CN1673267A - Microfiber technology process of preparing nanometer composite inorganic particle/polymer material - Google Patents
Microfiber technology process of preparing nanometer composite inorganic particle/polymer material Download PDFInfo
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- CN1673267A CN1673267A CN 200510033656 CN200510033656A CN1673267A CN 1673267 A CN1673267 A CN 1673267A CN 200510033656 CN200510033656 CN 200510033656 CN 200510033656 A CN200510033656 A CN 200510033656A CN 1673267 A CN1673267 A CN 1673267A
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Abstract
The present invention is microfiber technological process of preparing nanometer composite inorganic particle/polymer material. Radiation modified nanometer particle and polypropylene with relatively high viscosity are compounded through melting extrusion-extension-quenching process, so that the nanometer particle aggregate is deformed, crushed and separated in the continuous polymer phase to form nanometer level dispersive structure. Composite fiber is then mixed with polypropylene with relatively low viscosity through conventional process to prepare nanometer level dispersed composite nanometer inorganic particle/polymer material with maintained nanometer dispersive structure. The composite material has obviously raised processing flowability, tensile strength, impact strength and rigidity, and the technology may be used in preparing various kinds of composite material with nanometer inorganic particles.
Description
Technical field
The present invention relates to a kind of method that adopts microfiber technology to prepare nanometer composite inorganic particle/polymer material.
Technical background
Nano inoganic particle (size between 1～100nm) because of having small-size effect, big specific surface area and strong interfacial interaction, if can be in polymkeric substance with the nanoparticle good distribution, can under very low loading level, significantly improve the mechanical property of polymkeric substance and produce effects such as special light, electricity, magnetic, overcome the loading level that conventional inorganic particle filled modification brings big, can not strengthen simultaneously toughness reinforcing, processing fluidity reduces and problem such as proportion increase.Therefore the research of nanometer composite inorganic particle/polymer material in recent years causes people's attention day by day.
Yet just because of having higher surface activity, very easy gathering of nanoparticle self and reunion adopt conventional blend method to be difficult to obtain having nanostructure composite material.In order to obtain the nanoscopic level dispersion system, the comparatively special preparation method of normal at present employing mainly is to adopt the compound and in-situ compounding process of intercalation.Intercalation compounding is to make monomer insert polymerization between the inorganics interlayer in the presence of the laminated inorganic matter, or polymkeric substance directly injects and form mixture between interlayer, increases its interlamellar spacing thus, at nanometer level stripped laminar inorganics, forms nano composite material thus.According to different conditions, intercalation compounding can obtain interlayer insert type nano composite material or exfoliated nano-composite respectively.Yet the intercalation complex method generally is that a few has the mineral filler of laminate structure at clay etc., lacks other raw-material universality.In-situ compositing is that inorganic nano-particle is scattered in the monomer, again trigger monomer polymerization under proper condition; Or inorganic particulate is dissolved in the polymers soln, form stable sols, further the gel formation nano composite material; Perhaps in the forming process of nanometer strengthener, carry out polyreaction synchronously, as utilize combining of colloidal sol-gel reaction and polyreaction, make the organic-inorganic nano composite material of nanoscopic level dispersion.But because in-situ compounding process is loaded down with trivial details, workload is big, and solvent is selected difficulty, is difficult to form the batch process scale, has limited the application of this method.
Special preparation methods such as in sum, the compound and original position of intercalation is compound all can not resemble and be widely used in the polymer processing the conventional blending and modifying technology.The actual state of current domestic nano-powder is to have formed the industry size of the non-layered inorganic nanoparticle of annual thousands of tons of (as SiO
2, CaCO
3Deng), but application development relatively lags behind, and the utilisation technology that develops non-laminate structure inorganic nano-particle aspect modifying plastics is very necessary.And from the practical situation analysis of polymer processing, promote nanoparticle to use the method for most convenient and be still the melt blending technology of utilizing, key is how to solve the dispersion problem of nanoparticle in polymeric matrix.
Because in conventional melt blending process, limited shearing force is difficult to the coacervate of nanoparticle is smashed, loose aggregate structure often becomes the key of composite failure.If in the process of nano inoganic particle and polymer melt blend, adopt specific processing units that matrix material is applied stretching action, as long as nanoparticle and matrix have enough interface interactions, the nanoparticle coacervate just may be out of shape under outer field action-fragmentation, and polymeric matrix can effectively intercept reassociating of nanoparticle, thereby the nanoparticle coacervate is forced to draw diffusing and separation, and this nano-dispersed structure is fixed up, thereby realize the nanoscopic level dispersion of nanoparticle in polymeric matrix.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the method for nanometer composite inorganic particle/polymer material by microfiber technology, the nanometer composite inorganic particle/polymer material that obtains has remarkable enhancing toughening effect.
Purpose of the present invention can realize by following measure: at first by radiation chemistry graft modification nano inoganic particle, with nanoparticle after the radiation modification and polypropylene by melt extruding-stretch-the compound preparation fiber of quenching technology, again with conjugated fibre and polypropylene routinely blending technology be mixed with nano inoganic particle/polypropylene composite material with nano-dispersed structure.
Adopt radiation chemistry graft modification nano inoganic particle, combine with the interface of polymeric matrix, improve the dispersion of nanoparticle in polymkeric substance, make it to possess and to be combined into fine primary condition with polymeric matrix to strengthen nanoparticle.Select for use higher polypropylene of viscosity and radiation modification nanoparticle to carry out melt blending, the specific equipment of utilization in the blend process, under suitable outer field action, the nanoparticle coacervate is deformed-fragmentation-separation in polymkeric substance external phase, utilize polymeric matrix effectively to intercept reassociating of nanoparticle, thereby in conjugated fibre, form the nano-dispersed structure; Again that conjugated fibre and viscosity is lower polypropylene blending technology routinely mixes, and the control blending technology is kept the nano-dispersed structure, the novel nano composite inorganic particle/polymer material that preparation has nanoscopic level dispersion.
Specific practice of the present invention is: handle nano-silicon dioxide particle or Nano particles of calcium carbonate with pre-radiation or common method of radiating, make monomers such as esters of acrylic acid, vinylbenzene, vinylformic acid, methacrylic acid, iso-butylene or glycidyl methacrylate arrive nanoparticle surface through the gas-liquid graft polymerization, the monomer consumption is 100～400wt% of nanoparticle consumption.Nanoparticle mixes in the higher polypropylene fusion of 1～10wt% ratio and viscosity after the radiation modification, in the blend process, adopt kapillary extrusion neck ring mold and supporting with it traction, wind2, under suitable effects such as temperature field, stress field and velocity field, make matrix material become fine, in this process, draw diffusing the pressure of nanoparticle coacervate and separation, the conjugated fibre that obtains having the nano-dispersed structure.Again that conjugated fibre and viscosity is lower polypropylene blending technology routinely mixes, select and the control processing conditions by the matrix suitability, the nano-dispersed structure is fixed up in matrix material, thereby realizes the nanoscopic level dispersion of nanoparticle in polymeric matrix.
Used nano inoganic particle can be nano-silicon dioxide particle or Nano particles of calcium carbonate etc. in the aforesaid method, nano-silicon dioxide particle can be precipitator method nano silicon or fumed nano silicon-dioxide, median size is 7～50nm, and specific surface area is 150～640m
2/ g; Used acrylic ester monomer is generally ethyl propenoate (EA), butyl acrylate (BA), Isooctyl acrylate monomer (2-EHA) or methyl acrylic ester.
Used polymkeric substance can be polyethylene, polypropylene, polystyrene, nylon, poly terephthalic acid hexylene glycol ester etc. in the aforesaid method.
Because the present invention utilizes the monomer radiation grafting to handle nano inoganic particle earlier, 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 has fiberizability in drafting process, and in fibrillation, the nanoparticle aggregate structure forced to draw and loose and separate, obtain having the matrix material of nanoscopic level dispersion.Like this on the basis of the traditional plastic processing of maintenance, 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, obtain having the nanometer composite inorganic particle/polymer material of remarkable enhancing toughening effect.
The present invention is further illustrated to reach accompanying drawing by the following examples.
Description of drawings
Fig. 1 adopts Butyl Acrylate Monomer, and the infrared spectra graphic representation of back fumed nano silicon-dioxide sample (a) and undressed fumed nano silicon-dioxide sample (b) is handled in the radiation chemistry grafting.
Fig. 2 is the SEM photo that adopts the notch shock section of the embodiment of the invention 1 (a) that the JEOL-5400 sem observation arrives and comparative example (b) sample.
Embodiment
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 mixing tank of Hakke torque rheometer prepares masterbatch with graft modification nanoparticle and polypropylene, masterbatch and polypropylene is diluted in proportion again, melt extrude-stretch-quenching prepares conjugated fibre.Getting nano-silicon dioxide particle weight is 5g, and the polypropylene that conjugated fibre and viscosity is lower fusion plastification in the Hakke torque rheometer mixes, and is injected into the standard batten with injector.
Table 2 is each composition consumption proportion of comparative example, and preparation process sees Table 2 remarks.
Table 3 is embodiments of the invention 3 and embodiment 7 prepared matrix materials and the comparison of Comparative Examples performance of composites.
As seen from Table 3:
1, embodiment 3, the notch shock that the normal temperature simply supported beam notched Izod impact strength of 7 samples all is higher than comparative example is strong, the notched Izod impact strength of embodiment 3 is about 3 times of virgin pp (comparative example 1), under the similarity condition, the nano-silicon dioxide particle of radiation grafting butyl polyacrylate directly adds the comparative example 3 among the PP and does not add nanoparticle without the fibrillation step, only the notched Izod impact strength of the comparative example 4 that butyl polyacrylate is added does not all have obviously to improve, explanation can make nanoparticle that polypropylene is played toughening effect by microfiber technology, but not adds the butyl polyacrylate role.In addition, the tensile strength of embodiment 3,7 also increases than virgin pp.Illustrate that the inventive method can make nano silicon that polypropylene is played toughness reinforcing and enhancement simultaneously.
2, the modulus in flexure of the embodiment of the invention 3,7 samples is all than virgin pp (comparative example 1) height, and embodiment 3 even ratio are also high with the comparative example 2 that nanoparticle directly adds.The sample of comparative example 3 and comparative example 2 is formed identical, comparative example 3 is just through extruding-tensile fibrillation step, modulus in flexure is just than the height of comparative example 2, illustrate that microfiber technology that the present invention adopts can promote the dispersion of nanoparticle, strengthen the interface combination, the rigidity of obtained matrix material is better, and this point also can be confirmed from the crystallinity data of correspondence.
3, from the crystal property data, the fusing point of embodiment 3,7 samples is compared with virgin pp (Comparative Examples 1) and is changed not quite, and supercooling temperature Δ T scope reduces, and illustrates that nanoparticle plays the heterogeneous nucleation effect among the present invention, and the crystallization rate of polymkeric substance is accelerated.Degree of crystallinity is improved.
Fig. 1 be with Bruker Equinox 55 Fourier infrared spectrographs record through the acetone extracting after 48 hours, the infrared spectra graphic representation of fumed nano silicon-dioxide sample (a) is handled in the radiation chemistry grafting, percentage of grafting is 8.31%.Compare 1717cm in the nano silicon sample infrared spectrum after the radiation chemistry graft modification with undressed fumed nano silicon-dioxide sample (b)
-1The absorption peak that the place occurs shows the existence of carbonyl, proof through radiotreatment butyl polyacrylate chemical graft at nano-silica surface, can improve the surperficial affinity of nanoparticle, and pass through and the entanglement raising nanoparticle of polymeric matrix molecular chain and the interface combination of matrix, to help being drawn in the fine process that the nanoclusters aggressiveness is out of shape with matrix and broken, realize that nanostructure disperses at next step composite sample.
The SEM photo of the embodiment of the invention 3 (a) that employing JEOL-5400 sem observation arrives and the notch shock section of comparative example 3 (b) sample as shown in Figure 2.From microscopic pattern, radiation modification SiO
2Directly add without the fibrillation step on the impact section (b) of comparative example 3 matrix materials among the PP, the size of nanoparticle coacervate is bigger than the embodiment's 3 that makes through the fibrillation step, with the interface bonding of polymeric matrix also not as embodiment 3.The impact section (a) of embodiment 3 can see that the nanoparticle coacervate is elongated and deformed, have in addition drawn diffusingly, obtain the less coacervate of distribution of sizes, and closely be wrapped in the polymeric matrix.Prove further also that on microtexture the inventive method helps improving the dispersiveness of nanoparticle polymeric matrix, strengthen the interface combination of nanoparticle and polymeric matrix.
The technology of the present invention adopts general processing units, and technology is simple, and cost is low, and the tensile strength of obtained matrix material, shock strength and rigidity all are significantly improved.The technology of the present invention also can be used for preparing the nano composition of polyethylene, polystyrene, nylon and poly terephthalic acid hexylene glycol ester etc.
Each composition consumption proportion of table 1 part embodiment
| Nano silicon weight (g) | Butyl acrylate weight (g) | Percentage of grafting (%) | Polypropylene (g) | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 5 (vapor phase methods) 5 (vapor phase method), 5 (vapor phase methods) 5 (vapor phase method), 5 (vapor phase methods) 5 (vapor phase method) 5 (precipitation method) | ??1.5 ??3 ??5 ??10 ??15 ??20 ??5 | ????2.41 ????2.66 ????2.76 ????2.72 ????2.67 ????4.02 ????11.5 | ????93.5 ????92 ????90 ????85 ????80 ????75 ????90 |
*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 composition and consumption proportion
| Nano silicon weight (g) | Butyl acrylate weight (g) | Polypropylene (g) | Preparation process | |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | 5 (vapor phase processs) 5 (vapor phase process) | ??5 ??5 | ????100 ????95 ????90 ????95 | Pure PP is without via radiation grafting modification nanometer SiO 2Directly add via radiation grafting modification nanometer SiO among the PP 2Directly add among the PP at embodiment 3 via radiation grafting modification SiO without the fibrillation step 2In isolate the butyl polyacrylate homopolymer, make conjugated fibre with PP then, add among the PP again |
Table 3 embodiment 3 and embodiment 7 compare with the performance of the obtained material of Comparative Examples
| Embodiment | Comparative example | |||||
| ??3 | ??7 | ??1 | ??2 | ??3 | ??4 | |
| Simply supported beam notched Izod impact strength (kJ/m 2) | ??4.09 | ??2.63 | ??1.34 | ??1.63 | ??2.43 | ??1.73 |
| Tensile strength (MPa) | ??37.98 | ??37.03 | ??33.43 | ??37.63 | ??37.73 | ??35.81 |
| Modulus in flexure (GPa) | ??1.53 | ??1.42 | ??1.31 | ??1.50 | ??1.49 | ??1.30 |
| Fusing point T m(℃) | ??163.4 | ??163.9 | ??164.9 | ??164.2 | ??163.8 | ??163.3 |
| The fastest temperature T of crystallization c(℃) | ??117.4 | ??119.1 | ??110.4 | ??120.1 | ??115.4 | ??118.7 |
| ??ΔT＝T m-T c(℃) | ??46.0 | ??44.8 | ??54.5 | ??44.1 | ??48.4 | ??44.6 |
| Crystallinity X c(％) | ??47.2 | ??46.9 | ??43.5 | ??44.7 | ??45.2 | ??40.9 |
*Remarks: 1. press ISO 179-2 standard normal temperature and measure the simply supported beam notched Izod impact strength.
2. press ASTM D638-1998 standard test tensile strength and modulus in flexure.
3. measure T with DSC
m, T
cAnd X
c
Claims (5)
1. method of using the fibrillation means to prepare nanometer composite inorganic particle/polymer material, it is characterized in that with radiation method grafting modification nano inoganic particle, then nanoparticle after the radiation modification and polypropylene are extruded-stretched-quenching by specific equipment in the melt blending process, the conjugated fibre that preparation has the nano-dispersed structure, again with conjugated fibre and polypropylene routinely blending technology be mixed with nano composite material.
2. in accordance with the method for claim 1, it is characterized in that radiation method grafting modification nano inoganic particle adopts pre-radiation and common method of radiating, make esters of acrylic acid, vinylbenzene, vinylformic acid, methacrylic acid, iso-butylene or glycidyl methacrylate monomer arrive nanoparticle surface through the gas-liquid graft polymerization, the monomer consumption is 100～400wt% of nanoparticle consumption.
3. in accordance with the method for claim 1, it is characterized in that used nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, median size is 7～50nm, and specific surface area is 150～640m
2/ g, nano inoganic particle consumption are 1～10wt%.
4. in accordance with the method for claim 3, it is characterized in that used nano-silicon dioxide particle is precipitator method nano silicon or fumed nano silicon-dioxide.
5. in accordance with the method for claim 1, it is characterized in that preparing nano inoganic particle/used polypropylene of polypropylene conjugated fibre is the trade mark that viscosity is higher, be suitable for spinning; Be lower than the polyacrylic viscosity of conjugated fibre with conjugated fibre melt blending, the used polyacrylic viscosity of preparation matrix material subsequently.
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| CN101838414A (en) * | 2010-03-26 | 2010-09-22 | 中山大学 | Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material |
| CN102179920A (en) * | 2011-04-06 | 2011-09-14 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
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| CN101838414B (en) * | 2010-03-26 | 2013-04-03 | 中山大学 | Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material |
| CN101838414A (en) * | 2010-03-26 | 2010-09-22 | 中山大学 | Method for preparing oriented inorganic nanoparticles/thermoplastic polymer composite material |
| 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 |
| CN103980592B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
| CN103980591B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of electron radiation crosslinked polymeric materials for 3D printing and preparation method thereof and goods |
| 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 |
| CN110678605A (en) * | 2017-03-31 | 2020-01-10 | 日本制纸株式会社 | Method for producing inorganic particle composite fiber sheet |
| US11268241B2 (en) | 2017-03-31 | 2022-03-08 | Nippon Paper Industries Co., Ltd | Method for manufacturing inorganic particle composite fiber sheet |
| CN110678605B (en) * | 2017-03-31 | 2022-07-08 | 日本制纸株式会社 | Method for producing inorganic particle composite fiber sheet |
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