CN103044592A - Preparation method of polyethylene/montmorillonite nano-scale composite material - Google Patents
Preparation method of polyethylene/montmorillonite nano-scale composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyethylene/montmorillonite nano-scale composite material. The method comprises the following steps: (A) adding magnesium chloride and n-decane in nitrogen gas atmosphere, thoroughly mixing at 0-180 DEG C, adding alcohols to form a transparent solution, adding n-heptane and montmorillonite, vigorously stirring, washing off the supernatant turbid solution after the reaction is completed to obtain pellets, and drying the pellets by blowing nitrogen gas to obtain a magnesium chloride/montmorillonite carrier; (B) titanium loading: adding n-heptane into the powder of carrier obtained in the step (A), adding dropwise titanium tetrachloride, and adding esters after completing dropwise addition, washing with solvents after titanium loading to obtain pellets, and drying the pellets by blowing nitrogen gas to obtain a magnesium chloride/magnesium chloride/montmorillonite catalyst matrix; and (C) activating the catalyst with alkyl aluminum to initiate polymerization of ethylene, to obtain the final product of polyethylene/montmorillonite nano-scale composite material. The method provided by the invention has the benefits that the beginners of the carrier are dispersed more uniformly and have better morphology, so that the morphology of the PE/MMT nano-scale composite material is improved.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite material, relate in particular to a kind of by the synthesis condition of controlling catalyzer and then the preparation method who affects polyethylene and the Nano composite material of montmorillonite of nano composite material particle shape.
Background technology
Polyethylene (PE) is very widely general-purpose plastics of a kind of application, and its raw material is extensive, cheap, stable chemical nature, but because its mechanical property and poor heat stability, these have limited its application at engineering field.Therefore polyethylene/MMT(polynite) nano composite material becomes the focus of people's research, because this novel matrix material can combine rigidity, dimensional stability and the thermostability of inorganics and toughness, workability and the dielectric properties of polymkeric substance.But because not polar functionalities and the functional group that can react on the PE main chain, the MMT that therefore has high polarity is difficult to directly with the nanoscale Uniform Dispersion wherein.The main situ aggregation method that adopts prepares polyethylene/MMT nano composite material at present.But there is following shortcoming in the PE/MMT nano composite material that now successfully makes:
(1) because catalyst activity unstable, cause in production processes of polyalcohol polymerization rate to rise and fall very large, and the bad control of bulk density of the PE/MMT nano composite material that obtains.
(2) owing to adopting magnesium chloride and MMT as two carriers, cause the form of catalyzer uncertain, thereby cause the irregular, especially in the majority with powder of polyethylene product form that polyreaction generates, the bulk density of product changes greatly.
(3) because polyethylene powders causes the generation of static in the production process, easy caking on reaction wall and the stirring rod, what be unfavorable for producing carries out continuously.Thereby cause the bulk density of product greatly to descend.
CN 10143466A has invented the two carrier loaded Ziegler-Natta catalysts of a kind of magnesium chloride/mesoporous molecular sieve, catalyzed ethylene polymerization, the polymer stacks density that obtains is lower, at 0.13～0.25g/cm3, fails to solve PE and the low difficult problem of inorganics nano composite material bulk density.
Summary of the invention
In order to solve the problems of the technologies described above the preparation method who the invention provides a kind of polyethylene and Nano composite material of montmorillonite, purpose is by the form of control catalyzer and the polymerization activity of catalyzer, stable polymerization reaction is carried out, thereby make the form of PE/MMT nano composite material better, bulk density is higher.
To achieve these goals, the preparation method of polyethylene of the present invention and Nano composite material of montmorillonite, it is characterized in that may further comprise the steps: A: in nitrogen environment, add magnesium chloride and n-decane, stir under 0～180 ℃, add alcohol and form clear solution, then add normal heptane and polynite, vigorous stirring, reaction is precipitated with the turbid liquid in solvent flush away upper strata after finishing, and precipitation dries up through nitrogen and obtains magnesium chloride and montmorillonite carrier;
B: carry titanium: the support powder with steps A obtains, add normal heptane, drip titanium tetrachloride, after the titanium tetrachloride titration is complete, add ester; Use solvent wash after carrying titanium, be precipitated; Dry up with nitrogen, obtain magnesium chloride, polynite and TiCl 4 catalyst matrix;
C: activate this catalyzer with aluminum alkyls, be used for causing vinyl polymerization, preparation polyethylene and Nano composite material of montmorillonite.
Described alcohol is monohydroxy-alcohol, dibasic alcohol or both mixtures; Wherein monohydroxy-alcohol is ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, isooctyl alcohol, phenylcarbinol, lauryl alcohol, tetradecyl alcohol or hexadecanol; Dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, triethylene glycol, pentanediol, ethohexadiol, decanediol or cyclohexanediol; Washing used solvent is normal heptane, normal hexane, octane, n-decane, methylene dichloride or toluene, and washing times is 1～10 time.
The mass ratio of described magnesium chloride and polynite is 1:0.01～1:20.
Described ester is monoesters, dibasic acid esters, inorganic acid ester or acid anhydrides; Wherein monoesters is ethyl benzoate, n-butyl phthalate, butyl benzoate, ethyl acetate, this ethyl acetate, propyl benzoate or isopropyl benzoate; Dibasic acid esters is dimethyl phthalate, diethyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, dibutyl phthalate, diisobutyl phthalate, amyl phthalate or phthalic acid cyclohexyl; Inorganic acid ester is tetrabutyl titanate, tetraethoxy or tetramethoxy-silicane; Aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride etc., tri-n-octylaluminium or diisobutyl aluminium hydride.
Described polynite is the polynite of palmityl trimethyl ammonium chloride modification, the polynite of octadecyl trimethyl ammonium chloride modification, amino acid modified montmorillonite, the polymer monomer modified montmorillonoid, silane coupler modified polynite, calcium-base montmorillonite, sodium-based montmorillonite, the hydrogen base montmorillonite, the lithium base montmorillonite, the inorganic-organic hybrid modified montmorillonoid, the polynite of hydrochloric Acid Modification, sulfuric acid modified polynite, the Nitric Acid Modified polynite, hydrochloric acid and sulfuric acid modified polynite, the phosphoric acid modification polynite, aluminum salt modified polynite, the magnesium salts modified montmorillonoid, zinc salt modified montmorillonoid or mantoquita modified montmorillonoid.
Pressure is 0.1～10Mpa during vinyl polymerization, and hydrogen partial pressure is 0～2MPa.
The titanium content massfraction is 0.5～25% in the Kaolinite Preparation of Catalyst, and the mol ratio of aluminium and titanium is 0.5～200.
Temperature when nitrogen dried up when steps A prepared magnesium chloride montmorillonite carrier and step B and prepares magnesium chloride polynite titanium tertrachloride combi ned catalysts is 0～80 ℃.
After adding normal heptane and polynite, vigorous stirring 0.1～72h.
Step B carries out at least 1 time and carries titanium; At-60～130 ℃ of lower titanium tetrachlorides that drip, titanium tetrachloride dropwises rear adding ester, at-60～130 ℃ of lower reaction 0.1～48h.
Advantageous effect of the present invention:
1, use n-decane as the dispersion agent of magnesium chloride, the alcohol adduct that magnesium chloride powder and alcohol form can make the carrier initiator disperse more even as the carrier initiator, and form is better, thereby makes the form of PE/MMT nano composite material better.
2, owing in the catalyst preparation process, at first being prepared into the two carrier pressed powders of magnesium chloride/MMT, its form is homogeneous more, and therefore the form of synthetic PE/MMT nano composite material is better.The use of polynite has reduced the cost of catalyzer, also makes catalyzer that better flowability and intensity have been arranged.
3, ethyl benzoate in catalyst preparation process, n-butyl phthalate, butyl benzoate, ethyl acetate, this ethyl acetate, propyl benzoate, isopropyl benzoate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, dibutyl phthalate, diisobutyl phthalate, amyl phthalate, the phthalic acid cyclohexyl, tetrabutyl titanate, tetraethoxy, tetramethoxy-silicane is electron donor, so that the activity of catalyzer in polyreaction is in controlled range, guaranteed better catalyst activity stable and polyreaction steadily, avoided that local reaction is too fast to cause breaking of product form, improved the bulk density of PE/MMT nano composite material, made the form of product more regular.High (0.26～the 0.34cm of bulk density
3), good mechanical properties is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below by the description of embodiment, but this is not to be limitation of the present invention, those skilled in the art are according to basic thought of the present invention, can make various modifications or improvement, but only otherwise break away from basic thought of the present invention, all within the scope of the present invention.
Embodiment 1
(1) MgCl
2/ MMT/TiCl
4The preparation of catalyzer
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 4g magnesium chloride and 6ml n-decane, be warming up to 0 ℃ and stir 0.5h to evenly, then add 15ml ethanol synthesis 24h.In transparent alcohol adduct solution, add the polynite of 120ml normal heptane and 0.04g hydrochloric Acid Modification in 60 ℃ of lower vigorous stirring 72h, stopped reaction.Separate out precipitation, with normal heptane washing three times, the pressed powder that the throw out that obtains obtains after at room temperature drying up with nitrogen is magnesium chloride and montmorillonite carrier.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 10mlTiCl under 0 ℃
4With the 2ml tetraethoxy in reaction system, be warming up to 60 ℃ of lower reaction 2h, filter, with normal hexane washing 3 times, again under 0 ℃, dropwise add 10mlTiCl
4With the 2ml ethyl benzoate in reaction system, with n-decane washing 5 times, be precipitated, dry up at 0 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat1.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat1 catalyzer, the 6ml tri-butyl aluminum that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 80 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 0.8Mpa, and hydrogen pressure is 0.2Mpa, reaction 0.5h.The polymer quality that obtains is 326g.The character that obtains polymkeric substance sees attached list.
Embodiment 2
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 4g magnesium chloride and 6ml n-decane, be warming up to 180 ℃ and stir 0.5h to evenly, then add 16ml propyl carbinol reaction 2h.In transparent alcohol adduct solution, add 120ml normal heptane and 6g calcium-base montmorillonite in 70 ℃ of lower vigorous stirring 0.1h, stopped reaction.Separate out precipitation, with normal heptane washing 3 times, the pressed powder that the throw out that obtains obtains after drying up with nitrogen under 0 ℃ is magnesium chloride and montmorillonite carrier.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 10mlTiCl under 5 ℃
4With the 2ml tetramethoxy-silicane in reaction system, be warming up to 50 ℃ of lower reaction 3h, filter, with washed with dichloromethane 4 times, again under-40 ℃, dropwise add 10mlTiCl
4With the 2ml n-butyl phthalate in reaction system, with octane washing 4 times, be precipitated, dry up at 80 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat2.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat2 catalyzer, the 6ml ethyl aluminum dichloride that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 85 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 0.1Mpa, and hydrogen pressure is 2Mpa, reaction 2h.Obtaining polymer quality is 100g.The character that obtains polymkeric substance sees attached list.
Embodiment 3
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 4g magnesium chloride and 6ml n-decane, be warming up to 140 ℃ and stir 0.5h to evenly, then add 16ml isooctyl alcohol reaction 2h.In transparent alcohol adduct solution, add 120ml normal heptane and 10g inorganic-organic hybrid modified montmorillonoid in 60 ℃ of lower vigorous stirring 3h, stopped reaction.Separate out precipitation, with normal heptane washing 3 times, the throw out that obtains is magnesium chloride and montmorillonite carrier at 80 ℃ of pressed powders that obtain after drying up with nitrogen.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 10mlTiCl under 60 ℃
4With the 2ml butyl benzoate in reaction system, be warming up to 70 ℃ of lower reaction 48h, filter, with toluene wash 3 times, again under 60 ℃, dropwise add 10mlTiCl
4With the 2ml dimixo-octyl phthalate in reaction system, with toluene wash 5 times, be precipitated, dry up at 0 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat3.(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat3 catalyzer, the 6ml trimethyl aluminium that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 83 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 10Mpa during vinyl polymerization, and hydrogen pressure is 0.1Mpa, reaction 1h.Obtain polymkeric substance 120g.The character that obtains polymkeric substance sees attached list.
Embodiment 4
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 2g magnesium chloride and 3ml n-decane, be warming up to 130 ℃ and stir 0.5h to evenly, then add 8ml propyl alcohol reaction 2h.Adding 100ml normal heptane and 12g in transparent alcohol adduct solution uses the polynite (OMMT) of palmityl trimethyl ammonium chloride modification in 70 ℃ of lower vigorous stirring 24h, stopped reaction.Separate out precipitation, with normal heptane washing 3 times, the throw out that obtains is magnesium chloride and montmorillonite carrier at 80 ℃ of pressed powders that obtain after drying up with nitrogen.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 10mlTiCl under 0 ℃
4With the 1.5ml tetrabutyl titanate in reaction system, be warming up to 70 ℃ of lower reaction 1h, filter, with washing 10 times, be precipitated, dry up at 80 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat4.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat4 catalyzer, the 6ml tri-butyl aluminum that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 83 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 0.1Mpa, no hydrogen pressure, reaction 1h.Obtain polymkeric substance 145g.The character that obtains polymkeric substance sees attached list.
Embodiment 5
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 0.5g magnesium chloride and 3ml n-decane, be warming up to 130 ℃ and stir 0.5h to evenly, then add 16ml butyleneglycol reaction 8h.In transparent alcohol adduct solution, add 100ml normal heptane and the silane coupler modified polynite of 10g in 70 ℃ of lower vigorous stirring 48h, stopped reaction.Separate out precipitation, with normal heptane washing 3 times, the throw out that obtains is magnesium chloride and montmorillonite carrier at 0 ℃ of pressed powder that obtains after drying up with nitrogen.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 10mlTiCl under 15 ℃
4With the 1.5ml amyl phthalate in reaction system, be warming up to 70 ℃ of lower reaction 12h, filter, with washing 1 time, be precipitated, dry up at 0 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat4.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat5 catalyzer, the 6ml triethyl aluminum that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 83 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 1.2Mpa, and hydrogen pressure is 0.2Mpa, reaction 1h.Obtain polymkeric substance 65g.The character that obtains polymkeric substance sees attached list.
Embodiment 6
At first in the 250ml there-necked flask, be filled with N2 one hour, then add 2g magnesium chloride and 3ml n-decane, be warming up to 135 ℃ and stir 0.5h to evenly, then add 12ml n-hexyl alcohol reaction 4h.In transparent alcohol adduct solution, add the organo montmorillonite (OMMT) of 100ml normal heptane and the modification of 8g octadecyl trimethyl ammonium chloride in 70 ℃ of lower vigorous stirring 72h, stopped reaction.Separate out precipitation, with normal heptane washing 3 times, the throw out that obtains is magnesium chloride and montmorillonite carrier at 35 ℃ of pressed powders that obtain after drying up with nitrogen.Add the normal heptane dispersed with stirring in the pressed powder and open, dropwise add 15mlTiCl under 130 ℃
4(drip at twice, each 7.5ml) and 1.5ml phthalic acid cyclohexyl in reaction system, be warming up to 130 ℃ of lower reaction 0.1h, filter, with washing 3 times, be precipitated, dry up at 30 ℃ of lower nitrogen that to obtain the yellow solid powder be magnesium chloride, polynite and TiCl 4 catalyst matrix, be labeled as cat6.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 2L reactor, at first in still, be filled with nitrogen, then the normal hexane, 2gcat6 catalyzer, the 6ml diisobutyl aluminium hydride that add successively 1.5L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 85 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 0.8Mpa, and hydrogen pressure is 0.2Mpa, reaction 1h.Obtain polymkeric substance 160g.The character that obtains polymkeric substance sees attached list.
Embodiment 7
Change the organic montmorillonoid of the 100ml normal heptane in the embodiment 6 and the modification of 8g octadecyl trimethyl ammonium chloride into 120ml normal heptane and the sulfuric acid modified polynite of 10g, the phthalic acid cyclohexyl changes ethyl acetate into, n-hexyl alcohol changes isopropylcarbinol and Pentyl alcohol alcohol mixture into, other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat7.Other is with embodiment 6.Obtain polymkeric substance 145g.The character that obtains polymkeric substance sees attached list.
Embodiment 8
Change the polynite of the 100ml normal heptane in the embodiment 6 and the modification of 8g octadecyl trimethyl ammonium chloride into 140ml normal heptane and the polynite of 12g Nitric Acid Modified, n-hexyl alcohol changes primary isoamyl alcohol into, other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat8.The phthalic acid cyclohexyl changes dioctyl phthalate (DOP) into.It its with embodiment 6.Obtain polymkeric substance 135g.The character that obtains polymkeric substance sees attached list.
Embodiment 9
Change the polynite of the 100ml normal heptane in the embodiment 6 and the modification of 8g octadecyl trimethyl ammonium chloride into 160ml normal heptane and 24g hydrochloric acid and sulfuric acid modified polynite, n-hexyl alcohol changes n-Octanol and phenylcarbinol alcohol mixture into, other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat9.The phthalic acid cyclohexyl changes diethyl phthalate into.Other is with embodiment 6.Obtain polymkeric substance 89g.The character that obtains polymkeric substance sees attached list.
Embodiment 10
1.5ml phthalic acid cyclohexyl in the embodiment 6 is changed into the Phenylacetic acid ethylester of 0.8ml, n-hexyl alcohol changes lauryl alcohol into, the polynite of octadecyl trimethyl ammonium chloride modification changes the phosphoric acid modification polynite into, and other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat10.Other is with embodiment 6.Obtain polymkeric substance 190g.The character that obtains polymkeric substance sees attached list.
Embodiment 11
1.5ml phthalic acid cyclohexyl in the embodiment 6 is changed into the dibutyl phthalate of 2.5ml, n-hexyl alcohol changes the alcohol mixture of tetradecyl alcohol and pentanediol into, the polynite of octadecyl trimethyl ammonium chloride modification changes sodium-based montmorillonite into, other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat11.Other is with embodiment 6.Obtain polymkeric substance 200g.The character that obtains polymkeric substance sees attached list.
Embodiment 12
1.5ml phthalic acid cyclohexyl in the embodiment 6 is changed into the propyl benzoate of 2.0ml, n-hexyl alcohol changes ethylene glycol and mixed with propylene glycol alcohol into, the polynite of octadecyl trimethyl ammonium chloride modification changes the hydrogen base montmorillonite into, other condition remains unchanged, and the yellow solid powder that obtains is labeled as cat12.Other is with embodiment 6.Obtain polymkeric substance 186g.The character that obtains polymkeric substance sees attached list.
Embodiment 13
At first in the 1L there-necked flask, be filled with N2 about one hour, then add 12g magnesium chloride and 15ml n-decane, be warming up to 130 ℃ and stir 0.5h, then add 45ml triethylene glycol reaction 2h.In transparent alcohol adduct solution, add 100ml normal heptane and 48g polymer monomer modified montmorillonoid in 70 ℃ of lower vigorous stirring 3h, stopped reaction.Separate out precipitation, with the normal heptane washing once, the throw out that obtains obtains pressed powder after drying up with nitrogen.Add the normal heptane dispersed with stirring in the pressed powder and open ,-60 ℃ of lower 45mlTiCl that add
4(at twice each 10ml) dropwise drip and the 6ml diisobutyl phthalate in reaction system, be warming up to 60 ℃ of lower reaction 2h, filter, wash 3 times with normal hexane, nitrogen dries up and obtains the yellow solid powder, is labeled as cat13.
(2) preparation of polyethylene/MMT nano composite material
The in-situ polymerization of ethene carries out in the 5L reactor, at first in still, be filled with nitrogen, then the normal hexane, 35gcat11 catalyzer, the 10ml triisobutyl aluminium that add successively 4L, treat that temperature in the kettle begins to add ethene when rising to 50 ℃, at 85 ℃ of lower reaction 1h, reaction product obtains the PE/MMT nano composite material after drying.Reacting kettle inner pressure maintains 0.6Mpa, and hydrogen pressure is 0.4Mpa, and reaction 2h obtains polymkeric substance 1450g.The character that obtains polymkeric substance sees attached list.
Embodiment 14
Change triisobutyl aluminium among the embodiment 13 into aluminium diethyl monochloride, be 8ml, reaction 2h becomes 1h.The other the same as in Example 13.Tetrabutyl titanate changes isopropyl benzoate into; Triethylene glycol changes the alcohol mixture of ethohexadiol and hexadecanol into.The polymer monomer modified montmorillonoid changes the lithium base montmorillonite into.Obtain polymkeric substance 1200g.The character that obtains polymkeric substance sees attached list.
Embodiment 15
Change triisobutyl aluminium among the embodiment 13 into tri-n-octylaluminium, be 12ml, reaction 2h becomes 0.5h.The other the same as in Example 13.Tetrabutyl titanate changes dimethyl phthalate into; Triethylene glycol changes the alcohol mixture of decanediol or cyclohexanediol into.The polymer monomer modified montmorillonoid changes amino acid modified montmorillonite into.Obtain polymkeric substance 900g.The character that obtains polymkeric substance sees attached list.
Embodiment 16
Change polymer monomer modified montmorillonoid among the embodiment 13 into aluminum salt modified polynite, the other the same as in Example 13.Obtain polymkeric substance 980g.The character that obtains polymkeric substance sees attached list.
Embodiment 17
Change polymer monomer modified montmorillonoid among the embodiment 13 into the magnesium salts modified montmorillonoid, the other the same as in Example 13.Obtain polymkeric substance 960g.The character that obtains polymkeric substance sees attached list.
Embodiment 18
Change polymer monomer modified montmorillonoid among the embodiment 13 into the zinc salt modified montmorillonoid, the other the same as in Example 13.Obtain polymkeric substance 1000g.The character that obtains polymkeric substance sees attached list.
Embodiment 19
Change polymer monomer modified montmorillonoid among the embodiment 13 into the mantoquita modified montmorillonoid, the other the same as in Example 13.Obtain polymkeric substance 840g.The character that obtains polymkeric substance sees attached list.
Table 1 is the physical properties of the active PE/MMT nano composite material of catalyzer.
| Embodiment | Fusing point | Ctystallizing point | Bulk density | Tensile strength | Shock strength |
| 1 | 133.6 | 119.8 | 0.28 | 30.6 | 687 |
| 2 | 133.8 | 119.3 | 0.26 | 32.4 | 676 |
| 3 | 134.2 | 119.2 | 0.30 | 34.2 | 664 |
| 4 | 134.6 | 119.3 | 0.27 | 34.6 | 648 |
| 5 | 134.8 | 118.7 | 0.28 | 39.7 | 424 |
| 6 | 134.5 | 118.7 | 034 | 35.8 | 628 |
| 7 | 140.2 | 118.3 | 0.26 | 37.6 | 546 |
| 8 | 134.8 | 119.4 | 0.28 | 36.4 | 624 |
| 9 | 134.6 | 119.2 | 0.27 | 34.8 | 652 |
| 10 | 134.2 | 118.9 | 0.31 | 34.2 | 628 |
| 11 | 134.8 | 118.7 | 0.27 | 35.4 | 663 |
| 12 | 135.4 | 118.6 | 0.28 | 34.2 | 620 |
| 13 | 138.4 | 118.3 | 0.31 | 40.3 | 397 |
| 14 | 138.2 | 118.2 | 0.30 | 37.6 | 564 |
| 15 | 142.4 | 118.2 | 0.31 | 37.4 | 546 |
| 16 | 136.4 | 119.4 | 0.26 | 38.4 | 348 |
| 17 | 138.2 | 118.9 | 0.28 | 37.4 | 372 |
| 18 | 138.2 | 118.4 | 0.28 | 38.2 | 462 |
| 19 | 139.4 | 118.6 | 0.27 | 39.4 | 394 |
Table is annotated: fusing point unit: ℃; The ctystallizing point temperature: ℃; Bulk density unit: g/cm
3Tensile strength unit: MPa; Shock strength unit: J/m.
Claims (10)
1. the preparation method of polyethylene and Nano composite material of montmorillonite is characterized in that may further comprise the steps:
A: in nitrogen environment, add magnesium chloride and n-decane, stir under 0～180 ℃, add alcohol and form clear solution, then add normal heptane and polynite, vigorous stirring, reaction is precipitated with the turbid liquid in solvent flush away upper strata after finishing, and precipitation dries up through nitrogen and obtains magnesium chloride and montmorillonite carrier;
B: carry titanium: the support powder with steps A obtains, add normal heptane, drip titanium tetrachloride, after the titanium tetrachloride titration is complete, add ester; Use solvent wash after carrying titanium, be precipitated; Dry up with nitrogen, obtain magnesium chloride, polynite and TiCl 4 catalyst matrix;
C: activate this catalyzer with aluminum alkyls, be used for causing vinyl polymerization, preparation polyethylene and Nano composite material of montmorillonite.
2. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that described alcohol is monohydroxy-alcohol, dibasic alcohol or both mixtures; Wherein monohydroxy-alcohol is ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, isooctyl alcohol, phenylcarbinol, lauryl alcohol, tetradecyl alcohol or hexadecanol; Dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, triethylene glycol, pentanediol, ethohexadiol, decanediol or cyclohexanediol; Washing used solvent is normal heptane, normal hexane, octane, n-decane, methylene dichloride or toluene, and washing times is 1～10 time.
3. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite, the mass ratio that it is characterized in that described magnesium chloride and polynite is 1:0.01～1:20.
4. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that described ester is monoesters, dibasic acid esters, inorganic acid ester or acid anhydrides; Wherein monoesters is ethyl benzoate, n-butyl phthalate, butyl benzoate, ethyl acetate, this ethyl acetate, propyl benzoate or isopropyl benzoate; Dibasic acid esters is dimethyl phthalate, diethyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, dibutyl phthalate, diisobutyl phthalate, amyl phthalate or phthalic acid cyclohexyl; Inorganic acid ester is tetrabutyl titanate, tetraethoxy or tetramethoxy-silicane; Acid anhydrides is diacetyl oxide, butyryl oxide, Tetra hydro Phthalic anhydride or phenylsuccinic acid acid anhydride; Aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride etc., tri-n-octylaluminium or diisobutyl aluminium hydride.
5. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that described polynite is the polynite of palmityl trimethyl ammonium chloride modification, the polynite of octadecyl trimethyl ammonium chloride modification, amino acid modified montmorillonite, the polymer monomer modified montmorillonoid, silane coupler modified polynite, calcium-base montmorillonite, sodium-based montmorillonite, the hydrogen base montmorillonite, the lithium base montmorillonite, the inorganic-organic hybrid modified montmorillonoid, the polynite of hydrochloric Acid Modification, sulfuric acid modified polynite, the Nitric Acid Modified polynite, hydrochloric acid and sulfuric acid modified polynite, the phosphoric acid modification polynite, aluminum salt modified polynite, the magnesium salts modified montmorillonoid, zinc salt modified montmorillonoid or mantoquita modified montmorillonoid.
6. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite, pressure is 0.1～10Mpa when it is characterized in that vinyl polymerization, hydrogen partial pressure is 0～2MPa.
7. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that the titanium content massfraction is 0.5～25% in the Kaolinite Preparation of Catalyst, and the mol ratio of aluminium and titanium is 0.5～200.
8. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that the temperature when nitrogen dried up when steps A prepared magnesium chloride montmorillonite carrier and step B and prepares magnesium chloride polynite titanium tertrachloride combi ned catalysts is 0～80 ℃.
9. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite, it is characterized in that adding normal heptane and polynite after, vigorous stirring 0.1～72h.
10. the preparation method of polyethylene according to claim 1 and Nano composite material of montmorillonite is characterized in that step B carries out at least 1 time and carries titanium; At-60～130 ℃ of lower titanium tetrachlorides that drip, titanium tetrachloride dropwises rear adding ester, at-60～130 ℃ of lower reaction 0.1～48h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727637A (en) * | 2018-05-23 | 2018-11-02 | 芜湖航天特种电缆厂股份有限公司 | Cable nontoxic fire-retardant combination and preparation method thereof |
| CN110437354A (en) * | 2019-07-05 | 2019-11-12 | 深圳聚石新材料科技有限公司 | Ultra-high molecular weight polyethylene/Nano composite material of montmorillonite preparation method |
| CN112226070A (en) * | 2020-10-19 | 2021-01-15 | 山东博顺新材料有限责任公司 | High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof |
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| CN1330101A (en) * | 2001-08-03 | 2002-01-09 | 中国科学院长春应用化学研究所 | Montmorillonite-TiCl4 catalyst and process for preparing polyolefin/montmorillonite composition |
| CN1872908A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气股份有限公司 | Method for preparing catalyst of montmorillonite-titanium tetrachloride, and composite material of polyethylene/montmorillonite |
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| CN1330101A (en) * | 2001-08-03 | 2002-01-09 | 中国科学院长春应用化学研究所 | Montmorillonite-TiCl4 catalyst and process for preparing polyolefin/montmorillonite composition |
| CN1872908A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气股份有限公司 | Method for preparing catalyst of montmorillonite-titanium tetrachloride, and composite material of polyethylene/montmorillonite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727637A (en) * | 2018-05-23 | 2018-11-02 | 芜湖航天特种电缆厂股份有限公司 | Cable nontoxic fire-retardant combination and preparation method thereof |
| CN110437354A (en) * | 2019-07-05 | 2019-11-12 | 深圳聚石新材料科技有限公司 | Ultra-high molecular weight polyethylene/Nano composite material of montmorillonite preparation method |
| CN112226070A (en) * | 2020-10-19 | 2021-01-15 | 山东博顺新材料有限责任公司 | High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof |
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