Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-11-30
2002-11-26
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S332100, C525S338000, C526S145000, C526S146000, C526S147000, C526S281000, C526S283000
Reexamination Certificate
active
06486264
ABSTRACT:
TECHNICAL FIELD
This invention relates to a process for producing a hydrogenated product of a cyclic olefin polymer prepared through ring-opening polymerization, with enhanced efficiency.
BACKGROUND ART
A process for polymerizing a cyclic olefin by using a polymerization catalyst comprising a tungsten compound, a molybdenum compound, a ruthenium compound or an osmium compound has hitherto been well known. The polymer produced through ring-opening polymerization according to this process has poor heat-stability because of the presence of double bonds in the backbone chain. As an improvement of this process, a process for hydrogenating a polymer prepared through ring-opening polymerization has been proposed.
For example, a process has been proposed wherein a cyclic olefin is polymerized through metathesis ring-opening polymerization by using a transition metal compound having tungsten or molybdenum as a central atom, and then, a hydrogenation catalyst is added to hydrogenate carbon-carbon double bonds in the backbone chain of the polymer (Japanese Unexamined Patent Publication (hereinafter abbreviated to “JP-A”) No. H5-271326, JP-A H9-77853. and JP-A H10-195183). However, when a hydrogenation catalyst is added into a polymerization system as prepared by using a tungsten or molybdenum-containing polymerization catalyst, to hydrogenate a polymer thus-prepared through ring-opening polymerization, the polymerization catalyst poisons the hydrogenation catalyst. Therefore, the hydrogenation reaction must be carried out after the polymerization catalyst is removed from the polymerization system, or a large amount of the hydrogenation catalyst must be used.
In JP-A H10-195182, a process has been reported wherein a cyclic olefin is polymerized through ring-opening polymerization using a catalyst comprising ruthenium-carbene compound, then a modifier such as ethyl vinyl ether is added to modify the catalyst, and then the as-produced polymer is hydrogenated in the presence of the modified catalyst. This process is advantageous in that the polymerization step and the hydrogenation step can be consecutively carried out. However, the present inventors have found that hydrogenation reaction does not proceed often to the desired extent in this process. Further, the above-mentioned catalyst is a homogeneous catalyst and thus the separation and removal thereof from the polymerization system is troublesome.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide an industrially advantageous process for producing a hydrogenation product of a cyclic olefin polymer prepared through ring-opening polymerization, wherein the hydrogenation reaction can be carried out subsequent to polymerization without separation and removal of a polymerization catalyst from the polymerization system, and the amount of a hydrogenation catalyst can be small.
To achieve the above-mentioned object, the present inventors have made extensive research, and found that, in the case where a cyclic olefin is polymerized through ring opening polymerization using an organoruthenium compound or an organoosmium compound as a polymerization catalyst, and then the obtained polymer is hydrogenated, if a hydrogenation catalyst and hydrogen are added in the polymerization system as-obtained by polymerization, the hydrogenation takes place efficiently to give a hydrogenation product with a high yield; and further found that, when a heterogeneous catalyst supported on a carrier is used as the hydrogenation catalyst added after completion of polymerization, the polymerization catalyst can be easily removed. Further, when a polymerization catalyst containing an organoruthenium compound or an oranoosmium compound, and a heteroatom-containing carbene compound is used, the catalyst exhibits a higher activity for the ring-opening polymerization. Based on these findings, the present invention has been completed.
Thus, in accordance with the present invention, there is provided a process for producing a hydrogenated product of a polymer prepared through ring-opening polymerization which comprises:
a polymerization step of polymerizing a cyclic olefin through ring-opening polymerization in the presence of a polymerization catalyst comprising an organoruthenium compound or an organoosmium compound to prepare a polymer, and
a hydrogenation step of adding a hydrogenation catalyst and hydrogen into a polymerization system resulting from the polymerization step to hydrogenate the carbon-carbon double bonds in the polymer prepared through the ring-opening polymerization.
Further, in accordance with the present invention, there is provided a process for producing a polymer through ring-opening polymerization, characterized in that a cyclic olefin is polymerized through ring-opening polymerization using a polymerization catalyst comprising an organoruthenium compound or an organoosmium compound, and a heteroatom-containing carbene compound in the absence of a solvent or in the presence of a halogen-free solvent.
BEST MODE FOR CARRYING OUT THE INVENTION
The invention will be described on preferred embodiments thereof.
(Cyclic Olefin)
The cyclic olefin used in the present invention is chosen from (1) polycyclic olefins having a norbornene ring such as norbornenes, dicyclopentadienes and tetracyclododecenes, and (2) monocyclic olefins and monocyclic diolefins. These olefins may have a substituent such as an alkyl, alkenyl or alkylidene group, or may have a polar group, and further may have a double bond other than the double bonds of the norbornene ring.
Of these, to produce a polymer having excellent heat stability and solubility through ring-opening polymerization, cyclic olefins having three rings through six rings, which include a norbornene ring, are preferable. Cyclic olefins with three rings such as dicyclopentadienes, and cyclic olefins with four rings such as tetracyclododecenes are especially preferable.
Polycyclic Olefins with Norbornene Ring
(i) Dicyclopentadienes
By the term “dicyclopentadiene” used herein is meant cyclic olefins having three rings including a norbornene ring. The dicyclopentadienes may have a substituent such as an alkyl, alkenyl or alkylidene group.
As specific examples of the dicyclopentadienes, there can be mentioned dicyclopentadiene and methyl-dicyclopentadiene. Further, tricyclo[4.3.1
2,5
.0]-deca-3-ene also is included, which has a structure such that the double bonds in the five-membered ring of dicyclopentadiene are saturated.
(ii) Tetracyclododecenes
Tetracyclododecenes are represented by the following formula [4]:
wherein R
5
through R
12
represent a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, R
13
through R
16
represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a substituent having a halogen, silicon, oxygen or nitrogen atom, and R
13
and R
16
may form together a ring.
Tetracyclododecenes include four types of monomers: (a) monomers having no double bond except for the double bond of the norbornene ring, (b) monomers having a double bond in addition to the double bond of the norbornene ring, (c) monomers having an aromatic ring, and (d) monomers having a polar group.
(a) As specific examples of the monomers having no double bond except for the double bond of the norbornene ring, there can be mentioned tetracyclododecene, 8-methyl-tetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene and 8-cyclopentyl-tetracyclododecene. These tetracyclododecene monomers (a) may have a substituent.
(b) As specific examples of the monomers having a double bond in addition to the double bond of the norbornene ring, there can be mentioned 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene and 8-cyclopentenyltetracyclododecene.
(c) As a specific example of the monomers having an aromatic ring, there can be mentioned 8-phenyltetracyclododecene.
(d) As a specific example of the monomers having a polar group, there can be m
Sakamoto Masato
Taguchi Kazunori
Tokoro Masaharu
Tsunogae Yasuo
Lipman Bernard
Zeon Corporation
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