CN1872908A - Montmorillonite-titanium tetrachloride catalyst and preparation method of polyethylene/montmorillonite composite material thereof - Google Patents
Montmorillonite-titanium tetrachloride catalyst and preparation method of polyethylene/montmorillonite composite material thereof Download PDFInfo
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- CN1872908A CN1872908A CN 200510072368 CN200510072368A CN1872908A CN 1872908 A CN1872908 A CN 1872908A CN 200510072368 CN200510072368 CN 200510072368 CN 200510072368 A CN200510072368 A CN 200510072368A CN 1872908 A CN1872908 A CN 1872908A
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- -1 polyethylene Polymers 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 20
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 17
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000002131 composite material Substances 0.000 title abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 9
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 235000011147 magnesium chloride Nutrition 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000004760 silicates Chemical class 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 241001502050 Acis Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 claims description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000006399 behavior Effects 0.000 claims 2
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000002114 nanocomposite Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012662 bulk polymerization Methods 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000012685 gas phase polymerization Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 22
- 238000013019 agitation Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000008030 elimination Effects 0.000 description 16
- 238000003379 elimination reaction Methods 0.000 description 16
- 239000011949 solid catalyst Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000037048 polymerization activity Effects 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000012265 solid product Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000006392 deoxygenation reaction Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for preparing montmorillonite-titanium tetrachloride catalyst and its polyethylene/montmorillonite composite material includes dissolving magnesium compound in fatty alcohol to obtain 1 g-5 g/100ml transparent and stable solution, adding montmorillonite to the solution of magnesium compound in fatty alcohol at 5-15 g/100ml, stirring at 60 deg.C for 1 hr, filtering to remove excessive fatty alcohol, adding dry hexane, washing 3 times, adding dry hexane to the reaction system according to 10ml/g montmorillonite and removing 1ml/g montmorilloniteAdding orthosilicate and TiCl into earth4Stirring at 60 ℃, adding TiCl into the reaction system according to the calculated amount of 10ml/g montmorillonite at 80 DEG C4Stirred for 2 hours, under slurry polymerization conditions, with hexane solvent, [ Al ]]/[Ti]The molar ratio is 5-100, and the polymerization temperature is 50-90 ℃. Can be used for preparing the nano composite material of polyethylene and the copolymer thereof, and is suitable for slurry, gas phase and bulk polymerization processes.
Description
Technical field:
The present invention relates to the preparation method of polyethylene/montmorillonite matrix material, specifically, is the preparation method of a kind of montmorillonite-TiCl 4 catalyst and polyethylene/montmorillonite matrix material thereof.
Background technology:
In recent years, organic-inorganic nanocomposite has caused people's extensive attention.Especially the nano composite material of organic high molecular polymer and inorganic laminated silicate clay mineral more becomes the research focus because of its excellent performance.Compare with corresponding straight polymer, contain a small amount of (<5wt%) polymer clay nanocomposites of clay of laminar silicate has high strength, high-modulus, high heat resistance, good barrier performance and flame retardant properties and better dimensional stability, and do not increase the proportion of material basically.
Polyolefine is the output maximum, a most widely used base polymer.Olefin polymerization nanometer composite material is at polyolefinic high performance and improve polyolefinic range of application and use aspect the class significant.The preparation method of olefin polymerization nanometer composite material can simply be divided into two classes, both in-situ polymerization and physical mechanical blend.The physical mechanical blend method is to utilize the effect of mechanical force that montmorillonite layer is peeled off, be implemented in the dispersion in the polyolefin matrix, reported with physical method as people such as Hasegawa and to have prepared composite nanometer-level polypropylene/montmorillonoid material (J.Appl.Polym.Sci.1998,67).The deficiency of this method is that the mode of organising of need adopting montmorillonite and/or polyolefinic polar is to increase polynite and polyolefinic avidity, cause the increase of production cost, and mechanical blending is difficult to realize the production of extensive olefin polymerization nanometer composite material.
WO 99/47589 discloses the method that a kind of in-situ polymerization prepares olefin polymerization nanometer composite material, and gained polyethylene nano composite material has high tensile and modulus simultaneously.This method relates to complicated clay treatment, and need expend the MAO of a large amount of costlinesses, thereby industrialization meaning useless.
This seminar discloses a kind of in-situ polymerization and has prepared polyolefin/montmorillonite prepared in laboratory technology (US2003/0027711A1), and the gained polyethylene/montmorillonite nanometer composite material has high tensile and modulus and heat resisting temperature with respect to high density polyethylene(HDPE).But the prepared catalyzer hydrogen response of this technology is relatively poor, and the tap density of polymerisate is lower, is difficult to be put to industrial production.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of in-situ polymerization prepares the polyethylene/montmorillonite matrix material, the preparation method of promptly a kind of montmorillonite-TiCl 4 catalyst and polyethylene/montmorillonite matrix material thereof.Present method is that Ziegler-Natta catalyst is written between cheating engaging layer, uses positive silicate class as form and polymerization behavior improving agent, directly olefinic polymerization synthesis of polyolefins nano composite material.
The catalyst system that the present invention proposes consists of: 1) clay of laminar silicate specifically is polynite; 2) magnesium compound specifically is magnesium dichloride MgCl
2, alkoxyl magnesium Mg (OR)
2, R is the saturated alkyl of 1-4 carbon; 3) can make the fat alcohol compound of magnesium compound dissolved 1-4 carbon; 4) positive compound of silicate class Si (OR)
4, R is the saturated alkyl of 1-4 carbon; 5) titanium tetrachloride.
Catalyst preparation process and reaction conditions are as follows:
1) magnesium compound is dissolved in Fatty Alcohol(C12-C14 and C12-C18), being mixed with concentration is the transparent of 1-5g/100ml, stable solution.
2) be the ratio of 5-15g polynite/100ml Fatty Alcohol(C12-C14 and C12-C18) in add-on, polynite is added in the magnesium compound fatty alcohol solution, stirred 1 hour down at 60 ℃.
3) remove by filter excessive fatty alcohol, use then dry hexane (5ml/g imvite) washing 3 times.
4) add dry hexane, add positive esters of silicon acis and TiCl by amount of calculation 1ml/g imvite then to reaction system by 10ml/g imvite amount of calculation
4, 60 ℃ of lower stirrings.
5) filter, use then dry hexane (5ml/g imvite) washing 3 times.
6) under 80 ℃, in reaction system, add TiCl by amount of calculation 10ml/g imvite
4, stirred 2 hours.
7) reaction system is filtered, pressed powder is with dry hexane (5ml/g imvite) washing 5 times, and is dry rear stand-by.
Under slurry polymerization conditions, adopt hexane solvent, [Al]/[Ti] mol ratio is 5-100, polymerization temperature is 50~90 ℃.
Adopting hydrogen is the melt index conditioning agent, and it is 0-0.5 that hydrogen and ethene get intrinsic standoff ratio.
Catalyst system provided by the invention can be used for preparing the nano composite material of polyethylene and multipolymer thereof, is applicable to slurry, gas phase and bulk technique.
The prepared montmorillonite intercalation catalyzer of the present invention has the advantages that polymerization activity is good, hydrogen response is good, the polymerisate tap density is high, prepared polyethylene/montmorillonite matrix material has good mechanical intensity and thermotolerance, is the technology of preparing with polyethylene/montmorillonite matrix material of commercial exploitation prospect.
Embodiment
Below by embodiment, the invention will be further described, but these implement not limit the present invention.
Embodiment 1
Under nitrogen protection, with 2.5 gram magnesium dichloride MgCl
2, join in the refining butanols of 100ml and stir 2 hours formation homogeneous transparent solution, the insoluble impurity of elimination at 60 ℃.To MgCl
2Add the 10 sodium type polynites of gram after 400 ℃ of calcinings in the-butanol solution, 50ml exsiccant hexane wash 3 times of the excessive butanols of elimination after 60 ℃ of continuation are stirred 1 hour, solid product.In reaction system, add 100ml exsiccant hexane, 10ml titanium tetrachloride TiCl
4With the 10ml tetraethoxy, stirred 1 hour down at 60 ℃, behind the elimination liquid, solid product 50ml exsiccant hexane wash 3 times.In reaction system, add 100ml TiCl again
4, after stirring 2 hours under 80 ℃, the excessive TiCl of elimination
4, solid product 50ml exsiccant hexane wash 5 times behind drying under reduced pressure, obtain the solid catalyst powder.Catalyst fines is 0.5wt% through the icp analysis titanium content, Mg content is 7.5wt%, and through the X-ray diffraction analysis, the original soil interlamellar spacing is 1.15nm (2 θ=7.64 °), catalyzer medium clay soil interlamellar spacing is 1.71nm (2 θ=5.18 °), proves that catalyst component enters between cheating engaging layer.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 20mmol triethyl aluminum Al (C
2H
5)
3And 4 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 50, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 280 grams after the drying, polymerization activity is 700kg/molTihr, and polymer bulk density is 0.35g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 1.43wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.82g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 131.4 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 35.0MPa, elongation at break are 1100%.
Comparative example 1
Do not use positive silicon ester properties-correcting agent in catalyst preparation process, other conditions and embodiment 1 are identical, and made catalyst Ti content is 1.5wt%.
Use the catalyzer of comparative example 1 preparation, other polymerizing conditions are identical with embodiment 1 with the polymkeric substance test condition.Get polymer 240g, polymerization activity is 600kg/molTihr, and polymer bulk density is 0.17g/cm
3, melt index be 0.30g/10min (190 ℃, 2.16kg), resulting polymers imvite content is that the dimension card heat resisting temperature of 1.67wt%. polymer is 130.9 ℃, tensile strength is 32.5MPa, elongation at break is 800%.
Embodiment 2
Under nitrogen protection, with 1.0 gram magnesium dichloride MgCl
2, join in the refining methyl alcohol of 100ml and stir 2 hours formation homogeneous transparent solution, the insoluble impurity of elimination at 60 ℃.To MgCl
2Add the 5 sodium type polynites of gram after 400 ℃ of calcinings in the-methanol solution, 25ml exsiccant hexane wash 3 times of the excessive butanols of elimination after 60 ℃ of continuation are stirred 1 hour, solid product.In reaction system, add 50ml exsiccant hexane, 5ml titanium tetrachloride TiCl
4With the 5ml butyl silicate, stirred 1 hour down at 60 ℃, behind the elimination liquid, solid product 25ml exsiccant hexane wash 3 times.In reaction system, add 50ml TiCl again
4, after stirring 2 hours under 80 ℃, the excessive TiCl of elimination
4, solid product 25ml exsiccant hexane wash 5 times behind drying under reduced pressure, obtain the solid catalyst powder.Catalyst fines is 0.75wt% through the icp analysis Ti content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 20mmol triethyl aluminum Al (C
2H
5)
3And 2.67 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 50, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 320 grams after the drying, polymerization activity is 800kg/molTihr, and polymer bulk density is 0.38g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 0.83wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 2.09g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 130.1 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 32.0MPa, elongation at break are 1120%.
Embodiment 3
Under nitrogen protection, with 5 gram magnesium dichloride MgCl
2, join in the refining ethanol of 100ml and stir 2 hours formation homogeneous transparent solution, the insoluble impurity of elimination at 60 ℃.To MgCl
2Add the 8 sodium type polynites of gram after 400 ℃ of calcinings in the-ethanolic soln, elimination excess ethanol after 60 ℃ of continuation are stirred 1 hour, solid product 40ml exsiccant hexane wash 3 times.In reaction system, add 80ml exsiccant hexane, 8ml titanium tetrachloride TiCl
4With the 8ml tetraethoxy, stirred 1 hour down at 60 ℃, behind the elimination liquid, solid product 40ml exsiccant hexane wash 3 times.In reaction system, add 80ml TiCl again
4, after stirring 2 hours under 80 ℃, the excessive TiCl of elimination
4, solid product 40ml exsiccant hexane wash 5 times behind drying under reduced pressure, obtain the solid catalyst powder.Catalyst fines is 1.0wt% through the icp analysis Ti content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 24mmol triethyl aluminum Al (C
2H
5)
3And 1 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 60, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 200 grams after the drying, polymerization activity is 500kg/molTihr, and polymer bulk density is 0.36g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 0.5wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.69g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 130.2 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 32.9MPa, elongation at break are 1210%.
Embodiment 4
Under nitrogen protection, with 2.5 gram magnesium dichloride MgCl
2, join in the refining isopropyl alcohol of 100ml, stir at 60 ℃ and formed homogeneous transparent solution, the insoluble impurity of elimination in 2 hours.To MgCl
2Add the 15 sodium type polynites of gram after 400 ℃ of calcinings in the-aqueous isopropanol, 75ml exsiccant hexane wash 3 times of the excessive Virahol of elimination after 60 ℃ of continuation are stirred 1 hour, solid product.In reaction system, add 150ml exsiccant hexane, 15ml titanium tetrachloride TiCl
4With the 15ml methyl silicate, stirred 1 hour down at 60 ℃, behind the elimination liquid, solid product 75ml exsiccant hexane wash 3 times.In reaction system, again add 150mlTiCl
4, after stirring 2 hours under 80 ℃, the excessive TiCl of elimination
4, solid product washs 5 times with the hexane of 75ml drying, behind drying under reduced pressure, obtains the solid catalyst powder.Catalyst fines is 0.25wt% through the icp analysis Ti content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 20mmol triethyl aluminum Al (C
2H
5)
3And 8 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 50, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 360 grams after the drying, polymerization activity is 900kg/molTihr, and polymer bulk density is 0.39g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 2.22wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.52g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 132.6 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 38.1MPa, elongation at break are 920%.
Embodiment 5
With dimethoxy magnesium Mg (OCH
3)
2Replace magnesium dichloride MgCl
2, other conditions embodiment 1.Making the khaki color catalyst fines, is 0.6wt% through the icp analysis titanium content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 12mmol triethyl aluminum Al (C
2H
5)
3And 3.33 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 30, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.2Mpa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 330 grams after the drying, polymerization activity is 825kg/molTihr, and polymer bulk density is 0.36g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 1.0wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.63g/10min.
Embodiment 6
Other conditions and embodiment 5 are identical, only use diethoxy magnesium Mg (OC
2H
5)
2Replace dimethoxy magnesium Mg (OCH
3)
2, catalyst fines is 0.48wt% through the icp analysis Ti content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 16mmol triethyl aluminum Al (C
2H
5)
3And 4 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 40, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.1Mpa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 280 grams after the drying, polymerization activity is 700kg/molTihr, and polymer bulk density is 0.37g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 1.43wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.26g/10min.
Embodiment 7
Other conditions and embodiment 6 are identical, only use dibutoxy magnesium Mg (OC
4H
9)
2Replace magnesium methoxide, catalyst fines is 0.3wt% through the icp analysis Ti content.
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 8mmol triethyl aluminum Al (C
2H
5)
3And 6.4 the gram (0.4mmol) solid catalyst, [Al]/[Ti] mol ratio is 20, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, circulating water temperature is set at 70 ℃, polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 240 grams after the drying, polymerization activity is 600kg/molTihr, and polymer bulk density is 0.35g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 2.67wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.74g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 133.7 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 39.2MPa, elongation at break are 850%.
Embodiment 8
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 40mmol triethyl aluminum Al (C
2H
5)
3And the solid solid catalyst of 4 gram (0.4mmol) embodiment, 1 preparation, [Al]/[Ti] mol ratio is 100, pass into ethene/hydrogen gas mixture that pressure is 1.0MPa, wherein hydrogen partial pressure is 0.3MPa, and circulating water temperature is set at 50 ℃, and polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 220 grams after the drying, polymerization activity is 550kg/molTihr, and polymer bulk density is 0.39g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 1.82wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.42g/10min.
Embodiment 9
Under nitrogen protection, to the dry deoxygenation of 2L, be furnished with in the autoclave of mechanical agitation and chuck recirculated water temperature regulating device and add the dry hexane of 1000ml, under agitation add 8mmol triethyl aluminum Al (C
2H
5)
3And the solid solid catalyst of 1 gram (0.4mmol) embodiment, 3 preparations, [Al]/[Ti] mol ratio is 5, passes into ethene/hydrogen gas mixture that pressure is 1.0MPa, and wherein hydrogen partial pressure is 0.3MPa, and circulating water temperature is set at 90 ℃, and polymerisation begins.After the polymerization 60 minutes, add 2ml ethanol and stop polyreaction.Filter, get polymerisate 40 grams after the drying, polymerization activity is 100kg/molTihr, and polymer bulk density is 0.36g/cm
3, melting index is that (190 ℃, 2.16kg), resulting polymers polynite content is that 2.5wt%. polymkeric substance X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the polynite splitting to 1.03g/10min.
Embodiment 10
Use embodiment 1 to be prepared into solid catalyst, except that not using the hydrogen other polymerizing conditions with embodiment 1.Get polymerizate 300 grams, polymerization activity is 750kg/molTihr, and polymer bulk density is 0.35g/cm
3, melt index is that (190 ℃, 2.16kg), resulting polymers imvite content is that 1.25wt%. polymer X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the imvite splitting to 0.10g/10min.
The dimension card heat resisting temperature of polymkeric substance is with 5 ℃/min determination of heating rate, and measurement result is 132.5 ℃; The tensile property of polymkeric substance is measured on electronic tensile machine with 100mm/min., and the result is: tensile strength 33.0MPa, elongation at break are 1300%.
Embodiment 11
Use embodiment 1 to be prepared into solid catalyst, except that the hydrogen dividing potential drop is set at the 5MPa, other polymerizing conditions are with embodiment 1.Get polymerizate 160 grams, polymerization activity is 400kg/molTihr, and polymer bulk density is 0.36g/cm
3, melt index is that (190 ℃, 2.16kg), resulting polymers imvite content is that 2.5wt%. polymer X-ray diffraction shows that the peak crystallization between cheating engaging layer disappears, and proves the imvite splitting to 6.10g/10min.
Claims (4)
1. the preparation method of montmorillonite-TiCl 4 catalyst and polyethylene/montmorillonite matrix material thereof, it is characterized in that: catalyst system consists of: 1) clay of laminar silicate specifically is polynite; 2) magnesium compound specifically is magnesium dichloride MgCl
2, alkoxyl magnesium Mg (OR)
2, R is the saturated alkyl of 1-4 carbon; 3) can make the fat alcohol compound of magnesium compound dissolved 1-4 carbon; 4) positive compound of silicate class Si (OR)
4, R is the saturated alkyl of 1-4 carbon; 5) titanium tetrachloride TiCl
4,
Catalyst preparation process and reaction conditions are as follows:
1) magnesium compound is dissolved in Fatty Alcohol(C12-C14 and C12-C18), being mixed with concentration is the transparent of 1g-5g/100ml, stable solution;
2) be the ratio of 5-15g polynite/100ml Fatty Alcohol(C12-C14 and C12-C18) in add-on, polynite is added in the magnesium compound fatty alcohol solution, stirred 1 hour down at 60 ℃;
3) remove by filter excessive fatty alcohol, use then dry hexane (5ml/g imvite) washing 3 times;
4) add dry hexane, add positive esters of silicon acis and TiCl by amount of calculation 1ml/g imvite then to reaction system by 10ml/g imvite amount of calculation
4, 60 ℃ of lower stirrings;
5) filter, use then dry hexane (5ml/g imvite) washing 3 times;
6) under 80 ℃, in reaction system, add TiCl by amount of calculation 10ml/g imvite
4, stirred 2 hours;
7) reaction system is filtered, pressed powder is with dry hexane (5ml/g imvite) washing 5 times, and is dry rear stand-by;
Under slurry polymerization conditions, adopt hexane solvent, [Al]/[Ti] mol ratio is 5-100, polymerization temperature is 50~90 ℃;
Adopting hydrogen is the melt index conditioning agent, and it is 0-0.5 that hydrogen and ethene get intrinsic standoff ratio.
2. the preparation method of a kind of montmorillonite-TiCl 4 catalyst as claimed in claim 1 and Behaviors of Polyethylene/mmt Hybrid System thereof is characterized in that the alkoxyl magnesium compound is dimethoxy magnesium Mg (OCH
3)
2, diethoxy magnesium Mg (OC
2H
5)
2With dibutoxy magnesium Mg (OC
4H
9)
2
3. the preparation method of a kind of montmorillonite-TiCl 4 catalyst as claimed in claim 1 and polyethylene/montmorillonite matrix material thereof is characterized in that can make the fat alcohol compound of magnesium compound dissolved 1-4 carbon is methyl alcohol, ethanol, Virahol and butanols.
4. the preparation method of a kind of montmorillonite-TiCl 4 catalyst as claimed in claim 1 and polyethylene/montmorillonite matrix material thereof, it is characterized in that using positive compound of silicate class to be form and polymerization behavior improving agent, used positive compound of silicate class is methyl silicate, tetraethoxy and butyl silicate.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101024708B (en) * | 2007-02-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Method for preparing broad-peak polythenel montmorillonite nano composite material using mixed catalyst |
CN102627285A (en) * | 2012-04-25 | 2012-08-08 | 北京航空航天大学 | Novel montmorillonite nanometer complex and preparation method thereof |
CN103044592A (en) * | 2012-12-28 | 2013-04-17 | 沈阳工业大学 | Preparation method of polyethylene/montmorillonite nano-scale composite material |
CN103214603A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Magnesium ethoxide/montmorillonite/titanium tetrachloride polyethylene catalyst and preparation and application thereof |
CN105732854A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing polyethylene/kaolin composite material |
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2005
- 2005-05-31 CN CNB200510072368XA patent/CN100572437C/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101024708B (en) * | 2007-02-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Method for preparing broad-peak polythenel montmorillonite nano composite material using mixed catalyst |
CN103214603A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Magnesium ethoxide/montmorillonite/titanium tetrachloride polyethylene catalyst and preparation and application thereof |
CN102627285A (en) * | 2012-04-25 | 2012-08-08 | 北京航空航天大学 | Novel montmorillonite nanometer complex and preparation method thereof |
CN102627285B (en) * | 2012-04-25 | 2014-04-02 | 北京航空航天大学 | Novel montmorillonite nanometer complex and preparation method thereof |
CN103044592A (en) * | 2012-12-28 | 2013-04-17 | 沈阳工业大学 | Preparation method of polyethylene/montmorillonite nano-scale composite material |
CN105732854A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing polyethylene/kaolin composite material |
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