CN1563129A - Force-chemic method for preparing composite material of nano inorganic particles/polymer - Google Patents
Force-chemic method for preparing composite material of nano inorganic particles/polymer Download PDFInfo
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- CN1563129A CN1563129A CN 200410026564 CN200410026564A CN1563129A CN 1563129 A CN1563129 A CN 1563129A CN 200410026564 CN200410026564 CN 200410026564 CN 200410026564 A CN200410026564 A CN 200410026564A CN 1563129 A CN1563129 A CN 1563129A
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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 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
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- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
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Abstract
The invention relates to a mechanochemical preparation method of nano inorganic particle/polymer copmosite material. Said method utilizes coupling agent to teatment, and an organic gorup which can be directly polymerized is introduced into the surface of nano inorganic particle, the treated nano inorganic particle and a portion of monomers are uniformly mixed by using ball-griding process, after an initiator is added into another portion of monomers, said another portion of monomers and polymer powder material can be added into ball-grinding machine together, continuously ball-ground to make them be uniformly mixed. The obtained powder material can be directly made into the product, also can be processed according to conventional mixing method. The processing flowability, tensile strength, impact strength and rigidity of said obtained composite material can be obviously raised, and said invented technique also can be used for preparing nano particle composite materials of polyethylene, polypropylene, polysterol, polychlorovinyl or ethylene-vinyl acetate copolymer, etc.
Description
Technical field
The present invention relates to the method that a kind of power of employing chemical technology prepares nanometer composite inorganic particle/polymer material.
Background technology
Compare with micron order Inorganic Fillers Filled polymer composites, inorganic nano-particle/polymer composites has many excellent specific properties.(size can significantly improve the mechanical property of polymkeric substance and produce effects such as special light, electricity, magnetic between 1~100nm) because of having small-size effect, big specific surface area and strong interfacial interaction nano inoganic particle under very low loading level.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 sol gel reaction and polyreaction, make the organic-inorganic nanocomposite 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 and use the method for most convenient and be still the blending and modifying technology of utilizing.
When adopting the blending and modifying technology to prepare nanometer composite inorganic particle/polymer material,, generally need carry out surface modification, make it become lipophilicity by wetting ability to particle in order to improve the dispersiveness of nanoparticle in polymkeric substance.Being considered to preferably, surface modifying method mainly contains coupling agent modified and graft modification.Because the viscosity of high polymer molten is bigger, even increased the avidity of particle and matrix by coupling agent, the thermodynamics and kinetics factor has all determined superpolymer to be difficult to enter nanometer particle congery inside; And coupling agent itself is small molecules, and the nanoparticle coacervate that is wrapped up by coupling agent still is open structure, and is little to the resistance of crack propagation, and stress is concentrated and taken the lead in destroying easily.In this method of nano inoganic particle surface grafting polymerization thing, changed the surface property of particle on the one hand, increased the consistency between particle and matrix, dispersion of particles is improved; On the other hand, make nanoparticle reunite intravital each particle surface, thereby give its some new function all with the grafts of going up chemical bonding.But graft polymerization reaction is to carry out in solution usually, also must remove the solvent that is added behind the processing nanoparticle, and technology is complicated, and cost is increased.
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 the power chemical technology, this method technology is simple, and cost is low, improves the mechanical property that makes material greatly.
The concrete steps of the inventive method are: 1) use the coupling agent treatment nano inoganic particle, with toluene is solvent, with coupling agent and nano inoganic particle back flow reaction 8 hours under nitrogen protection, used coupling agent is γ-methacryloxypropyl trimethoxy silane, and consumption is 1~50wt% of nano inoganic particle; Used nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, and median size is 7~50nm, and specific surface area is 150~640m
2/ g;
2) will add in the ball mill through coupling agent treatment nano inoganic particle and a part of monomer, rotating speed 200~300rpm, 1 hour ball milling time, used monomer is esters of acrylic acid, vinylbenzene, vinylformic acid, methacrylic acid, maleic anhydride or glycidyl methacrylate, the nano inoganic particle consumption is 1~20wt%, the total consumption of monomer is 100~300wt% of nanoparticle consumption, and elder generation adds the monomer of total consumption 50wt%~80wt% in this step;
3) again initiator is added in another part monomer dissolving after, together add in the ball mill with polymer powders, rotating speed 400~500rpm, 1~2 hour ball milling time, radical initiator is azo-initiator or peroxide initiator, and the consumption that adds radical initiator is 0.1~0.5wt% of monomer consumption.
Used acrylic ester monomer can be ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester in the aforesaid method.Used radical initiator can be Diisopropyl azodicarboxylate or benzoyl peroxide.Used nano-silicon dioxide particle is precipitator method nano silicon or fumed nano silicon-dioxide.Used polymkeric substance can be powdered polypropylene, polyethylene, polystyrene, polyvinyl chloride or ethylene-vinyl acetate copolymer.
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 initiator is generally Diisopropyl azodicarboxylate or benzoyl peroxide.
Used polymkeric substance is powdered polypropylene, polyethylene, polystyrene, polyvinyl chloride or ethylene-vinyl acetate copolymer in the aforesaid method.
When handling, but introduce the organic group of direct polymerization in the inorganic nanoparticles sub-surface by silane coupling agent.Nano inoganic particle after handling used than slow speed of revolution ball milling with a part of monomer mixes, together add in the ball mill with polymer powders after another part monomer being added initiator again, the continuation ball milling is to mixing behind the raising rotating speed.During than slow speed of revolution ball milling, inorganic nanoparticles sub-surface coverlet body is fully wetting, but chemical reaction does not take place substantially; Improve rotating speed after adding polymkeric substance, the chemical graft of nanoparticle surface is reacted with the mixed uniformly high heat that produced and the mechanical force trigger monomer of utilizing simultaneously of polymkeric substance.In the technology of existing preparation nanometer composite inorganic particle/polymer material normal adopt earlier with after the nano particle grafting modification again with the method for polymeric matrix blend, limited shearing force is difficult to the nanoparticle that is wrapped up by grafts is smashed in the melt blending process, has limited nanoparticle at the intravital homodisperse of polymer-based carbon.And the employing of ball milled can promote monomer to infiltrate inside nanoparticles, reduce the size of nanoparticle coacervate, make nanoparticle and mixed with polymers even, in nanoparticle surface generation graft reaction, also may produce a spot of graft reaction at polymer surfaces, this will help the dispersion of nanoparticle in follow-up and polymeric matrix melt blending process, improve the interface combination between nanoparticle and matrix.
Because the present invention adopts liquid monomers such as esters of acrylic acid, thereby can make the even wetting inorganic nanoparticles sub-surface of monomer and distribute at surperficial lamellar by ball milling method, nanoparticle and resin are mixed under pulverulence, because the power chemical action makes monomer generation graft polymerization reaction, method is simple and treatment effect good simultaneously.This will help the homodisperse of nanoparticle in follow-up and matrix melt blending process, improve the interface combination between nanoparticle and matrix.The gained powder is fabricated product directly, need not further processing, has simplified technology, and cost is reduced.Also blend method is processed routinely.When compound material at high temperature during melt-processed, further chemical reaction (grafting and polymerization) can take place in unreacted monomer, and homopolymer wherein enters viscous state rapidly, rises to promote plastification, can improve the processing fluidity of material, help the homodisperse of nanoparticle in matrix; Graftomer will with matrix polymer generation physical entanglement, combine with interface between matrix resin thereby strengthened Nano filling, the mechanical property of material is improved.
The present invention is further illustrated to reach accompanying drawing by the following examples.
Description of drawings
Fig. 1 is an infrared spectra graphic representation of handling back fumed nano silicon-dioxide sample (a) and undressed fumed nano silicon-dioxide sample (b) with silane coupling agent.
Fig. 2 is the embodiment of the invention 1 and the torque-time curve of comparative example 1,2 samples in the fusion plastification process that the Hakke Rheocord 300p torque rheometer with German Hakke company records; Wherein a is embodiment 1, and b is a comparative example 1, and c is a comparative example 2.
Fig. 1 is the infrared spectra graphic representation through the ethanol extracting nano silicon sample (a) that silane coupling agent KH-570 handles after 48 hours that records with Bruker Equinox 55 Fourier infrared spectrographs, and the KH-570 consumption is the 10wt% of nano silicon.Compare 1704cm in the nano silicon sample infrared spectrum (a) after KH-570 handles with undressed fumed nano silicon-dioxide sample (b)
-1The absorption peak that the place occurs is when two keys resonate with carbonyl, and the absorption peak position that makes carbonyl is to due to the low frequency place moves.Proof will have two keys of reactive behavior and introduce nano-silica surface after KH-570 handles, this will help follow-up in-situ grafting polymerization reaction.
The embodiment of the invention 1 that records with the Hakke Rheocord 300p torque rheometer of German Hakke company and the torque-time curve in comparative example 1, the 2 sample fusion plastification processes are as shown in Figure 2.Can understand the rheological behaviour of matrix material in molding process by torque-time curve.As can be seen, the torque of carrying out embodiment 1 with plasticizing reduces more, balancing moment is lower than virgin pp (comparative example 1), and the balancing moment that directly adds nanoparticle sample (comparative example 2) is a little more than virgin pp (comparative example 1), illustrate that the present invention can improve the plasticizing flowability of matrix material, this is favourable to forming process, and this also is the more scabrous problem of general filler filled composite materials.
Embodiment
Each composition consumption proportion of embodiment 1-9 is as shown in table 1, and getting nano silicon weight is 5g.In the table 1; the concrete processing step of each embodiment is: handle nano inoganic particle with coupling agent γ-methacryloxypropyl trimethoxy silane (KH570); with toluene is solvent, with coupling agent and nano inoganic particle back flow reaction 8 hours under nitrogen protection.By required proportioning, will in coupling agent treatment nano inoganic particle and a part of acrylic ester monomer adding ball mill, make silica sphere by fully wetting, rotating speed 200~300rpm, 1 hour ball milling time to mixing by ball milling.After initiator (benzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN) being dissolved in another part monomer dissolving, together add in the ball mill with polypropylene powder, ball milling is to mixing rotating speed 400~500rpm, 2 hours ball milling time more again.
Each composition consumption proportion of comparative example 1-4 is as shown in table 2.
Table 3 is that the performance of embodiments of the invention 1 and embodiment 5 prepared materials and Comparative Examples material compares.Except that comparative example 4, each sample material all by the technological process preparation of the embodiment of the invention, is used Hakke torque rheometer fusion plastification then, is injected into the standard batten with injector in the table 3.Comparative example 4 is together to add in the ball mill through the nano-silicon dioxide particle of coupling agent treatment and Butyl Acrylate Monomer and BPO initiator, rotating speed 400~500rpm, behind the ball milling 2 hours, with the direct fusion plastification in the Hakke torque rheometer of polypropylene powder, be injected into the standard batten again with injector.
As seen from Table 3:
Balancing moment when 1, the embodiment of the invention 1,5 samples plastify has only 3~3.4Nm, better than the comparative example 1 of virgin pp and comparative example 2 that nano silicon is directly added, also good than the comparative example 4 that nanoparticle adds again the polypropylene plasticizing after with the butyl acrylate modification, illustrate that the present invention can improve the plasticizing flowability of matrix material, this is favourable to forming process, and this also is the more scabrous problem of general filler filled composite materials.
2, the normal temperature notched Izod impact strength of embodiment 1,5 samples is the highest, is about 2 times of virgin pp (comparative example 1), and toughening effect is obvious.The tensile strength of embodiment 1,5 also increases than virgin pp simultaneously.Illustrate that the inventive method can make nano silicon that polypropylene is played toughness reinforcing and enhancement simultaneously.
3, the modulus in flexure of the embodiment of the invention 1,5 samples is all than virgin pp (comparative example 1) height, embodiment 1 even also higher than the comparative example 2 that nanoparticle is directly added, though and comparative example 4 is identical with the consumption of butyl acrylate among the embodiment 1, the modulus in flexure of sample is descended to some extent.It is better to illustrate that the present invention makes the rigidity of matrix material, and this point also can be confirmed from the crystallinity data of correspondence.
4, from the crystal property data, the fusing point of embodiment 1,5 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, the crystallization rate of polymkeric substance is accelerated, degree of crystallinity is improved.
The technology of the present invention adopts general processing units, and technology is simple, and cost is low, and the processing fluidity of obtained matrix material, tensile strength, 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, polypropylene, polystyrene, polyvinyl chloride or ethylene-vinyl acetate copolymer etc.
Each composition consumption proportion of table 1 part embodiment
Nano-silica KH570 idol butyl acrylate weight initiator polypropylene
Change silicon weight connection agent weight (g) weight (g)
(g)???????????(g)?????????????????????????????(g)
Embodiment 1515 BPO 90
(vapor phase process) (adding 2.5 earlier) 0.025
Embodiment 2515 BPO 90
(vapor phase process) (adding 3 earlier) 0.025
Embodiment 3515 BPO 90
(vapor phase process) (adding 3.5 earlier) 0.025
Embodiment 4515 BPO 90
(vapor phase process) (adding 4 earlier) 0.025
Embodiment 551 10 BPO 85
(vapor phase process) (adding 5 earlier) 0.050
Embodiment 651 15 BPO 80
(vapor phase process) (adding 7.5 earlier) 0.075
Embodiment 75 2.5 5 BPO 90
(vapor phase process) (adding 2.5 earlier) 0.025
Embodiment 8515 AIBN 90
(vapor phase process) (adding 2.5 earlier) 0.025
Embodiment 9515 BPO 90
(precipitator method) (adding 2.5 earlier) 0.025
Table 2 comparative example composition and consumption proportion
Nano-silica KH570 idol butyl acrylate weight initiator polypropylene
Change silicon weight connection agent weight (g) weight (g)
(g)????????????(g)?????????????????????????????(g)
Comparative example 1 100
Comparative example 25 95
(vapor phase process)
Comparative example 351 95
(vapor phase process)
Comparative example 4515 BPO 90
(vapor phase process) 0.025
Table 3 embodiment 1 and embodiment 5 compare with the performance of the obtained material of Comparative Examples
The embodiment comparative example | |||||
????1 | ??5?????????1 | ??2 | ??3 | ??4 | |
Balancing moment during plasticizing (Nm) | ????3.4 | ??3.0???????5.4 | ??5.9 | ??5.4 | ??4.4 |
Simply supported beam notched Izod impact strength (KJ/m 2) | ???2.94 | ??3.21??????1.46 | ??1.63 | ??1.88 | ??2.06 |
Tensile strength (MPa) | ???44.71 | ??43.23?????41.34 | ??38.41 | ??38.59 | ??41.26 |
Modulus in flexure (MPa) | ???1523 | ??1442??????1306 | ??1501 | ??1544 | ??1344 |
Fusing point T m(℃) | ???165.4 | ??163.9?????164.9 | ??164.2 | ??163.8 | ??163.3 |
The fastest temperature T of crystallization c(℃) | ???120.1 | ??120.5?????110.4 | ??120.1 | ??115.4 | ??118.7 |
???ΔT=T m-T c(℃) | ???45.3 | ??43.4??????54.5 | ??44.1 | ??48.4 | ??44.6 |
Crystallinity X c(%) | ???49.2 | ??42.9??????35.9 | ??44.7 | ??45.2 | ??40.9 |
Annotate: 1. measure balancing moment with the Hakke torque rheometer.
2. press the ISO179-2 standard and measure the normal temperature notched Izod impact strength with the freely-supported beam type.
3. press ASTM D638-98 standard test tensile strength and modulus in flexure.
4. measure T with DSC
m, T
cAnd X
c
Claims (5)
1. the power chemical preparation process of a nanometer composite inorganic particle/polymer material, the concrete steps that it is characterized in that this method are: 1) use the coupling agent treatment nano inoganic particle, with toluene is solvent, with coupling agent and nano inoganic particle back flow reaction 8 hours under nitrogen protection, the nano inoganic particle consumption is 1~20wt%, used coupling agent is γ-methacryloxypropyl trimethoxy silane, and consumption is 1~50wt% of nano inoganic particle; Used nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, and median size is 7~50nm, and specific surface area is 150~640m
2/ g;
2) will add in the ball mill through coupling agent treatment nano inoganic particle and a part of monomer, rotating speed 200~300rpm, 1 hour ball milling time, used monomer is esters of acrylic acid, vinylbenzene, vinylformic acid, methacrylic acid, maleic anhydride or glycidyl methacrylate, radical initiator is azo-initiator or peroxide initiator, the monomer consumption is 100~300wt% of nanoparticle consumption, and the consumption of radical initiator is 0.1~0.5wt% of monomer consumption;
3) together add in the ball mill rotating speed 400~500rpm, 1~2 hour ball milling time with polymer powders after again another part monomer being added initiator.
2. in accordance with the method for claim 1, it is characterized in that used acrylic ester monomer is ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester.
3. in accordance with the method for claim 1, it is characterized in that used radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
4. in accordance with the method for claim 1, 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 used polymkeric substance is powdered polypropylene, polyethylene, polystyrene, polyvinyl chloride or ethylene-vinyl acetate copolymer.
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