JP2017203106A - Method for producing norbornene-diene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a norbornene-diene copolymer that can efficiently produce a norbornene-diene copolymer with a high molecular weight.SOLUTION: A method for producing a norbornene-diene copolymer includes copolymerization of a monomer containing norbornene and diene, using a catalyst containing a metal atom of group 4.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a norbornene-diene copolymer.

Conventionally, a method for producing a norbornene-diene copolymer by copolymerizing norbornene and a diene is known.
For example, in the Example of patent document 1, norbornene and a diene are copolymerized using the catalyst (nickel catalyst) containing a nickel atom.

JP 2002-249527 A

  Under these circumstances, when the present inventors copolymerized norbornene and diene using a nickel catalyst with reference to the example of Patent Document 1, it is difficult to increase the molecular weight and the physical properties as a polymer may be insufficient. It became clear that there was. It was also found that a long time must be spent in the polymerization in order to sufficiently increase the molecular weight.

  Then, in view of the said situation, this invention aims at providing the manufacturing method of the norbornene-diene copolymer which can manufacture a norbornene-diene copolymer with a high molecular weight efficiently.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a catalyst containing a Group 4 metal atom as a catalyst.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A method for producing a norbornene-diene copolymer, in which a monomer containing a group 4 metal atom is used to copolymerize a monomer containing norbornene and a diene.
(2) The method for producing a norbornene-diene copolymer according to (1), wherein the group 4 metal atom is a titanium atom.
(3) The method for producing a norbornene-diene copolymer according to the above (1) or (2), wherein the monomer further contains an olefin.

  As shown below, according to the present invention, it is possible to provide a method for producing a norbornene-diene copolymer that can efficiently produce a norbornene-diene copolymer having a high molecular weight.

Below, the manufacturing method of the norbornene-diene copolymer of this invention is demonstrated.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Method for producing norbornene-diene copolymer]
In the method for producing a norbornene-diene copolymer of the present invention (hereinafter also simply referred to as “the production method of the present invention”), a monomer containing a group 4 metal atom is used to co-polymerize a monomer containing norbornene and a diene. Polymerize.
First, the monomer and the catalyst will be described in detail, and then the polymerization method will be described.

〔monomer〕
The monomer used in the production method of the present invention contains norbornene and diene. The monomer may further contain another monomer.

<Norbornen>
The content of norbornene in the monomer is not particularly limited, but is preferably 1 to 99 mol%, more preferably 10 to 90 mol% in all monomers.

<Diene>
The diene is not particularly limited, and examples thereof include butadiene (for example, 1,3-butadiene), isoprene, chloroprene and the like. Of these, 1,3-butadiene and isoprene are preferable. These dienes can be used alone or in combination of two or more.
The content of diene in the monomer is not particularly limited, but is preferably 1 to 99 mol%, more preferably 2 to 90 mol% in all monomers.

<Other monomers>
The monomer used in the production method of the present invention may further contain another monomer. Such monomers include, for example, olefins; aromatic vinyls; α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid, and maleic anhydride. Products; unsaturated carboxylic esters such as methyl methacrylate, ethyl acrylate, and butyl acrylate; 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, and 5-ethylidene- Non-conjugated dienes such as 2-norbornene can be mentioned.

(Olefin)
The olefin is not particularly limited, but an olefin having 3 to 18 carbon atoms is preferable. Specific examples of olefins include propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, 3-methyl-butene-1, heptene-1, octene-1 and decene-1. Can be mentioned. These olefins can be used alone or in combination of two or more.

(Aromatic vinyl)
The aromatic vinyl is not particularly limited. For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2 , 4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylnaphthalene, dimethylaminomethylstyrene, and dimethylaminoethylstyrene. . Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable. These aromatic vinyls can be used alone or in combination of two or more.

  When the monomer contains another monomer, the content of the other monomer in the monomer is not particularly limited, but is preferably 0.1 to 30 mol%, more preferably 1 to 20 mol% in all monomers. preferable.

〔catalyst〕
The catalyst used in the production method of the present invention is a catalyst containing a Group 4 metal atom (hereinafter also referred to as “specific catalyst”).
The group 4 metal atom represents a group 4 metal atom in the periodic table, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Especially, it is preferable that it is a titanium atom from the reason for which the molecular weight of the copolymer obtained becomes higher. That is, the specific catalyst is preferably a catalyst containing titanium atoms (hereinafter also referred to as “titanium catalyst”). The titanium catalyst is also preferable from the following points (1) to (3).
(1) When the above-described monomer contains another monomer such as an olefin (that is, when a ternary or higher copolymer is produced), the polymerization reaction is more likely to proceed.
(2) The control of the molecular weight of the copolymer by the charging ratio of the monomer and catalyst becomes easier.
(3) The control of the microstructure of the diene becomes easier.

<Preferred embodiment 1>
As a suitable aspect of a specific catalyst, the compound represented by following formula (1) is mentioned, for example.
M (A) _a (B) _b (C) _c (D) _d (1)

In the above formula (1), M represents a Group 4 metal atom. Specific examples of the Group 4 metal atom are as described above.
In said formula (1), A, B, C, and D represent the organic group couple | bonded with M in Formula (1) each independently. The organic group may have a substituent. A, B, C and D may be bonded to each other to form a ring.
In said formula (1), a, b, c, and d represent the integer of 0-4, and satisfy | fill the relational expression of a + b + c + d = 4. When a, b, c, or d is an integer of 2 or more, a plurality of A, B, C, or D may be the same or different.

Examples of the organic group include a hydrogen atom, a halogen atom, an alkyl group (for example, a methyl group, a tert-butyl group) (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), and an alkenyl group (cycloalkenyl group). , Including bicycloalkenyl groups), alkynyl groups, aryl groups (eg, phenyl groups, naphthyl groups, cyclopentadienyl groups, indenyl groups, fluorenyl groups), heterocyclic groups (may be referred to as heterocyclic groups), cyano Group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) ), Ammonio group, acylamino group, a Nocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl Or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphini Examples include a ruamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (—B (OH) ₂ ), a phosphato group (—OPO (OH) ₂ ), and a sulfato group (—OSO ₃ H). It is done.
Specific examples of the substituent are the same as the organic group described above.

  Specific examples of the compound represented by the above formula (1) include compounds described in paragraphs [0055] to [0078] of JP-A No. 2005-162809.

(Preferred embodiment 1A)
As a suitable aspect of the compound represented by the said Formula (1), the compound represented by a following formula (1A) is mentioned, for example.

  Formula (1A)

  In the above formula (1A), M represents a Group 4 metal atom. Specific examples of the Group 4 metal atom are as described above.

In the above formula (1A), X ¹ and X ² are each independently an alkyl group or aryl group which may have a halogen atom having 1 to 10 carbon atoms, or a halogen atom, specifically, Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group and pentyl group, phenyl group and naphthyl group An aryl group such as a group, and a halogen-substituted aryl group such as a pentafluorophenyl group. X ¹ and X ² may have a substituent. Specific examples of the substituent are the same as the organic group described above.

In the above formula (1A), R ^{1 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom and an aryl group which may have a substituent having 1 to 10 carbon atoms, halogen The silyl group which may have an atom and a C1-C10 substituent is shown. Among them, R ¹ to R ³ are each independently preferably an alkyl group or aryl group having 1 to 10 carbon atoms, may contain a halogen atom. Specifically, R ^{1 to} R ¹¹ are methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, t-butyl groups, pentyl groups, hexyl groups and other alkyl groups, phenyl groups, naphthyl groups. And aryl groups such as pentafluorophenyl groups, silyl groups such as unsubstituted silyl groups, trimethylsilyl groups, triethylsilyl groups, and tripropylsilyl groups.
R ² and R ³ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ are bonded to each other to form a ring. It may be formed.
R ^{1 to} R ¹¹ may have a substituent. Specific examples of the substituent are the same as the organic group described above.

  In the production method of the present invention, the amount of the specific catalyst used is not particularly limited, but is preferably 0.00001 to 10 mol%, more preferably 0.0001 to 1 mol%, based on the monomer. A specific catalyst may be used individually by 1 type, or may use 2 or more types together.

[Co-catalyst]
In the production method of the present invention, a promoter may be used together with the specific catalyst described above.
The promoter is not particularly limited, but is preferably an organoaluminum compound. Examples of organoaluminum compounds include aluminoxanes and alkylaluminum compounds.

<Aluminoxane>
The aluminoxane is a product obtained by reaction of trialkylaluminum with water. Examples of the aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Among these, modified methylaluminoxane (modified methylaluminoxane) (MMAO) such as methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane is preferable. These aluminoxanes can be used alone or in combination of two or more.
In addition, you may process an aluminoxane with a phenol compound using phenol compounds, such as 2, 6- di-tert- butyl-p-cresol, with an aluminoxane. Although the usage-amount of a phenol compound is not restrict | limited in particular, It is preferable that it is 0.1-10 with the molar ratio of the phenol compound with respect to the aluminum atom in aluminoxane, and it is more preferable that it is 1-5.

<Alkyl aluminum compound>
The alkylaluminum compound is not particularly limited, but specific examples include alkylaluminum such as triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. And triarylaluminums such as triphenylaluminum and tritylaluminum, and halogen-containing alkylaluminums such as dimethylaluminum chloride and diethylaluminum chloride.

  In the production method of the present invention, the amount of the cocatalyst used when the cocatalyst is an organoaluminum compound is not particularly limited, but the molar ratio of aluminum atoms in the organoaluminum compound to the catalyst is 20 to 10,000. Is preferable, it is more preferable that it is 50-2,000, and it is further more preferable that it is 100-1,000.

[Polymerization method]
The method of copolymerizing the above-described monomer using the above-described specific catalyst is not particularly limited, and examples thereof include a method of stirring the monomer, the specific catalyst, and a co-catalyst as necessary in a solvent. The polymerization temperature is not particularly limited, but is preferably -30 to 100 ° C.

[Norbornene-diene copolymer]
The norbornene-diene copolymer of the present invention is a norbornene-diene copolymer produced by the production method of the present invention.
The norbornene-diene copolymer of the present invention is a binary copolymer of norbornene and diene when the above-mentioned monomer contains only norbornene and diene (one kind), and the above-mentioned monomer further contains another monomer. When it contains and when the monomer mentioned above contains two or more types of dienes, it is a ternary or more copolymer.

In the norbornene-diene copolymer of the present invention, the amount of repeating units derived from norbornene is not particularly limited, but is preferably 1 to 99 mol%, more preferably 10 to 90 mol% in all repeating units. .
In the norbornene-diene copolymer of the present invention, the amount of the repeating unit derived from the diene is not particularly limited, but is preferably 1 to 99 mol%, more preferably 2 to 90 mol% in all repeating units. .
In the norbornene-diene copolymer of the present invention, the amount of the repeating unit derived from norbornene is not particularly limited, but is preferably 0.1 to 30 mol%, and preferably 1 to 20 mol% in all repeating units. More preferred.

The molecular weight of the norbornene-diene copolymer of the present invention is preferably 10,000 or more in terms of number average molecular weight (Mn), and more preferably 10,000 to 1,000,000. The polydispersity (Mw / Mn) is preferably 1 to 5.
In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are standard polystyrene equivalent values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・ Solvent: Tetrahydrofuran ・ Detector: RI detector

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Production of norbornene-diene copolymer]
<Examples 1-8>
2,6-di-tert-butyl-p-cresol (DBC) was added to a hexane / toluene mixed solution of modified methylaluminoxane (MMAO) (molar ratio of DBC to aluminum atom in MMAO: 1.2). Stir at room temperature for 30 minutes.
Monomers shown in Table 1 below were added to the resulting solution in the proportions shown in the same table. Furthermore, 20 μmol of a catalyst containing titanium atoms (titanium catalyst) (the following structure) was added (molar ratio of aluminum atoms in MMAO to titanium atoms in the titanium catalyst: 462) and stirred at room temperature for 1 hour to copolymerize the monomers. (Polymerization solution: 30 ml).
Thereafter, hydrochloric acid and methanol were added to terminate the polymerization. After distilling off the volatile components, the residue was dissolved in toluene and dropped into methanol to separate methanol-insoluble components. In this way, a norbornene-diene copolymer was produced. The norbornene-diene copolymer obtained in Examples 1 to 5 is a binary copolymer of norbornene and diene, and the norbornene-diene copolymer obtained in Examples 6 to 8 is norbornene and diene. Is a terpolymer of olefin and olefin.

Titanium catalyst (where t-Bu represents a t-butyl group)

<Comparative Examples 1-2>
2,6-di-tert-butyl-p-cresol (DBC) was added to a hexane / toluene mixed solution of modified methylaluminoxane (MMAO) (molar ratio of DBC to aluminum atom in MMAO: 1.2), and 6.0 mg of nickel bis (2,4-pentadionate) (nickel catalyst) was added and stirred at room temperature for 30 minutes. Monomers shown in Comparative Examples 1 and 2 in Table 1 below were added to the resulting solution in the proportions shown in the same table, and the mixture was stirred at room temperature for 1 hour to copolymerize the monomers (polymerization solution: 30 ml).
Thereafter, hydrochloric acid and methanol were added to terminate the polymerization. After distilling off the volatile components, the residue was dissolved in toluene and dropped into methanol to separate methanol-insoluble components. In this way, a norbornene-diene copolymer was produced. The norbornene-diene copolymer obtained in Comparative Example 1 is a binary copolymer of norbornene and diene, and the norbornene-diene copolymer obtained in Comparative Example 2 is composed of norbornene, diene and olefin. A terpolymer.

[Evaluation]
<Measurement of molecular weight>
The obtained norbornene-diene copolymer was measured for number average molecular weight (Mn) and polydispersity (PDI = Mw / Mn). Some results are shown in Table 1. The method for measuring the number average molecular weight and polydispersity is as described above.

In Table 1, the column “Catalyst” represents the catalyst used.
In Table 1, the “yield” column represents the amount [g] of the norbornene-diene copolymer obtained.
In Table 1, the column of “activity” represents “amount of norbornene-diene copolymer obtained [kg]” / “amount of catalyst used [mol]” / “polymerization time [hour]”.
In Table 1, the “polymer” column represents the amount [mol%] of repeating units derived from each monomer in all repeating units in the obtained norbornene-diene copolymer. The amount of repeating units derived from each monomer in the norbornene-diene copolymer was determined by ¹ H NMR measurement (nuclear magnetic resonance measurement) (solvent: 1,1,2,2-tetrachloroethane-d ₂ ).

The norbornene-diene copolymer produced by the production method of Examples 1 to 5 using a specific catalyst is a norbornene-diene copolymer produced by the production method of Comparative Example 1 using a catalyst other than the specific catalyst. The molecular weight was higher than that of (binary copolymer). In Comparative Example 1, in order to make the molecular weight of the obtained norbornene-diene copolymer the same as that of the norbornene-diene copolymer produced by the production methods of Examples 1 to 5, the polymerization time was set to 1 It was necessary to extend from time to about 70 hours.
Similarly, the norbornene-diene copolymer produced by the production methods of Examples 6 to 8 using the specific catalyst is the norbornene-diene produced by the production method of Comparative Example 2 using a catalyst other than the specific catalyst. Compared to the copolymer, the molecular weight was higher (ternary copolymer). In Comparative Example 2, in order to make the molecular weight of the obtained norbornene-diene copolymer the same as that of the norbornene-diene copolymer produced by the production methods of Examples 6 to 8, the polymerization time was set to 1. It was necessary to extend from time to about 70 hours.
From the above results, it was found that the production method of the present example can efficiently produce a norbornene-diene copolymer having a high molecular weight.

Claims (3)

  A process for producing a norbornene-diene copolymer, wherein a monomer containing a group 4 metal atom is used to copolymerize a monomer containing norbornene and a diene.   The method for producing a norbornene-diene copolymer according to claim 1, wherein the Group 4 metal atom is a titanium atom.   The method for producing a norbornene-diene copolymer according to claim 1 or 2, wherein the monomer further contains an olefin.