CN101157742A - Catalytic system for preparing cycloolefine copolymer - Google Patents
Catalytic system for preparing cycloolefine copolymer Download PDFInfo
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- CN101157742A CN101157742A CNA2007100712862A CN200710071286A CN101157742A CN 101157742 A CN101157742 A CN 101157742A CN A2007100712862 A CNA2007100712862 A CN A2007100712862A CN 200710071286 A CN200710071286 A CN 200710071286A CN 101157742 A CN101157742 A CN 101157742A
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Abstract
The present invention discloses a catalyst system used for the preparation of a cycloolefin copolymer. The catalyst system comprises a main catalyst and an auxiliary catalyst, the main catalyst is a metallocene compound which has a structural formula of (I), and the auxiliary catalyst is an aluminum alkyl compound which has a structure of (II) or a structure of (III). A cycloolefin monomer of the cycloolefin copolymer which is prepared by the catalyst system for the preparation of cycloolefin copolymer has high insertion rate, the mole fraction can achieve 90 percent, and the heat-resistance of the cycloolefin copolymer is improved.
Description
Technical field
The present invention is a kind of catalyst system that is used to prepare cyclic olefine copolymer.
Background technology
The cycloolefin co-polymer is called for short COC (Cyclic-Olefin Copolymers), is a kind of high added value thermoplastic engineering plastic that is formed by cyclic olefin polymerization.The COC resin has very high transparency, extremely low specific inductivity, good in moist, thermotolerance, chemical stability and dimensional stability, has been widely used at present and has made various optical lens, auto bulb, LCD assembly, electronics and electric component, medicine and packaging material for food etc.In addition, the COC resin also is considered to replace the best materials that PC is used to produce high-density DVD of future generation.COC is obtained by addition polymerization by catalyzer such as metallocenes usually.
Patents such as DE P4343566, DE P4422157, DE P4304307, DE P4304293, DE P4304292 all adopt bridging type metallocene catalyst to prepare COC by the addition polymerization process, and temperature of reaction 40-80 ℃, pressure is from the normal pressure to 20bar.The general formula of bridging type metallocene catalyst can be expressed as:
In the general formula, M is titanium, zirconium; R
4, R
5Be halogen etc.R in the DE P4343566 catalyst system therefor
1, R
2Be cyclopentadienyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DEP4422157, R
1, R
2Be cyclopentadienyl or indenyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DE P4304307, R
1Be cyclopentadienyl, R
2Be indenyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DE P4304293, R
1Be cyclopentadienyl, R
2Be fluorenyl or indenyl, R
3Be silane (as dimethylsilane).Among the DE P4304292, R
1Be cyclopentadienyl, R
2Be fluorenyl, R
1And R
2In at least one base be substituted, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).
CN1585781, CN1592765 have adopted the catalysis of rear transition metal element catalyst and have contained the addition polymerization of ester group or acetylnorbornene.
By the synthetic late transition metal catalyst of hydroxyl imide and rear transition metal compound,, carry out the copolymerization of monomeric homopolymerization such as norbornylene, propylene cyanogen, vinylbenzene, methyl methacrylate and above-mentioned monomer and ethene among the CN1563111 by addition polymerization.
CN1563113 adopts nitrogen-oxygen nickel complex catalytic system to carry out the addition polymerization of norbornylene and derivative thereof.
CN1335325 adopts neutral catalyst for polymerization of pyrroimino nickel cycloolefine catalysis norbornylene and derivative addition polymerization thereof, preparation high-molecular-weight poly cycloolefin.
Above catalyst system is when carrying out cycloolefin monomers and the monomeric copolymerization of non-ring olefin, all there is the lower problem of cycloolefin monomers insertion rate, this had both influenced the effective rate of utilization of cycloolefin monomers, had limited the further raising of cyclic olefine copolymer resistance toheat again.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst system that helps improving the preparation cyclic olefine copolymer of cycloolefin monomers effective rate of utilization.
The catalyst system that is used to prepare cyclic olefine copolymer of the present invention comprises Primary Catalysts and promotor, and Primary Catalysts is the metallocene compound with structural formula (I)
In the formula, R
6, R
7For replacing or unsubstituted aryl, C
1-C
6Alkyl, preferable methyl, ethyl, propyl group, phenyl or naphthyl, R
6, R
7Can be identical also can be inequality, preferably identical; R
8, R
9Be hydrogen, C
1-C
12Alkyl, alkoxyl group, siloxy, aryl, aralkoxy, hydroxyl, halogen, preferred hydrogen, methyl, ethyl, propyl group, R
8, R
9The position can be in arbitrary position of cyclopentadienyl, fluorenyl; Me is a kind of element of IVB family in the periodic table of elements, preferred titanium, zirconium; Q is a halogen, preferred chlorine;
Promotor is the alkylaluminium cpd with structure (II) or structure (III)
R in the formula
20-R
24Be identical or different C
1-C
18Alkyl, aryl or hydrogen;
R in the formula
25Be identical or different C
1-C
18Alkyl, aryl or hydrogen, the preferable methyl aikyiaiurnirsoxan beta.
The method that catalyst system of the present invention is used to prepare cyclic olefine copolymer is as follows:
Under the anhydrous and oxygen-free condition, in reactor, add the straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon or aromatic hydrocarbons are as solvent, with at least a structure suc as formula (IV), polycyclic olefin monomer shown in the formula V, and structure is suc as formula the non-ring olefin monomer shown in (VI), the monomeric mol ratio of cycloolefin monomers and non-ring olefin is 0.5-50, at 30-100 ℃, the 1-50 normal atmosphere, stir and add promotor and Primary Catalysts down successively, the mol ratio of promotor and Primary Catalysts is 1000-10000, carry out polyreaction
In the formula (IV), R
16-R
19Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality;
In the formula V, R
20-R
25Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality;
In the formula (VI), R
26-R
29Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality.
Among the present invention, the preferred norbornylene of polycyclic olefin monomer, methyl norbornylene, tetracyclododecane or their mixture.Non-ring olefin monomer optimal ethylene, propylene, m-pentadiene or their mixture.The preferred toluene of solvent, normal hexane, hexanaphthene or their mixture.
The invention has the advantages that: adopt the metallocene catalysis system that comprises Primary Catalysts and promotor of the present invention, improved the insertion rate of cycloolefin monomers and non-ring olefin monomer copolymerizable process cycloolefin monomers, the mole fraction of cycloolefin can reach 90% in the gained cyclic olefine copolymer, the cycloolefin monomers effective rate of utilization is increased, and the cyclic olefine copolymer thermotolerance improves.
Embodiment
Further specify the present invention below by example, but the present invention is not limited thereto.
Following examples, the second-order transition temperature of polymkeric substance is measured with differential scanning calorimeter, 10 ℃/minute of temperature rise rates, 10 ℃/minute of rate of temperature fall, adopt the secondary temperature elevation curve by sweep limit 30-220 ℃.
Embodiment 1
The refining norbornylene of 3.6 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming I.Solution I is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 2 ml concns are the methylaluminoxane of 1.72 mol, 1.3 milligrams of different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichlorides then successively.Polymerization is 1 hour under 50 ℃, 250 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 1.2 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 2
Method by embodiment 1 prepares polymkeric substance, and refining norbornylene add-on is reduced to 0.7 gram, catalyst activity 1.5 * 10 by 3.6 grams
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 3
Method by embodiment 1 prepares polymkeric substance, and refining norbornylene add-on is restrained catalyst activity 1.0 * 10 by 3.6 gram liters to 5.4
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 4
The refining methyl norbornylene of 12 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming II.Solution II is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 12.7 ml concns are the methylaluminoxane of 1.72 mol, 1.3 milligrams of different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichlorides then successively.Polymerization is 1 hour under 30 ℃, 250 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 0.5 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 5
Method by embodiment 4 prepares polymkeric substance, and refining methyl norbornylene add-on is reduced to 0.3 gram by 12 grams, 80 ℃ of following polymerization half an hour, catalyst activity 2.0 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 1
The refining norbornylene of 3.6 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming I.Solution I is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 2 ml concns are the methylaluminoxane of 1.72 mol, 0.8 milligram of rac-vinyl-(two indenyls)-zirconium dichloride then successively.Polymerization is 1 hour under 50 ℃, 750 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 2.55 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 2
Method by comparative example 1 prepares polymkeric substance, and refining norbornylene add-on is reduced to 0.7 gram, catalyst activity 2.86 * 10 by 3.6 grams
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 3
Method by comparative example 1 prepares polymkeric substance, and refining norbornylene add-on is restrained catalyst activity 2.11 * 10 by 3.6 gram liters to 5.4
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Table 1 polymkeric substance rerum natura
| Sequence number | Cycloolefin content/mol% | Tg/℃ |
| Embodiment 1 | 56.4 | 149 |
| Embodiment 2 | 37.2 | 84 |
| Embodiment 3 | 60.1 | 16l |
| Embodiment 4 | 90.0 | 200 |
| Embodiment 5 | 10.0 | 20 |
| Comparative example 1 | 49.3 | 125 |
| Comparative example 2 | 29.6 | 59 |
| Comparative example 3 | 53.5 | 139 |
By table as seen, the cycloolefin monomers insertion rate height of the prepared cyclic olefine copolymer of the present invention, its mole fraction can reach 90%, and the cyclic olefine copolymer thermotolerance improves.
Claims (1)
1. be used to prepare the catalyst system of cyclic olefine copolymer, it is characterized in that comprising Primary Catalysts and promotor, Primary Catalysts is the metallocene compound with structural formula (I)
In the formula, R
6, R
7For replacing or unsubstituted aryl, C
1-C
6Alkyl, R
6, R
7Can be identical also can be inequality; R
8, R
9Be hydrogen, C
1-C
12Alkyl, alkoxyl group, siloxy, aryl, aralkoxy, hydroxyl, halogen, R
8, R
9The position can be in arbitrary position of cyclopentadienyl, fluorenyl; Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen;
Promotor is the alkylaluminium cpd with structure (II) or structure (III)
R in the formula
20-R
24Be identical or different C
1-C
18Alkyl, aryl or hydrogen;
R in the formula
25Be identical or different C
1-C
18Alkyl, aryl or hydrogen.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100712862A CN101157742A (en) | 2007-09-11 | 2007-09-11 | Catalytic system for preparing cycloolefine copolymer |
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|---|---|---|---|
| CNA2007100712862A CN101157742A (en) | 2007-09-11 | 2007-09-11 | Catalytic system for preparing cycloolefine copolymer |
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|---|---|
| CN101157742A true CN101157742A (en) | 2008-04-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669902A (en) * | 2014-12-03 | 2016-06-15 | 魏东初 | Novel cycloolefin copolymer catalyst and synthetic method thereof |
| WO2021083309A1 (en) * | 2019-10-30 | 2021-05-06 | 中国石油化工股份有限公司 | Metallocene compound, and preparation method therefor and application thereof |
| CN115677879A (en) * | 2021-07-31 | 2023-02-03 | 华为技术有限公司 | Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer |
-
2007
- 2007-09-11 CN CNA2007100712862A patent/CN101157742A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669902A (en) * | 2014-12-03 | 2016-06-15 | 魏东初 | Novel cycloolefin copolymer catalyst and synthetic method thereof |
| WO2021083309A1 (en) * | 2019-10-30 | 2021-05-06 | 中国石油化工股份有限公司 | Metallocene compound, and preparation method therefor and application thereof |
| CN115677879A (en) * | 2021-07-31 | 2023-02-03 | 华为技术有限公司 | Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer |
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