CN101177466A - Method for in-situ preparation of polyethylene-LDHs nano composite material by organic modified LDHs loaded acenaphthenequinonediimine nickel catalyst - Google Patents
Method for in-situ preparation of polyethylene-LDHs nano composite material by organic modified LDHs loaded acenaphthenequinonediimine nickel catalyst Download PDFInfo
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Abstract
The invention discloses an in-situ preparation method of polyethylene-LDHs nanocomposite with acenaphthene diimine nickel catalyst loaded on organic modification LDHs. N,N'-2 (2, 6-diisopropyl-phenyl) acenaphthene diimine (ArN=C(An)-C(An)=Nar, An=acenaphthene, Ar=2, 6-(i-Pr)2C6H3) nickel complex is loaded on organic modification LDHs which is activated by alkyl aluminium. Aluminium diethyl monochloride is used as a cocatalyst, and polyethylene-LDHs nanocomposite is obtained by in-situ catalyzing ethylene to polymerization in nonpolar solvent. The invention can stabilize catalyst active center and control morpha of polyethylene product by using organic modification LDHs as a carrier of acenaphthene diimine nickel complex. The invention has the advantages that the thermal stability of polyethylene-LDHs nanocomposite is greatly improved, and storage modulus, loss modulus and compound viscosity are enhanced compared with pure polyethylene obtained in the same polymerization condition using homogeneous catalyst.
Description
Technical field
The invention belongs to polyethylene-inorganic nano toughener technical field of composite materials, the method for particularly a kind of organically-modified LDHs (layered double-hydroxide) loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material.
Background technology
For many years, polyethylene-inorganic nano toughener matrix material is the focus that people study always, studies show that the workability with rigidity, thermostability, barrier, flame resistivity and the polyethylene matrix of inorganic nano toughener combines, and can effectively improve the over-all properties of gained matrix material.And it is the most extensive with the research of laminar silicic acid salt clay in employed nanometer strengthener, but then less relatively for the research of other inorganic nano toughener.
On the other hand, LDHs (layered double-hydroxide) has new polymers nanometer strengthener with the similar structure of layered silicate to be subjected to people more and more to pay close attention to as a kind of.LDHs has another name called anionic clay or hydrotalcite, is made up of the lamella of nano-grade size, and lamellar spacing is about 0.4 nanometer.Because the wetting ability of LDHs sheet interlayer microenvironment, in order to increase compatible between it and the polymeric matrix, to carry out organically-modifiedly usually to it, method is with the organic modifiers that has long alkane group the hydration anionresin of LDHs sheet interlayer to be come out.The preparation of LDHs and the organically-modified regulating and controlling that is easy to, and its polymer nanocomposites is at fire-retardant/thermally-stabilised, ultraviolet/infrared absorption, optical clear, all there is wide application prospect aspects such as that mechanics strengthens is toughness reinforcing, life science and high-performance electronic device, are considered to a kind of ideal novel layered nano toughener.Therefore LDHs is effectively applied to the polyethylene matrix as nanometer strengthener, very important meaning is arranged for the raising of polythene material over-all properties and the expansion of Application Areas.
People such as Qu BJ are at Chemistry OF Materials, 16 (3), 368-370, the method by solution blending of having reported in 2004 prepares polyethylene/LDHs nano composite material solution, its weak point is: blending method need be used deleterious high boiling point benzene class organic solvent, bring difficulty not only for the aftertreatment of product, and cause environmental pollution easily; People such as Costa FR are at Polymer, and 46 (12), 4447-4453 has reported that the method by melt blending prepares polyethylene/LDHs nano composite material solution in 2005, its weak point is: the dispersion effect of prepared its LDHs of matrix material is relatively poor.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide the method for a kind of organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material.
Purpose of the present invention is achieved through the following technical solutions: the method for a kind of organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material, be with N, N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex (NiLBr
2) be carried on and on the organically-modified LDHs of aluminum alkyls activatory, obtain organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst, make promotor with aluminium diethyl monochloride, the original position catalyzed ethylene polymerization prepares polyethylene-LDHs nano composite material in non-polar solvent.
The method of described organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material comprises the steps:
(1) preparation of inorganic LDHs
With Zn (NO
3)
26H
2O and Al (NO
3) 9H
2O is that 2～3: 1 ratio is dissolved in and forms mixing solutions in the distilled water in molar ratio, drips NaOH solution then to pH=10～11, obtains slurries; The gained slurries with the filter cake wash clean, obtain inorganic LDHs (being ZnAl-LDH) at 16～24 hours after-filtration of 60～80 ℃ of following slakings after the drying.
(2) preparation of organically-modified LDHs
The inorganic LDHs of 10.0g is joined in 0.08～0.1 mole of sodium dodecyl sulfate solution, at 16～24 hours after-filtration of 60～80 ℃ of following stirring reactions that filter cake washing is clean, obtain organically-modified LDHs (being O-ZnAl-LDH) after the drying.
(3) activation of organically-modified LDHs
In 50～100ml hexane or heptane, add the organically-modified LDHs of 10.0g and stir the formation slurries, add 5～10ml aluminum alkyls again, stirred 12～20 hours, and will obtain after the drying through the organically-modified LDHs of aluminum alkyls activatory through the organically-modified LDHs washes clean of aluminum alkyls processing.
(4) load of acenaphthene diimine nickel complex
In dichloromethane solvent, add 10.0g through the organically-modified LDHs of aluminum alkyls activatory, add 0.2～0.6g N again, N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex (NiLBr
2), stir under the room temperature and make organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst (NiLBr/O-ZnAl-LDH) after 12～20 hours.
(5) in-situ polymerization of polyethylene-LDHs nano composite material preparation
50～100ml non-polar solvent, promotor aluminium diethyl monochloride and organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst (NiLBr/O-ZnAl-LDH) are added mixing and stirring in the reaction flask, under constant ethylene pressure 106.7kPa, carry out polyreaction, wherein the mol ratio of contained nickel complex (being aluminium nickel mol ratio) AlEt in promotor one chlorine dihexyl aluminium and the organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst
2Cl: NiLBr
2=(300～2000): 1, polyethylene-LDHs nano composite material is cleaned, is drying to obtain to the reaction terminating after-filtration with filter cake.
Aluminum alkyls is a kind of in aluminium diethyl monochloride, triethyl aluminum or the triisobutyl aluminium in the described step (3).
Non-polar solvent is a kind of in toluene, heptane or the hexane in the described step (5), and the polymeric reaction temperature scope is 0～60 ℃, and polymerization reaction time is 1.5～4.5 hours.
Catalyst component of the present invention comprises Primary Catalysts and promotor, with N, and N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex (NiLBr
2) be carried on the organically-modified LDHs carrier of aluminum alkyls activatory as Primary Catalysts, make promotor with aluminium diethyl monochloride.LDHs among polymerization process and polymerization played the part of two different roles after finishing, it is the carrier of catalyzer among polymerization process, the LDHs lamella of peeling off after polymerization is finished then is the nanometer strengthener of gained matrix material.
The present invention compared with prior art has following advantage and beneficial effect:
Organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst synthetic method among the present invention is simple, and in ethylene polymerisation process, only need general aluminium diethyl monochloride as promotor, do not relate to and use expensive MAO, help in actual production, applying.The present invention uses organically-modified LDHs as N, N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) carrier of nickel complex, can play the effect of stabilizing catalyst activity center and control polyethylene product form.Compare with the pure polyethylene that uses homogeneous catalyst to make under the same polymeric condition, the polyethylene that the present invention makes-its thermostability of LDHs nano composite material has had significantly raising, and the storage modulus under the molten state, out-of-phase modulus and complex viscosity all increase.
Description of drawings
Fig. 1 is the transmission electron microscope photo of organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst catalyzed ethylene in-situ polymerization gained polyethylene-LDHs nano composite material appearance form.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
Embodiment 1
(1) preparation of inorganic LDHs
With 0.03mol Zn (NO
3)
26H
2O and 0.01mol Al (NO
3) 9H
2O is dissolved in the 100ml distilled water and forms mixing solutions, and the NaOH solution that drips 1.0mol/L then is to pH=10.The gained slurries with the filter cake wash clean, obtain inorganic LDHs (ZnAl-LDH) with deionized water at 60 ℃ of following slaking 24h after-filtration then after 60 ℃ of following vacuum-drying.
(2) preparation of organically-modified LDHs
The ZnAl-LDH of 10.0 grams is joined in the sodium dodecyl sulfate solution of 1000ml 0.1mol/L, at 60 ℃ of following stirring reaction 24h after-filtration, with a large amount of deionized waters that filter cake washing is clean, after 60 ℃ of following vacuum-drying, obtain organically-modified LDHs (O-ZnAl-LDH) then.
(3) activation of organically-modified LDHs
The N2 protection adds 10.0g O-ZnAl-LDH down and stirs the formation slurries in the 50ml hexane, add the 10ml triethyl aluminum again, stirs 20h, solution is partly inclined remove then.To wash for several times through the O-ZnAl-LDH that triethyl aluminum is handled with hexane, after 60 ℃ of following vacuum-drying, obtain then through the organically-modified LDHs of aluminum alkyls activatory.
(4) load of acenaphthene diimine nickel complex
At N
2Protection adds 10.0g down through the organically-modified LDHs of triethyl aluminum activatory in dichloromethane solvent, add 0.3gN again, and N '-two (2; the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr; An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex (NiLBr
2), stir 20h under the room temperature, solution is partly inclined remove then.With washed with dichloromethane three times (20ml * 3), vacuum removal solvent, obtain the organically-modified layered double-hydroxide nickel-loaded back transition catalyzer (NiLBr of system
2/ O-ZnAl-LDH).
(5) in-situ polymerization of polyethylene-LDHs nano composite material preparation
250ml Schlenk three neck round-bottomed flasks are through infrared lamp baking and vacuumize continuously after 0.5h dewaters with deoxygenation, feed ethene displacement three times, add 50ml heptane solvent, 2.5ml promotor aluminium diethyl monochloride and 0.18g NiLBr more successively
2/ O-ZnAl-LDH supported catalyst, aluminium nickel mol ratio is 2000, and mechanical stirring is carried out polyreaction under constant ethylene pressure (106.7kPa), and polymerization temperature is 0 ℃; Polymerization reaction time is 1.5h.Reaction stops with the NaOH-alcohol saturated solution, with the polymer filtration that obtains, uses the washing with alcohol polymerisate, filters and obtain after 60 ℃ of following vacuum-drying polyethylene-LDHs nano composite material.
Under above-mentioned polymerizing condition, organically-modified LDHs can play the stabilizing catalyst activity center, and can control the effect (see figure 1) of polyethylene product form.The activity of supported catalyst catalyzed ethylene polymerization is 2.59 * 10
5GC
2H
4/ (molNih), the LDHs content of prepared polyethylene-LDHs nano composite material, product degree of crystallinity and molecular weight see Table 1.
Through transmission electron microscope observing, the LDHs lamella is partly peeled off and is uniformly distributed in the polyethylene matrix.Prepared polyethylene-its thermostability of LDHs nano composite material has had significantly raising (seeing Table 2), and the storage modulus under the molten state, out-of-phase modulus and complex viscosity all increase (seeing Table 3).
Embodiment 2
Other condition of present embodiment is with specific embodiment 1: polymerization reaction time is 3h in the step (5).
Under above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is 2.03 * 10
5GC
2H
4/ (molNih), the LDHs content of prepared polyethylene-LDHs nano composite material, product degree of crystallinity and molecular weight see Table 1.
Through transmission electron microscope observing, the LDHs lamella is partly peeled off and is uniformly distributed in the polyethylene matrix.Prepared polyethylene-its thermostability of LDHs nano composite material has had significantly raising (seeing Table 2), and the storage modulus under the molten state, out-of-phase modulus and complex viscosity all increase (seeing Table 3).
Embodiment 3
Other condition of present embodiment is with specific embodiment 1: polymerization reaction time is 4.5h in the step (5).
Under above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is 1.78 * 10
5GC
2H
4/ (molNih), the LDHs content of prepared polyethylene-LDHs nano composite material, product degree of crystallinity and molecular weight see Table 1.
Through transmission electron microscope observing, the LDHs lamella is partly peeled off and is uniformly distributed in the polyethylene matrix.Prepared polyethylene-its thermostability of LDHs nano composite material has had significantly raising (seeing Table 2), and the storage modulus under the molten state, out-of-phase modulus and complex viscosity all increase (seeing Table 3).
Embodiment 4
Other condition of present embodiment is with specific embodiment 1: polymerization temperature is 0 ℃ in the step (5); Aluminium nickel mol ratio 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 2.06 * 10
5GC
2H
4/ (molNih).
Embodiment 5
Other condition of present embodiment is with specific embodiment 1: polymerization temperature is 15 ℃ in the step (5); Aluminium nickel mol ratio 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 3.12 * 10
5GC
2H
4/ (molNih).
Embodiment 6
Other condition of present embodiment is with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5); Aluminium nickel mol ratio 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.89 * 10
5GC
2H
4/ (molNih).
Embodiment 7
Other condition of present embodiment is with specific embodiment 1: polymerization temperature is 45 ℃ in the step (5); Aluminium nickel mol ratio 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.94 * 10
5GC
2H
4/ (molNih).
Embodiment 8
Other condition of present embodiment is with specific embodiment 1: polymerization temperature is 60 ℃ in the step (5); Aluminium nickel mol ratio 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 3.38 * 10
5GC
2H
4/ (molNih).
Embodiment 9
Other condition of present embodiment is with specific embodiment 1: aluminium nickel mol ratio 300 in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 1.32 * 10
5GC
2H
4/ (molNih).
Embodiment 10
Other condition of present embodiment is outer with specific embodiment 1: aluminium nickel mol ratio is 600 in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 1.50 * 10
5GC
2H
4/ (molNih).
Embodiment 11
Other condition of present embodiment is outer with specific embodiment 1: aluminium nickel mol ratio is 900 in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 1.91 * 10
5GC
2H
4/ (molNih).
Embodiment 12
Other condition of present embodiment is outer with specific embodiment 1: aluminium nickel mol ratio is 1200 in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 1.92 * 10
5GC
2H
4/ (molNih).
Embodiment 13
Other condition of present embodiment is outer with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 3.62 * 10
5GC
2H
4/ (molNih).
Embodiment 14
Other condition of present embodiment is outer with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5); Aluminium nickel mol ratio is 600.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.18 * 10
5GC
2H
4/ (molNih).
Embodiment 15
Other condition of present embodiment is outer with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5); Aluminium nickel mol ratio is 900.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.46 * 10
5GC
2H
4/ (molNih).
Embodiment 16
Other condition of present embodiment is outer with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5); Aluminium nickel mol ratio is 1200.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.88 * 10
5GC
2H
4/ (molNih).
Embodiment 17
Other condition of present embodiment is outer with specific embodiment 1: polymerization temperature is 30 ℃ in the step (5); Aluminium nickel mol ratio is 1500.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 4.94 * 10
5GC
2H
4/ (molNih).
Embodiment 18
(1) preparation of inorganic LDHs
0.04mol Zn (NO
3)
26H
2O and 0.02mol Al (NO
3) 9H
2O is dissolved in the 100ml distilled water and forms mixing solutions, and the NaOH solution that drips 1.0mol/L then is to pH=11.The gained slurries with the filter cake wash clean, obtain inorganic LDHs (ZnAl-LDH) with deionized water at 80 ℃ of following slaking 16h after-filtration then after 80 ℃ of following vacuum-drying.
(2) preparation of organically-modified LDHs
The ZnAl-LDH powder of 10.0 grams is joined in the sodium dodecyl sulfate solution of 800ml 0.1mol/L, at 80 ℃ of following stirring reaction 16h after-filtration, with a large amount of deionized waters that filter cake washing is clean, after 80 ℃ of following vacuum-drying, obtain organically-modified LDHs (O-ZnAl-LDH) then.
(3) activation of organically-modified LDHs
N
2Protection adds 10.0g O-ZnAl-LDH down and stirs the formation slurries in the 100ml heptane, add the 5ml triisobutyl aluminium again, stirs 12h, solution is partly inclined remove then.To wash for several times through the O-ZnAl-LDH that triisobutyl aluminium is handled with heptane, after 70 ℃ of following vacuum-drying, obtain then through the organically-modified LDHs of aluminum alkyls activatory.
(4) load of acenaphthene diimine nickel complex
At N
2Protection adds 10.0g down through the organically-modified LDHs of triisobutyl aluminium activatory in dichloromethane solvent, add 0.6gN again, and N '-two (2; the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr; An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex (NiLBr
2), stir 12h under the room temperature, solution is partly inclined remove then.With washed with dichloromethane three times (20ml * 3), vacuum removal solvent, obtain the organically-modified layered double-hydroxide nickel-loaded back transition catalyzer (NiLBr of system
2/ O-ZnAl-LDH).
(5) in-situ polymerization of polyethylene-LDHs nano composite material preparation
250ml Schlenk three neck round-bottomed flasks are through infrared lamp baking and vacuumize continuously after 0.5h dewaters with deoxygenation, feed ethene displacement three times, add 80ml toluene solvant, 2ml promotor aluminium diethyl monochloride and 0.11g NiLBr more successively
2/ O-ZnAl-LDH supported catalyst; Aluminium nickel mol ratio 1500, mechanical stirring is carried out polyreaction under constant ethylene pressure (106.7kPa), and polymerization temperature is that 0 ℃ of polymerization reaction time is 1.5h.Reaction stops with the NaOH-alcohol saturated solution, with the polymer filtration that obtains, uses the washing with alcohol polymerisate, filters and obtain after 80 ℃ of following vacuum-drying polyethylene-LDHs nano composite material.
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 1.86 * 10
5GC
2H
4/ (molNih), viscosity-average molecular weight is 5.67 * 10
5G/mol.
Embodiment 19
Other condition of present embodiment is outer with specific embodiment 18: polymerization temperature is 30 ℃ in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 3.64 * 10
5GC
2H
4/ (molNih), viscosity-average molecular weight is 4.98 * 10
5G/mol.
Embodiment 20
Other condition of present embodiment is outer with specific embodiment 18: polymerization temperature is 50 ℃ in the step (5).
Under the above-mentioned polymerizing condition, the activity of supported catalyst catalyzed ethylene polymerization is: 3.03 * 10
5GC
2H
4/ (molNih), viscosity-average molecular weight is 4.52 * 10
5G/mol.
LDHs content, molecular weight and the degree of crystallinity of table 1 embodiment 1～3 prepared polyethylene-LDHs nano composite material
| Sample number into spectrum | LDHs content (wt%) | Viscosity-average molecular weight M v (g/mol) | Degree of crystallinity (%) |
| Pure polyethylene embodiment 1 embodiment 2 embodiment 3 | - 10.32 6.82 4.89 | 5.82×10 5 5.95×10 5 6.52×10 5 6.13×10 5 | 52 28 32 45 |
The heat decomposition temperature of table 2 embodiment 1～3 prepared polyethylene-LDHs nano composite material
| Sample number into spectrum | Decomposition 30wt% (℃) | Decomposition 40wt% (℃) | Decomposition 50wt% (℃) | Decomposition 60wt% (℃) |
| Pure polyethylene embodiment 1 embodiment 2 embodiment 3 | 402.3 462.8 454.6 436.6 | 410.3 474.0 464.7 442.1 | 415.0 481.3 471.7 451.8 | 424.6 484.8 476.6 455.3 |
The rheological property (sweep rate 0.1Hz) of table 3 embodiment 1～3 prepared polyethylene-LDHs nano composite material
| Sample number into spectrum | Storage modulus (Pa) | Out-of-phase modulus (Pa) | Complex viscosity (Pa.S) |
| Pure polyethylene embodiment 1 embodiment 2 embodiment 3 | 6742 18776 15292 11481 | 3152 7454 5208 4274 | 73902 200590 160410 121650 |
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. the method for organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material is with N, N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex is carried on and obtains organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst on the organically-modified LDHs of aluminum alkyls activatory, make promotor with aluminium diethyl monochloride, the original position catalyzed ethylene polymerization prepares polyethylene-LDHs nano composite material in non-polar solvent.
2. the method for organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene according to claim 1-LDHs nano composite material is characterized in that comprising following concrete steps:
(1) preparation of inorganic LDHs
With Zn (NO
3)
26H
2O and Al (NO
3) 9H
2O is that 2～3: 1 ratio is dissolved in and forms mixing solutions in the distilled water in molar ratio, drips NaOH solution then to pH=10～11, obtains slurries; The gained slurries with the filter cake wash clean, obtain inorganic LDHs at 16～24 hours after-filtration of 60～80 ℃ of following slakings after the drying;
(2) preparation of organically-modified LDHs
The inorganic LDHs of 10.0g is joined in 0.08～0.1 mole of sodium dodecyl sulfate solution, at 16～24 hours after-filtration of 60～80 ℃ of following stirring reactions that filter cake washing is clean, obtain organically-modified LDHs after the drying;
(3) activation of organically-modified LDHs
In 50～100ml hexane or heptane, add the organically-modified LDHs of 10.0g and stir the formation slurries, add 5～10ml aluminum alkyls again, stirred 12～20 hours, and will obtain after the drying through the organically-modified LDHs of aluminum alkyls activatory through the organically-modified LDHs washes clean of aluminum alkyls processing;
(4) load of acenaphthene diimine nickel complex
In dichloromethane solvent, add 10.0g through the organically-modified LDHs of aluminum alkyls activatory, add 0.2～0.6gN again, N '-two (2, the 6-diisopropyl phenyl) acenaphthene diimine (ArN=C (An)-C (An)=NAr, An=acenaphthene, Ar=2,6-(i-Pr)
2C
6H
3) nickel complex, stir under the room temperature and make organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst after 12～20 hours;
(5) in-situ polymerization of polyethylene-LDHs nano composite material preparation
50～100ml non-polar solvent, promotor aluminium diethyl monochloride and organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst are added mixing and stirring in the reaction flask, under constant ethylene pressure 106.7kPa, carry out polyreaction, wherein the mol ratio AlEt of contained nickel complex in promotor one chlorine dihexyl aluminium and the organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst
2Cl: NiLBr
2=300～2000: 1, polyethylene-LDHs nano composite material is cleaned, is drying to obtain to the reaction terminating after-filtration with filter cake.
3. the method for organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene according to claim 2-LDHs nano composite material is characterized in that: aluminum alkyls is a kind of in aluminium diethyl monochloride, triethyl aluminum or the triisobutyl aluminium in the described step (3).
4. the method for organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene according to claim 2-LDHs nano composite material, it is characterized in that: non-polar solvent is a kind of in toluene, heptane or the hexane in the described step (5), the polymeric reaction temperature scope is 0～60 ℃, and polymerization reaction time is 1.5～4.5 hours.
Priority Applications (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976417A (en) * | 2012-11-01 | 2013-03-20 | 同济大学 | Preparation method and application of layered double-metal hydroxides containing transition metal |
| CN107108799A (en) * | 2015-01-06 | 2017-08-29 | Scg化学有限公司 | SiO2Layered double-hydroxide microballoon and its purposes as the catalyst carrier in vinyl polymerization |
| CN111278870A (en) * | 2017-11-03 | 2020-06-12 | Scg化学有限公司 | Solid support material |
| CN115260345A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of composite catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976417A (en) * | 2012-11-01 | 2013-03-20 | 同济大学 | Preparation method and application of layered double-metal hydroxides containing transition metal |
| CN107108799A (en) * | 2015-01-06 | 2017-08-29 | Scg化学有限公司 | SiO2Layered double-hydroxide microballoon and its purposes as the catalyst carrier in vinyl polymerization |
| CN111278870A (en) * | 2017-11-03 | 2020-06-12 | Scg化学有限公司 | Solid support material |
| CN115260345A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of composite catalyst |
| CN115260345B (en) * | 2021-04-29 | 2023-07-21 | 中国石油化工股份有限公司 | Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of supported diimine catalyst |
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