CN100410314C - Polyethylene /montmorillonite nanometer composite material and preparation method - Google Patents
Polyethylene /montmorillonite nanometer composite material and preparation method Download PDFInfo
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Abstract
The present invention relates to a polyethylene and montmorillonite nanometer composite material and a preparation method thereof. Sheet layers of montmorillonite are homogeneously dispersed in a polyethylene base body after being partially or whole stripped, and the content of the montmorillonite in a nanometer composite material is from 1 to 10%. The polyethylene is a copolymer of alpha-olefin and ethene. In the preparation method, an ethylene oligomerization catalyst is loaded among the montmorillonite layers, and the alpha-olefin generated at the original position is copolymerized with an ethene monomer among the montmorillonite layers to obtain the intercalation type or the stripping type polyethylene and montmorillonite nanometer composite material. The method particularly comprises: 1) preparing a montmorillonite carrier; 2) preparing the ethylene oligomerization catalyst of a montmorillonite load; 3) preparing the polyethylene and montmorillonite nanometer composite material by the ethylene oligomerization catalyst of the montmorillonite load.
Description
Technical field
The present invention relates to a kind of polyethylene/montmorillonite nanometer composite material.
The invention still further relates to the preparation method of above-mentioned matrix material.
Background technology
Polyolefin/montmorillonite nano composite material is because the dimensional effect (one dimension is less than 100nm at least) of nano imvite lamella, the workability of rigidity, barrier property and the polyolefin substrate of inorganic nano-particle is combined, obtain the matrix material of physical and mechanical property excellence.
Polymer melt intercalation compound (Macromol Rapid Commun, 1999,20:423; J EngMater Technol, 1999,121:483; Macromolecules, 1997,30:6333; Synthetic resins and plastics, 2000,17:44; Macromolecules, 2003,36:8919) usually with the two-step approach synthetic composite material.At first replace the basic metal or the alkaline-earth metal ions of clay or layered silicate interlayer by ion-exchange with organic ammonium or other functionalization organosilicon, make the common hydrophilic mica type silicate oleophylic that becomes, and the interlamellar spacing of silicate lamella is increased, help modified inorganic particles and be dispersed in the polymeric matrix.Secondly, polymkeric substance that can melt-processed combines together with modification organic clay particle under high-shear, obtains the polymer composites of high physicals.But this preparation method is difficult to prepare polyethylene/montmorillonite nanometer composite material.Although can be used to prepare polypropylene composite material, also organic ammonium modified montmorillonoid, modified propylene oligopolymer and polypropylene fusion must be extruded.
Polymers soln intercalation compound (Polym Bull, 1998,41:107; J Mater Sci Lett, 1997,16:1670; J Mater Sci, 2000,35:1045) montmorillonite layer is disperseed with 2~5 strata collectives, can not get exfoliated polyethylene/montmorillonite nanometer composite material.Owing to the use of organic solvent, be unfavorable for aftertreatment and environment protection when organic ammonium modified montmorillonoid, modification polyene and polypropylene solution blending prepare matrix material simultaneously.
Monomer intercalation in-situ polymerization compound (Chem Commun, 1999:2179; Macromol RapidCommun, 1999,20:423; DE 19846314 (2000); Macromol Rapid Commun, 2000,21:57; USP 6,613,711 (2003)) be the best polyolefin/montmorillonite nano composite material preparation method of present effect, but in the existing report or use the organic ammonium modified montmorillonoid, perhaps in polymerization process, add common monomer, increase the complicacy and the production cost of system, be unfavorable for commercialization.
Summary of the invention
The object of the present invention is to provide a kind of polyethylene/montmorillonite nanometer composite material.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned matrix material.
For achieving the above object, after polyethylene/montmorillonite nanometer composite material provided by the invention, montmorillonite layer are partly or entirely peeled off, be dispersed in the polyethylene, the content of polynite in nano composite material is 1-10wt%.
Described polyethylene is the multipolymer of alpha-olefin and ethene.
Described polynite is an inorganic materials, can be Na-polynite, Mg-polynite or Ca-polynite, its specific surface area 50-1000m
2/ g, aperture 5-50nm, pore volume 0.3-500cm
3/ g, cation exchange capacity are 80-120meq/100g.
The present invention has overcome the shortcoming that montmorillonite layer in the prior art is peeled off weak effect or preparation process complexity, the rear transition metal ethylene oligomerization catalyst is carried between cheating engaging layer, original position generates alpha-olefin, obtains exfoliated polyethylene/montmorillonite nanometer composite material with ethylene copolymer between cheating engaging layer.
The method for preparing polyethylene/montmorillonite nanometer composite material provided by the invention, carry out in the following order:
1. the preparation of montmorillonite carrier
Polynite is made montmorillonite carrier with cyclodextrin and aluminum alkyls processing, and concrete grammar is as follows:
Polynite is disperseed the weight ratio 1 of polynite and water: 20-1 in water: 500, behind the stirring 10-120min, obtain mashed prod A; Cyclodextrin is water-soluble, the weight ratio 1 of cyclodextrin and water: 50-1: 500, slowly add among the A, stirring also is warming up to 50-100 ℃, after keeping 5-60min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the organic solvent weight ratio 1 of B and organic solvent: 3-1: 20, stir 10-60min under the room temperature, slowly add the aluminum alkyls toluene solution down and temperature is controlled at 0 ± 5 ℃ at-10-0 ℃, the weight ratio 1 of aluminum alkyls and B: 5-1: 100, slowly be warming up to 10-60 ℃ then, continue reaction 2-10h, use organic solvent washing, filter and drying, obtain montmorillonite carrier.
2. the preparation of montmorillonite load ethylene oligomerization catalyst
The non-polar organic solvent solution of ethylene oligomerization catalyst will be added in the above gained montmorillonite carrier, reactive metal and polynite weight ratio 1: 500-1 in the described catalyst for oligomerization: 2000, at 20-80 ℃ of reaction 2-20h, with the non-polar organic solvent flush away catalyst for oligomerization of load not, drying obtains the montmorillonite load ethylene oligomerization catalyst.
3. the preparation of polyethylene/montmorillonite nanometer composite material
Under nitrogen or argon gas atmosphere, aluminum alkyls or alkylalumoxane solution and montmorillonite load ethylene oligomerization catalyst are scattered in the non-polar organic solvent, the reactive metal mol ratio 100-2000 of described aluminum alkyls or alkylaluminoxane and catalyst for oligomerization, feed vinyl monomer, carried out oligomerisation reaction 1-20 minute at 10-80 ℃, continue to feed ethene, press the reactive metal mol ratio 100 of aluminum alkyls or alkylaluminoxane and olefin-copolymerization catalyst: 1-2000: 1 adds promotor, olefin-copolymerization catalyst is (as the dicyclopentadiene zirconium dichloride, methyl silicon bridge two indenyl zirconium dichlorides, ethyl bridge two indenyl zirconium dichlorides, titanium chloride/magnesium chloride/electron donor) carries out polyreaction 0.5-2 hour, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
The method that the present invention prepares polyethylene/montmorillonite nanometer composite material has following characteristics:
1) preparation method of the present invention be the catalytic active center of catalyst for oligomerization between cheating engaging layer or the oligomerisation of surface catalysis vinyl monomer form alpha-olefin, alpha-olefin and ethene in-situ copolymerization between cheating engaging layer under the effect of catalyst for copolymerization then forms montmorillonite layer and is dispersed in matrix material in the polyethylene matrix.
2) matrix material of the present invention can be used for preparing ethene-alpha-olefin copolymer/Nano composite material of montmorillonite.
3) the montmorillonite carrier process for synthetic catalyst among the preparation method of the present invention is simple, helps suitability for industrialized production.
4) matrix material wide accommodation of the present invention, the molecular weight of polymkeric substance is controlled, can adopt slurry polymerization to prepare polyethylene/montmorillonite nanometer composite material.
5) preparation method of the present invention, when being used for alpha-olefin and ethylene copolymer, molecular weight of copolymer distributes wide.
Embodiment
Following specific embodiment will be made detailed explanation with regard to nano composite material of the present invention and preparation method.But these embodiment are not intended to limit by any way or limit scope of the present invention, also should not think at condition, parameter or numerical value that necessary unique utilization is provided.Unless otherwise noted, all umbers and percentage ratio are by weight.
Embodiment 1
The preparation of montmorillonite carrier: the 1g polynite is dispersed in the 20g water, stirs 10min, obtain mashed prod A; The 1g alpha-cylodextrin is dissolved in 500g water, slowly adds among the A, stir and be warming up to 50 ℃, keep 60min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 20g toluene, stirs 60min under the room temperature, slowly add at-10 ℃ and contain the toluene solution of 0.06g trimethyl aluminium and temperature is controlled at-5 ℃, slowly be warming up to 60 ℃ then, continue reaction 2h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned illiteracy of 0.3g take off ±, add and contain 0.6mg 2, the toluene solution of 4-dimethyl diimine pyridine iron title complex (according to Chin.Sci.Bull.2002,47 (19): 1616-1618 is synthetic) reacts 20h down at 20 ℃; With the toluene flush away not load 2,4-dimethyl diimine pyridine iron title complex; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.2wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add the 100mL hexane in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down and add 2mL triethyl aluminum toluene solution (1.8M) in 10 ℃, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.0838g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 1min, add 2.9mL methylaluminoxane toluene solution (1.4M) and 2 μ mol dimethyl-silicon bridgings, two indenyl zirconium dichlorides again, behind the polyreaction 30min, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 2
The preparation of montmorillonite carrier: the 3g polynite is dispersed in the 1500g water, stirs 120min, obtain mashed prod A; The 1g beta-cyclodextrin is dissolved in 50g water, slowly adds among the A, stir and be warming up to 100 ℃, keep 5min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 3g toluene, stirs 10min under the room temperature, slowly add at 0 ℃ and contain the toluene solution of 0.2g triethyl aluminum and temperature is controlled at 0 ℃, slowly be warming up to 10 ℃ then, continue reaction 10h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned polynite of 1g, add the toluene solution contain 2mg 2-sec.-propyl diimine pyridine iron title complex (according to J.Am.Chem.Soc.1998,120,7143-7144 is synthetic), at 80 ℃ of reaction 2h down; With the toluene flush away 22-sec.-propyl diimine pyridine iron title complex of load not; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.5wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add 100mL toluene in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down in 80 ℃ of toluene solutions (1M) that add the 1mL trimethyl aluminium, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.3723g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 20min, add 0.29mL methylaluminoxane toluene solution (1.4M) and 4 μ mol ethylene bridge di-indenyl zirconium dichlorides again, behind the polyreaction 2h, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 3
The preparation of montmorillonite carrier: the 2g polynite is dispersed in the 300g water, stirs 60min, obtain mashed prod A; The 2g γ-Huan Hujing is dissolved in 150g water, slowly adds among the A, stir and be warming up to 80 ℃, keep 30min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 15g hexane, stirs 30min under the room temperature, slowly add at-5 ℃ and contain the toluene solution of 0.06g triisobutyl aluminium and temperature is controlled at 5 ℃, slowly be warming up to 30 ℃ then, continue reaction 6h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned polynite of 1.5g, add the toluene solution contain 1mg 2-methyl diimine pyridine iron title complex (according to J.Am.Chem.Soc.1998,120,7143-7144 is synthetic), at 50 ℃ of reaction 8h down; With the toluene flush away 2-methyl diimine pyridine iron title complex of load not; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.8wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add 100mL toluene in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down and add 2mL triisobutylaluminum toluene solution (1.0M) in 60 ℃, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.0621g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 10min, add 3.2mL methylaluminoxane toluene solution (1.4M) and 3 μ mol dicyclopentadiene zirconium dichlorides again, behind the polyreaction 60min, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 4
The preparation of montmorillonite carrier: the 1.5g polynite is dispersed in the 600g water, stirs 45min, obtain mashed prod A; The 1.5g alpha-cylodextrin is dissolved in 300g water, slowly adds among the A, stir and be warming up to 60 ℃, keep 45min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 10g hexanaphthene, stirs 45min under the room temperature, slowly add at-8 ℃ and contain the toluene solution of 0.1g trimethyl aluminium and temperature is controlled at-3 ℃, slowly be warming up to 45 ℃ then, continue reaction 5h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned polynite of 1g, add and contain 1.5mg 2-methyl-4-methoxyl group diimine pyridine iron title complex (according to Chin.Sci.Bull.2002,47 (19): 1616-1618 is synthetic) toluene solution, at 30 ℃ of reaction 10h down; With the toluene flush away 2-methyl of load-4-methoxyl group diimine pyridine iron title complex not; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.1wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add the 100mL hexane in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down and add 3mL triethyl aluminum toluene solution (1.8M) in 30 ℃, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.2742g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 15min, add 0.8mL triethyl aluminum toluene solution (1.8M) and 10 μ mol CS-II catalyzer (company of section provides) more on the sunny side, behind the polyreaction 120min, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 5
The preparation of montmorillonite carrier: the 2.5g polynite is dispersed in the 1000g water, stirs 100min, obtain mashed prod A; The 2g beta-cyclodextrin is dissolved in 250g water, slowly adds among the A, stir and be warming up to 70 ℃, keep 50min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 12g hexane, stirs 50min under the room temperature, slowly add at-6 ℃ and contain the toluene solution of 0.15g trimethyl aluminium and temperature is controlled at 2 ℃, slowly be warming up to 25 ℃ then, continue reaction 8h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned polynite of 0.5g, add and contain 1mg 2, the toluene solution of 4-dimethyl diimine pyridine iron title complex (according to Chin.Sci.Bull.2002,47 (19): 1616-1618 is synthetic) is at 60 ℃ of reaction 8h; With the toluene flush away not load 2,4-dimethyl diimine pyridine iron title complex; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.0wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add the 100mL hexanaphthene in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down and add 3mL aluminium diethyl monochloride toluene solution (1.0M) in 50 ℃, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.0838g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 10min, add 2.1mL methylaluminoxane toluene solution (1.4M) and 3 μ mol ethylene bridge di-indenyl zirconium dichlorides again, behind the polyreaction 80min, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 6
The preparation of montmorillonite carrier: the 2g polynite is dispersed in the 1200g water, stirs 80min, obtain mashed prod A; The 1.2g γ-Huan Hujing is dissolved in 400g water, slowly adds among the A, stir and be warming up to 90 ℃, keep 25min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, B is scattered in the 15g heptane, stirs 25min under the room temperature, slowly add at-3 ℃ and contain the toluene solution of 0.1g triisobutyl aluminium and temperature is controlled at-1 ℃, slowly be warming up to 50 ℃ then, continue reaction 3h,, obtain montmorillonite carrier with organic solvent washing, filtration and dry.
The preparation of montmorillonite load ethylene oligomerization catalyst: take by weighing the above-mentioned polynite of 1g, add the toluene solution contain 3mg 2-ethyl diimine pyridine iron title complex (according to J.Am.Chem.Soc.1998,120,7143-7144 is synthetic), at 70 ℃ of reaction 6h; With the toluene flush away not load 2,4-dimethyl diimine pyridine iron title complex; Vacuumize drying and obtain the montmorillonite load ethylene oligomerization catalyst of iron level 1.6wt ‰.
The preparation of polyethylene/montmorillonite nanometer composite material: add the 100mL heptane in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, stir down and add 4mL trimethyl aluminium toluene solution (1.0M) in 70 ℃, add the above-mentioned montmorillonite load ethylene oligomerization catalyst of 0.0931g again, keep ethylene pressure 0.1MPa, after carrying out oligomerisation reaction 20min, add 1.1mL triethyl aluminum toluene solution (1.4M) and 10 μ mol BCH catalyzer (research institute of Yan Hua company provides) again, behind the polyreaction 30min, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
The concrete outcome of the foregoing description can be referring to table 1.
Table 1 result
*Mt refers to the reactive metal of catalyst for copolymerization
Claims (9)
1. the preparation method of a polyethylene/montmorillonite nanometer composite material, carry out in the following order:
A) preparation of montmorillonite carrier
Polynite is made montmorillonite carrier with cyclodextrin and aluminum alkyls processing, and concrete grammar is as follows:
Polynite is disperseed the weight ratio 1 of polynite and water: 20-1 in water: 500, behind the stirring 10-120min, obtain mashed prod A; Cyclodextrin is water-soluble, the weight ratio 1 of cyclodextrin and water: 50-1: 500, add among the mashed prod A, stirring also is warming up to 50-100 ℃, after keeping 5-60min, remove by filter supernatant liquid, with distilled water wash and dry, obtain the polynite B that cyclodextrin is handled, polynite B is scattered in the organic solvent weight ratio 1 of polynite B and organic solvent: 3-1: 20, stir 10-60min under the room temperature, slowly add the aluminum alkyls toluene solution down and temperature is controlled at 0 ± 5 ℃ at-10-0 ℃, the weight ratio 1 of aluminum alkyls and polynite B: 5-1: 100, slowly be warming up to 10-60 ℃ then, continue reaction 2-10 hour, use organic solvent washing, filter and drying, obtain montmorillonite carrier;
B) preparation of montmorillonite load ethylene oligomerization catalyst
The non-polar organic solvent solution that adds ethylene oligomerization catalyst in the montmorillonite carrier that step a is made, reactive metal and polynite weight ratio 1: 500-1 in the described catalyst for oligomerization: 2000,20-80 ℃ of reaction 2-20 hour, with the non-polar organic solvent flush away catalyst for oligomerization of load not, drying obtains the montmorillonite load ethylene oligomerization catalyst;
C) preparation of polyethylene/montmorillonite nanometer composite material
Under nitrogen or argon gas atmosphere, aluminum alkyls or alkylalumoxane solution and montmorillonite load ethylene oligomerization catalyst are scattered in the non-polar organic solvent, the reactive metal mol ratio 100-2000 of described aluminum alkyls or alkylaluminoxane and catalyst for oligomerization, feed vinyl monomer, carried out oligomerisation reaction 1-20 minute at 10-80 ℃, continue to feed ethene, press the reactive metal mol ratio 100 of aluminum alkyls or alkylaluminoxane and olefin-copolymerization catalyst: 1-2000: 1 adds promotor, olefin-copolymerization catalyst carried out polyreaction 0.5-2 hour, add acidifying ethanol termination reaction, washing, drying obtains polyethylene/montmorillonite nanometer composite material.
2. according to the preparation method of claim 1, it is characterized in that described cyclodextrin is: alpha-cylodextrin, beta-cyclodextrin or γ-Huan Hujing.
3. according to the preparation method of claim 1, it is characterized in that described organic solvent is: toluene, hexane, hexanaphthene or heptane,
4. according to the preparation method of claim 1, it is characterized in that described aluminum alkyls is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium.
5. according to the preparation method of claim 1, it is characterized in that described ethylene oligomerization catalyst is an alpha-diimine pyridine iron complex compound.
6. according to the preparation method of claim 5, it is characterized in that, described alpha-diimine pyridine iron complex compound is: 2, and 4-dimethyl diimine pyridine iron complex compound, 2-methyl diimine pyridine iron complex compound, 2-methyl-4-methoxyl group diimine pyridine iron complex compound, 2-ethyl diimine pyridine iron complex compound or 2-sec.-propyl diimine pyridine iron complex compound.
7. according to the preparation method of claim 1, it is characterized in that described olefin-copolymerization catalyst is metallocene catalyst or Ziegler-Natta catalyst.
8. according to the preparation method of claim 7, it is characterized in that described metallocene catalyst is: dicyclopentadiene zirconium dichloride, methyl silicon bridge two indenyl zirconium dichlorides or ethyl bridge two indenyl zirconium dichlorides.
9. according to the preparation method of claim 7, it is characterized in that described Ziegler-Natta catalyst is titanium chloride/magnesium chloride/electron donor.
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CN1510059A (en) * | 2002-12-20 | 2004-07-07 | 中国科学院化学研究所 | Polyethylene nanometer composite material and preparing method thereof |
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