CN108034014A - A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst - Google Patents
A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst Download PDFInfo
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- CN108034014A CN108034014A CN201711440797.7A CN201711440797A CN108034014A CN 108034014 A CN108034014 A CN 108034014A CN 201711440797 A CN201711440797 A CN 201711440797A CN 108034014 A CN108034014 A CN 108034014A
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- transition metal
- metal dichalcogenide
- magnesium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Abstract
The invention discloses a kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst, belong to catalyst preparation technical field.This method comprises the following steps：1) transition metal dichalcogenide/magnesium chloride complex carrier is obtained with Grignard Reagent processing transition metal dichalcogenide；2) titanium tetrachloride is carried on transition metal dichalcogenide/magnesium chloride complex carrier, obtains catalyst prod.The catalyst prepares polyolefin/transition metal dichalcogenide nanocomposite available for situ aggregation method, and transition metal dichalcogenide is uniformly dispersed in the composite material obtained, does not have the phenomenon reunited.The catalytic activity for the catalyst that the introducing of transition metal dichalcogenide not only improves, also improves the mechanical property and heat endurance of polyolefin products.The present invention is simple and practicable, and to equipment without particular/special requirement, cost is low, efficient, easily extensive to implement.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of transition metal dichalcogenide/magnesium chloride load
The technology of preparing of catalyst.
Background technology
Transition metal dichalcogenide with class graphene two-dimensional structure is because of the side such as its excellent optics, electricity, electrochemistry
The property in face and cause the extensive concern of people.The basic chemical formula of transition metal dichalcogenide is MX2, wherein M is transition gold
Belong to element, X is chalcogen, wherein with molybdenum disulfide (MoS2) and tungsten disulfide (WS2) it is Typical Representative.With MoS2Exemplified by, it is grand
MoS in sight2With layer structure, o layers of transition metal M is embedded among two S atom layers, is connected in layer by chemical bond,
It is combined between layers with weak Van der Waals force, interlamellar spacing isSince transient metal sulfide material interlayer is weaker
Van der Waals force, this cause transition metal dichalcogenide interlayer be easy to by classes of compounds institute intercalation, peel off.Experiment proves stripping
MoS from after2Nanometer sheet has an excellent mechanical property, its Young ' s Modulus is up to 0.33TPa, nearly in the world most
The half of hard material-graphene, the graphene (0.25TPa) reduced far above chemical method, therefore transition metal curing
Thing has wide prospects for commercial application in polymer high performance field.
It is well known that polyolefin is the chemically inert non-polar polymer that yield is maximum, most widely used in the world, by nothing
The transition metal dichalcogenide nano-particle of machine with nanoscale uniformly, to be stably scattered in polyolefin substrate be one huge
Challenge.The technology of preparing of polyolefin/inorganic nanometer particle compesite is made a general survey of, situ aggregation method is to prepare polyolefin/nothing at present
The most effectual way of machine nano composition, wherein the catalyst preparation containing inorganic nano-particle is the core of the technology.
Therefore, develop a kind of simple efficient preparation catalyst containing transition metal dichalcogenide to have great importance, particularly polyene
The common Ziegler-Natta catalyst of hydrocarbon industrialized production.
The content of the invention
It is simple and practicable the purpose of the present invention is developing a kind of method for overcome the deficiencies in the prior art, to equipment without special
It is required that cost is low, efficient, small, the preparation transition metal dichalcogenide/magnesium chloride load catalyst easily implemented on a large scale is polluted
Method, to prepare polyolefin/transition metal curing available for situ aggregation method by the catalyst prepared by this method
Thing nanocomposite.
The present invention is achieved by the following technical programs.
A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst of the present invention, includes the following steps：
(1) transition metal dichalcogenide/magnesium chloride complex carrier is obtained with Grignard Reagent processing transition metal dichalcogenide；
The molar ratio of the Grignard Reagent and transition metal dichalcogenide is 1~10：1；
(2) titanium tetrachloride is carried on transition metal dichalcogenide/magnesium chloride complex carrier, obtains target product；
The Grignard Reagent molar ratio of the titanium tetrachloride and step (1) is 1~10：1；
The Grignard Reagent structural formula is as follows：
R-Mg-X
Wherein：X is chlorine or bromine, and R is alkyl.
Further, the transition metal dichalcogenide of the step (1) is molybdenum disulfide or tungsten disulfide.
Transition metal dichalcogenide/magnesium chloride load catalyst prepared by the above method can gather in polymerization preparation in the original location
It is applied in alkene/transition metal dichalcogenide nanocomposite.
Compared with prior art, the present invention has following technique effect：
1st, preparation transition metal dichalcogenide/magnesium chloride load catalyst that the present invention is developed is technically simple easy,
To equipment without particular/special requirement, cost is low, efficient, easily extensive to implement.
2nd, transition metal dichalcogenide/magnesium chloride load catalyst prepared by the present invention can be used for situ aggregation method to prepare poly-
Alkene/transition metal dichalcogenide nanocomposite, transition metal dichalcogenide is uniformly dispersed in the composite material obtained,
There is no the phenomenon reunited.
3rd, the catalytic activity for the catalyst that the introducing of transition metal dichalcogenide of the present invention not only improves, also improves polyene
The mechanical property and heat endurance of hydrocarbon product.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiments.
Embodiment 1
1g molybdenum disulfide and 100mL tetrahydrofurans are added in the round-bottomed flask that the nitrogen of 250mL is protected, under stirring action
In making molybdenum disulfide dispersed with tetrahydrofuran solvent, then by 20mL n-butylmagnesium chlorides magnesium (2.0M, tetrahydrofuran solvent)
It is slowly dropped into above-mentioned system, when the lower reaction 48 of 80 degree of nitrogen protections is small, is cooled to 30 degree, is filtered to remove excessive normal-butyl
Magnesium chloride and tetrahydrofuran solvent, then carry out 3 times (100mL/ times) of cleaning, n-hexane solvent cleaning 3 with tetrahydrofuran solvent
Secondary (100mL/ times), then adds 200mL n-hexane solvents, and ultrasonic disperse 1 obtains molybdenum disulfide/magnesium chloride complex carrier when small
Suspension, 10mL titanium tetrachlorides are added drop-wise in above-mentioned suspension, and 80 degree, when reaction 4 is small are to slowly warm up to after being added dropwise, will
Temperature is down to 30 degree, is filtered to remove titanium tetrachloride, and cleans solid product with 60 alkane of redeeming oneself, until unreacted titanium tetrachloride is whole
Remove, molybdenum disulfide/magnesium chloride load catalyst is obtained after vacuum drying.Catalyst forms：Molybdenum disulfide:22.6wt%, magnesium:
9.2wt%, titanium:7.5wt%.
Vinyl polymerization:300mL glass reactors are replaced 3 times through ethene pump drainage, 40 degree of design temperature, magnetic agitation, successively
100mL hexanes are added, triethyl aluminum ([Al]/[Ti]=100), 50 milligrams of catalyst, polymerization starts, and backward system adds within 30 minutes
Enter acidic ethanol and terminate reaction, product is dried under vacuum to constant weight after ethanol cleaning filtering, and polymer performance is shown in Table 1.
Embodiment 2
Molybdenum disulfide and 100mL tetrahydrofurans that 1g is peeled off, stirring are added in the round-bottomed flask that the nitrogen of 250mL is protected
Make under effect stripping molybdenum disulfide it is dispersed with tetrahydrofuran solvent in, then by 20mL n-butylmagnesium chlorides magnesium (2.0M, four
Hydrogen THF solvent) it is slowly dropped into above-mentioned system, when the lower reaction 48 of 80 degree of nitrogen protections is small, 30 degree are cooled to, is filtered to remove
Excessive n-butylmagnesium chloride magnesium and tetrahydrofuran solvent, then carries out 3 times (100mL/ times) of cleaning with tetrahydrofuran solvent, just oneself
Alkane solvents clean 3 times (100mL/ times), then add 200mL n-hexane solvents, and ultrasonic disperse 1 obtains molybdenum disulfide/chlorine when small
Change magnesium complex carrier suspension, 10mL titanium tetrachlorides be added drop-wise in above-mentioned suspension, 80 degree are to slowly warm up to after being added dropwise,
React 4 it is small when, cool the temperature to 30 degree, be filtered to remove titanium tetrachloride, and solid product is cleaned with 60 alkane of redeeming oneself, until unreacted
Titanium tetrachloride all removes, the molybdenum disulfide peeled off after vacuum drying/magnesium chloride load catalyst.Catalyst forms：Two
Molybdenum sulfide:21.8wt%, magnesium:9.7wt%, titanium:9.5wt%.
Vinyl polymerization:300mL glass reactors are replaced 3 times through ethene pump drainage, 40 degree of design temperature, magnetic agitation, successively
100mL hexanes are added, triethyl aluminum ([Al]/[Ti]=100), 50 milligrams of catalyst, polymerization starts, and backward system adds within 30 minutes
Enter acidic ethanol and terminate reaction, product is dried under vacuum to constant weight after ethanol cleaning filtering, and polymer performance is shown in Table 1.
Embodiment 3
Tungsten disulfide and 100mL tetrahydrofurans that 1g is peeled off, stirring are added in the round-bottomed flask that the nitrogen of 250mL is protected
Make under effect stripping tungsten disulfide it is dispersed with tetrahydrofuran solvent in, then by 20mL n-butylmagnesium chlorides magnesium (2.0M, four
Hydrogen THF solvent) it is slowly dropped into above-mentioned system, when the lower reaction 48 of 80 degree of nitrogen protections is small, 30 degree are cooled to, is filtered to remove
Excessive n-butylmagnesium chloride magnesium and tetrahydrofuran solvent, then carries out 3 times (100mL/ times) of cleaning with tetrahydrofuran solvent, just oneself
Alkane solvents clean 3 times (100mL/ times), then add 200mL n-hexane solvents, and ultrasonic disperse 1 obtains molybdenum disulfide/chlorine when small
Change magnesium complex carrier suspension, 10mL titanium tetrachlorides be added drop-wise in above-mentioned suspension, 80 degree are to slowly warm up to after being added dropwise,
React 4 it is small when, cool the temperature to 30 degree, be filtered to remove titanium tetrachloride, and solid product is cleaned with 60 alkane of redeeming oneself, until unreacted
Titanium tetrachloride all removes, the tungsten disulfide peeled off after vacuum drying/magnesium chloride load catalyst.Catalyst forms：Two
Tungsten sulfide:24.5wt%, magnesium:9.1wt%, titanium:9.1wt%.
Vinyl polymerization:300mL glass reactors are replaced 3 times through ethene pump drainage, 40 degree of design temperature, magnetic agitation, successively
100mL hexanes are added, triethyl aluminum ([Al]/[Ti]=100), 50 milligrams of catalyst, polymerization starts, and backward system adds within 30 minutes
Enter acidic ethanol and terminate reaction, product is dried under vacuum to constant weight after ethanol cleaning filtering, and polymer performance is shown in Table 1.
Embodiment 4
Molybdenum disulfide and 100mL tetrahydrofurans that 1g is peeled off, stirring are added in the round-bottomed flask that the nitrogen of 250mL is protected
Make under effect stripping molybdenum disulfide it is dispersed with tetrahydrofuran solvent in, then by 5mL n-butylmagnesium chlorides magnesium (2.0M, four
Hydrogen THF solvent) it is slowly dropped into above-mentioned system, when the lower reaction 48 of 80 degree of nitrogen protections is small, 30 degree are cooled to, is filtered to remove
Excessive n-butylmagnesium chloride magnesium and tetrahydrofuran solvent, then carries out 3 times (100mL/ times) of cleaning with tetrahydrofuran solvent, just oneself
Alkane solvents clean 3 times (100mL/ times), then add 200mL n-hexane solvents, and ultrasonic disperse 1 obtains molybdenum disulfide/chlorine when small
Change magnesium complex carrier suspension, 10mL titanium tetrachlorides be added drop-wise in above-mentioned suspension, 80 degree are to slowly warm up to after being added dropwise,
React 4 it is small when, cool the temperature to 30 degree, be filtered to remove titanium tetrachloride, and solid product is cleaned with 60 alkane of redeeming oneself, until unreacted
Titanium tetrachloride all removes, the molybdenum disulfide peeled off after vacuum drying/magnesium chloride load catalyst.Catalyst forms：Two
Molybdenum sulfide:25.2wt%, magnesium:6.9wt%, titanium:6.2wt%.
Vinyl polymerization:300mL glass reactors are replaced 3 times through ethene pump drainage, 40 degree of design temperature, magnetic agitation, successively
100mL hexanes are added, triethyl aluminum ([Al]/[Ti]=100), 50 milligrams of catalyst, polymerization starts, and backward system adds within 30 minutes
Enter acidic ethanol and terminate reaction, product is dried under vacuum to constant weight after ethanol cleaning filtering, and polymer performance is shown in Table 1.
Comparative example 1
Added in the round-bottomed flask that the nitrogen of 250mL is protected 200mL hexanes and 20mL n-butylmagnesium chlorides magnesium (2.0M, four
Hydrogen THF solvent), 10mL titanium tetrachlorides are added drop-wise in above-mentioned suspension, 80 degree are to slowly warm up to after being added dropwise, reaction 4 is small
When, 30 degree are cooled the temperature to, is filtered to remove titanium tetrachloride, and solid product is cleaned with 60 alkane of redeeming oneself, until four chlorination of unreacted
Titanium all removes, and the catalyst of magnesium chloride load is obtained after vacuum drying.Catalyst forms：Magnesium:2.2wt%, titanium:
13.9wt%.
Vinyl polymerization:300mL glass reactors are replaced 3 times through ethene pump drainage, 40 degree of design temperature, magnetic agitation, successively
100mL hexanes are added, triethyl aluminum ([Al]/[Ti]=100), 50 milligrams of catalyst, polymerization starts, and backward system adds within 30 minutes
Enter acidic ethanol and terminate reaction, product is dried under vacuum to constant weight after ethanol cleaning filtering, and polymer performance is shown in Table 1.
Table 1, polymer performance compare
Claims (3)
1. the preparation method of a kind of transition metal dichalcogenide/magnesium chloride load catalyst, it is characterised in that include the following steps：
(1) transition metal dichalcogenide/magnesium chloride complex carrier is obtained with Grignard Reagent processing transition metal dichalcogenide；
The molar ratio of the Grignard Reagent and transition metal dichalcogenide is 1~10：1；
(2) titanium tetrachloride is carried on transition metal dichalcogenide/magnesium chloride complex carrier, obtains target product；
The Grignard Reagent molar ratio of the titanium tetrachloride and step (1) is 1~10：1；
The Grignard Reagent structural formula is as follows：
R-Mg-X
Wherein：X is chlorine or bromine, and R is alkyl.
2. the preparation method of transition metal dichalcogenide as claimed in claim 1/magnesium chloride load catalyst, its feature exist
In the transition metal dichalcogenide of the step (1) is molybdenum disulfide or tungsten disulfide.
3. transition metal dichalcogenide/magnesium chloride load catalyst prepared by method as claimed in claim 1 polymerization in the original location
Prepare the application in polyolefin/transition metal dichalcogenide nanocomposite.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613880A (en) * | 2004-08-12 | 2005-05-11 | 浙江大学 | Main of component catalyst of olefin polymer and preparation thereof |
| CN1966536A (en) * | 2006-11-10 | 2007-05-23 | 沈阳化工学院 | Spherical carrier loaded late transition metal catalyst and its preparing process |
| CN103374084A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof |
| CN106058206A (en) * | 2016-08-03 | 2016-10-26 | 复旦大学 | Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof |
| CN107469838A (en) * | 2017-09-24 | 2017-12-15 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of molybdenum disulfide load molybdenum cobalt oxide catalyst |
-
2017
- 2017-12-27 CN CN201711440797.7A patent/CN108034014A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613880A (en) * | 2004-08-12 | 2005-05-11 | 浙江大学 | Main of component catalyst of olefin polymer and preparation thereof |
| CN1966536A (en) * | 2006-11-10 | 2007-05-23 | 沈阳化工学院 | Spherical carrier loaded late transition metal catalyst and its preparing process |
| CN103374084A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof |
| CN106058206A (en) * | 2016-08-03 | 2016-10-26 | 复旦大学 | Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof |
| CN107469838A (en) * | 2017-09-24 | 2017-12-15 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of molybdenum disulfide load molybdenum cobalt oxide catalyst |
Non-Patent Citations (1)
| Title |
|---|
| HE-XIN ZHANG ET AL.: "Preparation and properties of PE/MoS2 nanocomposites with an exfoliated-Mos2/MgCl2-supported Ziegler-Natta catalyst via an in situ polymerization", 《COMPOSITES:PART A》 * |
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