CN100509893C - Fluorine-containing nano inorganic particle toughening polymer and preparing method thereof - Google Patents
Fluorine-containing nano inorganic particle toughening polymer and preparing method thereof Download PDFInfo
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- CN100509893C CN100509893C CNB2007100270513A CN200710027051A CN100509893C CN 100509893 C CN100509893 C CN 100509893C CN B2007100270513 A CNB2007100270513 A CN B2007100270513A CN 200710027051 A CN200710027051 A CN 200710027051A CN 100509893 C CN100509893 C CN 100509893C
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Abstract
The invention discloses a making method of toughening polymer with inorganic fluorine nanometer particle, which comprises the following steps: leading fluorine polymer into the surface of inorganic nanometer particle; fluxing modified nanometer particle and polymer; obtaining the composite material of nanometer particle filling polymer; reducing mutual action among nanometer particle when reinforcing the mutual action of nanometer particle and polymer base through self-lubricating property; irradiating energy to toughen polymer base.
Description
Technical field
The present invention relates to nano-inorganic particle filled polymer composites, specifically, relate to a kind of fluorine-containing nano inorganic particle toughening polymer and preparation method thereof.
Background technology
(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 nano-inorganic particle filled polymer composites 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, need carry out surface treatment to nano inoganic particle, the repulsion potential energy between gravitational potential energy between the minimizing particle or the increase particle.Relatively effective means is that nano inoganic particle is carried out surface chemical modification at present, mainly contains coupling agent modified and graft modification.
Coupling agents such as coupling agent modified common employing silicane, titanate ester or phosphoric acid ester, owing to contain two kinds of groups of different nature in the coupling agent molecule structure, a kind of can have an effect with inorganic material surface (chemical reaction or physical adsorption), another kind can have an effect with macromolecular material (chemical reaction or physical adsorption), thereby can on the interface of inorganic materials and macromolecular material, play bridge joint, improve the bonding interface of material.It is pointed out that the coupling agent modified distinct disadvantage that exists, coupling agent all is small-molecule substances, the many mechanical properties that can influence material of consumption, and that consumption can disperse less is inhomogeneous, influence treatment effect, and price is more expensive, makes the cost increase of final material.
Graft modification is meant by various means receives inorganic nanoparticles sub-surface with polymkeric substance by chamical binding in inorganic nanoparticles sub-surface initiation grafting polyreaction.The grafting process helps strutting the coacervate of nanoparticle, promotes the dispersion of nanoparticle, and graftomer molecular chain and matrix polymer molecule interchain tangle simultaneously, have also increased the interface interaction between particle and matrix; On the other hand, utilize graft modification suitable graftomer to be introduced nanoparticle surface, change the surface property of nanoparticle, thereby give nanoparticle some new functions by molecular designing and INTERFACE DESIGN.In the technology of implementing graft modification, the irradiation grafting comparative maturity, it is to make the hydroxyl of nanoparticle surface or lattice imperfection place produce the spike with initiating activity by the high-energy radiation effect, trigger monomer is in its surperficial polymerization.
Many about studies show that of nano-inorganic particle filled polymkeric substance, although the adding of nanoparticle can improve the rigidity and the intensity of polymeric matrix, the toughness of material is decreased.And show about polymer nanocomposites destructive molecular mechanism research recently, improve the flowability of nanoparticle in polymeric matrix when stressed, can in matrix material, introduce the diffusing consumption mechanism of new energy, thereby improve the toughness of nano composite material greatly.
Summary of the invention
The objective of the invention is to the deficiency that exists on the existing nano composite material preparation method, provide that a kind of cost is low, the preparation method of the fluorine-containing nano inorganic particle toughening polymer of gained nano composite material toughness enhanced.
Another object of the present invention provides the fluorine-containing nano inorganic particle toughening polymer that utilizes above-mentioned preparation method to obtain.
To achieve these goals, the present invention adopts the way of irradiation grafting modification, introduce fluoropolymer in the inorganic nanoparticles sub-surface, in the interfacial interaction of strengthening between nanoparticle and polymeric matrix, utilize the self-lubricating property of fluoropolymer, weaken the interaction between the nanoparticle, thereby improve the flow capacity of nanoparticle, play the purpose that strengthens the toughening polymer matrix.
The concrete preparation process of fluorine-containing nano inorganic particle toughening polymer of the present invention is:
(1) with ultra-sonic dispersion after nano inoganic particle, grafted monomer and the solvent, carry out irradiation with gamma-rays, irradiation dose is 2～16Mrad; The effect of irradiation is to cause the graft polymerization reaction of nano inoganic particle and grafted monomer;
Described nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, and particle diameter is 7～50nm, and specific surface area is 150～640m
2/ g;
Described grafted monomer is fluorinated acrylate, fluorine-containing methacrylate, fluorine-containing or hydrocarbon compoud containing fluorine, and monomer weight is 50～300% of a nano inoganic particle weight;
(2) with nano inoganic particle behind the irradiation in 70 ℃ of following vacuum-dryings 24 hours, remove and to desolvate and unreacted grafted monomer, and then, obtain the inorganic nano-particle of graft modification in 100 ℃ of following vacuum-dryings 1 hour;
(3) inorganic nano-particle and the polymkeric substance with graft modification carries out melt blending, the mass ratio of modified inorganic nano-particle and polymkeric substance is 1:99～10:90, blending temperature is 180 ℃, the Banbury mixer rotating speed is 40～80rpm, the blend time is 6～15min, makes the nano inorganic particle toughening polymer of different inorganic nano-particle content.
In the preparation process of above-mentioned fluorine-containing nano inorganic particle toughening polymer, in order to mix better effects if with polymer melt, the modified inorganic nano-particle that obtains in the step (2) can be carried out ball milling, rotating speed 200～400rpm, half an hour ball milling time, obtain the superfine modified inorganic nano-particle, carry out the reaction of step (3) again.
In the preparation process of above-mentioned fluorine-containing nano inorganic particle toughening polymer, the preferred vinylformic acid trifluoro ethyl ester of described fluorinated acrylate, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or vinylformic acid 19 fluorine esters; Described fluorine-containing methacrylate preferable methyl vinylformic acid trifluoro ethyl ester, methacrylic acid hexafluoro butyl ester or methacrylic acid ten difluoro heptyl esters; Preferred trifluoropropyl olefin(e) acid of described fluorine-containing or trifluoromethyl acrylate; The preferred 2-bromine of described hydrocarbon compoud containing fluorine trifluoro propene.
In the preparation process of above-mentioned fluorine-containing nano inorganic particle toughening polymer, the described solvent preferred alcohol of step (1), butanone, normal hexane or toluene, the weight of solvent is 40 times of nano inoganic particle.
In the preparation process of above-mentioned fluorine-containing nano inorganic particle toughening polymer, the nano silicon that described nano-silicon dioxide particle makes for the nano silicon that adopts the precipitator method and make or vapor phase process.
In the preparation process of above-mentioned fluorine-containing nano inorganic particle toughening polymer, described polymkeric substance preferably polyethylene, polypropylene or polystyrene.
When nano inoganic particle, fluorine-containing grafted monomer and solvent uniform mixing, nano inoganic particle by monomer fully moistening after, this mixture is carried out mutual radiation with the gamma-rays of radio isotope cobalt-60, high-energy radiation can make the hydroxyl of nanoparticle surface or lattice imperfection place produce the spike with initiating activity, the initiation grafting monomer is at the graft polymerization reaction of inorganic nanoparticles sub-surface, thereby fluoropolymer is grafted to nanoparticle surface.
Compare with existing chemical graft method, irradiation grafting method of the present invention has been saved the step of coupling agent treatment at nanoparticle surface introducing reactive group, need not use initiator yet, and the monomer in solution is easy to infiltrate the inside of nanoparticle coacervate, helps improving the homogeneity of percentage of grafting and surface grafting.Because the molecular chain and the matrix polymer molecule interchain of graftomer tangle mutually, have strengthened the interface interaction between particle and matrix; On the other hand, because nanoparticle surface grafted fluoropolymer has the self-lubricating effect, make that the interaction between the nanoparticle weakens greatly.Therefore when matrix material is subjected to the external force effect, nanoparticle and small coacervate thereof can be subjected to the stretching action that forces of substrate molecule chain movement, take place to flow and distortion, consume lot of energy, and can suppress the formation and the expansion of crackle effectively, thereby introduce the diffusing consumption mechanism of new energy, significantly improve the toughness of nano composite material.
The present invention adopts conventional irradiance method and general processing units, and technology is simple, and cost is low, and the toughness of obtained matrix material is greatly improved, and tensile strength, rigidity, processing fluidity all are significantly improved simultaneously.Utilize the technology of the present invention to can be used for preparing the nano composite material of general-purpose plastics such as polyethylene, polypropylene and polystyrene for matrix.
Description of drawings
Fig. 1 is the infrared spectra graphic representation of embodiment 2 and comparative example 1;
Fig. 2 is embodiment 2 and the torque-time plot of comparative example 1,2 in the fusion plastification process that Hakke Rheocord 300p torque rheometer records;
Fig. 3 is the transmission electron microscope photo of part embodiment of the present invention.
Wherein, a is PDFA-g-SiO among Fig. 1
2(embodiment 2), b is undressed fumed nano SiO
2(comparative example 1).Among Fig. 2, a is embodiment 2, and b is a comparative example 1, and c is a comparative example 2.
Embodiment
Below by polyacrylic acid ten difluoro heptyl ester (PDFA) graft modification nano silicons (are designated as PDFA-g-SiO
2) filled polypropylene (PP) and unmodified nanometer SiO
2Filled polypropylene, butyl polyacrylate (PBA) graft modification nanometer SiO
2(be designated as PBA-g-SiO
2) the present invention is further illustrated for the comparing embodiment of filled polypropylene and accompanying drawing.
Each composition consumption proportion of embodiment 1-11 is as shown in table 1.In the table 1, the concrete processing step of each embodiment is: nanoparticle, grafted monomer and solvent (butanone) are mixed back ultra-sonic dispersion half an hour, gamma-rays with radio isotope cobalt-60 carries out irradiation, and irradiation dose is 8Mrad, and the weight ratio of nano inoganic particle and solvent is 1/40.With the nanometer SiO behind the radiation modification
2Particle removes and desolvates and unreacted monomer in 70 ℃ of following vacuum-dryings 24 hours, and then in 100 ℃ of following vacuum-dryings 1 hour.With dried modified Nano particle ball milling half an hour, rotating speed 200～400rpm obtains superfine modification SiO
2Particle carries out melt blending with polymeric matrix again, and the mass ratio of modified inorganic nano-particle and polymkeric substance is 1:99～10:90, blending temperature is 180 ℃, the Banbury mixer rotating speed is 40～80rpm, and the blend time is 6～15min, makes the polymer matrix composite of different nanoparticle content.To be injected into the standard batten with injector after the matrix material fragmentation that make.
Each composition consumption proportion of comparative example 1-4 is as shown in table 2, fumed nano SiO
2Weight is 5g.In the table 2, the processing step of comparative example 1 is for directly to be injected into the standard batten with injector with pure PP; The processing step of comparative example 2 is with unmodified nanometer SiO
2Particle and polymeric matrix carry out melt blending, make the polymer matrix composite of different nanoparticle content, with after its fragmentation, are injected into the standard batten with injector then; Comparative example 3 and 4 concrete processing step are: with nanometer SiO
2, grafted monomer and an amount of solvent (butanone) mix back ultra-sonic dispersion half an hour, carries out irradiation with the gamma-rays of radio isotope cobalt-60, irradiation dose is 8Mrad, the weight ratio of nano inoganic particle and solvent is 1/40.With the nanometer SiO behind the radiation modification
2Particle removes and desolvates and unreacted monomer in 70 ℃ of following vacuum-dryings 24 hours, and then in 100 ℃ of following vacuum-dryings 1 hour.With dried modified Nano particle ball milling half an hour, rotating speed 200～400rpm obtains superfine modification SiO
2Particle carries out melt blending with polypropylene again, makes the polypropylene composite material of different nanoparticle content.To be injected into the standard batten with injector after the matrix material fragmentation that make.
Table 3 is that embodiments of the invention 1,2 and comparative example 1-4 prepared performance of composites compare.
As seen from Table 3:
1. be added with fluoropolymer graft modification nanometer SiO
2Embodiment 1 and 2 normal temperature notched Izod impact strength be the highest, compare with pure PP and improved 1.31 times and 1.76 times respectively, toughening effect is the most remarkable.And add other polymer graft modification nanometer SiO
2Though comparative example 3 compare with pure PP with 4 normal temperature notched Izod impact strength and improved 0.61 times and 0.36 times respectively, more much lower than embodiment 1 and 2.Add unmodified nanometer SiO
2The normal temperature notched Izod impact strength of comparative example 2 reduced by 0.14 times than pure PP on the contrary.Nanoparticle flowability order from high to low is in each example: embodiment 2〉embodiment 1〉comparative example 3〉comparative example 4〉comparative example 2, the notched Izod impact strength of each routine sample order from big to small is: embodiment 2〉embodiment 1〉comparative example 3〉comparative example 4〉comparative example 2, illustrate that the inventive method is by improving the impelling strength that the flowability of nanoparticle in polymeric matrix can improve matrix material.
2. each routine elongation at break order from big to small is embodiment 2〉embodiment 1〉comparative example 3〉comparative example 4〉comparative example 2, further illustrate the inventive method by improving the tensile toughness that the flowability of nanoparticle in polymeric matrix also can improve matrix material.
3. the tensile strength of the embodiment of the invention 1 and 2 samples also is the highest.Illustrate that the inventive method can strengthen and toughened composite polymer material simultaneously.
4. though the Young's modulus of the embodiment of the invention 1 and 2 samples is lower than comparative example 3 and 4 samples, but still than pure PP (comparative example 1) height, though the interfacial layer of having introduced relative flexibility in the matrix material that the present invention makes is described, material still has higher rigidity.
5. from the crystal property data, the fusing point of embodiment 1 and embodiment 2 samples is compared with pure PP (comparative example 1) and is changed not quite, but condensate depression △ T scope reduces, and illustrate that nanoparticle plays the heterogeneous nucleation effect in the inventive method, makes the crystallization rate quickening of polymkeric substance.On the other hand, the introducing of modified Nano particle surface graftomer can influence the crystalline degree of perfection in the inventive method, and crystallinity of polymer is slightly descended, and this also helps the raising of toughness of polymers.
Can draw from accompanying drawing:
Fig. 1 is the infrared spectra graphic representation of embodiment 2 and comparative example 1.As can be seen from Figure 1, with unmodified fumed nano SiO
2INFRARED SPECTRUM (b) compare PDFA-g-SiO
2INFRARED SPECTRUM (a) at 1761cm
-1The absorption peak of carbonyl appears in the place, proves and PDFA is introduced nanometer SiO
2The surface.
Fig. 2 is the embodiment of the invention 2 and the torque-time plot of comparative example 1,2 in the fusion plastification process that Hakke Rheocord 300p torque rheometer records, and wherein a is embodiment 2, and b is a comparative example 1, and c is a comparative example 2.Can understand the rheological behaviour of matrix material in molding process by torque-time curve of Fig. 2, add PDFA-g-SiO
2The balancing moment of PP matrix material (embodiment 2) be lower than pure PP (comparative example 1), and directly add unmodified nanometer SiO
2The balancing moment and the pure PP (comparative example 1) of sample (comparative example 2) about the same, illustrating that the present invention has improves the mobile characteristics of matrix material plasticizing, and this is the more scabrous problem of general micron order filler filled composite materials.
Fig. 3 is transmission electron microscope (TEM) photo of part embodiment of the present invention, wherein (a), (c), (e) are respectively the TEM photo of comparative example 2,3 and embodiment 2 battens, (b), (d), (f) be respectively the TEM photo after comparative example 2,3 and the stretched test of embodiment 2 battens.By relatively finding unmodified nanometer SiO
2The dispersion of particle in polymeric matrix is relatively poor, form bigger coacervate (Fig. 3 (a)), after graft modification is handled, the dispersion of nanoparticle in matrix makes moderate progress, and the nanoparticle coacervate has certain deformation and orientation (Fig. 3 (c), (e)) because of shear action in injection process.After the stretched experiment, unmodified nanometer SiO
2The deformation extent of particle cluster aggressiveness very little (Fig. 3 (b)), PBA-g-SiO
2Significant change (Fig. 3 (d)) do not take place in the shape of particle cluster aggressiveness yet; And PDFA-g-SiO
2The particle cluster aggressiveness under the stretching action, obviously is elongated and deformed, and arranges (Fig. 3 (f)) along draw direction outside, has proved that the motor capacity of nanoparticle in matrix improves greatly behind the grafted fluoropolymer.
Each composition consumption proportion of table 1 embodiment
Each composition consumption proportion of table 2 comparative example
The comparison of table 3 part embodiment and the obtained composite property of comparative example
Annotate: 1. measure balancing moment with the Hakke torque rheometer.
2. press ISO 179-2 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 (8)
1, a kind of preparation method of fluorine-containing nano inorganic particle toughening polymer is characterized in that comprising the steps:
(1) with ultra-sonic dispersion after nano inoganic particle, grafted monomer and the solvent, carry out irradiation with gamma-rays, irradiation dose is 2～16Mrad;
Described nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, and particle diameter is 7～50nm, and specific surface area is 150～640m
2/ g; Described solvent is a butanone;
Described grafted monomer is fluorinated acrylate, fluorine-containing methacrylate or fluorine-containing, and monomer weight is 50～300% of a nano inoganic particle weight;
(2) with nano inoganic particle behind the irradiation in 70 ℃ of following vacuum-dryings 24 hours, remove and to desolvate and unreacted grafted monomer, and then, obtain the inorganic nano-particle of graft modification in 100 ℃ of following vacuum-dryings 1 hour;
(3) inorganic nano-particle and the polymkeric substance with graft modification carries out melt blending, the mass ratio of modified inorganic nano-particle and polymkeric substance is 1:99～10:90, blending temperature is 180 ℃, the Banbury mixer rotating speed is 40～80rpm, the blend time is 6～15min, makes the nano inorganic particle toughening polymer of different inorganic nano-particle content.
2, preparation method as claimed in claim 1, it is characterized in that the modified inorganic nano-particle that obtains to be carried out ball milling in the step (2), rotating speed 200～400rpm, half an hour ball milling time, obtain the superfine modified inorganic nano-particle, carry out the reaction of step (3) again.
3, preparation method as claimed in claim 1 is characterized in that described fluorinated acrylate is vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or vinylformic acid 19 fluorine esters; Described fluorine-containing methacrylate is trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester or methacrylic acid ten difluoro heptyl esters; Described fluorine-containing is trifluoropropyl olefin(e) acid or trifluoromethyl acrylate.
4, preparation method as claimed in claim 1, the weight that it is characterized in that the described solvent of step (1) are 40 times of nano inoganic particle.
5, preparation method as claimed in claim 1 is characterized in that the nano silicon that described nano-silicon dioxide particle makes for the nano silicon that adopts the precipitator method and make or vapor phase process.
6, preparation method as claimed in claim 1 is characterized in that described polymkeric substance is polyethylene, polypropylene or polystyrene.
7, preparation method as claimed in claim 1 is characterized in that the time of the described ultra-sonic dispersion of step (1) is half hour.
8, the fluorine-containing nano inorganic particle toughening polymer that utilizes the described preparation method of claim 1 to obtain.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101497749B (en) * | 2009-03-06 | 2012-02-15 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
| CN102492096A (en) * | 2011-11-11 | 2012-06-13 | 中国科学院长春应用化学研究所 | Polypropylene-polystyrene resin and preparation method thereof |
| CN109734995A (en) * | 2018-11-29 | 2019-05-10 | 柳州市海达新型材料科技有限公司 | Soft sense of touch scratch antibacterial polypropylene material |
| CN109679204A (en) * | 2018-11-29 | 2019-04-26 | 柳州市海达新型材料科技有限公司 | The preparation method of the polypropylene material of height filling inorganic filler |
| CN109705430A (en) * | 2018-11-29 | 2019-05-03 | 柳州市海达新型材料科技有限公司 | The filling master batch preparation process of plastics tensile strength and elongation at break can be improved |
| CN109679121A (en) * | 2018-11-29 | 2019-04-26 | 柳州市海达新型材料科技有限公司 | High-content inorganic particle modified filler masterbatch |
| 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 |
| CN114262485B (en) * | 2022-03-03 | 2022-05-24 | 上海科进生物技术有限公司 | Modified high polymer material and preparation method and application thereof |
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