CN1289783A - Process for inserting oligomerizing catalyst between montmorillonite layers - Google Patents
Process for inserting oligomerizing catalyst between montmorillonite layers Download PDFInfo
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- CN1289783A CN1289783A CN 99119651 CN99119651A CN1289783A CN 1289783 A CN1289783 A CN 1289783A CN 99119651 CN99119651 CN 99119651 CN 99119651 A CN99119651 A CN 99119651A CN 1289783 A CN1289783 A CN 1289783A
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- polynite
- catalyst
- zrcl
- catalyzer
- engaging layer
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
A process for inserting oligomerizing catalyst between montmorillonite layers for generating nm-class dispersion features the exchange reaction of H-montmorillonite with the toluene solution which is oligomerized or bipolymerized with ethylene takes place at 30-160 deg.C for 2-60 hr, to make ethylene to absorb and polymerize in montmorillonite layers and release polymerizing heat.
Description
The present invention relates to the method between a kind of superpolymer catalyzer intercalation cheating engaging layer, the method between particularly a kind of polyolefin catalyst intercalation cheating engaging layer.
To be the preparation precursor of studying a kind of modified montmorillonoid of nano composite material in recent years between polar compound intercalation cheating engaging layer, wherein successful method be a PA-6/ clay mixed system (CN96105362.3) in the molecular composite material of inorganic-organic complex system the most.This method at first exchanges the 12-aminolauric acid in montmorillonite layered, and successfully is applied in molecular composite material synthetic of PA-6 and polynite.
The disperse power of this method is that the laminated clay component (polynite) that is mixed with the 12-aminolauric acid has certain polarity, when mixing with ε-Ji Neixianan, because polynite has certain exchanging equivalent, ε-Ji Neixianan monomer partly at first is inserted between cheating engaging layer.
But the deficiency of this method is because the exchanging equivalent of polynite is limited, can not have very a large amount of monomers to enter interlayer.
The present invention is in order to solve monomer in the low shortcoming of the exchange content of the interlayer of polynite, and provides a kind of new catalyst for oligomerization that can adsorb non-polar monomer to exchange method between cheating engaging layer.
The present invention can be adsorbed the catalyzer of non-polar monomer and polynite at 30-160 ℃, react and carried out permutoid reaction in 2-60 hour and make the catalyzer intercalation between cheating engaging layer, wherein polynite refers to the polynite for H-, and catalyzer refers to that ethylene oligomerization or dimerization catalyst system comprise 1). beta-diketon zirconium dichloride (acac)
2ZrCl
22) .ZrCl
43) .Zr (CH
2Ph)
44) replace beta-diketon zirconium dichloride 5). nickel type ethylene oligomerization compound 6) .TiCl
47) .Ti (OBu)
48) .WCl
6Deng.Oligomerisation or dimerization catalyst exchanged follow these steps to carry out between the H-cheating engaging layer: the 1.H-polynite need be dewatered or deshydroxy is handled, employing vacuumizes, chemical processes such as heating and use aluminum alkyls or grignard reagent, heating means commonly used, temperature is 70-400 ℃, and the time is 2-12h.2. with oligomerisation or dimerization catalyst Ti (OBu)
4, (acac)
2ZrCl
2Or ZrCl
4Be dissolved in hexane, ethylene dichloride, toluene, dimethylbenzene, in the exsiccant inert solvents such as chlorobenzene (also available mixed solvent), the most frequently used solvent is toluene or chlorobenzene.Its catalyst concn is 0.01-30mol/l.3. will carry out permutoid reaction under H-polynite and the catalyzer toluene solution normal pressure, temperature of reaction is 30-160 ℃, the best is 50-100 ℃, reaction times is 2-60 hour, the best is 2-12 hour, and exchanged form can be that catalyst solution is added in the H-polynite also can be that the H-polynite is joined in the catalyst solution.4. filter, with hexane wash for several times, drying makes oligomerisation or dimerization catalyst intercalation in the polynite of interlayer.
The method that the present invention relates between a kind of inserting oligomerizing catalyst cheating engaging layer has following feature: 1. the present invention selects for use the H-polynite as intercalation material, selects down the oligomerisation of array structure or the dimerization catalyst exchange ion as polynite for use:
1)．
2) .ZrCl
43) .Zr (CH
2Ph)
4, 4). (acac)
2ZrCl
25). nickel type ethylene oligomerization compound 6) .TiCl
47) Ti (OBu)
48) .WCl
62. the present invention exchanges ethylene oligomerization or dimerization catalyst in polynite, has changed the interlayer structure of polynite, make ethene interlayer endless carry out adsorpting polymerization, emit a large amount of heat of polymerizations, guarantee that polynite forms nano-dispersed in this process.3.H-polynite and catalyzer carry out permutoid reaction under solution solution normal pressure, temperature of reaction is 30-160 ℃, the best is 50-100 ℃, reaction times is 2-60 hour, the best is 2-12 hour, and exchanged form can be that catalyst solution is added in the H-polynite also can be that the H-polynite is joined in the catalyst solution.4. the concentration of catalyst for oligomerization in solution is 0.01-30mol/l.
Embodiment
Embodiment 1.
The H-polynite was handled 2 hours under 400 ℃ of conditions, and is standby in the protection of exsiccant condition of nitrogen gas.
1). with 0.0038mol (acac)
2ZrCl
2Be dissolved in the 50ml toluene, stirred 20 minutes.2). above-mentioned H-polynite 0.5g is placed the 250ml flask with three necks,round bottom that is connected to prolong, vacuumize the displacement nitrogen protection, add toluene 50ml, stirred 20 minutes.3) with 1) in drips of solution be added on 2) in suspension, after dropwising, heating reflux reaction 6 hours is cooled to 40 ℃ then, filters, with 40 ℃ toluene agitator treatings 10 minutes, behind the triplicate, as above the method washed twice vacuumized drying 4 hours then.Obtain powdered modified polynite 0.5g.
Embodiment 2.
The H-polynite was handled 12 hours under 170 ℃ of conditions, and is standby in the protection of exsiccant condition of nitrogen gas.
1). with 0.0038molZrCl
4Be dissolved in the 50ml toluene, stirred 20 minutes.2). above-mentioned H-polynite 0.5g is placed the 250ml flask with three necks,round bottom that is connected to prolong, vacuumize the displacement nitrogen protection, add toluene 50ml, stirred 20 minutes.3). with 1) in drips of solution be added on 2) in suspension, after dropwising, heating reflux reaction 6 hours, be cooled to 40 ℃ then, filter, with 40 ℃ toluene agitator treatings 10 minutes, behind the triplicate, as above the method washed twice vacuumized dry 4 hours then.Obtain powdered modified polynite 0.43g
Embodiment 3.
The H-polynite was handled 12 hours under 70 ℃ of conditions, and is standby in the protection of exsiccant condition of nitrogen gas.
1) with 0.0038mol Ti (OBu)
4Be dissolved in the 50ml toluene, stirred 20 minutes.2). above-mentioned H-polynite 0.5g is placed the 250ml flask with three necks,round bottom that is connected to prolong, vacuumize the displacement nitrogen protection, add toluene 50ml, stirred 20 minutes.3). with 1) in drips of solution be added on 2) in suspension, after dropwising, heating reflux reaction 6 hours, be cooled to 40 ℃ then, filter, with 40 ℃ toluene agitator treatings 10 minutes, behind the triplicate, as above the method washed twice vacuumizes then and obtained powdered modified polynite 0.48g in dry 4 hours.
Claims (4)
1. the method between an inserting oligomerizing catalyst cheating engaging layer is characterized in that following these steps to
Carry out:
1). at 70-400 ℃, heating 2-12h dewaters or deshydroxy is handled with the H-polynite;
2). with Ti (OBu)
4, (acac)
2ZrCl
2Or ZrCl
4, be dissolved in the toluene, obtain catalyzer
Concentration is 0.01-30mol/l;
3). with H-polynite and above-mentioned concentration is that the 0.01-30mol/l catalyzer advances at 30-160 ℃
Row permutoid reaction 2-60 hour obtains H-polynite and Ti (OBu)
4, (acac)
2ZrCl
2
Or ZrCl
4Mixing solutions;
4). above-mentioned mixing solutions is filtered, and with hexane wash for several times, drying makes oligomerisation or dimerization
The catalyzer intercalation is in the polynite of interlayer.
2. the method between a kind of inserting oligomerizing catalyst cheating engaging layer according to claim 1, its
The temperature that is characterised in that H-polynite dehydration deshydroxy is 70-170 ℃.
3. the method between a kind of inserting oligomerizing catalyst cheating engaging layer according to claim 1, its
Be characterised in that H-polynite and concentration are 50-100 ℃ for the 0.01-30mol/l catalyst reaction temperatures.
4. the method between a kind of inserting oligomerizing catalyst cheating engaging layer according to claim 1, its
Be characterised in that H-polynite and catalyzer carried out permutoid reaction 2-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119651 CN1289783A (en) | 1999-09-24 | 1999-09-24 | Process for inserting oligomerizing catalyst between montmorillonite layers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119651 CN1289783A (en) | 1999-09-24 | 1999-09-24 | Process for inserting oligomerizing catalyst between montmorillonite layers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1289783A true CN1289783A (en) | 2001-04-04 |
Family
ID=5281015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99119651 Pending CN1289783A (en) | 1999-09-24 | 1999-09-24 | Process for inserting oligomerizing catalyst between montmorillonite layers |
Country Status (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314760C (en) * | 2005-12-13 | 2007-05-09 | 西北师范大学 | Montmorillonite/Ce(OH)3, Pr2O3/ polyaniline nano-rod three phase composite material and its preparation method |
-
1999
- 1999-09-24 CN CN 99119651 patent/CN1289783A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314760C (en) * | 2005-12-13 | 2007-05-09 | 西北师范大学 | Montmorillonite/Ce(OH)3, Pr2O3/ polyaniline nano-rod three phase composite material and its preparation method |
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