CN106749787B - A kind of preparation method of the mesoporous material of polyethylene filling - Google Patents
A kind of preparation method of the mesoporous material of polyethylene filling Download PDFInfo
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- CN106749787B CN106749787B CN201611069308.7A CN201611069308A CN106749787B CN 106749787 B CN106749787 B CN 106749787B CN 201611069308 A CN201611069308 A CN 201611069308A CN 106749787 B CN106749787 B CN 106749787B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation methods of the mesoporous material of polyethylene filling, its feature in metal salt solution the following steps are included: impregnate 1-7 days for the mesoporous material of aperture 5-50nm, the wherein weight ratio 1wt%-20wt% of the metal in metal salt and mesoporous material；Metal salt is reduced to 0 valence metal in the gaseous mixture of hydrogen and nitrogen volume ratio 1%-10% by the mesoporous material after dipping again, obtains the mesoporous material of metal filling；Then the mesoporous material that the metal of acquisition is filled is placed 1-7 days in ethylene；Then after polyethylene catalysts and co-catalyst being complexed in toluene solution, the mesoporous material of ethylene adsorption is soaked；With diffusion of the polyethylene catalysts and co-catalyst of complexing in mesoporous material, promotes the ethylene of absorption that polymerization reaction occurs, obtain the mesoporous material of polyethylene filling；The present invention can prepare the mesoporous material of polyethylene filling under room temperature, normal pressure, can greatly improve the mechanical property of mesoporous material.
Description
Technical field
The present invention relates to macromolecule/inorganic composite materials technical fields, refer specifically to a kind of mesoporous material of polyethylene filling
Preparation method.
Background technique
The mesoporous materials such as mesopore molecular sieve, silica, titanium dioxide are widely used in the necks such as absorption, catalysis, separation
Domain.However the ability that its poor mechanical strength makes mesoporous material resist external force is not high, is easily broken.Improve the knot of molecular sieve
Brilliant degree is the method currently used for solving molecular screen material bad mechanical strength, however this method is not particularly suited for unbodied dioxy
SiClx mesoporous material.Santoro etc. reports a kind of preparation method (Nature of the mesopore molecular sieve of polyethylene filling
Communications,2013,4,1557-1563).Ethylene absorption is entered in the duct of mesopore molecular sieve, at -10 DEG C,
Cause the free radical polymerization of ethylene under the ethylene atmosphere of super-pressure (0.5-1.5GPa) by ultraviolet irradiation.In restricted clearance
Limited free-radical contents reduce the overlapping probability of happening of chain.Finally, the molecular sieve for obtaining low entanglement polyethylene filling is compound
Material.The hardness of product is 5 times of UHMWPE, 2 times of molecular sieve.Currently, not yet finding it except the work of Santoro et al.
The method that he prepares the mesoporous material of polyethylene filling.However, polymerization temperature mistake in the preparation method of Santoro et al. report
Low, pressure is too high, substantially increases production cost and control difficulty, and the transformation efficiency of ethylene is low.It would therefore be highly desirable to develop height
Effect prepares the mild production technology of polyethylene filling mesoporous material.
Summary of the invention
The technical problem to be solved by the invention for the present situation of prior art is to provide a kind of polyethylene to fill mesoporous material
The efficient mild preparation method of material.
The technical scheme of the invention to solve the technical problem is: a kind of system of the mesoporous material of polyethylene filling
Preparation Method, feature the following steps are included:
(1) mesoporous material of aperture 5-50nm is impregnated 1-7 days in metal salt solution, wherein the metal in metal salt with
The weight ratio 1wt%-20wt% of mesoporous material；
(2) mesoporous material in step 1 after impregnating metal salt is in the gaseous mixture of hydrogen and nitrogen volume ratio 1%-10%
The high-valence state metal of metal salt is reduced to 0 valence metal, obtains the mesoporous material of metal filling；
(3) mesoporous material of the metal filling obtained in step 2 is placed 1-7 days in ethylene, obtains being adsorbed with ethylene
Mesoporous material；
(4) after polyethylene catalysts and co-catalyst being complexed in toluene solution, ethylene is adsorbed in moistening step 3
Mesoporous material；
(5) diffusion with the polyethylene catalysts of complexing and co-catalyst in mesoporous material promotes the ethylene of absorption
Polymerization reaction occurs, obtains the mesoporous material of polyethylene filling.
The further preferred embodiment of the present invention are as follows: the mesoporous material is selected from molecular sieve, silica, aluminium oxide, oxygen
Change one or more of zirconium, titanium dioxide, silica-alumina.
The further preferred embodiment of the present invention are as follows: the metal salt includes silver nitrate, silver chlorate, gold chloride, palladium chloride
One or more of.
The further preferred embodiment of the present invention are as follows: the metal salt solution is selected from the aqueous solution of metal salt, metal salt
One or more of formic acid solution and the acetic acid solution of metal salt.
The further preferred embodiment of the present invention are as follows: the polyethylene catalysts are metallocene catalyst, late transition metal
One or more of catalyst, Ziegler-Natta catalyst and FI catalyst.
The further preferred embodiment of the present invention are as follows: the co-catalyst is one of alkyl aluminum and aluminum alkoxide or two
Kind.
The further preferred embodiment of the present invention are as follows: the co-catalyst and catalyst molar ratio 1-1000.
The further preferred embodiment of the present invention are as follows: 0-100 DEG C of the reaction temperature of the ethylene polymerization.
The further preferred embodiment of the present invention are as follows: the polymerization time 10min-2h of the ethylene polymerization.
The further preferred embodiment of the present invention are as follows: the weight average molecular weight range 1000- of the polyethylene in mesoporous material
10000000g/mol
Compared with the prior art, the advantages of the present invention are as follows: mesoporous material will be immersed in the gaseous mixture of hydrogen and nitrogen
Metallic compound in duct is reduced into the metallic particles of 0 valence.(such as Ag, Au, Pb).Since this kind of metal surface is with high
Surface free energy and electronics unoccupied orbital, being capable of chemisorption C=C, such as ethylene.The ethylene of chemisorption is steadily wrapped in gold
Around metal particles, will not because of surrounding atmosphere change and be desorbed.Then, the pre- network of co-catalyst and polyethylene catalysts is introduced
Product is closed, which is capable of forming cation activity center required for vinyl polymerization.When the complex thereof metallic particles
After the ethylene on surface, polyethylene can be converted by catalyzed ethylene polymerization rapidly.Due to being limited the second of metallic particles absorption in duct
Alkene is limited, and the tension generated when polymerizeing is not enough to burst mesoporous material, and then can obtain the mesoporous material of polyethylene filling.
Meanwhile the polyethylene of generation can be wrapped in surface of metal particles in situ.Compared with prior art, the present invention can be in room temperature
The mesoporous material that polyethylene filling is prepared under normal pressure, greatly reduces technique controlling difficulty and process costs.And pass through control gold
The contents of metal particles and reduction form (nano particle, nano wire), can adjust content of the polyethylene in mesopore molecular sieve and
Accumulation shape.The introducing of polyethylene soft segment greatly improves the deformability of mesoporous material under external force, substantially mentions
The mechanical strength of mesoporous material is risen.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
The operation of all air-sensitive substances is all made of the double line anhydrous and oxygen-free operating method of standard vacuum；Agents useful for same is equal
It is used after needing refinement treatment.
The mesoporous material of polyethylene filling impregnates 7 days in 10% ethanol solution hydrochloride, rear to filter.Gained white solid is
Polymer.The molecular weight of polymer and its distribution are characterized with gel permeation chromatograph (PL-GPC-220).1,2,4- trichloro-benzenes is made
For solvent, sample preparation is filtered at 160 DEG C, using the polystyrene of narrower molecular weight distribution as standard specimen, is measured at 160 DEG C.
Polymerized ethylene content is determined using TGA in the mesoporous material of polyethylene filling.Sample is risen from 50 DEG C with 10 DEG C/min
For temperature to 600 DEG C, the weight loss of sample is the loading of polyethylene in mesoporous material.
The mechanical performance of the mesoporous material of polyethylene filling is using the education measurement of high pressure XRD method.Sample is used on press machine
After different pressure treatments, XRD is measured.Observe mesoporous material crystalline structure.When sample is after a certain pressure treatment, mesoporous material
Expect that crystalline structure disappears, which can quantitatively characterize the mechanical strength of the material.Experiment measures pure mesopore molecular sieve (aperture
Mechanical strength 5nm) is 8GPa；The mechanical strength of pure mesoporous silica gel (aperture 50nm) is 1Gpa；Pure meso-porous alumina (aperture
Mechanical strength 4GPa 20nm)；Pure mesoporous TiO 2 (aperture 10nm) mechanical strength is 3.5GPa；Pure zirconia (aperture
Mechanical strength 10GPa 10nm)；Pure silicon dioxide-aluminium oxide (aperture 20nm) mechanical strength 3GPa；.
Embodiment 1:
The mesopore molecular sieve (ZSM-5) of the aperture 1.0g 5nm is impregnated 7 days in the aqueous solution of silver nitrate, wherein Ag and is situated between
The weight ratio 1wt% of porous molecular sieve；AgNO will be impregnated3Mesoporous material afterwards is in hydrogen and the gaseous mixture of nitrogen volume ratio 1%
10h is restored, the particles filled mesopore molecular sieve of 0 valence Ag is obtained；After the mesoporous material that metal Ag is filled places 7 days in ethylene
It takes out；By the metallocene catalyst Cp of 10 μm of ol2ZrCl2With co-catalyst trimethyl aikyiaiurnirsoxan beta 10mmol (co-catalyst and catalysis
The molar ratio 1000 of agent) in 30mL toluene solution 20min is complexed, the metal Ag filling mesoporous material of ethylene adsorption is added；60
DEG C, reaction 2h, obtain polyethylene filling mesoporous material.Wherein, polymerized ethylene content 5.4wt%, molecular weight 330000g/mol,
The mechanical strength of composite material is 23.3GPa.
Embodiment 2:
The mesoporous silicon oxide of the aperture 1.0g 50nm is impregnated 1 day in the formic acid solution of silver chlorate, wherein Ag with it is mesoporous
The weight ratio 20wt% of molecular sieve；By the mesoporous material after dipping silver chlorate in hydrogen and the gaseous mixture of nitrogen volume ratio 10%
3h is restored, the particles filled mesoporous silicon oxide of 0 valence Ag is obtained；The mesoporous material that metal Ag is filled is placed 1 day in ethylene
After take out；By late transition metal catalyst pyridine diimine/frerrous chloride of 10 μm of ol and co-catalyst trimethyl aikyiaiurnirsoxan beta
20min is complexed in 30mL toluene solution in 1mmol (molar ratio 100 of co-catalyst and catalyst), and the gold of ethylene adsorption is added
Belong to Ag and fills mesoporous material；0 DEG C, reaction 1h, obtain the mesoporous material of polyethylene filling.Wherein, polymerized ethylene content 20wt%, point
Son amount 3000000g/mol, the mechanical strength of composite material are 6.8GPa.
Embodiment 3:
The meso-porous alumina of the aperture 1.0g 20nm is impregnated 3 days in the acetic acid solution of gold chloride, wherein Au with mesoporous point
The weight ratio 10wt% of son sieve；In hydrogen and the gaseous mixture of nitrogen volume ratio 5% also by the mesoporous material after dipping gold chloride
Former 3h obtains the particles filled meso-porous alumina of 0 valence Au；It is taken after the mesoporous material that metal Au is filled is placed 3 days in ethylene
Out；By the Ziegler-Natta catalyst (TiCl of 10 μm of ol4/MgCl2) and 10 μm of ol (co-catalysts of co-catalyst triethyl aluminum
With the molar ratio 1 of catalyst) in 30mL toluene solution 20min is complexed, the metal Au filling mesoporous material of ethylene adsorption is added；
100 DEG C, reaction 10min, obtain the mesoporous material of polyethylene filling.Wherein, polymerized ethylene content 13.2wt%, molecular weight 1000g/
Mol, the mechanical strength of composite material are 4.8GPa.
Embodiment 4:
The mesoporous TiO 2 of the aperture 1.0g 10nm is impregnated 5 days in the aqueous solution of palladium chloride, wherein Pb with mesoporous point
The weight ratio 5wt% of son sieve；Mesoporous material after dipping palladium chloride is restored in hydrogen and the gaseous mixture of nitrogen volume ratio 3%
5h obtains the particles filled mesoporous TiO 2 of 0 valence Pb；It is taken after the mesoporous material that metal Pb is filled is placed 3 days in ethylene
Out；By FI the catalyst ([3-t-Bu-2-O-C of 10 μm of ol6H3CH]N(C6F5)]2TiCl2) and co-catalyst trimethyl aikyiaiurnirsoxan beta
20min is complexed in 30mL toluene solution in 100 μm of ol (molar ratio 10 of co-catalyst and catalyst), and the gold of ethylene adsorption is added
Belong to Pb and fills mesoporous material；30 DEG C, reaction 80min, obtain the mesoporous material of polyethylene filling.Wherein, polymerized ethylene content
16.2wt%, molecular weight 10000000g/mol, the mechanical strength of composite material are 15.0GPa.
Embodiment 5:
The mesoporous zircite of the aperture 1.0g 10nm is impregnated 5 days in the aqueous solution of silver nitrate, wherein Ag and mesoporous molecular
The weight ratio 3wt% of sieve；Mesoporous material after dipping silver nitrate is restored in hydrogen and the gaseous mixture of nitrogen volume ratio 5%
5h obtains the particles filled mesoporous zircite of 0 valence Ag；It is taken out after the mesoporous material that metal Ag is filled is placed 3 days in ethylene；
By FI the catalyst ([3-t-Bu-2-O-C of 10 μm of ol6H3CH]N(C6F5)]2TiCl2) and co-catalyst trimethyl aikyiaiurnirsoxan beta 1000
20min is complexed in 30mL toluene solution in μm ol (molar ratio 100 of co-catalyst and catalyst), and the metal of ethylene adsorption is added
Ag fills mesoporous material；30 DEG C, reaction 2h, obtain the mesoporous material of polyethylene filling.Wherein, polymerized ethylene content 10.2wt%,
Molecular weight 9000000g/mol, the mechanical strength of composite material are 13.4GPa.
Embodiment 6:
Mesoporous silicon oxide-aluminium oxide of the aperture 1.0g 20nm is impregnated 5 days in the aqueous solution of palladium chloride, wherein Pb with
The weight ratio 5wt% of mesopore molecular sieve；By impregnate palladium chloride after mesoporous material hydrogen and nitrogen volume ratio 3% gaseous mixture
Middle reduction 5h obtains the particles filled mesoporous silicon oxide-aluminium oxide of 0 valence Pb；The mesoporous material that metal Pb is filled is in ethylene
Middle placement is taken out after 3 days；By FI the catalyst ([3-t-Bu-2-O-C of 10 μm of ol6H3CH]N(C6F5)]2TiCl2) and co-catalyst
10min is complexed in 200 μm of ol of trimethyl aikyiaiurnirsoxan beta (molar ratio 20 of co-catalyst and catalyst) in 30mL toluene solution, is added
The metal Pb of ethylene adsorption fills mesoporous material；30 DEG C, reaction 10min, obtain the mesoporous material of polyethylene filling.Wherein, gather
Ethylene contents 6.2wt%, molecular weight 5000000g/mol, the mechanical strength of composite material are 6.5GPa.
Claims (9)
1. a kind of preparation method of the mesoporous material of polyethylene filling, feature the following steps are included:
(1) mesoporous material of aperture 5-50nm is impregnated 1-7 days in metal salt solution, wherein the metal in metal salt with it is mesoporous
The weight ratio 1wt%-20wt% of material；
(2) mesoporous material in step (1) after impregnating metal salt will in the gaseous mixture of hydrogen and nitrogen volume ratio 1%-10%
The high-valence state metal of metal salt is reduced to 0 valence metal, obtains the mesoporous material of metal filling；
(3) mesoporous material of the metal filling obtained in step (2) is placed 1-7 days in ethylene, obtains Jie for being adsorbed with ethylene
Porous materials；
(4) after polyethylene catalysts and co-catalyst being complexed in toluene solution, Jie of ethylene is adsorbed in moistening step (3)
Porous materials；
(5) diffusion with the polyethylene catalysts of complexing and co-catalyst in mesoporous material promotes the ethylene of absorption to occur
Polymerization reaction obtains the mesoporous material of polyethylene filling；The weight average molecular weight range 1000- of polyethylene in mesoporous material
10000000g/mol。
2. a kind of preparation method of the mesoporous material of polyethylene filling according to claim 1, it is characterised in that: described
Mesoporous material be selected from one of molecular sieve, silica, aluminium oxide, zirconium oxide, titanium dioxide, silica-alumina or
It is several.
3. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: the gold
Belonging to salt includes one or more of silver nitrate, silver chlorate, gold chloride, palladium chloride.
4. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: the gold
Belong to salting liquid and is selected from one or more of the aqueous solution of metal salt, the formic acid solution of metal salt and acetic acid solution of metal salt.
5. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: described is poly-
Catalyst for ethylene is one in metallocene catalyst, late transition metal catalyst, Ziegler-Natta catalyst and FI catalyst
Kind is several.
6. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: described helps
Catalyst is one or both of alkyl aluminum and aluminum alkoxide.
7. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: described helps
Catalyst and catalyst molar ratio 1-1000.
8. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: the second
0-100 DEG C of the reaction temperature of alkene polymerization reaction.
9. according to a kind of preparation method of the mesoporous material of polyethylene filling described in claim 1, it is characterised in that: the second
The polymerization time 10min-2h of alkene polymerization reaction.
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| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
| CN102580725A (en) * | 2012-01-11 | 2012-07-18 | 清华大学 | Preparation method and application of nano monocrystal Pd core-shell catalyst |
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| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
| CN102580725A (en) * | 2012-01-11 | 2012-07-18 | 清华大学 | Preparation method and application of nano monocrystal Pd core-shell catalyst |
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