoparticle coacervate just outside under the force field deformation along with polymkeric substance deform, promote the dispersion of nanoclusters aggressiveness, and induced polymer matrix special construction occurs, and significantly improves the mechanical property of polymkeric substance.And a small amount of nano-particles filled can significantly improve the performance of material, and material can be recycled, and high filler loading capacity and difficult recovery of comparing glass fibre have larger practical value.
Summary of the invention
The object of the invention is to basis to the high filler loading capacity of existing polymer materials, the problem that difficulty reclaims, requirement of strength is more and more higher, a kind of preparation method of oriented inorganic nanoparticles/thermoplastic polymer composite material is provided, the method can significantly improve the mechanical property of polymkeric substance, and induced polymer matrix special construction occurs.
The object of the invention is achieved by the following technical programs:
A kind of preparation method of oriented inorganic nanoparticles/thermoplastic polymer composite material, comprise the steps: by radiation chemistry Grafted Nano-scale inorganic particulate, again with the nanoparticle after the modification and thermoplastic polymer melt blending, compacting, under the temperature between glass transition temperature of polymer and the fusing point, with constant speed nano composite material is stretched, crystallisation by cooling obtains oriented inorganic nanoparticles/thermoplastic polymer composite material.
Particularly, preparation method of the present invention comprises the steps: by pre-radiation or is total to radiation chemistry Grafted Nano-scale inorganic particulate, make monomer arrive nanoparticle surface through the gas-liquid graft polymerization, with the nano inoganic particle after the modification and thermoplastic polymer melting mixing, be pressed into thin slice, under the temperature between glass transition temperature of polymer and the fusing point, carry out the stretch orientation preparation, by suitable temperature field, make the matrix material molecular orientation under the effect such as stress field and velocity field, in this process, vertically the nanoparticle coacervate is forced to draw loose and separation, laterally make nanoparticle mutually close, produce the osmosis network, make nanoparticle can give full play to stress transmission and dissipation effect.After the stretching, rapidly with the sample cool to room temperature, at this moment the molecular orientation of material is kept, for hemicrystalline polymkeric substance, formed the shish-kebab of uncrimping chain, raising to the strength of materials has better effect, and the nano-dispersed structure is fixed up in matrix material, thereby realizes the nanoscopic level dispersion of nanoparticle in polymeric matrix.
Among the present invention, adopt radiation chemistry Grafted Nano-scale inorganic particulate, to improve the dispersion of nanoparticle in polymkeric substance, and the reinforcement nanoparticle is combined with the interface of polymeric matrix, when tensile deformation, the nanoparticle of modification can effectively be moved along with the molecular chain movement of polymeric matrix, thereby the three-dimensional order of control nanoparticle is arranged, the go forward side by side appearance of special construction in the one-step inducing matrix, thereby the novel nano composite inorganic particle/polymer material that obtains being orientated.
As a kind of preferred version, among the above-mentioned preparation method, described nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate.Wherein, described nano-silicon dioxide particle is precipitator method nano silicon or fumed nano silicon-dioxide, and median size is 7~50nm, and specific surface area is 150~640m
2/ g.
As a kind of preferred version, among the above-mentioned preparation method, described thermoplastic polymer is polyethylene, polypropylene, polystyrene, tetrafluoroethylene, nylon or poly terephthalic acid hexylene glycol ester.
As a kind of preferred version, among the above-mentioned preparation method, the temperature between described glass transition temperature of polymer and the fusing point is 90~150 ℃.
As a kind of preferred version, among the above-mentioned preparation method, the speed of described stretching is 10~50mm/min.
As a kind of preferred version, among the above-mentioned preparation method, described monomer is esters of acrylic acid, acrylate containing fluorine, vinylbenzene or glycidyl methacrylate.Wherein, acrylic ester monomer is ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester.
As a kind of preferred version, among the above-mentioned preparation method, the consumption of described nano inoganic particle is 1~3wt% of thermoplastic polymer, and the consumption of monomer equates with nano inoganic particle.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention at first utilizes method for radio-grafting to process nano inoganic particle, make monomer form grafted chain in nanoparticle surface, improved the consistency between nano inoganic particle and polymeric matrix, simultaneously because the osmosis of gas (liquid) attitude monomer and the penetrativity of energetic ray, even be in the particle of nanoparticle coacervate inside also by effective grafting and parcel, and the coacervate that in this process, struts and swell, the interface keying action has also been strengthened in mutual winding between graftomer molecular chain and matrix polymer molecular chain, thereby matrix material is in the solid state drawing process, the nanoparticle aggregate structure is forced to draw loose and separates, and obtains having the matrix material of nanoscopic level dispersion.Like this on the basis that obtains the orientation complete processing, use the method that changes processing conditions and processing means rationally to control the morphological structure of nano composite material, solve nano inoganic particle and be difficult to homodisperse problem in polymeric matrix, the nanometer composite inorganic particle/polymer material that obtains having remarkable reinforced effects;
(2) processing units that adopts of the technology of the present invention is simple, and technique is easily gone, and tensile strength and the rigidity of obtained matrix material all are significantly improved.The technology of the present invention also can be used for preparing the nano composition of polyethylene, polystyrene, tetrafluoroethylene, nylon and poly terephthalic acid hexylene glycol ester etc.
Description of drawings
Fig. 1 is the solid state drawing process schematic representation.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of restriction to the present invention.
Embodiment 1~3
Table 1 is each composition consumption proportion of the embodiment of the invention, and the preparation process of each embodiment is identical, and concrete steps are: nano inoganic particle is at first through the radiation chemistry grafting, and grafted monomer is butyl acrylate, and consumption proportion sees Table 1.Melt blending in the Hakke torque rheometer prepares masterbatch with Grafted Nano-scale particle and polypropylene, masterbatch and polypropylene is diluted in proportion again.By the matrix material that solid state drawing technique obtains being orientated, the matrix material with orientation is prepared into test bars by the ASTM3039 standard again.
Comparative example 1~3
Moulding technique is different from embodiment is identical for each composition consumption proportion of comparative example, the preparation process of each comparative example is identical, the concrete preparation process of comparative example is: nano inoganic particle is at first through the radiation chemistry grafting, and grafted monomer is butyl acrylate, and consumption proportion sees Table 2.Melt blending in the mixing tank of Hakke torque rheometer prepares masterbatch with Grafted Nano-scale particle and polypropylene, again masterbatch and polypropylene are diluted in proportion, the matrix material of required proportioning is become the standard batten with the injector direct injection, process without solid state drawing.
Table 3 be the prepared matrix material of embodiments of the invention and Comparative Examples matrix material Performance Ratio.
As seen from Table 3:
1. after processing through solid state drawing, the tensile strength of embodiment 1~3 all is higher than the tensile strength of same recipe comparative example 1~3 far away, wherein the tensile strength of embodiment 3 is the highest, be about 10 times of virgin pp (comparative example 1) tensile strength, illustrate that our cold stretching technique can improve the tensile strength of material significantly.The nano-silicon dioxide particle of radiation grafting butyl polyacrylate is processed (embodiment 3) through solid state drawing and all is significantly improved than the tensile strength through the matrix material (embodiment 2) of the pure PP (embodiment 1) of solid state drawing and the unmodified nanoparticle of adding, illustrates that the modified Nano particle plays enhancement by solid state drawing technique to polypropylene.
2. all the Young's modulus than the comparative example 1~3 of processing without solid state drawing is high for the Young's modulus of the embodiment of the invention 1~3 sample, and the technology that the solid state drawing of the present invention's employing be described can make the arrangement of molecular chain orientation, the rigidity of reinforced composite.
Fig. 1 is the synoptic diagram of the solid state drawing technique that adopts, with bulk each to the sample of equal property at glass transition temperature of polymer (T
g) and fusing point (T
m) between temperature under (T
g<T<T
m), with constant speed sample is carried out stretch processing.Owing to be in elastomeric state, polymer molecular chain has suitable mobility, under external force, molecular chain can be in the arrangement of the action direction orientation of power, the nanoparticle of simultaneously modification can effectively move along with the molecular chain movement of polymeric matrix, thereby the three-dimensional order of control nanoparticle is arranged, and the change of induced polymer matrix crystalline texture, as makes the crystal formation of polymer crystals be transformed into the shish-kebab of uncrimping chain from spherocrystal.
Table 1 embodiment 1~3 each composition consumption proportion
*Remarks: SiO
2The radiation chemistry graft modification adopt
60Co-gamma-rays room temperature mutual radiation, solvent is butanone, radiation dose 8Mrad.Sample after 48 hours, is measured the percentage of grafting of particle surface through the acetone extracting after the radiation modification by thermogravimetic analysis (TGA).
Table 2 comparative example 1~3 composition and consumption proportion
The Performance Ratio of table 3 embodiment and the obtained material of comparative example
*Remarks: 1. press ASTM D638-1998 standard test comparative example tensile strength and Young's modulus, press ASTM3039 and measure embodiment tensile strength and Young's modulus.2. measure T with DSC
m
Claims (9)
1. the preparation method of an oriented inorganic nanoparticles/thermoplastic polymer composite material, it is characterized in that comprising the steps: by radiation chemistry Grafted Nano-scale inorganic particulate, again with the nanoparticle after the modification and thermoplastic polymer melt blending, compacting, under the temperature between glass transition temperature of polymer and the fusing point, with constant speed nano composite material is carried out solid state drawing, crystallisation by cooling obtains oriented inorganic nanoparticles/thermoplastic polymer composite material.
2. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1, it is characterized in that comprising the steps: by pre-radiation or common radiation chemistry Grafted Nano-scale inorganic particulate, make monomer arrive nanoparticle surface through the gas-liquid graft polymerization, with the nano inoganic particle after the modification and thermoplastic polymer melting mixing, be pressed into thin slice, under the temperature between glass transition temperature of polymer and the fusing point, carry out the preparation of solid state drawing orientation, after the stretching, obtain oriented inorganic nanoparticles/thermoplastic polymer composite material through crystallisation by cooling.
3. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1 and 2 is characterized in that described nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate.
4. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1 and 2 is characterized in that described thermoplastic polymer is polyethylene, polypropylene, polystyrene, tetrafluoroethylene, nylon or poly terephthalic acid hexylene glycol ester.
5. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1 and 2 is characterized in that the temperature between glass transition temperature of polymer and the fusing point is 90~150 ℃.
6. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1 and 2, the speed that it is characterized in that described solid state drawing is 10~50mm/min.
7. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 2 is characterized in that described monomer is esters of acrylic acid, acrylate containing fluorine, vinylbenzene or glycidyl methacrylate.
8. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 7 is characterized in that described acrylic ester monomer is ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester.
9. the preparation method of described oriented inorganic nanoparticles/thermoplastic polymer composite material according to claim 1 and 2, the consumption that it is characterized in that described nano inoganic particle is 1~3wt% of thermoplastic polymer, the consumption of monomer equates with nano inoganic particle.
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CN102179920B (en) * | 2011-04-06 | 2012-10-10 | 中山大学 | Method for preparing high-strength polymer composite material |
CN104327373B (en) * | 2014-10-08 | 2017-08-01 | 浙江工业大学 | The preparation method of nano-particle polymer based nanocomposites height-oriented in polymeric matrix |
CN104695043B (en) * | 2015-02-12 | 2017-03-01 | 浙江理工大学 | A kind of grafting SiO2The preparation method of Particle Cluster orientational strengthening polyster fibre |
CN105482228A (en) * | 2016-01-05 | 2016-04-13 | 广州枫叶管业有限公司 | Polyethylene nano-modified composite and preparing method and application thereof |
CN109777153A (en) * | 2019-03-12 | 2019-05-21 | 中国工程物理研究院核物理与化学研究所 | A kind of method of modifying of inorganic nano-particle |
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