JPH10324737A - Purification of cyclic olefin ring-opening metathesis polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject colorless polymer little in degradative deterioration by bringing the ring-opening metathesis polymer of a specific cyclic olefinic monomer or the hydrogenation product of the polymer into contact with a basic compound and an acidic compound to remove metal components and metal compound components originating from a polymerization catalyst and a hydrogenation catalyst contained in the polymer without bringing the polymer into contact with water. SOLUTION: This method for purifying the polymer comprises bringing the ring-opening metathesis polymer of a cyclic olefinic monomer of the formula [R<1> to R<4> are each an aryl, etc.; (x) is 0-3] (e.g. 5-cyanobicyclo[2.2.1]hept-2-ene) or the hydrogenation product of the polymer into contact with a basic compound (e.g. methylamine) and an acidic compound (e.g. formic acid) without bringing it into contact with water to remove metal components and metal compound components originating from a polymerization catalyst [e.g. Ru(CHCHCPh2 )(PPh3 )2 (Ph is phenyl) and a hydrogenation catalyst (e.g. rhodium acetate) contained in the polymer or the hydrogenation product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ring-opening metathesis polymer of a cyclic olefin monomer and a method for purifying a hydrogenated product of the polymer.

[0002]

2. Description of the Related Art Ring-opening metathesis polymers of cyclic olefin monomers and hydrogenated ring-opening metathesis polymers have attracted attention as resins having excellent optical properties, electrical properties, high rigidity, heat resistance and weather resistance. Various ring-opening metathesis polymers and methods for producing the hydrogenated polymers have been proposed.

However, if metal and metal compound components derived from the ring-opening metathesis catalyst or the hydrogenation catalyst remain in the ring-opening metathesis polymer and the hydrogenated product of the polymer, coloring and decomposition degradation of the resin occur, There is a problem that the above excellent characteristics cannot be obtained.

Heretofore, as a method of removing metals and metal compound components from resins, a method has been used in which a polymer solution is discharged into a large amount of a poor solvent, and the polymer is coagulated, filtered, recovered, and washed repeatedly. However, this method requires a large amount of poor solvent and requires large-scale equipment in industrial practice, and the recovered polymer is not necessarily one from which the metal and metal compound components have been sufficiently removed. There is a problem that there is no. In JP-A-49-130500, a system containing a polar group-substituted cyclic olefin polymer is
A method has been proposed in which a treating agent such as an alcoholic compound, a phenolic compound, or a nitrile compound is added to perform a contact treatment, and then treated with water or an aqueous solution containing a compound that forms a chelate bond. Further, Japanese Patent Application Laid-Open No. 8-20874
In Japanese Patent Publication No. 2 (1994), an organic acid such as lactic acid, a poor solvent and water are added to a solution of a cyclic olefin polymer in a good solvent,
A method has been proposed in which this system is stirred and mixed at room temperature or under heating. However, in these methods, the addition of water is essential, so that the purification treatment of the mixed solvent after washing, the drying step of the recovered polymer, and the like become complicated, and the metal and metal in the polymer are not necessarily required. The compound components were not sufficiently removed, and particularly when the ring-opening metathesis polymer and the hydrogenated polymer thereof had a nitrile group, it was very difficult to remove the metal and metal compound components.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel cyclic olefin-based ring-opening metathesis polymer which has solved the above-mentioned problems of the prior art, and a method for purifying a hydrogenated polymer thereof. Things.

[0006]

Means for Solving the Problems The present inventors diligently studied a method for purifying a cyclic olefin-based ring-opening metathesis polymer which solved the above problems and a hydrogenated product of the polymer, and completed the present invention.

The method for purifying a cyclic olefin ring-opening metathesis polymer of the present invention is represented by the general formula [1]:

[0008]

Embedded image (Wherein, R ^{1 to} R ⁴ may be the same or different, and each represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen,
Selected from halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups of from 1 to 12, and x represents an integer of from 0 to 3. A) a ring-opening metathesis polymer of a cyclic olefin-based monomer represented by the following formula or a hydrogenated product of the polymer, wherein a metal and a metal compound component derived from a polymerization catalyst or a hydrogenation catalyst contained therein are converted to water and It is characterized in that it is removed by contacting with a basic compound and an acidic compound without being contacted and treating.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the cyclic olefin-based monomer represented by the general formula [1] in the present invention, a derivative of bicycloheptoene where x is 0 and a derivative of tetracyclododecene where x is 1 , X is 2 and the derivative of hexacycloheptadecene, x is 3 and the derivative of octacyclodcocene. R ^{1 to} R ⁴ may be the same or different, and each represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t
-Butyl, an alkyl group such as cyclohexyl, phenyl,
Aryl groups such as naphthyl, aralkyl groups such as benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-naphthylethyl, and 2-naphthylisopropyl;
Alkoxy groups such as methoxy, ethoxy, and menthoxy; halogens such as chlorine, bromine, iodine and fluorine; fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, etc. A halogenated alkyl group having 1 to 12 carbon atoms, a nitrile group, a carboxyl group or an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, and mentoxycarbonyl; and at least one of R ^{1 to} R ⁴ is a nitrile group. Are preferably used.

As specific examples, 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-6-cyanobicyclo [2.2.
1] Hept-2-ene, 5-cyano-6-trifluoromethylbicyclo [2.2.1] 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, 5-cyano-6-cyclohexylbicyclo [2.
2.1] Cyanobicycloheptoenes such as hept-2-ene, 8-cyanotetracyclo [4.4.0.1 ^2,5 .
17,10] -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-methoxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Cyano-9-carboxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyano-9
-Carbonoxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8-cyano-9-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyano-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Cyano-9-fluorotetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyano-9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8-cyano-9-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Cyano-9-benzyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyano-9-cyclohexyltetracyclo [4.4.0.1 ^2,5 .
Cyanotetracyclododecenes such as 1 ^7,10 ] -3-dodecene; 11-cyanohexacyclo [6.6.1.1
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-11-methyl-hexa cyclo [6.
6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-dicyano hexa cyclo [6.6.
1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-12-methyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14 ] −
4-heptadecene, 11-cyano-12-methoxyhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0
^9,14] -4-heptadecene, 11-cyano-12-carboxymethyl Nikishi methylhexahydrophthalic cyclo [6.6.1.1 ^{3, 6.} 1
^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-
Cyano-12-carboxyhexacyclo [6.6.1.
^13-6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-12-cyanohexadecanoic cyclo [6.
6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-12-trifluoromethyl hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0
^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano -1
2-fluorohexacyclo [6.6.1.1 ^3,6 . 1
^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-
Cyano-12-difluorohexacyclo [6.6. 1.
^13-6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-12-phenyl-hex cyclo [6.
6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyano-12-benzyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14 ]
-4-heptadecene, 11-cyano-12-cyclohexylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0
^2,7 . 0 ^9,14] -4-cyano hexa cycloheptanone decene such as heptadecene, 14-cyano octa cyclo [8.
8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 .
0 ^3,8 . 0 ^12,17 ] -5-docosene, 14-cyano-1
4-methyloctacyclo [8.8.0.1 ^2,9 . 1
^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5
Dococene, 14-dicyanooctacyclo [8.8.0.
12 ⁹ . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5-docosene, 14-cyano-15-methyloctacyclo [8.8.0.1 ^2,9 . ^14,7 . 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^{12 , 17} ] -5-docosene, 14-cyano-15-methoxyoctacyclo [8.
8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0
^3,8 . 0 ^12,17 ] -5-docosene, 14-cyano-15
-Carboxymethyloctacyclo [8.8.0.1
^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5-docosene, 14-cyano-15-carboxyoctacyclo [8.8.0.1 ^2,9 . ^14,7 . 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 14-cyano-15-cyanooctacyclo [8.
8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0
^3,8 . 0 ^{12 , 17} ] -5-docosene, 14-cyano-15
-Trifluoromethyloctacyclo [8.8.0.1
^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5-docosene, 14-cyano-15-fluorooctacyclo [8.8.0.1 ^2,9 . ^14,7 . 1 ^11,18
. 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 1
4-cyano-15-difluorooctacyclo [8.8.
0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5-docosene, 14-cyano-15-phenyloctacyclo [8.8.0.1 ^2,9 . ^14,7 . 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 14-cyano-15-benzyloctacyclo [8.
8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0
^3,8 . 0 ^12,17 ] -5-docosene, 14-cyano-15
-Cyclohexyloctacyclo [8.8.0.1 ^2,9 .
^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5
-Cyanooctacyclodcocenes such as dococene and the like.

Furthermore, bicyclo [2.2.1] hept-
2-ene, 5-methylbicyclo [2.2.1] hept-
2-ene, 5-ethylbicyclo [2.2.1] hept-
2-ene, 5-carboxybicyclo [2.2.1] hep
To-2-ene, 5-carboxymethylbicyclo [2.
2.1] Hept-2-ene, 5-benzylbicyclo
[2.2.1] Hept-2-ene, 5-chlorobicyclo
[2.2.1] Hept-2-ene, 5-bromobicyclo
[2.2.1] Hept-2-ene, 5-methoxybisic
B [2.2.1] hept-2-ene, 5-ethoxybishi
Black [2.2.1] hept-2-ene, 5-methyl-6
-Methylbicyclo [2.2.1] hept-2-ene and the like
Bicycloheptoene derivative, tetracyclo [4.4.
0.1^2,5 . 1^{7, Ten}] -3-dodecene, 8-methyltet
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8-ethyltetracyclo [4.4.0.1^2,5 . 1
^7,10] -3-dodecene, 8-carboxytetracyclo
[4.4.0.1^2,5 . 1^7,10] -3-dodecene, 8-
Carboxymethyltetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene, 8-benzyltetracyclo
[4.4.0.1^2,5 . 1^7,10] -3-dodecene, 8-
Chlorotetracyclo [4.4.0.1^2,5 . 1^7,10]-
3-dodecene, 8-bromotetracyclo [4.4.0.
1^2,5 . 1^7,10] -3-dodecene, 8-methoxytetra
Cyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8-ethoxytetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene, 8-methyl-9-methyltet
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8-methyl-9-carboxymethyltetracyclo
[4.4.0.1 ^2,5 . 1^7,10] -3-dodecene, 8-
Phenyltetracyclo [4.4.0.1^{2, Five} . 1^7,10]
Tetracyclododecene derivatives such as -3-dodecene;
Sacyclo [6.6.1.1^3,6 . 0^2,7 . 0^9,14] -4
-Heptadecene, 11-methylhexacyclo [6.6.
1.1^3,6 . 1^10,13 . 0^2,7 . 0^9,14] -4-hepta
Decene, 11-ethylhexacyclo [6.6.1.1
^3,6 . 1^10,13 . 0^2,7 . 0^{9, 14}] -4-heptadece
, 11-carboxyhexacyclo [6.6.1.1
^3,6. 0^10,13 . 0^2,7 . 0^9,14] -4-heptadece
, 11-benzylhexacyclo [6.6.1.1
^3,6 . 0^10,13 . 0^2,7 . 0^9,14] -4-heptadece
, 11-carboxymethylhexacyclo [6.6.
1.1^3,6 . 1^10,13 . 0^2,7 . 0^9,14] -4-hepta
Decene, 11-methoxyhexacyclo [6.6.1.1
^{3, 6} . 1^10,13 . 0^2,7 . 0^9,14] -4-heptadece
, 11-ethoxyhexacyclo [6.6.1.1
^3,6 . 1^10,13 . 0^2,7 . 0^9,14] -4-heptadece
, 11-methyl-12-carboxymethylhexacyclo
B [6.6.1.1^3,6 . 1 ^10,13 . 0^2,7 . 0^9,14]
Hexacycloheptadecene derivatives such as -4-heptadecene
Body, octacyclo [8.8.0.1^2,9 . 1^4,7 . 1
^11,18 . 1^13,16 . 0^{3, 8} . 0^12,17 ] -5-docose
, 14-methyloctacyclo [8.8.0.1^{2, 9} .
1^4,7 . 1^11,18 . 1^13,16 . 0^3,8 . 0^12,17 ] -5
-Docosene, 14-ethyloctacyclo [8.8.0.
1^2,9 . 1^4,7 . 1^11,18 . 1^13,16 . 0^{3, 8} . 0
^12,17 ] -5-docosene, 14-carboxyoctacyclic
B [8.8.0.1^2,9 . 1^4,7 . 1^11,18 . 1
^13,16 . 0^3,8 . 0^12,17 ] -5-docosene, 14-b
Ndyl octacyclo [8.8.0.1^2,9 . 1^4,7 . 1
^11,18 . 1^13,16. 0^3,8 . 0^12,17 ] -5-docose
, 14-carboxymethyloctacyclo [8.8.
0.1^2,9 . 1^4,7 . 1^11,18 . 1^13,16 . 0^3,8 . 0
^12,17 ] -5-Docosene, 14-methoxyoctacyclo
[8.8.0.1^2,9 . 1^4,7 . 1^{11,1 8} . 1^13,16 .
0^3,8 . 0^12,17 ] -5-Docosene, 14-ethoxy
Kutacyclo [8.8.0.1^2,9 . 1^4,7 . 1^11,18 .
1^13,16 . 0^3,8 . 0^12,17 ] -5-docosene, 14-
Methyl-15-carboxymethyloctacyclo [8.
8.0.1^2,9 . 1^4,7 . 1^11,18 . 1^13,16 . 0
^3,8 . 0^12,17 Octacyclodoko such as -5-docosene
Cene derivatives. As monocyclic olefin
Is cyclobutene, cyclopentene, cycloheptene,
Cycloolefins such as cyclooctene;
A dimer of lopentadiene can be mentioned. Especially d
When a ring-containing metathesis polymer containing a tolyl group is used,
Good physical properties are preferable.

These cyclic olefin monomers need not necessarily be used alone, and ring-opening copolymerization can also be carried out by using two or more kinds at an arbitrary ratio.

Further, as the polymerization catalyst used in the present invention,
Is any catalyst capable of ring-opening metathesis polymerization.
May be used as a specific example of the ring-opening metathesis polymerization catalyst.
Is W (N-2,6-C₆ H_Three Prⁱ _Two) (CHBu^t )
(OBu^t )_Two , W (N-2,6-C₆ H_Three Prⁱ _Two)
(CHBu^t ) (OCMe_Two CF_Three )_Two , W (N−2,
6-C₆ H_Three Prⁱ _Two) (CHBu^t ) (OCMe_Two (C
F_Three )_Two )_Two , W (N-2,6-C₆ H_Three Prⁱ _Two) (C
HCMe_Two Ph) (OBu^t )_Two , W (N-2,6-C
₆ H_Three Prⁱ _Two) (CHCMe_Two Ph) (OCMe_Two CF
_Three )_Two , W (N-2,6-C₆ H_Three Prⁱ _Two) (CHCM
e_Two Ph) (OCMe_Two (CF_Three )_Two )_Two, (P in the formula
rⁱ Is an iso-propyl group, Bu^t Is tert-butyl
The group, Me represents a methyl group, and Ph represents a phenyl group. )
Tungsten-based alkylidene catalyst, W (N-2,6-M
e_Two C₆ H_Three ) (CHCHCMePh) (O-Bu^t )
_Two (PMe_Three ), W (N-2,6-Me)_Two C₆ H_Three )
(CHCHCMe_Two ) (O-Bu^t )_Two (PMe_Three ),
W (N-2,6-Me_Two C₆ H_Three ) (CHCHCP
h_Two) (O-Bu^t )_Two (PMe_Three ), W (N-2, 6)
-Me_Two C₆ H_Three ) (CHCHCMePh) (OCMe
_Two (CF_Three ))_Two (PMe_Three ), W (N-2,6-Me)
_Two C₆ H_Three ) (CHCHCMe_Two ) (OCMe_Two (CF
_Three ))_Two (PMe_Three ), W (N-2,6-Me)_Two C₆ H
_Three ) (CHCHCPh_Two ) (OCMe_Two (CF _Three ))_Two 
(PMe_Three ), W (N-2,6-Me)_Two C₆ H_Three ) (C
HCHCMe_Two) (OCMe (CF_Three )_Two )_Two (PMe_Three
 ), W (N-2,6-Me)_Two C₆ H_Three) (CHCHCM
e_Two ) (OCMe (CF_Three )_Two )_Two (PMe_Three ), W
(N-2,6-Me_Two C₆ H_Three ) (CHCHCPh_Two )
(OCMe (CF_Three )_Two )_Two (PMe_Three ), W (N-
2,6-Prⁱ _TwoC₆ H_Three ) (CHCHCMePh) (O
CMe_Two (CF_Three ))_Two (PMe_Three ), W (N-2, 6)
-Prⁱ _TwoC₆ H_Three ) (CHCHCMePh) (OCMe
(CF_Three )_Two )_Two (PMe_Three ), W (N-2,6-Pr)
ⁱ _TwoC₆ H_Three ) (CHCHCMePh) (OPh)_Two (P
Me_Three ), (Pr in the formulaⁱ Is an iso-propyl group, Bu
^t Is a tert-butyl group, Me is a methyl group, and Ph is
Represents a nyl group. ) And other tungsten-based alkylidene
Medium, Mo (N-2,6-Prⁱ _TwoC₆ H_Three ) (CHBu
^t ) (OBu^t )_Two , Mo (N-2,6-Prⁱ _TwoC₆ H
_Three ) (CHBu^t ) (OCMe_Two CF_Three )_Two , Mo (N
−2,6-Prⁱ _TwoC₆ H_Three ) (CHBu^t ) (OCMe
(CF_Three )_Two )_Two , Mo (N-2,6-Prⁱ _TwoC₆ H
_Three ) (CHCMe_Two Ph) (OBu^t )_Two , Mo (N-
2,6-Prⁱ _TwoC₆ H_Three ) (CHCMe_Two Ph) (OC
Me_Two CF_Three )_Two , Mo (N-2,6-Prⁱ _TwoC₆ H
_Three ) (CHCMe_Two Ph) (OCMe (CF_Three )_Two )
_Two , (Pr in the formulaⁱ Is an iso-propyl group, Bu^t Is t
ert-butyl group, Me is methyl group, Ph is phenyl group
Represents ) And other molybdenum alkylidene catalysts, Re
(CBu^t ) (CHBu^t ) (O-2,6-Prⁱ _TwoC₆ 
H_Three )_Two , Re (CBu^t) (CHBu^t ) (O-2-
Bu^t C₆ H_Four )_Two , Re (CBu^t ) (CHBu ^t )
(OCMe_Two CF_Three )_Two , Re (CBu^t ) (CHBu
^t ) (OCMe (CF_Three )_Two )_Two , Re (CBu^t )
(CHBu^t ) (O-2,6-MeC)₆ H_Three ) _Two ,(formula
Bu inside^t Represents a tert-butyl group. ) Such as Reniu
-Based alkylidene catalyst, Ta [C (Me) C (Me) C
HMe_Three ] (O-2,6-Prⁱ _TwoC₆ H _Three )_Three Py, T
a [C (Ph) C (Ph) CHMe_Three ] (O-2,6-
Prⁱ _TwoC ₆ H_Three )_Three Py, (where Me is a methyl group, P
h represents a phenyl group, and Py represents a pyridine group. ) Etc. tongue
Tall alkylidene catalyst, Ru (CHCHCPh)_Two )
(PPh_Three )_Two Cl_Two , (Where Ph represents a phenyl group.
You. ) And other ruthenium-based alkylidene catalysts and titanasic
Lobutanes. The ring-opening metathesis catalyst,
They may be used alone or as a mixture of two or more.

In addition to the above, Olefin Met
athesis (KennethJ Ivin, Aca
demic Press, New York 198
Ring opening metathesis catalyst systems with a combination of a transition metal compound and a Lewis acid as cocatalyst as described in 3), for example molybdenum, tungsten, vanadium,
A ring-opening metathesis catalyst comprising a transition metal halide such as titanium and an organoaluminum compound, an organotin compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium or boron can be used as a co-catalyst.

Specific examples of the transition metal halide include:
MoBr_Two , MoBr_Three , MoBr _Four , MoCl_Four , M
ocl_Five , MoF_Four , MoOCl_Four , MoOF_Four Etc.
Ribden halide, WBr_Two , WBr_Four , WCl
_Two , WCl_Four , WCl_Five , WCl₆ , WF_Four , WI_Two ,
WOBr_Four , WOCl_Four , WOF_Four , WCl_Four (OC₆
H_Four Cl_Two )_Two , Such as tungsten halide, VO
Cl_Three , VOBr_Three , Etc., vanadium halides, T
iCl_Four , TiBr_Four , Etc.
I can do it.

Specific examples of the organometallic compound as a promoter include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride, -Organic aluminum compounds such as n-butylaluminum, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, tetramethyltin, diethyldimethyltin, tetraethyltin,
Dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride,
Organic tin compounds such as dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, and butyltin triiodide;
Organic lithium compounds such as n-butyllithium, organic sodium compounds such as n-pentyl sodium, methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesium bromide, t-butylmagnesium chloride, allylmagnesium chloride and the like Examples thereof include organic magnesium compounds, organic zinc compounds such as diethyl zinc, organic cadmium compounds such as diethyl cadmium, and organic boron compounds such as trimethyl boron, triethyl boron, and tri-n-butyl boron.

The molar ratio of the cyclic olefin monomer to the ring-opening metathesis catalyst is such that tungsten, molybdenum, rhenium, tantalum,
Alternatively, in the case of an alkylidene catalyst such as ruthenium or titanacyclobutane, the amount is 0.01 to 10 mol, preferably 0.1 to 5 mol. In a ring-opening metathesis catalyst comprising a transition metal halide and an organometallic compound, the transition metal halide is 0.001 to 5 mol, preferably 0.01 to 3 mol, and the organometallic compound as a promoter is 0.005 mol. The range is from 10 to 10 mol, preferably from 0.02 to 5 mol.

Solvents used in the ring-opening metathesis polymerization include tetrahydrofuran, diethyl ether,
Dibutyl ether, ethers such as dimethoxyethane, benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, pentane, hexane, aliphatic hydrocarbons such as heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane,
Examples include aliphatic cyclic hydrocarbons such as decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, and trichlorobenzene. These may be used in combination of two or more.

Further, in order to control the molecular weight, ethylene, propylene, 1-butene, isobutene, styrene,
Ring-opening metathesis polymerization may be performed in the presence of an olefin such as 1-hexene, 4-methylpentene, and hexadiene.

In the ring-opening metathesis polymerization, the concentration of the monomer / ring-opening metathesis catalyst in the solvent varies from 0.1 to 100, depending on the reactivity of the monomer and the solubility in the polymerization solvent.
The reaction is usually performed at a reaction temperature of -30 to 150 ° C. for 1 minute to 10 hours, and the reaction is terminated with a deactivator such as an aldehyde, a ketone, or an alcohol, and the ring-opening metathesis polymer is obtained. A solution can be obtained.

The ring-opening metathesis polymer obtained by the above method can be hydrogenated using a hydrogenation catalyst.

Examples of the hydrogenation catalyst in the hydrogenation reaction of the ring-opening metathesis polymer of a cyclic olefin monomer include:
Known ones can be used. As a specific example, a heterogeneous catalyst is a supported metal catalyst in which a metal such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina, titania, magnesia, diatomaceous earth, synthetic zeolite, and the like. The catalyst includes nickel naphthenate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, dichlorobis (triphenylphosphine) palladium, chlorotris (tri Phenylphosphine) rhodium, dichlorotetrakis (triphenylphosphine)
Examples thereof include ruthenium and dihydridotetrakis (triphenylenephosphine) ruthenium.

As the solvent used in the hydrogenation reaction of the ring-opening metathesis polymer, any solvent may be used as long as it dissolves the ring-opening metathesis polymer and does not hydrogenate the solvent itself. Ethers, ethers such as dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, pentane, hexane,
Aliphatic hydrocarbons such as heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and decalin; halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, trichlorobenzene, etc. And these may be used as a mixture of two or more.

The hydrogenated cyclic olefin ring-opening polymer can be produced by isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution and then dissolving it in a solvent. Instead, a method of performing hydrogenation by adding the above-described hydrogenation catalyst may be employed.

The hydrogenation reaction of the ring-opening metathesis polymer is as follows:
The hydrogen pressure is usually normal pressure ~300kg / cm ^2, preferably carried out in the range of 20 to 200 kg / cm ^2, the reaction temperature is a temperature of usually 0 to 200 ° C., a temperature of preferably from room temperature to 150 DEG ° C. Range.

Generally, the weight ratio of the ring-opening metathesis polymer to the hydrogenation catalyst is from 100: 0.005 to 100: 100.
And preferably from 100: 0.01 to 100: 10
It is.

As a method for removing a metal and a metal compound component from a ring-opening metathesis polymer solution of a cyclic olefin-based monomer and a hydrogenated product of the polymer, a solution or slurry of the polymer solution or the hydrogenated product may be used. The treatment is performed by contacting with a basic compound, but after the contact treatment with a basic compound or simultaneously with the contact treatment with an acidic compound, the removal efficiency of the metal and the metal compound component is improved. It becomes possible.

Examples of the basic compound include aliphatic amine compounds such as methylamine, triethylamine, trimethylenediamine, diethylenetriamine and dimethylamine, and aromatic compounds such as aniline, N-methylaniline, N, N-dimethylaniline and O-phenylenediamine. Group amine compounds,
Cyclic amine compounds such as pyridine and biperidine; amide compounds such as ethanediamide and N, N-dimethylacetamide; and hydroxide compounds such as potassium hydroxide, sodium hydroxide, lithium hydroxide, magnesium hydroxide and calcium hydroxide. Can be.

As the acidic compound, formic acid, acetic acid,
Butyric acid, aliphatic carboxylic acids such as oxalic acid, glycolic acid,
Lactic acid, malic acid, tartaric acid, acidic organic compounds such as hydroxyaliphatic carboxylic acids such as citric acid, benzoic acid, aromatic carboxylic acids such as phthalic acid, and the like, and furthermore, metal salts of these acidic organic compounds or hydrochloric acid And an acidic inorganic compound such as sulfuric acid.

These basic compounds and acidic compounds may be used in combination of two or more kinds at any ratio. The addition amount is 10% by weight based on the ring-opening metathesis polymer of the cyclic olefin monomer or the hydrogenated polymer.
0: 0.001 to 100: 100, preferably 100: 0.01 to 100: 10.

The temperature at which the contact treatment is carried out is usually -30.degree.
0 ° C., preferably 0 ° C. to 100 ° C. The processing time is generally 1 minute to 12 hours, preferably 5 minutes to 3 hours.

The contact treatment may be performed in any atmosphere, but is usually performed in an atmosphere of an inert gas such as nitrogen or argon, but may be performed in an atmosphere of a hydrogen gas, a carbon dioxide gas, or air. Good.

The method for recovering the polymer from the ring-opening metathesis polymer solution or slurry or the hydrogenated polymer solution or slurry which has been subjected to the contact treatment with the above-mentioned basic compound and acidic compound is not particularly limited. Can be used. For example, in the case of a solution, a method may be mentioned in which the solution is discharged into a poor solvent under stirring to coagulate the ring-opening metathesis polymer or a hydrogenated product of the polymer, and is recovered by filtration, centrifugation, decantation, or the like. In the case of slurry,
A method of collecting by filtration, centrifugation or the like can be used.

The metal and metal compound components are obtained by subjecting the above ring-opening metathesis polymer of a cyclic olefin monomer or a hydrogenated product of the polymer to a basic compound and an acidic compound without contact with water. The ring-opening metathesis polymer having excellent optical properties, high rigidity, heat resistance and weather resistance or a hydrogenated product of the polymer can be recovered with extremely high efficiency.

[0035]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The physical properties of the polymers obtained in the examples were measured by the following methods.

Average molecular weight: The obtained cyclic olefin-based ring-opening metathesis polymer or the hydrogenated polymer was dissolved in chloroform using GPC, and 830-RI and UVIDEC-100-VI manufactured by JASCO Corporation were used as detectors. ,
Shodexk-805, 804, 80 as a column
3,802.5, flow rate 1.0 ml at room temperature
The molecular weight was calibrated by a polystyrene standard at / min.

Glass transition temperature; DSC-5 manufactured by Shimadzu Corporation
0, 3.5 mg at a rate of 10 ° C./min in nitrogen
Using a powder of a cyclic olefin-based ring-opening metathesis polymer or a hydrogenated product of the polymer.

Molybdenum and tungsten concentrations; a finely weighed powder of a cyclic olefin-based ring-opening metathesis polymer or a hydrogenated polymer thereof was pyrolyzed in an oven at 500 ° C. for 3 hours, and the remaining metal was analyzed by thiocyanic acid spectrophotometry. Quantified.

Ruthenium concentration: The powder of the hydrogenated cyclic olefin-based ring-opening metathesis polymer was ashed using a microwave type wet ashing device and quantified by an ICP measuring device.

Hydrogenation rate: The powder of the hydrogenated cyclic olefin-based ring-opening metathesis polymer was dissolved in deuterated chloroform, and δ = 4.5 to 6.6 using 90 MHz-NMR.
The magnitude at which the peak attributed to the carbon-carbon double bond of the main chain at 0 ppm was reduced by the hydrogenation reaction was calculated.

Example 1 Under a nitrogen atmosphere, 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene (3.0 g, 16.26 mmol
l) was dissolved in tetrahydrofuran (120 ml) and stirred. Mo ring as a ring-opening metathesis polymerization catalyst
_{(N-2,6-C 6 H} 3 Pr i 2) (CHCMe 2 Ph)
(OBu ^t ) ₂ (90 mg, 0.162 mmol) was added and reacted at room temperature for 1 hour. Thereafter, benzaldehyde (84 mg, 0.810 mmol) was added and the mixture was stirred for 30 minutes to stop the reaction.

Trimethylenediamine (120 mg, 1.62 mmol) was added to the ring-opening metathesis polymer solution, and the mixture was stirred at room temperature for 30 minutes, and then methanol (600 ml) was added.
In addition, a ring-opening metathesis polymer was precipitated, separated by filtration, vacuum-dried, and again dissolved in tetrahydrofuran (60 ml). Citric acid (310 mg, 1.62)
mmol). After stirring at room temperature for 30 minutes as it was, the solution was added to methanol (300 ml) to precipitate a ring-opening metathesis polymer, which was separated by filtration and vacuum-dried to obtain a white powdery ring-opening metathesis polymer. The weight average molecular weight Mw of the recovered ring-opening metathesis polymer measured by GPC was 17,200, and the number average molecular weight Mn was 171.
30, Mw / Mn was 1.00, and the glass transition temperature measured by DSC was 243 ° C. The molybdenum metal concentration was 30 ppm.

Example 2 As a ring-opening metathesis polymerization catalyst, Mo (N-2,6-C _{6
^{H 3 Pr i 2) (CHCMe}} 2 Ph) (OBu t) 2 in place of _{W (N-2,6-C 6} H 3 Me 2) (CHCHCM
ePh) (OBu ^t ) ₂ (PMe ₃ ) (100.43 m
g, 0.162 mmol) to carry out ring-opening metathesis polymerization and removal of metal compound components in the same manner as in Example 1.

The weight average molecular weight Mw of the recovered ring-opening metathesis polymer measured by GPC was 18,500, the number average molecular weight Mn was 18450, Mw / Mn was 1.00, and D
The glass transition temperature measured by SC was 245 ° C. The tungsten metal concentration was 19 ppm.

Example 3 Ring-opening metathesis polymerization was carried out in the same manner as in Example 1, and trimethylenediamine (120 mg, 1.62 mmol) and citric acid (310 mg, 1.62 mmol) were simultaneously added. The weight average molecular weight Mw of the recovered ring-opening metathesis polymer measured by GPC was 17,600, the number average molecular weight Mn was 17530, Mw / Mn was 1.00, and DS
The glass transition temperature measured at C was 243 ° C. The molybdenum metal concentration was 27 ppm.

Example 4 Under a nitrogen atmosphere, 8-cyanotetracyclo [4.4.0.1 ^2,5 .1 was placed in a 500 ml flask equipped with a magnetic stirrer.
1 ^7,10 ] -3-dodecene (10.00 g, 54.20 m
mol) was dissolved in tetrahydrofuran (400 ml) and stirred. In addition, M is used as a ring-opening metathesis polymerization catalyst.
_{o (N-2,6-C 6} H 3 Pr i 2) (CHCMe 2 P
h) (OBu ^t ) ₂ (300 mg, 0.540 mmol)
l) was added and reacted at room temperature for 1 hour. Thereafter, benzaldehyde (252 mg, 2.700 mmol) was added and 3
The reaction was stopped by stirring for 0 minutes.

This ring-opening metathesis polymer solution was added to methanol (2000 ml) to precipitate a ring-opening metathesis polymer.
After washing in 1), vacuum drying was performed to obtain 10.00 g of ring-opening metathesis polymer powder.

Thereafter, in a 5000 ml autoclave, 10.00 g of the ring-opening metathesis polymer powder and dihydridotetrakis (triphenylphosphine) ruthenium (0.050 g, 0.043 mmol) as a hydrogenation catalyst were added.
l) in tetrahydrofuran (880 ml)
After a hydrogenation reaction was performed at 100 ° C. and a hydrogen pressure of 85 kg / cm ² for 5 hours, the temperature was returned to room temperature, and hydrogen gas was released.

This hydrogenated solution of the ring-opening metathesis polymer is concentrated to half the volume, and trimethylene diamine (40%) is concentrated.
0 mg, 5.40 mmol) and stirred at room temperature for 30 minutes, and then added to methanol (2000 ml) to precipitate a hydrogenated ring-opening metathesis polymer. The polymer was dissolved again in tetrahydrofuran (300 ml) and citric acid ( 1.033 g, 5.40 mmol). After stirring for 30 minutes at room temperature, methanol (1500 m
In addition, a hydrogenated product of the ring-opening metathesis polymer was precipitated in addition to l), and separated by filtration, followed by vacuum drying to obtain a hydrogenated product of the ring-opening metathesis polymer in the form of a white powder. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer calculated from ¹ H-NMR did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 1810
0, the number average molecular weight Mn is 18020, and the Mw / Mn is 1.
The glass transition temperature measured by DSC was 206
° C. The molybdenum metal concentration was 27 ppm, and the ruthenium metal concentration was 52 ppm.

Comparative Example 1 Ring-opening metathesis polymerization was carried out in the same manner as in Example 1, and the resulting ring-opening metathesis polymer solution was dissolved in methanol (600 ml).
Then, a ring-opening metathesis polymer was precipitated, separated by filtration, washed with methanol (300 ml), and dried in vacuo to obtain a ring-opening metathesis polymer powder. The weight average molecular weight Mw of the recovered polymer measured by GPC was 17,500, the number average molecular weight Mn was 17410, and Mw / M
n was 1.00, and the glass transition temperature measured by DSC was 236 ° C. The molybdenum metal concentration is 430.
ppm.

Comparative Example 2 Ring-opening metathesis polymerization was carried out in the same manner as in Example 1, and the resulting ring-opening metathesis polymer solution was dissolved in methanol (600 ml).
In addition, a ring-opening metathesis polymer was precipitated. The recovered polymer was dissolved in 1,2-dichloroethane (100 ml), a 1% by weight aqueous solution of trisodium nitrilotriacetate (100 ml) was added, and the mixture was stirred at room temperature for 30 minutes. After standing, the mixture was separated into a 1,2-dichloroethane phase and an aqueous phase, and the aqueous phase was removed. After repeating this operation three times, the resultant was washed three times with water and added to methanol (500 ml) to precipitate a ring-opening metathesis polymer, separated by filtration, further washed with methanol (300 ml), and then dried under vacuum. Thus, a ring-opening metathesis polymer powder was obtained. The weight average molecular weight Mw of the recovered polymer measured by GPC was 17470, the number average molecular weight Mn was 17400, Mw / Mn was 1.00, and D
The glass transition temperature measured by SC was 236 ° C. The molybdenum metal concentration was 437 ppm.

Comparative Example 3 Ring-opening metathesis polymerization and hydrogenation were carried out in the same manner as in Example 4 to obtain a hydrogenated product of a ring-opening metathesis polymer.

This hydrogenated solution of the ring-opening metathesis polymer was concentrated to half the volume, and methanol (2000 m
In addition, a hydrogenated product of the ring-opening metathesis polymer was precipitated in addition to l), separated by filtration and dried in vacuo to obtain a hydrogenated product of the ring-opening metathesis polymer in the form of a pale yellow powder. The hydrogenation rate calculated from ¹ H-NMR of the obtained hydrogenated ring-opening metathesipolymer showed no peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 1820
0, number average molecular weight Mn is 18,150, Mw / Mn is 1.
The glass transition temperature measured by DSC was 202
° C. The molybdenum metal concentration is 445 ppm,
The ruthenium metal concentration was 366 ppm.

[0055]

The cyclic olefin-based ring-opening metathesis polymer and its hydrogenated product recovered by the purification method of the present invention have extremely small amounts of residual metal and metal compound components which cause coloration and decomposition deterioration. It has excellent optical properties, electrical properties, high rigidity, heat resistance, weather resistance, and the like.

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Tadashi Asanuma 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemicals Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula [1] (Wherein, R ^{1 to} R ⁴ may be the same or different, and each represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen,
Selected from halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups of from 1 to 12, and x represents an integer of from 0 to 3. From the ring-opening metathesis polymer of the cyclic olefinic monomer represented by the above) or a hydrogenated product of the polymer, the metal and metal compound components derived from the polymerization catalyst or the hydrogenation catalyst contained therein are converted into water A method for purifying a cyclic olefin-based ring-opening metathesis polymer, which comprises removing a base compound and an acidic compound by contacting and treating the base compound without contacting the base compound with the base compound and the acidic compound. 2. The method according to claim 1, wherein the basic compound is an amino compound. 3. The method according to claim 1, wherein the acidic compound is a carboxylic acid compound.