CN1324886A - Composite nanometer montmorillonoid-polyolefine material and its prepn. - Google Patents
Composite nanometer montmorillonoid-polyolefine material and its prepn. Download PDFInfo
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Abstract
The present invention relates to a montmorillonite nanometer composite polyolefine material, and is characterized by that the flake layer portion of montmorillonite or completely-decomposed montmorillonite can be uniformly dispersed in the polyolefine, the weight ratio of montmorillonite and polyolefine is 1:4-1:99, the montmorillonite adopted by this invention is H-montmorillonite, Na-montmorillonite, Mg-montmorillonite or Ca-montmorillonite, and the polyolefine is polyethylene, polypropylene or polystyrene. Its synthesis method is simple, and is favorable for industrial production, can be used for stereo-oriented polymerization of alpha-olefine, and in the obtained montmorillonite nanometer composite polyolefine material, the polyolefine possesses high degree of stereoorientation.
Description
The invention relates to a kind of composite nanometer montmorillonoid-polyolefine material and preparation method thereof.
(one dimension is less than 10 at least because of its nanometer size effect for polymer nanocomposites
2Nm) produce very strong interface interaction, the performance and the polymer properties of inorganics perfectly combined, obtain the matrix material of excellent combination property.
In-situ polymerization prepares inorganics composite polyethylene material, as U.S. Pat 3,950,303, US 4,104,243, US4,473,672 and US4,564,674 catalyst system activity is low, and Composite Preparation efficient is not high, be difficult to the compositely proportional of controlling polymers and inorganics and the molecular weight of polymkeric substance, can not autotelic preparation have the matrix material of excellent mechanical property and excellent machinability concurrently.
CN96105362.3 adopts the molten monomer intercalation, and the in-situ polycondensation method has prepared clay layer and has been dispersed in cleavage type nano composite material among the matrix PA-6.Its preparation method is that amino acid monomer is distributed in the polynite, mixes with the ε-Ji Neixianan monomer again, and through melt polycondensation reaction, the synthetic compound PA-6 material of montmorillonite-based nano.The shortcoming of this method is the restriction that is subjected to the exchanging equivalent of polynite, can not have a large amount of monomers to enter interlayer, in the interlayer opening procedure its heat release limited, layer launches to be short of power, the poor repeatability of preparation molecular composite material, preparation condition complexity; In addition, this method is only applicable to strong polar monomer synthetic composite material, and to nonpolar or low-pole monomer, as ethene, propylene etc. can not adopt this method to prepare molecular composite material.
GB2008598A. and WO, 79/01029 employing molecule complex method prepares the molecular composite material of inorganic/organic complex system, these methods are only applicable to the preparation of ethene/composite material of inorganic matter, can not be used for the stereospecific polymerization of alpha-olefin, one originating party face is the electronic effect that these class methods do not have magnesium halide carrier, and catalyst activity is low; Be the synergy that does not have electron donor and magnesium halide on the other hand, can not get the poly-alpha olefins of stereospecific polymerization.
It is low that the present invention has overcome in the prior art Composite Preparation efficient, poor repeatability, the dispersion of inorganic materials in polyolefine do not reach nano level, in-situ polymerization can not prepare the shortcoming of stereotaxis poly-alpha olefins matrix material, adopt magnesium chloride and oxygen-containing organic compound to prepare high stereotaxis poly-alpha olefins matrix material, and a kind of composite nanometer montmorillonoid-polyolefine material and preparation method thereof is provided
A kind of composite nanometer montmorillonoid-polyolefine material of the present invention with the part or all of cleavage of montmorillonite layer after, be dispersed in the polyolefine polynite and polyolefinic weight ratio 1: 4～1: 99.
A kind of composite nanometer montmorillonoid-polyolefine material of the present invention is an inorganic materials with porous laminated polynite, comprises the H-polynite, Na-polynite, Mg-polynite or Ca-polynite, the specific surface area 50-1000m of polynite
2/ g, the aperture is 50-500A, and pore volume is 0.3-500cc/g, and exchange capacity is 80-120meq/100g, and the percentage composition of polynite in nano combined polyolefine material is 1-20%.
Polyolefine in a kind of composite nanometer montmorillonoid-polyolefine material of the present invention is a polyethylene, polypropylene, polystyrene, second-Ding, second-the third, second-oneself, second-Xin multipolymer or relevant binary or multiple copolymer, the percentage composition of polyolefine in nano combined polyolefine material is 80-99%.
The preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention carries out in the following order: one. the preparation of method 11. polynite magnesium chloride complex carriers
Magnesium chloride is dissolved in the ethanol, obtaining concentration is 3%-15% magnesium chloride ethanolic soln, at 0-90 ℃ polynite is joined in the excessive magnesium chloride alcoholic solution, after carrying out abundant ion-exchange, filter, again with identical magnesium chloride ethanolic soln washing, polynite after the washing is distributed to going in the magnesium chloride ethanolic soln of 3%-15%, obtain magnesium chloride polynite alcohol cpd, magnesium chloride weight ratio in polynite and the magnesium chloride ethanolic soln is 85-97, said mixture is splashed in-25 ℃ of-0 ℃ of titanium tetrachlorides, the weight ratio 10～50 of titanium tetrachloride and polynite magnesium chloride is filtered, with hexane or toluene wash, obtain polynite magnesium chloride complex carrier after the drying, 2. the preparation of supported catalyst polynite
Titanium tetrachloride is joined in the above-mentioned polynite magnesium chloride complex carrier, titanium tetrachloride and polynite magnesium chloride complex carrier weight ratio are 10～50, slowly be warming up to 40-100 ℃ and add oxygen-containing organic compound, 40-130 ℃ of reaction 2 hours, after the filtration, add titanium tetrachloride again in 40-130 ℃ of reaction 2 hours, filter washing, dry supported catalyst polynite, magnesium chloride and oxygen-containing organic compound mol ratio are 1-30, above-mentioned oxygen-containing organic compound is a dibutyl phthalate, 2, and 2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether, 9, two (methoxymethyl) fluorenes of 9-, methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO), 3-indenyl methyl ethyl diketone or 3-benzyl methyl ethyl diketone, the 3. preparation of composite nanometer montmorillonoid-polyolefine material
Under nitrogen or argon gas atmosphere, toluene or hexane equal solvent are placed reactor, add triethyl aluminum or methylaluminoxane successively, the supported catalyst polynite, Al: Ti is 20-1000 in molar ratio, add olefinic monomer, after carrying out polyreaction 0.5-2 hour under the 0-100 ℃ of condition, add acidifying ethanol and stop polyreaction, washing, drying obtains composite nanometer montmorillonoid-polyolefine material, polynite and polyolefinic weight ratio 1: 4～1: 99.Two. the preparation of method 21. polynite magnesium chloride complex carriers
With H-polynite and inertia dispersion agent hexane, decane is after toluene or kerosene mix, add the halide reagent silicon tetrachloride, thionyl chloride or phosphorus oxychloride, the weight ratio of polynite and above-mentioned halide reagent are 40～2, in 40-60 ℃ of reaction 1-3 hour, washing adds alkyl magnesium chloride isopropylmagnesium chloride or benzylmagnesium chloride to non-halogen reagent, and the weight ratio of polynite and alkyl magnesium chloride is 40～2, reacted 1-4 hour, washing, drying obtains polynite magnesium chloride complex carrier.2. the preparation of supported catalyst polynite
Titanium tetrachloride is joined in the above-mentioned polynite magnesium chloride complex carrier, titanium tetrachloride and polynite magnesium chloride complex carrier weight ratio are 10～50, slowly be warming up to 40-100 ℃ and add oxygen-containing organic compound, 40-130 ℃ of reaction 2 hours, after the filtration, add titanium tetrachloride again in 40-130 ℃ of reaction 2 hours, filter washing, dry supported catalyst polynite, magnesium chloride and oxygen-containing organic compound mol ratio are 1-30, above-mentioned oxygen-containing organic compound is a dibutyl phthalate, 2, and 2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether, 9, two (methoxymethyl) fluorenes of 9-, methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO), 3-indenyl methyl ethyl diketone or 3-benzyl methyl ethyl diketone, the 3. preparation of composite nanometer montmorillonoid-polyolefine material
Under nitrogen or argon gas atmosphere, toluene or hexane equal solvent are placed reactor, add triethyl aluminum or methylaluminoxane successively, the supported catalyst polynite, Al: Ti is 20-1000 in molar ratio, add olefinic monomer, after carrying out polyreaction 0.5-2 hour under the 0-100 ℃ of condition, add acidifying ethanol and stop polyreaction, washing, drying obtains composite nanometer montmorillonoid-polyolefine material, polynite and polyolefinic weight ratio 1: 4～1: 99.
The preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention has following characteristics: 1. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention is that catalytic active center is between cheating engaging layer or surface catalysis olefinic monomer in-situ polymerization, obtain montmorillonite layer and be dispersed in nano composite material in the polyolefin substrate, have excellent mechanical property.2. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention can be used for preparing montmorillonite-based nano composite polyethylene material, montmorillonite-based nano polypropylene composite material, the compound benzene polythene material of montmorillonite-based nano and the compound olefin-copolymerization material of montmorillonite-based nano.3. the preparation method's of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention polynite magnesium halide complex carrier synthetic method is simple, helps suitability for industrialized production.4. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention can make it be applicable to the synthetic of different composite nanometer montmorillonoid-polyolefine materials by selecting and using oxygen-containing organic compound.5. preparation method's adaptability of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention is good, and the molecular weight of polymkeric substance is controlled, can adopt mass polymerization or slurry polymerization to prepare composite nanometer montmorillonoid-polyolefine material.6. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material of the present invention, it is fashionable to be used for alpha-olefines polymerization, and stereospecificity is good, makes that polyolefine has high stereotaxis degree in the composite nanometer montmorillonoid-polyolefine material.
Embodiment
The preparation of embodiment 1. polynite magnesium chloride complex carriers: under nitrogen atmosphere, the Na-polynite, Ca-polynite or Mg-polynite 20g add in the 80mL ethanol, and in 25 ℃ of stirrings 30 minutes, adding concentration again was 8%MgCl
2Ethanolic soln 100mL in 50 ℃ of reactions 3 hours, uses the MgCl of same concentration again after the filtration
2Ethanolic soln 100mL, in 50 ℃ the reaction 1 hour, handles three times after, the filtration, vacuum-drying obtains polynite magnesium chloride complex carrier.The preparation of supported catalyst polynite: in reactor, add TiCl
475ml is cooled to-15 ℃, slowly adds above-mentioned polynite magnesium chloride complex carrier 5.0g, rises to 120 ℃ of reactions 2 hours in 3 hours temperature, filters, and adds TiCl again
475mL was in 120 ℃ of reactions 2 hours.After the filtration, use the 50mL hexane in 60 ℃ of washings 5 times at every turn, wash once under room temperature with the 50mL hexane, vacuum-drying gets the supported catalyst polynite.The preparation of montmorillonite-based nano composite polyethylene material: the heptane that adds 100mL in the there-necked flask of the 250mL after nitrogen and ethene fully exchange, under agitation in 70 ℃ of n-heptane solutions (0.9mmol/mL) that add triethyl aluminum, add above-mentioned supported catalyst polynite again, pressure at ethene is under the condition of 770mmHg, carried out polyreaction 1 hour, add acidifying ethanol and carry out termination reaction, and use washing with alcohol, vacuum-drying obtains montmorillonite-based nano composite polyethylene material, and operational condition and montmorillonite-based nano composite polyethylene properties of materials are listed in table 1.
The preparation of embodiment 2. polynite magnesium chloride complex carriers: the polynite magnesium chloride complex carrier 15.5g that embodiment 1 is obtained joins in the hexane of 200mL, under agitation be cooled to-50 ℃, add triethyl aluminum 20mL, slowly be warming up to 70 ℃ of reactions 2 hours, after the filtration, add hexane 180mL, be cooled to-50 ℃, add triethyl aluminum 20mL, slowly be warming up to 70 ℃ of reactions 2 hours, after the filtration, use hexane wash 5 times, vacuum-drying obtains polynite magnesium chloride complex carrier.Supported catalyst polynite preparation: the preparation method is with embodiment 1.The preparation of montmorillonite-based nano composite polyethylene material: the preparation method is with embodiment 1, and operational condition and montmorillonite-based nano composite polyethylene properties of materials are listed in table 1.
The preparation of embodiment 3. supported catalyst polynites: under nitrogen atmosphere, the Na-polynite, Ca-polynite or Mg-polynite 15g, adding concentration is 8%MgCl
2Ethanolic soln 125mL in 50 ℃ of reactions 3 hours, filters the MgCl of back with same concentration
2Ethanolic soln 100mL in 50 ℃ of reactions 1 hour, handles three times, and adding 75mL concentration is 5% MgCl in the solid matter after filtering
2Ethanolic soln stirs and obtains colloidal solution.
In reactor, add TiCl
4450mL is cooled to 0 ℃, slowly adds above-mentioned colloid liquid, after adding finishes, is warming up to 120 ℃ of reactions 2 hours, after the filtration, adds TiCl again
4300mL in 120 ℃ of reactions 2 hours, after the filtration, uses the 50mL hexane in 60 ℃ of washings 5 times at every turn, washs once under room temperature with the 50mL hexane, and vacuum-drying gets the supported catalyst polynite.The preparation of montmorillonite-based nano composite polyethylene material: the preparation method is with embodiment 1, and operational condition and montmorillonite-based nano composite polyethylene properties of materials are listed in table 1.
Table 1. embodiment 1～3
Sequence number titanium content MT AlEt3 P/MT fusing point M
w
(％) (g) (mL) (℃) (×10
5)
Example 1 0.95 0.6273 5.2 8.5 140.5 8.454
Example 2 0.74 0.5365 4.1 11.1 138.6 7.976
Example 3 1.18 0.4522 7.3 16.4 139.2 4.231
Polymerizing condition: 70 ℃, 1 hour, [AlEt
3]=3.6mmol/mL, MT are the amount of supported catalyst polynite,
P/MT is matrix material/supported catalyst polynite
The preparation of embodiment 4. polynite magnesium chloride complex carriers: after 15g H-polynite and 250 milliliters of hexanes are mixed, the silicon tetrachloride that adds 1.5g, in 40-60 ℃ of reaction 1-3 hour, washing is to there not being silicon tetrachloride, add concentration and be 6 milliliters of the isopropylmagnesium chloride solution of 2M, react 1-4 hour, wash, drying obtains polynite magnesium halide complex carrier.The preparation of supported catalyst polynite: in reactor, add TiCl
4125mL is cooled to-5 ℃, slowly adds above-mentioned polynite magnesium chloride complex carrier 8.5g.Temperature rises to 60 ℃, adds dibutyl phthalate 0.8mL, is warming up to 120 ℃ of reactions 2 hours, filters, and adds TiCl again
4115mL was in 120 ℃ of reactions 2 hours.Filter, use the 65mL hexane in 60 ℃ of washings 5 times at every turn, wash once under room temperature with the 65mL hexane, vacuum-drying gets the supported catalyst polynite.The preparation of montmorillonite-based nano polypropylene composite material: the heptane that adds 100mL in the there-necked flask of the 250ml after nitrogen and propylene fully exchange, under agitation add the n-heptane solution (0.9mmol/mL) of triethyl aluminum and the heptane molten (0.5mmol/mL) of phenylbenzene dimethoxy silicon (DDS) in 70 ℃, add above-mentioned supported catalyst polynite again, be to carry out polyreaction 1 hour under the condition of 770mmHg at the pressure of propylene, add acidifying ethanol and carry out termination reaction, and use washing with alcohol, vacuum-drying obtains the montmorillonite-based nano polypropylene composite material, and the characteristic of operational condition and montmorillonite-based nano polypropylene composite material is listed in table 2.
Embodiment 5-6. polynite magnesium chloride complex carrier, the preparation method of supported catalyst polynite and montmorillonite-based nano polypropylene composite material is with embodiment 4, but when the preparation of supported catalyst polynite, adopt thionyl chloride and benzylmagnesium chloride, the characteristic of operational condition and montmorillonite-based nano polypropylene composite material is listed in table 2.
Table 2. embodiment 4～6
Sequence number titanium content MT AlEt3 DDS P/MT fusing point M
w
(％) (g) (mL) (mL) (℃) (×10
5)
Example 4 0.85 0.7335 6.2 4.5 28.5 162.3 3.478
Example 5 0.78 0.5962 11.2 8.1 19.3 161.5 2.987
Example 6 0.93 0.6617 12.7 9.1 41.4 160.9 5.562
Polymerizing condition: 70 ℃, 1 hour, [AlEt
3]=3.6mmol/mL, MT are the amount of supported catalyst polynite,
P/MT is matrix material/supported catalyst polynite
The preparation method of embodiment 7～21. embodiment, 7～11. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 1, when but the supported catalyst polynite prepares, add 2,2-two replaces-1, and the 3-Propanal dimethyl acetal replaces dibutyl phthalate to make electron donor.The preparation of montmorillonite-based nano polypropylene composite material is with embodiment 4, but need not to add dimethoxydiphenylsilane, 2 of use, 2-two replaces-1, and the characteristic of 3-Propanal dimethyl acetal, operational condition and montmorillonite-based nano polypropylene composite material is listed in table 3, and the preparation method of embodiment 12～16. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 3, when but the supported catalyst polynite prepares, add 2,2-two replaces-1, the 3-Propanal dimethyl acetal.The preparation of montmorillonite-based nano polypropylene composite material is with embodiment 7,2 of use, 2-two replaces-1, the characteristic of 3-Propanal dimethyl acetal, operational condition and montmorillonite-based nano polypropylene composite material is listed in table 3, the preparation method of embodiment 17～21. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 5, but when the supported catalyst polynite prepares, adds 2,2-two replaces-1, the 3-Propanal dimethyl acetal.The preparation embodiment 7 of montmorillonite-based nano polypropylene composite material, 2 of use, 2-two replaces-1, and the characteristic of 3-Propanal dimethyl acetal, operational condition and montmorillonite-based nano polypropylene composite material is listed in table 3,
Table 3 embodiment 7～21
Sequence number diether titanium content MT AlEt3 P/MT M
wFusing point
(％) (g) (mL) (×105) (℃)
Example 7 B 0.82 0.4532 2.2 11.8 6.5421 156.7
Example 8 BE 0.76 0.5211 2.3 10.8 7.523 157.4
Example 9 CP 0.96 0.3465 1.9 7.9 6.556 158.7
Example 10 IB 1.01 0.6703 3.9 43.5 4.322 160.2
Example 11 F 1.22 0.2205 1.6 18.4 2.312 160.4
Example 12 B 0.72 0.6502 4.1 9.4 5.342 155.4
Example 13 BE 1.89 0.4454 4.9 8.4 6.651 159.2
Example 14 CP 1.94 0.3893 4.4 4.6 5.532 157.4
Example 15 IB 1.12 0.5780 5.6 19.2 3.312 161.5
Example 16 F 0.98 0.2133 1.9 9.7 3.124 160.5
Example 17 B 1.45 0.3201 2.4 12.8 5.522 155.8
Example 18 BE 1.23 0.5760 4.1 4.2 4.415 157.4
Example 19 CP 0.98 0.7782 6.6 5.9 4.334 158.0
Example 20 IB 1.55 0.4102 6.1 22.6 1.980 159.9
Example 21 F 1.14 0.3108 8.5 17.3 2.115 159.4
Polymerizing condition: 70 ℃, 1 hour, [AlEt
3]=3.6mmol/mL, MT are that loading type covers the amount that soil is taken off in catalysis,
P/MT is matrix material/supported catalyst polynite, B:2,2-dibutyl-1,3-Propanal dimethyl acetal;
BE:2,2-dibenzyl-1,3-Propanal dimethyl acetal; CP:2,2-two cyclopentyl-1,3-Propanal dimethyl acetal;
IB: diisobutyl Propylene Glycol Dimethyl Ether; F:9, two (methoxymethyl) fluorenes of 9-
The preparation method of embodiment 22～33. embodiment, 22～25. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 3, the preparation of montmorillonite-based nano polypropylene composite material is with embodiment 7, when but the supported catalyst polynite prepares, add beta-diketon and make electron donor.The characteristic of beta-diketon electron donor, operational condition and the montmorillonite-based nano polypropylene composite material that uses is listed in table 4, the preparation method of embodiment 26～29. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 5, the preparation of montmorillonite-based nano polypropylene composite material is with embodiment 7, when but the supported catalyst polynite prepares, add beta-diketon and make electron donor.The characteristic of beta-diketon electron donor, operational condition and the montmorillonite-based nano polypropylene composite material that uses is listed in table 4, the preparation method of embodiment 30～33. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 2, the preparation of montmorillonite-based nano polypropylene composite material is with embodiment 7, when but the supported catalyst polynite prepares, add the beta-diketon electron donor, when preparation montmorillonite-based nano polypropylene composite material, the promotor that uses is methylaluminoxane (MAO).The characteristic of beta-diketon electron donor, operational condition and the montmorillonite-based nano polypropylene composite material that uses is listed in table 4.,
Table 4. embodiment 22～33 sequence number diketone titanium content MT AlEt3 MAO P/MT M
wFusing point
(%) (g) (mL) (mL) (* 10
5) (℃) example 22 acac 4.21 0.7843 9.6 0 10.1 5.621 153.2 examples 23 DBM 3.04 0.6470 11.4 0 17.3 4.776 154.5 examples 24 IDBM 3.66 0.5431 5.8 0 36.3 3.522 155.3 examples 25 BDBM 2.31 0.5874 7.8 0 46.3 4.084 155.6 examples 26 acac 3.26 0.6503 6.1 0 12.4 4.215 152.6 examples 27 DBM 2.87 0.5298 4.4 0 5.4 3.208 152.9 examples 28 IDBM 2.10 0.7824 9.5 0 37.3 4.092 154.7 examples 29 BDBM 3.12 0.4530 4.1 0 17.5 3.886 155.0 examples 30 acac 3.04 0.2470 0 4.4 10.3 2.980 152.9 examples 31 DBM 1.76 0.5411 0 5.5 30.1 2.556 152.8 examples 32 IDBM 2.23 0.6203 0 8.0 54.3 3.774 154.7 examples 33 BDBM 0.97 0.7792 0 8.7 55.7 4.107 155.2 polymerizing condition: 70 ℃; 1 hour, [AlEt3]=3.6mmol/mL, [MAO]=1.8mmol/ml, MT are the amount of supported catalyst polynite, P/MT is matrix material/supported catalyst polynite, acac: methyl ethyl diketone; DBM: diphenylpropane-1,3-dione(DPPO); IDBM:3-indenyl methyl ethyl diketone; The preparation method of BDBM:3-benzyl methyl ethyl diketone embodiment 34～37. embodiment, 34～37. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 30.The preparation of montmorillonite-based nano composite polystyrene material: the vinylbenzene that adds 100ml in the there-necked flask of the 250ml after nitrogen fully exchanges, stirring down in 70 ℃ of adding methylaluminoxane (MAO) solution (1.4mmol/mL), add above-mentioned supported catalyst polynite again, polyreaction is 1 hour under nitrogen atmosphere, add acidifying ethanol and carry out termination reaction, and use washing with alcohol, vacuum-drying obtains montmorillonite-based nano composite polystyrene material, and operational condition and montmorillonite-based nano composite polystyrene properties of materials are listed in table 5.
Table 5. embodiment 34～37 sequence number diketone titanium content MT MAO P/MT M
wNormality between fusing point
(%) (g) (mL) (* 10
5) (℃) (%) example 34 acac 3.04 0.4531 7.9 8.5 2.342 256.4 88.6 examples 35 DBM 1.76 0.4307 4.4 20.6 1.986 258.7 89.9 examples 36 IDBM 2.23 0.2108 2.8 19.3 2.672 265.8 94.6 examples 37 BDBM 0.97 0.6534 7.3 50.3 2.854 267.5 95.1 polymerizing condition: 50 ℃, 1 hour, methylaluminoxane (MAO) concentration is 1.4mmol/mL, MT is the amount of supported catalyst polynite, P/MT is matrix material/supported catalyst polynite, acac: methyl ethyl diketone; DBM: diphenylpropane-1,3-dione(DPPO); IDBM:3-indenyl methyl ethyl diketone; BDBM:3-benzyl methyl ethyl diketone
The preparation method of embodiment 38～41. embodiment, 38～41. polynite magnesium chloride complex carriers and supported catalyst polynite is with embodiment 34.The preparation of montmorillonite-based nano composite polypropylene-styrene materials: the vinylbenzene that adds 100mL in the there-necked flask of the 250mL after nitrogen and propylene fully exchange, stirring down in 70 ℃ of adding methylaluminoxane (MAO) solution (1.4mmol/mL), add above-mentioned supported catalyst polynite again, pressure at propylene is the condition F of 770mmHg, carried out polyreaction 1 hour, add acidifying ethanol and carry out termination reaction, and use washing with alcohol, vacuum-drying obtains montmorillonite-based nano composite polypropylene-styrene materials, and operational condition and montmorillonite-based nano composite polypropylene-styrene materials characteristic are listed in table 6.
Table 6. embodiment 38～41 sequence number diketone titanium content MT MAO P/MT fusing point sPS/PP
(%) (g) (mL) (℃) example 38 acac 2.04 0.6607 11.6 36.6 151.2/254.1 6.7/3.3 examples 39 DBM 1.76 0.8704 8.8 84.2 152.7/256.4 7.1/2.9 examples 40 IDBM 2.23 0.5576 7.2 61.2 155.8/262.3 6.1/3.9 examples 41 BDBM 1.97 0.5943 6.7 46.3 156.3/263.0 5.8/4.2 polymerizing conditions: 45 ℃, 1 hour, [MAO]=1.4mmol/mL, MT is the amount of supported catalyst polynite, P/MT is matrix material/supported catalyst polynite, syndiotactic polystyrene/polypropylene acac: methyl ethyl diketone; DBM: diphenylpropane-1,3-dione(DPPO); IDBM:3-indenyl methyl ethyl diketone; BDBM:3-benzyl methyl ethyl diketone
Claims (7)
1. a composite nanometer montmorillonoid-polyolefine material is characterized in that described polynite sheet is dispersed in the polyolefine, and polynite and polyolefinic weight ratio are 1: 4～1: 99.
2. a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1 is characterized in that the specific surface area 50-1000m of described polynite
2/ g, the aperture is 50-500A, pore volume is 0.3-500cc/g.
3. a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1, the exchange capacity that it is characterized in that described polynite is 80-120meq/100g.
4. a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1 is characterized in that described polynite is the H-polynite, Na-polynite, Mg-polynite or Ca-polynite.
5. a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1 is characterized in that described polyolefine is polyethylene, polypropylene or polystyrene.
6. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1 is characterized in that carrying out in the following order:
(1) preparation of polynite magnesium chloride complex carrier
1. magnesium chloride is dissolved in ethanol, obtaining concentration is the magnesium chloride ethanolic soln of 3%-15%, 2. at 0-90 ℃ ion-exchange is carried out in polynite and magnesium chloride ethanolic soln, filter, washing, 3. the polynite after will washing is distributed in the magnesium chloride ethanolic soln of 3%-15%, obtain polynite magnesium chloride alcohol mixture, magnesium chloride weight ratio in polynite and the magnesium chloride ethanolic soln is 85-97,4. said mixture is splashed in the titanium tetrachloride weight ratio 10～50 of titanium tetrachloride and polynite and magnesium chloride, filter, washing, drying obtains polynite magnesium chloride complex carrier
(2) preparation of supported catalyst polynite
Titanium tetrachloride is joined in the above-mentioned polynite magnesium chloride complex carrier, and titanium tetrachloride and polynite magnesium chloride complex carrier weight ratio are 10～50, are warming up to 40-100 ℃ and add oxygen-containing organic compound, 40-130 ℃ of reaction 2 hours, after the filtration, add titanium tetrachloride again in 40-130 ℃ of reaction 2 hours, filter washing, dry supported catalyst polynite, magnesium chloride and oxygen-containing organic compound mol ratio are 1-30, above-mentioned oxygen-containing organic compound is a dibutyl phthalate, 2, and 2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3～Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether, 9, two (methoxymethyl) fluorenes of 9-, methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO), 3-indenyl methyl ethyl diketone or 3-benzyl methyl ethyl diketone
(3) preparation of composite nanometer montmorillonoid-polyolefine material
Under nitrogen or argon gas atmosphere, toluene or hexane equal solvent are placed reactor, add triethyl aluminum or methylaluminoxane, the supported catalyst polynite, Al: Ti is 20-1000 in molar ratio, add olefinic monomer, after carrying out polyreaction 0.5-2 hour under the 0-100 ℃ of condition, add acidifying ethanol and stop polyreaction, washing, drying obtains composite nanometer montmorillonoid-polyolefine material, polynite and polyolefinic weight ratio 1: 4～1: 99.
7. the preparation method of a kind of composite nanometer montmorillonoid-polyolefine material according to claim 1 is characterized in that carrying out in the following order:
(1) preparation of polynite magnesium chloride complex carrier
With H-polynite and inertia dispersion agent hexane, decane is after toluene or kerosene mix, add the halide reagent silicon tetrachloride, thionyl chloride or phosphorus oxychloride, the weight ratio of polynite and halide reagent are 40～2, in 40-60 ℃ of reaction 1-3 hour, washing adds alkyl magnesium chloride isopropylmagnesium chloride or benzylmagnesium chloride to non-halogen reagent, and the weight ratio of polynite and alkyl magnesium chloride is 40～2, reacted 1-4 hour, washing, drying obtains polynite magnesium chloride complex carrier.
(2) preparation of supported catalyst polynite
Titanium tetrachloride is joined in the above-mentioned polynite magnesium chloride complex carrier, and titanium tetrachloride and polynite magnesium chloride complex carrier weight ratio are 10～50, are warming up to 40-100 ℃ and add oxygen-containing organic compound, 40-130 ℃ of reaction 2 hours, after the filtration, add titanium tetrachloride again in 40-130 ℃ of reaction 2 hours, filter washing, dry supported catalyst polynite, magnesium chloride and oxygen-containing organic compound mol ratio are 1-30, above-mentioned oxygen-containing organic compound is a dibutyl phthalate, 2, and 2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, diisobutyl Propylene Glycol Dimethyl Ether, 9, two (methoxymethyl) fluorenes of 9-, methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO), 3-indenyl methyl ethyl diketone or 3-benzyl methyl ethyl diketone
(3) preparation of composite nanometer montmorillonoid-polyolefine material
Under nitrogen or argon gas atmosphere, toluene or hexane equal solvent are placed reactor, add triethyl aluminum or methylaluminoxane, the supported catalyst polynite, Al: Ti is 20-1000 in molar ratio, add olefinic monomer, after carrying out polyreaction 0.5-2 hour under the 0-100 ℃ of condition, add acidifying ethanol and stop polyreaction, washing, drying obtains composite nanometer montmorillonoid-polyolefine material, polynite and polyolefinic weight ratio 1: 4～1: 99.
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| CN100410314C (en) * | 2004-11-05 | 2008-08-13 | 中国科学院化学研究所 | Polyethylene /montmorillonite nanometer composite material and preparation method |
| CN1318498C (en) * | 2005-04-30 | 2007-05-30 | 浙江大学 | Nano composite material of polyethylene/montorillonite clay in high density and preparation method thereof |
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| US11807648B2 (en) | 2016-06-20 | 2023-11-07 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
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