CN101838414A - Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material - Google Patents
Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material Download PDFInfo
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- CN101838414A CN101838414A CN 201010136266 CN201010136266A CN101838414A CN 101838414 A CN101838414 A CN 101838414A CN 201010136266 CN201010136266 CN 201010136266 CN 201010136266 A CN201010136266 A CN 201010136266A CN 101838414 A CN101838414 A CN 101838414A
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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 field of compound material, 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 performance of composites, and as high strength, high-modulus, lightweight etc., it is urgent that the development of the high-strength polymer of various particular requirements more and more shows.Metal and ceramic actual modular ratio polymkeric substance are high, calculate theoretically intensity that metallic bond obtains and we actual record intensity near or equate, and 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 weak relatively 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 in time, temperature and changing, and a certain amount of free volume is arranged all in the polymkeric substance, these all cause theoretical strength and actual strength that bigger difference is arranged.By utilize consciously in the macromolecular chain with macromole between different reactive forces, stretch as much as possible with C-C key bonded macromolecular chain, cause the upright and outspoken orientation of chain, just might obtain high-modulus, high-intensity polymer materials.The flexible chain polymer if can improve its orientation degree and degree of crystallinity to heavens, 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, promptly allow the inner macromole of polymer materials along the stress direction ordered arrangement, under the certain situation of chemical bond energy, macroscopical intensity 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 technology 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.Characteristics such as particle diameter is little, specific surface area is big because of having for nanoparticle, surperficial non-matching atom is many, if can be in polymkeric substance with the nanoparticle good distribution, 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 spot 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 bigger practical value.
Summary of the invention
The objective 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, this 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 graft modification nano inoganic particle, 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 graft modification nano inoganic particle, make monomer arrive nanoparticle surface through the gas-liquid graft polymerization, with 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 and loose and separation, laterally make nanoparticle close mutually, 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 graft modification nano inoganic particle, to improve the dispersion of nanoparticle in polymkeric substance, and the reinforcement nanoparticle combines 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, described tensile speed 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 monomeric consumption 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 handle nano inoganic particle, make monomer form grafted chain in nanoparticle surface, improved the consistency between nano inoganic particle and polymeric matrix, simultaneously because the penetrativity of monomeric osmosis of gas (liquid) attitude and energetic ray, even the particle that is in nanoparticle coacervate inside is 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 diffusing and separates, and obtains having the matrix material of nanoscopic level dispersion.Like this on the basis that obtains the orientation complete processing, the method of utilization change processing conditions and processing means is rationally controlled 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 the technology of the present invention adopted is simple, and technology is easily gone, and the 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 qualification 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 a butyl acrylate, and consumption proportion sees Table 1.Melt blending in the Hakke torque rheometer prepares masterbatch with graft modification nanoparticle and polypropylene, masterbatch and polypropylene is diluted in proportion again.By the matrix material that solid state drawing technology obtains being orientated, the matrix material with orientation becomes test bars by the ASTM3039 standard fabrication again.
Comparative example 1 ~ 3
Moulding technology is different with 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 a butyl acrylate, and consumption proportion sees Table 2.Melt blending in the mixing tank of Hakke torque rheometer prepares masterbatch with graft modification nanoparticle 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, handle without solid state drawing.
Table 3 is that prepared matrix material of embodiments of the invention and Comparative Examples performance of composites compare.
As seen from Table 3:
1. after handling 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 technology can improve the tensile strength of material significantly.The nano-silicon dioxide particle of radiation grafting butyl polyacrylate is handled (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 technology to polypropylene.
2. all the Young's modulus than the comparative example of handling without solid state drawing 1 ~ 3 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 is 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 technology 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 modification simultaneously 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 a 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 of table 3 embodiment and the obtained material of comparative example relatively
*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 (10)
1. the preparation method of an oriented inorganic nanoparticles/thermoplastic polymer composite material, it is characterized in that comprising the steps: by radiation chemistry graft modification nano inoganic particle, 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.
2. according to the preparation method of the described oriented inorganic nanoparticles/thermoplastic polymer composite material of claim 1, it is characterized in that comprising the steps: by pre-radiation or common radiation chemistry graft modification nano inoganic particle, make monomer arrive nanoparticle surface through the gas-liquid graft polymerization, with 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, after the stretching, obtain oriented inorganic nanoparticles/thermoplastic polymer composite material through crystallisation by cooling.
3. according to the preparation method of claim 1 or 2 described oriented inorganic nanoparticles/thermoplastic polymer composite materials, it is characterized in that described nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate.
4. according to the preparation method of the described oriented inorganic nanoparticles/thermoplastic polymer composite material of claim 3, it is characterized in that described nano-silicon dioxide particle is precipitator method nano silicon or fumed nano silicon-dioxide, median size is 7 ~ 50nm, and specific surface area is 150 ~ 640m
2/ g.
5. according to the preparation method of claim 1 or 2 described oriented inorganic nanoparticles/thermoplastic polymer composite materials, it is characterized in that described thermoplastic polymer is polyethylene, polypropylene, polystyrene, tetrafluoroethylene, nylon or poly terephthalic acid hexylene glycol ester.
6. according to the preparation method of claim 1 or 2 described oriented inorganic nanoparticles/thermoplastic polymer composite materials, it is characterized in that the temperature between described glass transition temperature of polymer and the fusing point is 90 ~ 150 ℃.
7. according to the preparation method of claim 1 or 2 described oriented inorganic nanoparticles/thermoplastic polymer composite materials, it is characterized in that described tensile speed is 10 ~ 50mm/min.
8. according to the preparation method of the described oriented inorganic nanoparticles/thermoplastic polymer composite material of claim 2, it is characterized in that described monomer is esters of acrylic acid, acrylate containing fluorine, vinylbenzene or glycidyl methacrylate.
9. the preparation method of described according to Claim 8 oriented inorganic nanoparticles/thermoplastic polymer composite material is characterized in that described acrylic ester monomer is ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester.
10. according to the preparation method of claim 1 or 2 described oriented inorganic nanoparticles/thermoplastic polymer composite materials, the consumption that it is characterized in that described nano inoganic particle is 1 ~ 3wt% of thermoplastic polymer, and monomeric consumption equates with nano inoganic particle.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179920A (en) * | 2011-04-06 | 2011-09-14 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN102464845A (en) * | 2010-11-11 | 2012-05-23 | 天津市天塑科技集团有限公司技术中心 | Nano-silica-filled modified PTFE (Polytetrafluorethylene) resin |
| CN104327373A (en) * | 2014-10-08 | 2015-02-04 | 浙江工业大学 | Preparation method for polymer base nanometer composite material with highly oriented nanoparticles in polymer matrix |
| CN104695043A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Preparation method of grafted SiO2 particle cluster orientation reinforced polyester fiber |
| 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 |
| CN114213903A (en) * | 2021-12-16 | 2022-03-22 | 抚州贝尔斯涂料有限公司 | Water-oil universal color paste and production process thereof |
| CN115637033A (en) * | 2022-08-31 | 2023-01-24 | 四川大学 | Method for realizing monodisperse agglomerated nano filler by using high-elasticity polymer |
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| CN1228443A (en) * | 1999-01-19 | 1999-09-15 | 中山大学 | Nanometre inorganic particle toughened reinforced plastics and preparation method thereof |
| EP1054036A1 (en) * | 1999-05-18 | 2000-11-22 | Fina Research S.A. | Reinforced polymers |
| CN1673267A (en) * | 2005-03-23 | 2005-09-28 | 中山大学 | Microfiber technology process of preparing nanometer composite inorganic particle/polymer material |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1228443A (en) * | 1999-01-19 | 1999-09-15 | 中山大学 | Nanometre inorganic particle toughened reinforced plastics and preparation method thereof |
| EP1054036A1 (en) * | 1999-05-18 | 2000-11-22 | Fina Research S.A. | Reinforced polymers |
| CN1673267A (en) * | 2005-03-23 | 2005-09-28 | 中山大学 | Microfiber technology process of preparing nanometer composite inorganic particle/polymer material |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464845A (en) * | 2010-11-11 | 2012-05-23 | 天津市天塑科技集团有限公司技术中心 | Nano-silica-filled modified PTFE (Polytetrafluorethylene) resin |
| CN102179920A (en) * | 2011-04-06 | 2011-09-14 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN102179920B (en) * | 2011-04-06 | 2012-10-10 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN104327373A (en) * | 2014-10-08 | 2015-02-04 | 浙江工业大学 | Preparation method for polymer base nanometer composite material with highly oriented nanoparticles in polymer matrix |
| 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 |
| CN104695043A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Preparation method of grafted SiO2 particle cluster orientation reinforced polyester fiber |
| 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 |
| CN114213903A (en) * | 2021-12-16 | 2022-03-22 | 抚州贝尔斯涂料有限公司 | Water-oil universal color paste and production process thereof |
| CN115637033A (en) * | 2022-08-31 | 2023-01-24 | 四川大学 | Method for realizing monodisperse agglomerated nano filler by using high-elasticity polymer |
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