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
1998-05-27
2001-03-06
Teskin, Fred (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, C525S379000, C525S382000
Reexamination Certificate
active
06197894
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a process for preparing a hydrogenated product of a cyclic olefin ring-opening metathesis polymer.
The hydrogenated products of a cyclic olefin ring-opening metathesis polymer and copolymer have attracted attention as resins having excellent optical and electric properties, high rigidity, heat resistance and weather-tightness. Therefore, many processes for preparing various ring-opening metathesis polymers and hydrogenated products of the polymers have been proposed.
Some processes for hydrogenating carbon-carbon double bonds in the main chain of a cyclic olefin ring-opening metathesis polymer are known. For example, heterogeneous catalysts that are metal-supported catalysts are used. In the catalysts, a metal such as palladium, platinum, rhodium, ruthenium or nickel is supported on a carrier such as carbon, silica, alumina, titania, magnesia., diatomaceous earth and synthetic zeolite. JP-A-3-174406 (Tokkaihei) and JP-A-4-363312 (Tokkaihei) each disclose a process in which some of these catalysts are used to hydrogenate ring-opening metathesis polymers.
In homogeneous catalysts, nickel naphthenate/triethylaluminum, nickel acetylacetonate/triisobutylaluminum, cobalt octenate
-butyllithium, titanocene/diethylaluminummonochloride, rhodium acetate, dichlorobis (triphenylphosphine)palladium, chlorohydridocarbonyltris(triphenylphosphine)ruthenium or chlorotris(triphenylphosphine)rhodium is used. JP-A-5-239124 (Tokkaihei) and JP-A-7-41549 (Tokkaihei) each disclose a process in which some of these catalysts are used to hydrogenate ring-opening polymers.
However, the hydrogenation reaction is heterogeneous when a metal-supported catalyst is used. Therefore, there is a problem in that such catalyst is used in large quantities to obtain high hydrogenation rate. On the other hand, the homogeneous catalyst has a property that the hydrogenation reaction proceeds even when small amounts of the catalyst are used. However, the Ziegler catalysts consisting of an organic salt of nickel, cobalt or titanium and an organometallic compound containing a metal such as aluminum, lithium, magnesium or tin are deactivated by water, air or polar compounds. Therefore, there is a problem in that the treatment is complex and a solvent having large polarity can not be used.
Furthermore, there is a problem in that metallic complexes such as a complex of rhodium are expensive and their activity is not always high enough. These catalysts have a large steric hindrance to, for example, the hydrogenation of a cyclic olefin ring-opening metathesis polymer because there is a bulky tricyclododecenoic ring in the neighborhood of the carbon-carbon double bond in the ring-opening metathesis polymer. Therefore, it has been considered that it is difficult to hydrogenate the polymer in high hydrogenation rate. Especially it has been considered that it is difficult to hydrogenate the polymer in high hydrogenation rate when there are polar substituents such as hydroxyl, carbonyl, carboxyl, and nitrile groups in the ring-opening metathesis polymer.
Therefore, there have been demands for processes in which hydrogenation is easily carried out in high hydrogen conversion even in a cyclic olefin ring-opening metathesis polymer having a polar substituent such as nitrile group.
SUMMARY OF THE INVENTION
A general object of the present invention is to provide a new process that is free from the above-mentioned problems and that enables the preparation of a hydrogenated product of a cyclic olefin ring-opening metathesis polymer.
The present inventors earnestly studied a process for preparing a hydrogenated product of a cyclic olefin ring-opening metathesis polymer that is free from the above-mentioned problems to complete the present invention.
That is, one object of the present invention is to provide a process for preparing a hydrogenated product of a cyclic olefin ring-opening polymer. The process comprises the steps of hydrogenating a ring-opening metathesis polymer of a cyclic olefin represented by the general formula (1):
wherein R
1
, R
2
, R
3
and R
4
may be the same or different from each other and are individually one member selected from the group consisting of hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group having 1 to 12 carbon atoms, cyano group, carboxyl group and an alkoxycarbonyl group and x is an integer of 0 to 3 in the presence of hydrogen using a hydrogenation catalyst consisting of an amine compound and an organometallic complex represented by the general formula (2):
MH
k
Q
m
T
p
Z
q
(2)
wherein k is an integer of 0 or 1, m is an integer of 1 to 3, p is an integer of 0 or 1, q is an integer of 2 to 4, M is a ruthenium, rhodium, osmium, iridium, palladium, platinum or nickel atom, H is a hydrogen atom, Q is a halogen atom, T is CO, NO, toluene, acetonitrile or tetrahydrofuran, Z is an organic phosphorous compound represented by the general formula (3):
PR′
1
R′
2
R′
3
(3)
wherein P is phosphorous atom, R′
1
, R′
2
and R′
3
may be the same or different from each other and are individually one member selected from the group consisting of a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, a linear, branched or cyclic aryl group, a linear, branched or cyclic alkoxy group and a linear, branched or cyclic aryloxy group.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As cyclic olefin monomers of the present invention that are represented by the formula (1), derivatives of bicycloheptene in which x is 0, derivatives of tetracyclododecene in which x is 1, derivatives of hexacycloheptadecene in which x is 2 and derivatives of octacyclodocosene in which x is 3 are illustrated. Substituents R
1
, R
2
, R
3
and R
4
may be the same or different from each other.
Each of the substituents is selected from the following members.
(1) Hydrogen atom
(2) Alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and cyclohexyl
(3) Aryl groups such as phenyl and naphthyl
(4) Aralkyl groups such as benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-naphthylethyl and 2-naphthylisopropyl
(5) Alkoxy groups such as methoxy, ethoxy and menthoxy
(6) Halogen atoms such as chlorine, bromine, iodine and fluorine
(7) Halogenated alkyl groups having 1 to 12 carbon atoms such as fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl and tribromomethyl
(8) Cyano group
(9) Carboxyl group
(10) Alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and menthoxycarbonyl.
Especially when at least one of the substituents is nitryl group, the monomer is preferred.
The examples are illustrated below.
(1) Cyanobicyclohept-enes such as 5-cyanobicyclo[2.2.1]hept-2-ene, 5-cyano-
-5
methylbicyclo[2.2.1]hept-2-ene, 5-dicyanobicyclo[2.2.1]hept-2-ene, 5-cyano-6-methylbicyclo[2.2.1]hept-2-ene, 5-cyano-6-methoxybicyclo[2.2.1]hept-2-ene, 5-cyano-6-carboxymethylbicyclo[2.2.1]hept-2-ene, 5-cyano-6-carboxybicyclo[2.2.1]hept-2-ene, 5-cyano-6cyanobicyclo[2.2.1]hept-2-ene, 5-cyano-6-trifluoromethylbicyclo[2.2.l]hept-2-ene, 5-cyano-6-fluorobicyclo[2.2.1]hept-2-ene, 5-cyano-6-difluorobicyclo[2.2.1]hept-2-ene, 5-cyano-6-phenylbicyclo[2.2.1]hept-2-ene, 5-cyano-6-benzylbicyclo[2.2.1]hept-2-ene and 5-cyano-6-cyclohexylbicyclo[2.2.1]hept-2-ene
(2) Cyanotetracyclododecenes such as 8-cyanotetracyclo[4.4.0.1
2,5
.1
7,10
]-3-dodecene, 8-cyano-8-methyltetracyclo[4.4.0.1
2,5
.1
7,10
]-3-dodecene, 8-dicyanotetracyclo[4.4.0.1
2,5
.1
7,10
]-3-dodecene, 8-cyano-9-methyltetracyclo[4.4.0.1
2,5
.1
7,10
]-3-dodecene, 8-cyano-9-methoxytetracyclo[4.4.0.1
2,5
.1
7,10
]-3-dodecene, 8-cyano-9-carboxymethyltetracyclo[4.4.0.1
2,5
.1
7,10
Asanuma Tadashi
Okita Masumi
Sunaga Tadahiro
Burns Doane Swecker & Mathis L.L.P.
Mitsui Chemicals Inc.
Teskin Fred
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