PRODUCTION METHOD FOR CYCLIC OLEFIN COPOLYMER AND CATALYST COMPOSITION FOR COPOLYMERIZATION OF NORBORNENE MONOMER AND ETHYLENE

Abstract

A production method for a cyclic olefin copolymer which is capable of efficiently producing a cyclic olefin copolymer by copolymerizing monomers including a norbornene monomer and ethylene while suppressing the formation of a polyethylene-like impurity, and a catalyst composition for the copolymerization of a norbornene monomer and ethylene. Monomers including a norbornene monomer and ethylene are polymerized in the presence of a metal-containing catalyst, and the metal-containing catalyst has a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of the periodic table and an atom of Group 15 of the periodic table.

Claims

1. A method for producing a cyclic olefin copolymer comprising a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, the method comprising: charging at least the norbornene monomer and the ethylene as monomers into a polymerization vessel, and polymerizing the monomers in the polymerization vessel in presence of a metal-containing catalyst, the metal-containing catalyst having a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of periodic table and an atom of Group 15 of periodic table, wherein the metal-containing catalyst is a metal-containing compound represented by formula (a1): ##STR00016## wherein in the formula (a1), M represents Ti, Zr or Hf, X represents an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or a halogen atom, L.sup.1 represents a group represented by formula (a1a) or (a1b): ##STR00017## wherein in the formula (a1a), R.sup.a1 to R.sup.a5 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or an inorganic substituent, two groups adjacent on the 5-membered ring of R.sup.a1 to R.sup.a5 are optionally bonded to each other to form a ring, wherein in the formula (a1b), R.sup.a6 to R.sup.a8 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or an inorganic substituent, two groups selected from R.sup.a6 to R.sup.a8 are optionally bonded to each other to form a ring, wherein the organic substituent as R.sup.a6 to R.sup.a8 in the formula (a1b) is a group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, an α-naphthylcarbonyl group, a β-naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a monosubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and a disubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and L.sup.2 represents the group represented by the formula (a1b).

2. The method for producing a cyclic olefin copolymer according to claim 1, wherein the atom of Group 15 of the periodic table is a phosphorus atom.

3. (canceled)

4. The method for producing a cyclic olefin copolymer according to claim 1, wherein the transition metal of Group 4 of the periodic table is Ti.

5. The method for producing a cyclic olefin copolymer according to claim 1, wherein the polymerizing of the monomers is performed in the presence of the metal-containing catalyst and a co-catalyst.

6. The method for producing a cyclic olefin copolymer according to claim 5, wherein the co-catalyst comprises at least one of an aluminoxane and a borate compound.

7. The method for producing a cyclic olefin copolymer according to claim 1, wherein the polymerizing of the monomers is performed in the presence of a hydrocarbon solvent.

8. The method for producing a cyclic olefin copolymer according to claim 1, wherein a DSC curve obtained in measurement of a sample of the cyclic olefin copolymer according to a method defined in JIS K7121 using a differential scanning calorimeter in a nitrogen atmosphere under a condition of a rate of temperature increase of 20° C./min shows no peak of a melting point assigned to a polyethylene-like impurity in a range of 100° C. to 140° C.

9. A catalyst composition for copolymerization of a norbornene monomer and ethylene, comprising a metal-containing catalyst having a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of periodic table and an atom of Group 15 of periodic table, wherein the metal-containing catalyst is a metal-containing compound represented by formula (a1): ##STR00018## wherein in the formula (a1), M represents Ti, Zr or Hf, X represents an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or a halogen atom, L.sup.1 represents a group represented by formula (a1a) or (a1b): ##STR00019## wherein in the formula (a1a), R.sup.a1 to R.sup.a5 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or an inorganic substituent, two groups adjacent on the 5-membered ring of R.sup.a1 to R.sup.a5 are optionally bonded to each other to form a ring, wherein in the formula (a1b), R.sup.a6 to R.sup.a8 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or an inorganic substituent, two groups selected from R.sup.a6 to R.sup.a8 are optionally wherein the organic substituent as R.sup.a6 to R.sup.a8 in the formula (a1b) is a group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, an α-naphthylcarbonyl group, a β-naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a monosubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and a disubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and L.sup.2 represents the group represented by the formula (a1b) wherein the norbornene monomer is one or more selected from a norbornene and a substituted norbornene represented by formula (I): ##STR00020## wherein in the formula (I), R.sup.1 to R.sup.8 are identical to or different from one another, and selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms, R.sup.9 to R.sup.12 are identical to or different from one another, and selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an unsubstituted aromatic hydrocarbon group, and an aralkyl group, R.sup.9 and R.sup.10 or R.sup.11 and R.sup.12 are not taken together to form a divalent hydrocarbon group, R.sup.9 or R.sup.10 and R.sup.11 or R.sup.12 optionally form a ring with each other, the ring that R.sup.9 or R.sup.10 and R.sup.11 or R.sup.12 form is not a ring having a double bond, n represents 0 or a positive integer, when n is two or more, R.sup.5 to R.sup.8 are identical to or different from each other in the respective repeating units, and when n is 0, at least one of R.sup.1 to R.sup.4 and R.sup.9 to R.sup.12 is not a hydrogen atom.

10. The catalyst composition for the copolymerization of the norbornene monomer and the ethylene according to claim 9, wherein the atom of Group 15 of the periodic table is a phosphorus atom.

11. (canceled)

12. The catalyst composition for the copolymerization of the norbornene monomer and the ethylene according to claim 9, wherein the transition metal of Group 4 of the periodic table is Ti.

13. The catalyst composition for the copolymerization of the norbornene monomer and the ethylene according to claim 9, further comprising a co-catalyst.

14. The catalyst composition for the copolymerization of the norbornene monomer and the ethylene according to claim 13, wherein the co-catalyst comprises at least one of an aluminoxane and a borate compound.

Description

EXAMPLES

[0088] In the following, the present invention is specifically described with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 17, and Comparative Examples 1 to 3

[0089] In Examples 1 to 15, the compound C1 shown below was used as a metal-containing catalyst in the production of a cyclic olefin resin composition.

##STR00013##

[0090] In Examples 16 to 17, the compound C2 shown below was used as a metal-containing catalyst.

##STR00014##

[0091] In Comparative Examples 1 to 3, the compound C3 shown below was used as a metal-containing catalyst.

##STR00015##

[0092] In the Examples and Comparative Examples, the following co-catalysts were used.

CC1: a 6.5% by mass (in terms of the content of the Al atom) MMAO-3A solution in toluene (a solution of a methylisobutylaluminoxane represented by [(CH.sub.3).sub.0.7 (iso-C.sub.4H.sub.9).sub.0.3AlO].sub.n; from Tosoh Finechem Corporation; this solution contained 6 mol % of trimethylaluminum based on the total Al)
CC2: a 9.0% by mass (in terms of the content of the Al atom) TMAO-211 solution in toluene (a solution of methylaluminoxane; from Tosoh Finechem Corporation; this solution contained 26 mol % of trimethylaluminum based on the total Al)
CC3: N-methyldialkylammonium tetrakis(pentafluorophenyl)borate (alkyl: C14 to C18 (average: C17.5) (from Tosoh Finechem Corporation)
CC4: triisobutylaluminum (from Tosoh Finechem Corporation)

[0093] To a 150 mL, adequately-dried stainless-steel autoclave containing a stirring bar were added a polymerization solvent specified in Table 2 and 2-norbornene in an amount specified in Table 2 (30 to 160 mmol). Then, a co-catalyst specified in Table 1 was added as described below. In Examples 1 to 7 and Comparative Examples 1 to 3, CC1 or CC2 was added. In Examples 8 to 17, CC4 was added, followed by the addition of the solution of the metal-containing catalyst, and thereafter CC3 was added. The solution of the metal-containing catalyst was prepared in toluene. After the addition of the co-catalyst as described above, the autoclave was heated until the polymerization temperature specified in Table 2 was reached, and then the solution of the metal-containing catalyst was added such that the amount of the metal-containing catalyst was as specified in Table 1. Then, an ethylene pressure (gauge pressure) of 0.9 MPa was applied, and the time when 30 seconds had elapsed after the application of the ethylene pressure was considered to be the polymerization starting point. However, in Examples where CC3 was used in combination, the solution of the metal-containing catalyst was added such that the amount of the metal-containing catalyst was as specified in Table 1, then the solution of CC3 prepared in the polymerization solvent specified in Table 2, and thereafter an ethylene pressure (gauge pressure) of 0.9 MPa was applied. Incidentally, the total volume of the monomer solution immediately before the application of the ethylene pressure was 80 mL. Fifteen minutes after the start of the polymerization, the ethylene feed was stopped, the pressure was carefully reduced to the atmospheric pressure, and then isopropyl alcohol was added to the reaction solution to quench the reaction. Subsequently, the polymerization solution was poured into a solvent mixture of 300 mL of acetone, 200 mL of methanol or isopropyl alcohol, and 5 mL of hydrochloric acid to precipitate the copolymer. The copolymer was collected via suction filtration, followed by washing with acetone and methanol, and then the copolymer was dried in vacuo at 110° C. for 12 h, to give a copolymer of norbornene and ethylene. The copolymer yield (kg) per gram of the catalyst, which is calculated from the amount of the catalyst used and the amount of the copolymer obtained thus, is listed in Table 2.

[0094] In addition, the measurement of the glass transition temperature, the thermal analysis of a polyethylene-like impurity, and a turbidity test were performed according to the following methods. The results of these measurements and the test are listed in Table 2.

<Glass Transition Temperature (Tg)>

[0095] The Tg of the cyclic olefin copolymer was measured according to the DSC method (the method defined in JIS K7121). DSC apparatus: differential scanning calorimeter (DSC-Q1000, manufactured by TA Instrument)

measurement atmosphere: nitrogen
condition for temperature increase: 20° C./min

<Thermal Analysis for Impurity>

[0096] The amount of exotherm (mJ/mg) was calculated based on an area of a peak assigned to the melting point of the polyethylene-like impurity, which was observed in the range of 100° C. to 140° C. on the DSC curve obtained in the measurement of the glass transition temperature. A larger calculated amount of exotherm indicates a higher content of the polyethylene-like impurity. It should be noted that “ND” in Table 2 indicates that no peak assigned to the melting point of the polyethylene-like impurity was detected on the DSC curve.

<Turbidity Test>

[0097] After the dissolution of 0.1 g of the obtained cyclic olefin copolymer in 10 g of toluene, the presence or absence of the turbidity in the solution was observed. The case where the turbidity was found was determined to be B, whereas the case where the turbidity was not found was determined to be A.

TABLE-US-00001 TABLE 1 Catalyst Molar ratio: Molar ratio: Molar ratio: Molar ratio: Amount Co- CC1/Transition CC2/Transition CC3/Transition CC4/Transition Type (μmol) catalyst metal metal metal metal Ex. 1 C1 0.5 CC1 5000 — — — Ex. 2 C1 0.5 CC1 5000 — — — Ex. 3 C1 0.5 CC1 5000 — — — Ex. 4 C1 0.5 CC1 2000 — — — Ex. 5 C1 0.5 CC1 5000 — — — Ex. 6 C1 0.5 CC1 5000 — — — Ex. 7 C1 0.5 CC1 5000 — — — Ex. 8 C1 0.5 CC3/CC4 — — 3 2000 Ex. 9 C1 0.5 CC3/CC4 — — 3 2000 Ex. 10 C1 0.5 CC3/CC4 — — 3 500 Ex. 11 C1 0.5 CC3/CC4 — — 3 500 Ex. 12 C1 0.5 CC3/CC4 — — 3 500 Ex. 13 C1 0.5 CC3/CC4 — — 3 500 Ex. 14 C1 0.5 CC3/CC4 — — 3 500 Ex. 15 C1 0.5 CC3/CC4 — — 3 500 Ex. 16 C2 0.5 CC3/CC4 — — 3 500 Ex. 17 C2 0.5 CC3/CC4 — — 3 500 Comp. Ex. 1 C3 1.8 CC2 — 1000 — — Comp. Ex. 2 C3 2.0 CC2 — 1200 — — Comp. Ex. 3 C3 1.8 CC2 — 900 — —

TABLE-US-00002 TABLE 2 Thermal Copolymer Amount of analysis yield per 2-norbornene Polymerization for gram of charged Polymerization temperature Tg impurity catalyst Turbidity (mmol) solvent (° C.) (° C.) (mJ/mg) (kg/g) test Ex. 1 30 Isododecane 90 25 N.D. 14 A Ex. 2 45 Isooctane 90 42 N.D. 13 A Ex. 3 60 Decalin 90 57 N.D. 13 A Ex. 4 85 Decalin 90 79 N.D. 13 A Ex. 5 110 Decalin 90 104 N.D. 12 A Ex. 6 150 Decalin 90 145 N.D. 10 A Ex. 7 160 Toluene 90 151 N.D. 18 A Ex. 8 45 Decalin 90 50 N.D. 15 A Ex. 9 90 Decalin 90 79 N.D. 13 A Ex. 10 90 Decalin 90 88 N.D. 19 A Ex. 11 90 Decalin 100 83 N.D. 23 A Ex. 12 90 Toluene 100 96 N.D. 62 A Ex. 13 90 Decalin 120 77 N.D. 24 A Ex. 14 90 Decalin 140 71 N.D. 17 A Ex. 15 70 Toluene 90 83 N.D. 66 A Ex. 16 70 Toluene 90 91 N.D. 10 A Ex. 17 120 Toluene 90 77 N.D. 11 A Comp. Ex. 1 90 Isododecane 90 72 0.18 6 B Comp. Ex. 2 90 Isooctane 90 81 0.11 2 B Comp. Ex. 3 90 Decalin 90 77 0.10 5 B

[0098] It can be seen from Tables 1 and 2 that in the production of a cyclic olefin copolymer by the polymerization of monomers including a norbornene monomer and ethylene in the presence of a metal-containing catalyst, the use of a metal-containing catalyst having a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of the periodic table (Ti) and a transition metal of Group V of the periodic table (P) results in efficient production of the cyclic olefin copolymer, while suppressing the formation of a polyethylene-like impurity. Since a cyclic olefin copolymer yield of 10 kg or more per gram of the catalyst can be achieved, the production method is practically preferable. On the other hand, in Comparative Example 1 where a metal-containing compound not having a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of the periodic table (Ti) and a transition metal of Group V of the periodic table (P) was used as a catalyst, the cyclic olefin copolymer yield per gram of the catalyst was significantly lower than 10 kg, and, in addition, failed to suppress the formation of the polyethylene-like impurity.