JP3141190B2 - Cyclic conjugated diene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 6-membered cyclic conjugated diene copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Numerous proposals have been made for conjugated diene-based polymers, some of which have been widely used as important industrial materials. Typical conjugated diene-based polymers include homopolymers such as polybutadiene and polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, propylene-butadiene copolymer, styrene-isoprene copolymer, α- Methylstyrene-butadiene copolymer, α-methylstyrene-
Block, graft, taper or random copolymer of isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer, isoprene-methyl methacrylate copolymer, and more These hydrogenated polymers are known as known materials, and plastics, elastomers, machine parts, tires, belts, insulating agents, adhesives, modifiers for other resins, etc., for various purposes as required. -Used in application fields.

[0003] On the other hand, many methods have been proposed for the polymerization of conjugated diene polymers, and they play an extremely important role in industry. In particular, for the purpose of obtaining a conjugated diene-based polymer having improved thermal and mechanical properties, many polymerization catalysts providing a high cis 1,4-bond content have been studied and developed. For example, a catalyst system mainly containing an alkali metal compound such as lithium and sodium, or a composite catalyst system mainly containing a transition metal compound such as nickel, cobalt and titanium is known, and some of them are already known. , Butadiene, isoprene and the like are industrially employed as polymerization catalysts [End. Ing. Che
m. , 48, 784 (1956), Japanese Patent Publication No. 37-819.
No. 8, publication].

On the other hand, in order to achieve a higher cis 1,4-bond content and excellent polymerization activity, rare earth metal compounds and I
Composite catalyst systems comprising organometallic compounds of Group III metals have been studied and developed, and studies on highly stereospecific polymerization have been actively conducted [J. Polym. Sci. , Pol
ym. Chem. Ed. , 18 , 3345 (198
0), Sci, Sinica. , 2/3 , 734 (19
80), Makromol. Chem. Suppl,
4 , 61 (1981), German patent application 2,848,96
No. 4, Rubber Chem. Technol. , 5
8 , 117 (1985)].

[0005] Among these catalyst systems, composite catalysts containing a neodymium compound and an organoaluminum compound as main components include:
It has been confirmed that it has a high cis 1,4-bond content and excellent polymerization activity, and has already been industrialized as a polymerization catalyst for butadiene and the like [Makromol. Chem. , 9
4 , 119 (1981), Macromolecule
s, 15 , 230 (1982)]. However, with recent advances in industrial technology, the market requirements for polymer materials have become increasingly sophisticated, and higher thermal (melting point, glass transition temperature, thermal deformation temperature, etc.) and mechanical properties (tensile) There is a strong demand for the development of a polymer material having elastic modulus, flexural modulus, and the like.

As one of the most powerful means for solving this problem, not only monomers having relatively small steric hindrance, such as butadiene and isoprene, but also monomers having large steric hindrance, that is, cyclic conjugated diene-based monomers, have been proposed. Research activities to improve the structure of polymer chains of conjugated diene polymers by copolymerizing monomers and obtain polymer materials with advanced thermal and mechanical properties have been actively conducted. It has become. However, in the prior art, a catalyst system exhibiting a satisfactory polymerization activity for a monomer having relatively small steric hindrance such as butadiene and isoprene has been proposed, but a monomer having large steric hindrance, that is, a cyclic conjugated diene, has been proposed. As for the system monomer, a catalyst system having a sufficiently satisfactory polymerization activity has not yet been found. In other words, in the prior art, cyclic conjugated diene-based monomers are difficult to homopolymerize, so that not only a high molecular weight polymer cannot be obtained, but also optimization of thermal and mechanical properties to meet various market requirements. Even when the copolymerization with another monomer was attempted for the purpose, only a low molecular weight substance of the oligomer level could be obtained.

That is, an excellent cyclic conjugated diene copolymer which can be sufficiently satisfied as an industrial material has not yet been obtained, and this solution has been strongly desired. J. Am. Che
m. Soc. , 81 , 448 (1959) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene which is a cyclic conjugated diene monomer using a composite catalyst comprising titanium tetrachloride and triisobutylaluminum. A polymerization method is disclosed. The polymerization method described here not only requires a large amount of a polymerization catalyst and a long reaction time, but also has a very low molecular weight of the obtained polymer and has no industrial value.

[0008] Polym. Sci. , Pt. A,
2, the 3277 (1964) are 1,3-cyclohexadiene, a radical, cationic, anionic, polymerization of cyclohexadiene homopolymer polymerized by various methods, such as coordination polymerization are disclosed. In any of the polymerization methods described herein, the molecular weight of the obtained polymer is extremely low in any case, and has no industrial value.

British Patent 1,042,625 discloses a method for polymerizing cyclohexadiene homopolymer in which 1,3-cyclohexadiene is polymerized using a large amount of an organolithium compound as a catalyst. The polymerization method disclosed herein requires the use of as much as 1 to 2% by weight of a catalyst with respect to the monomer, which is not only economically disadvantageous but also has a very low molecular weight. Will be. Further, there is no suggestion or teaching as to the possibility of obtaining a copolymer. On the other hand, in this polymerization method, it is difficult to remove a large amount of catalyst residue remaining in the polymer, and the polymer obtained by this polymerization method has no commercial value.

J. Polym. Sci. , Pt. A,
3 , 1553 (1965) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organolithium compound as a catalyst. The polymer obtained here had a limit of number average molecular weight of 20,000, although the polymerization reaction was continued for 5 weeks. Polym. Prepr. (Amer. Chem.
Soc. , Div. Polym. Chem. ) 12,4
02 (1971) discloses that when 1,3-cyclohexadiene is polymerized using an organolithium compound as a catalyst, the number average molecular weight of the cyclohexadiene homopolymer has a limit of 10,000 to 15,000. For this reason, it is taught that, simultaneously with the polymerization reaction, a transfer reaction accompanied by extraction of lithium cation and a elimination reaction of lithium hydride occur simultaneously.

[0011] Die Makromolekulare
Chemie. , 163 , 13 (1973)
A cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst is disclosed. The oligomeric polymer obtained here has a number average molecular weight of only 6,500. European Polymer J. et al. , 9,8
95 (1973) describes a copolymer of 1,3-cyclohexadiene, butadiene, and isoprene using a π-allyl nickel compound as a polymerization catalyst. However, it has been reported that the polymer obtained here is a very low molecular weight oligomer and has a single glass transition temperature suggestive of a random copolymer.

Polymer Collection, Vol. 34, no. 5,
333 (1977) uses zinc chloride as a polymerization catalyst.
Copolymers of 1,3-cyclohexadiene and acrylonitrile are described. The alternating copolymer obtained here is an oligomer having a very low molecular weight. Makrom
ol. Chem. , 191 , 2743 (1990) disclose 1,3-polystyrene using lithium as a polymerization initiator.
A method for polymerizing cyclohexadiene is described. In the polymerization method described here, it is taught that a transfer reaction accompanied by abstraction of lithium cation and a elimination reaction of lithium hydride occur considerably simultaneously with the polymerization reaction, and the polymerization reaction is performed using polystyryllithium as an initiator. In spite of performing the test, it was reported that at room temperature, a styrene-cyclohexadiene block polymer was not obtained, but only a cyclohexadiene homopolymer was obtained.

Similarly, it was reported that a block copolymer of styrene-cyclohexadiene having a molecular weight of about 20,000 was obtained together with a cyclohexadiene homopolymer in an extremely low yield when blocking was carried out at -10 ° C. using polystyryllithium as an initiator. Have been. However, the copolymer obtained here has not only a very small content of cyclohexadiene block, but also block copolymerization with a chain conjugated diene-based monomer, multiblock or triblock or more radial, There is no suggestion or teaching about blocks and the like. That is, in the prior art, an excellent cyclic conjugated diene-based copolymer which is sufficiently satisfactory as an industrial material has not yet been obtained, and no industrially practicable production method has been known.

[0014]

DISCLOSURE OF THE INVENTION The present invention relates to a novel cyclic conjugated diene system wherein the repeating unit constituting the polymer chain contains a molecular structural unit derived from a cyclic conjugated diene monomer comprising a 6-membered ring. Provided are a copolymer and a method for producing the copolymer.

[0015]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors succeeded in synthesizing a novel cyclic conjugated diene-based copolymer which has never been reported before.
In addition, the repeating unit constituting the polymer chain is a six-membered ring.
The present invention was completed by establishing a technique for introducing a molecular structural unit derived from a cyclic conjugated diene monomer at an arbitrary ratio and form.

That is, the present invention provides: [1] a copolymer in which the repeating unit constituting the polymer chain contains a molecular structural unit derived from a cyclic conjugated diene-based monomer, wherein the polymer chain has the following structure: A cyclic conjugated diene copolymer represented by the formula (I):

Embedded image [Formula (I) represents a composition formula of a polymer. (A) to (D) represent molecular structural units constituting the polymer main chain. 1 to p represent wt% of each molecular structural unit contained in the polymer chain. The number average molecular weight of the polymer is 25,000 to 5,000,000
Range. (A): a molecular structural unit derived from one or more monomers selected from the cyclic conjugated diene monomers represented by the following formula (2) .

Embedded image [In the formula (2), R represents a hydrogen atom or an alkyl
Group, alkenyl group, aryl group, cycloalkyl group,
At least one selected from a chromodienyl group and a heterocyclic group
Species of organic substituents. However, double bonds are not hydrogenated
No. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): a molecular structural unit derived from one or more monomers selected from vinyl aromatic monomers. (D): a molecular structural unit derived from one or more monomers selected from polar monomers. (E): a molecular structural unit derived from one or more monomers selected from ethylene and α-olefin monomers. However, 1 + m + n + o + p = 100, 0.5 ≦ 1
<100, 0 ≦ m <100, 0 ≦ n <100, 0 ≦ o <
100, 0 ≦ p <100, 0 <m + n + o + p <100
It is. ]

[2] The cyclic conjugated diene-based block copolymer according to [1], which has a block unit containing a molecular structural unit derived from the cyclic conjugated diene-based monomer. [3] The cyclic conjugated diene-based copolymer according to [1], comprising a block unit consisting of only a molecular structural unit derived from the cyclic conjugated diene-based monomer. [ 4 ] The cyclic conjugated diene-based monomer is 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative or a cyclic conjugated diene having a carbon-carbon 6-membered ring structure in a molecule thereof [1] to [1]. The cyclic conjugated diene-based copolymer according to any one of [3].

[ 5 ] The polymer chain comprising a cyclic conjugated diene monomer is a copolymer represented by the following formula (I):
A cyclic conjugated diene copolymer in which a polymer chain is polymerized using a complex compound of an organic metal compound containing a Group IA metal as a catalyst.

Embedded image [Formula (I) represents a composition formula of a polymer. (A) to (D) represent molecular structural units constituting the polymer main chain. 1 to p represent wt% of each molecular structural unit contained in the polymer chain. The number average molecular weight of the polymer is 25,000 to 5,000,000
Range. (A): a molecular structural unit derived from one or more monomers selected from the cyclic conjugated diene monomers represented by the following formula (2) .

Embedded image [In the formula (2), R represents a hydrogen atom or an alkyl
Group, alkenyl group, aryl group, cycloalkyl group,
At least one selected from a chromodienyl group and a heterocyclic group
Species of organic substituents. However, double bonds are not hydrogenated
No. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): a molecular structural unit derived from one or more monomers selected from vinyl aromatic monomers. (D): a molecular structural unit derived from one or more monomers selected from polar monomers. (E): a molecular structural unit derived from one or more monomers selected from ethylene and α-olefin monomers. However, 1 + m + n + o + p = 100, 0.5 ≦ 1
<100, 0 ≦ m <100, 0 ≦ n <100, 0 ≦ o <
100, 0 ≦ p <100, 0 <m + n + o + p <100
It is. ]

[ 6 ] A cyclic conjugated diene monomer and one or more monomers copolymerizable therewith are copolymerized using a complex compound of an organic metal compound containing a Group IA metal as a catalyst. The method for polymerizing a cyclic conjugated diene-based copolymer according to any one of [1] to [ 5 ]. [ 7 ] A cyclic conjugated diene monomer and one or two or more monomers copolymerizable therewith are copolymerized using a complex compound containing a Group IA metal and an amine as a catalyst,
The method for polymerizing a cyclic conjugated diene-based copolymer according to [ 7 ]. It is.

The cyclic conjugated diene-based copolymer in the present invention means that the repeating unit constituting the polymer chain is a 6-membered ring.
It is a copolymer containing a molecular structure unit derived from Ranaru cyclic conjugated diene monomer. As a typical cyclic conjugated diene copolymer of the present invention, a cyclic conjugated diene monomer having a 6-membered ring and a molecular structural unit derived from a monomer copolymerizable therewith are contained as a repeating unit. Copolymers can be exemplified.

More specifically, a copolymer containing a cyclic conjugated diene monomer having a 6-membered ring and a molecular structural unit derived from a monomer copolymerizable therewith as a repeating unit of a polymer chain. A polymer can be exemplified. More specifically, a cyclic conjugated diene monomer having a 6-membered ring and a copolymer of a monomer copolymerizable therewith can be exemplified. As the most preferred cyclic conjugated diene-based copolymer, a molecular structural unit derived from a cyclic conjugated diene-based monomer comprising a 6-membered ring contained in its polymer chain is a molecular structural unit containing a cyclohexene ring. Copolymers can be exemplified.

Preferably, a cyclic conjugated diene copolymer is used.
Containing a cyclic conjugated diene monomer comprising a 6-membered ring
Copolymers having block units can be exemplified .
Furthermore, it is derived from a cyclic conjugated diene monomer comprising a 6-membered ring
Has a block unit consisting of only the molecular structural unit
Copolymers can be exemplified . The cyclic conjugated diene monomer (A) in the present invention is a 6-membered cyclic conjugated diene constituted by carbon-carbon bonds. For example , as the cyclic conjugated diene-based monomer (A ), 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative or a cyclic conjugated diene having a 6-membered ring structure in the molecule can be exemplified. The most preferred cyclic conjugated diene monomer is
1,3-cyclohexadiene.

As the other monomer copolymerizable with the cyclic conjugated diene monomer (A) having a six-membered ring of the present invention, there may be mentioned conventionally known monomers polymerizable by anionic polymerization. Can be. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Chain conjugated diene-based monomers (B) such as pentadiene and 1,3-hexadiene; styrene, α-methylstyrene, o-
Methylstyrene, p-methylstyrene, p-tert-
Vinyl aromatic monomers (C) such as butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene, and vinylpyridine; methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, α- Polar vinyl monomers (D ) such as methyl cyanoacrylate; and polar monomers such as ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, and cyclic siloxane; or ethylene and α-olefin monomers (E ) Can be exemplified. These monomers may be used alone or in combination of two or more as necessary.

[0024] The mode of copolymerization is also variously selected as necessary. For example, block copolymerization such as diblock, triblock, tetrablock, multiblock, and radial block, graft copolymerization, taper copolymerization, random copolymerization, and alternate copolymerization can be exemplified. In the cyclic conjugated diene-based copolymer of the present invention, the molecular structural unit composed of another copolymerizable monomer is a molecular structural unit derived by hydrogenation, halogenation, or the like after completion of the polymerization reaction. Is not particularly limited.

[0025] 6 of cyclic conjugated diene copolymer of the present invention
When the content of the molecular structural unit derived from the cyclic conjugated diene monomer composed of a membered ring is defined as X wt%, the value of X cannot be particularly limited because it is variously set depending on the intended use. 0.5 ≦ X <100 wt%
Ri is preferably in the range of 1 ≦ X <100wt%. When the cyclic conjugated diene-based copolymer of the present invention is used in applications / fields requiring high thermal / mechanical properties, it contains a molecular structural unit derived from the cyclic conjugated diene-based monomer. The amount is preferably in the range of 5 ≦ X <100 wt%, particularly preferably in the range of 10 ≦ X <100 wt%, and most preferably in the range of 15 ≦ X <100 wt%.

The molecular weight of the cyclic conjugated diene copolymer of the present invention is not particularly limited because it can be arbitrarily adjusted according to the intended use, but generally the number average molecular weight is 25,000 to 25,000. In the range of 5,000,000, preferably in the range of 25,000 to 3,000,000, and more preferably in the range of 30,000 to 2,000,000.
And particularly preferably 35,000 to 1,0.
In the range of 10,000, most preferably 40,0.
The range is from 00 to 500,000. Number average molecular weight is 2
If it is less than 5,000, it becomes a very fragile solid or viscous liquid, and its value as an industrial material is extremely low. When the number average molecular weight is 5,000,000 or more, unfavorable results in industrial production such as a long polymerization time and a remarkably high melt viscosity are caused. The number average molecular weight in the present invention is a number average molecular weight of a polymer chain in terms of standard polystyrene.

When the cyclic conjugated diene-based copolymer of the present invention is a cyclic conjugated diene-based block copolymer containing a block unit in a polymer chain, the block unit may be
A block unit composed of a molecular structural unit derived from a cyclic conjugated diene monomer composed of a 6-membered ring,
With a block unit composed of a cyclic conjugated diene-based monomer and a molecular structural unit derived from another monomer copolymerizable therewith, and a cyclic conjugated diene-based monomer having a 6-membered ring. Block units consisting of molecular structural units derived from other polymerizable monomers can be designed.If necessary, various block units are designed and polymerized, and these are combined according to the purpose. And a cyclic conjugated diene-based block copolymer.

The block unit of the present invention, when they contain a part or cyclic conjugated diene molecular structural units derived from monomers consisting of all the 6-membered ring, at least 10 minutes child is in blocks It is preferable that molecular structural units derived from a cyclic conjugated diene-based monomer having a 6-membered ring are continuously bonded, and it is more preferable that 20 or more molecular structural units are continuously bonded. It is particularly preferable that 30 or more molecular structural units are continuously bonded in order to improve thermal and mechanical properties.

The method for producing the cyclic conjugated diene-based block copolymer of the present invention includes the following steps: (a) one or two or more 6-membered rings;
A block unit composed of a molecular structural unit derived from a cyclic conjugated diene monomer composed of: (b) a cyclic conjugated diene monomer composed of one or two or more 6-membered rings and copolymerizable therewith (C) a block unit composed of molecular structural units derived from one or more other monomers;
Further, a block unit composed of a molecular structural unit derived from one or two or more other monomers copolymerizable with a cyclic conjugated diene monomer having a 6-membered ring is polymerized according to the purpose. A method of bonding and performing hydrogenation or the like as necessary can be exemplified.

[0030] For example, or block units containing a molecular structure units derived from cyclic conjugated diene monomer consisting of 6-membered ring, the block units derived from cyclic conjugated diene monomer consisting of 6-membered ring Polymerized in advance,
A method of polymerizing one or two or more other monomers copolymerizable therewith from one or both ends of the polymer and performing hydrogenation or the like as necessary; cyclic conjugate comprising a 6-membered ring One or more other monomers copolymerizable with the diene monomer are polymerized in advance, and a cyclic conjugated diene monomer having a six-membered ring from one or both terminals of the polymer is obtained. how, if the body and require the cyclic conjugated diene monomer copolymerizable with one or polymerizing two or more kinds of other monomers, hydrogenation is performed such further depending on the purpose;

A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer having a 6-membered ring or a block unit derived from a cyclic conjugated diene monomer having a 6-membered ring is polymerized. then copolymerizable therewith one or polymerizing two or more other monomers, further 6
A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer comprising a six-membered ring , or a six-membered ring
Sequentially polymerized block units derived from Ranaru cyclic conjugated diene monomer, the method performs such as hydrogen, if necessary: cyclic conjugated diene consists of 6-membered ring monomers copolymerizable with one Alternatively, two or more kinds of other monomers are polymerized in advance, and a block unit containing a molecular structural unit derived from a cyclic conjugated diene-based monomer having a 6-membered ring , or
Polymerizing the block unit derived from a cyclic conjugated diene monomer consisting of 6-membered ring, further said cyclic conjugated diene monomer copolymerizable with one or sequentially two or more other monomers To polymerize and, if necessary, hydrogenate;

A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer having a 6-membered ring or a block unit derived from a cyclic conjugated diene-based monomer having a 6-membered ring is polymerized. Then, one or two or more other monomers copolymerizable therewith are polymerized, and the polymer terminal is terminated with a conventionally known bifunctional or higher coupling agent (for example, dimethyldichlorosilane, methyltrichlorosilane, dimethyl (Dibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, and other halides, epoxidized soybean oil, esters, etc.) bound method performs hydride optionally; molecule derived from a cyclic conjugated diene monomer consisting of 6-membered ring structure Alternatively block containing position, the block units derived from cyclic conjugated diene monomer consisting of 6-membered cyclic polymer previously polymerized,
A method in which a functional group is introduced by reacting a terminal modifier with a polymer terminal, hydrogenation or the like is performed as necessary, and the functional group is bonded to another polymer having a functional group bonded thereto;

A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer having a 6-membered ring or a block unit derived from a cyclic conjugated diene-based monomer having a 6-membered ring is polymerized. Then, one or two or more other monomers copolymerizable therewith are polymerized, and a functional group is introduced by reacting a terminal modifier with a polymer terminal, and hydrogenation or the like is performed as necessary. performed, the method is combined with other polymer having a functional group bonded thereto; 6-membered or ring
And Ranaru cyclic conjugated diene monomer, which the polymerization rate is different copolymerizable one or more other monomers simultaneously polymerized with the tapered block copolymer, hydrogenated if desired A cyclic conjugated diene-based monomer comprising a 6-membered ring and one or more other monomers copolymerizable therewith are charged at different composition ratios and simultaneously polymerized. Examples of the method include a method of performing hydrogenation and the like, and a method of forming various block copolymers as necessary.

The block unit derived from a cyclic conjugated diene monomer having a 6-membered ring is a molecular structural unit derived from one or more other monomers copolymerizable therewith. Is not particularly limited. Further, in the polymer chain cyclic conjugated diene monomer copolymerizable with one or consisting of 6-membered ring is a molecular structure unit derived from two or more other monomers, from 6 membered ring The inclusion of a molecular structural unit derived from the cyclic conjugated diene-based monomer is not particularly limited.

The most preferred molecular structural unit or block unit derived from the cyclic conjugated diene monomer having a 6-membered ring in the present invention is a molecular structural unit containing a cyclohexene ring, or containing or having a cyclohexene ring. It is a block unit that is configured. In the cyclic conjugated diene-based copolymer of the present invention, from the six-membered ring contained in part or all of the repeating units constituting the polymer chain
Comprising molecular structure derived from cyclic conjugated diene monomer single
The position is a molecular structural unit represented by the following formula (2) .

Embedded image [In the formula (2), R represents a hydrogen atom or at least one selected from an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cyclodienyl group, and a heterocyclic group.
Species of organic substituents. However, the double bond is not hydrogenated. )

The molecular structural unit derived from the cyclic conjugated diene monomer having a 6-membered ring according to the present invention is composed of a carbon atom and a hydrogen atom as represented by the above formula (2). , An alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a heterocyclic group or the like, and may have one or more, one or two or more substituents. Examples of the substituent selected from the organic compounds include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a vinyl group, a phenyl group, a tolyl group, a naphthyl group, and a cyclopentadienyl group. , An indenyl group, a pyridyl group, a piperidyl group, or-(CR ¹ R
² ) _-n [R ¹ and R ² are each a hydrogen atom or the same substituent as the above organic compound. n is 1 to 10
Is an integer. And a substituent having a bridge structure on the ring represented by the formula: These may be one kind or a mixture of two or more kinds.

Further , the most preferred polymerization method for obtaining the novel cyclic conjugated diene copolymer of the present invention is disclosed.
That is, the novel cyclic conjugated diene-based copolymer of the present invention is not particularly limited as long as it is a polymer within the scope of the present invention, even if obtained by any polymerization method. Although not particularly preferred, a particularly preferred polymerization method for obtaining the cyclic conjugated diene-based copolymer of the present invention is to use a complex compound of an organometallic compound containing a Group IA metal in the periodic table as a polymerization catalyst. Is a polymerization method.
More specifically, it is a polymerization method characterized by using a mononuclear or dinuclear or higher, preferably dinuclear or polynuclear complex compound of an organometallic compound containing a Group IA metal as a polymerization catalyst. The feature of the polymerization method of the cyclic conjugated diene copolymer disclosed in the present invention is that, in the prior art, the steric hindrance of the cyclic conjugated diene copolymer was difficult to polymerize,
That is, it enables high molecular weight and copolymerization. In particular, from the 6-membered ring , which was considered unsolvable in the prior art
Comprising cyclic conjugated diene monomer itself by abstraction by transfer reactions and IA Group IA metal cations polymer terminal
It is an object of the present invention to suppress the elimination reaction of group hydride by complexing an organic metal compound containing a group IA metal, thereby making it possible to increase the molecular weight and copolymerize.

In the method for polymerizing a cyclic conjugated diene copolymer of the present invention, the group IA metal in the periodic table that can be used as a polymerization catalyst includes lithium, sodium, potassium,
Rubidium, cesium, and francium. Preferred group IA metals include lithium, sodium, and potassium, and particularly preferred group IA metals include lithium. These may be one kind or, if necessary, a mixture of two or more kinds.

The preferred complex compound used in the method for polymerizing a cyclic conjugated diene copolymer of the present invention is an organic metal compound containing a Group IA metal, that is, a complex of an organic lithium compound, an organic sodium compound, and an organic potassium compound. A compound, more specifically a mononuclear or polynuclear complex compound, and as the most preferred complex compound, a mononuclear or dinuclear complex compound of an organolithium compound, particularly preferably a dinuclear or polynuclear complex compound Can be illustrated. The type of compound (complexing agent) that forms a complex with an organic metal compound containing a Group IA metal is not particularly limited, and the Group IA metal cation is most effectively protected according to the polymerization conditions. One or two or more compounds may be appropriately selected. More specifically, an organic compound having an electron donating ability for a Group IA metal is useful as a complexing agent. For example, there is an unshared electron pair that can coordinate to an organic metal compound containing a Group IA metal. polar group _{(RO-, R 2 N-, RS-} , 2- oxazoline group: R represents an alkyl group.) can be exemplified an organic compound having a. More preferred organic compounds include amines, ethers, and thioethers. These complexing agents may be one kind or, if necessary, a mixture of two or more kinds.

In the method for polymerizing a cyclic conjugated diene copolymer of the present invention, amines and ethers are exemplified as preferable complexing agents for organometallic compounds containing Group IA metals from an industrial viewpoint. Can do things. As the most preferred complexing agent, amines can be exemplified. That is, in the polymerization method for obtaining the cyclic conjugated diene-based copolymer of the present invention, a mononuclear or dinuclear or higher complex compound synthesized from an organometallic compound containing a Group IA metal and an amine is used as a polymerization catalyst. It is particularly preferable to use a mononuclear or dinuclear or higher complex compound formed from an organolithium compound and an amine as a polymerization catalyst.

The organic lithium compound suitably used in the method for polymerizing a cyclic conjugated diene copolymer of the present invention includes an organic molecule containing at least one carbon atom or one or two carbon atoms bonded to an organic polymer. Conventionally known compounds containing the above lithium atom, for example, methyl lithium,
Ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, allyl lithium, cyclohexyl lithium, phenyl lithium, hexamethylene dilithium, cyclopentane Oligomers containing lithium atoms in part of the polymer chain, such as dienyllithium, indenyllithium, butadienyldilithium, isoprenyllithium, or polybutadienyllithium, polyisoprenyllithium, and polystyryllithium Alternatively, a conventionally known organic lithium in the form of a polymer can be exemplified.

Preferred organic lithium compounds include methyl lithium, ethyl lithium, n-butyl lithium,
Cyclohexyllithium can be exemplified. As the most preferred organolithium compounds that can be industrially adopted,
n-Butyl lithium can be exemplified. In the method for polymerizing a cyclic conjugated diene-based copolymer of the present invention, the amines, which are the most preferred complexing agents for the organometallic compound containing a Group IA metal, are coordinated with the organometallic compound containing a Group IA metal. R ¹ R ² N-groups (R ¹ and R ^{2 each} represent an alkyl group, an aryl group, or a hydrogen atom, which is a polar group in which an unshared electron pair exists. Or an organic polymer compound containing one or two or more compounds.
Among these amines, the most preferred amines are tertiary (tertiary) amine compounds.

Preferred tertiary (tertiary) amine compounds include trimethylamine, triethylamine, tetramethyldiaminomethane, tetramethylethylenediamine, tetramethyl-1,3-propanediamine, tetramethyl-1,3-butanediamine and tetramethylamine. -1,4-butanediamine, tetramethyl-1,6-hexanediamine, tetramethyl-1,4-phenylenediamine, tetramethyl-1,8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-1,3 -Propanediamine, tetramethyldiethylenetriamine, pentamethyldiethylenetriamine,
Diazabicyclo [2,2,2] octane, 1,4,8,
11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine,
Hexamethylphosphoric triamide can be exemplified. Particularly preferred tertiary amine compounds include tetraethylethylenediamine (TEEDA), tetramethylethylenediamine (TMEDA), tetramethyldiethylenetriamine (TMEDTA), pentamethyldiethylenetriamine (PMDT), diazabicyclo [2,
2,2] octane (DABACO) and hexamethylphosphoric triamide (HMPA). The most industrially preferred tertiary amine compounds include:
Tetramethylethylenediamine (TMEDA) can be exemplified. These compounds may be one kind or a mixture of two or more kinds as necessary, and are appropriately selected according to the purpose.

The method for synthesizing the complex compound of an organometallic compound containing a Group IA metal, which is the most preferred polymerization catalyst in the method for polymerizing a cyclic conjugated diene copolymer of the present invention, is not particularly limited. Conventionally known techniques can be applied depending on the nature of the complexing agent. For example, a method of dissolving an organometallic compound in an organic solvent under an inert gas atmosphere and adding a solution of a complexing agent thereto;
A method of dissolving a complexing agent in an organic solvent under an inert gas atmosphere and adding a solution of an organometallic compound thereto; a method of simultaneously adding an organometallic compound and a complexing agent to an organic solvent under an inert gas atmosphere And the like.

In the preparation of the complex compound of an organometallic compound containing a Group IA metal, which is the most preferred polymerization catalyst in the method for polymerizing a cyclic conjugated diene copolymer of the present invention, a complexing agent molecule and a Group IA compound to be compounded. Amo for each metal atom
When 1 and B mol are used, the general compounding ratio is: A / B = 1000/1 to 1/1000, and A / B = 100/1 to 1/100. Advantageously, especially in the case of a complex compound having two or more nuclei, A / B is preferably in the range of 60/1 to 1/60, and A / B is preferably in the range of 50/1 to 1/50. More preferably, A / B is in the range of 30/1 to 1/30, and A / B is preferably in the range of 20/1 to 1/20. It is most preferable to obtain the combined product in a high yield as a high molecular weight product or a copolymer. If the compounding ratio of the complexing agent and the group IA metal atom is out of the range of the present invention, not only is it economically disadvantageous, but also the complex compound becomes unstable, and a polymerization reaction and a transfer reaction or a group IA metal hydride occur simultaneously with the polymerization reaction. Undesirable results, such as simultaneous occurrence of undesired side reactions such as elimination reaction of phenol.

The polymerization method of the cyclic conjugated diene copolymer of the present invention is carried out by bulk polymerization or solution polymerization in the presence of a complex compound of an organic metal compound containing a Group IA metal as a polymerization catalyst. Polymerization solvents that can be used in the case of solution polymerization include butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane,
aliphatic hydrocarbons such as n-nonane and n-decane; cyclopentane, methylcyclopentane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Ethers such as diethyl ether and tetrahydrofuran can be exemplified. These polymerization solvents may be used alone or, if necessary, in a mixture of two or more.

The amount of the polymerization catalyst used in the method for polymerizing a cyclic conjugated diene copolymer of the present invention is not particularly limited because it varies depending on the purpose. On the other hand, 1 × 10
^-6 mol to ¹ × 10 ^-1 mol, preferably 5 × 10 ^-6 mol to 5 × 10 ^-2 mol.

The polymerization temperature in the polymerization method of the cyclic conjugated diene copolymer of the present invention is set to various different ones as required, but is generally -100 to 150 ° C, preferably -80 to 120 ° C. And particularly preferably -30 to 11
It can be carried out at 0 ° C, most preferably in the range of 0 to 100 ° C. Further, from an industrial viewpoint, it is advantageous to carry out the reaction in the range of room temperature to 80 ° C. The time required for the polymerization reaction varies depending on the purpose and polymerization conditions and cannot be particularly limited. However, it is usually within 48 hours, and particularly preferably 1 to 10 hours. Further, the atmosphere of the polymerization system is preferably an inert gas such as nitrogen, argon, and helium, particularly an inert gas which is sufficiently dried. The pressure of the polymerization system is not particularly limited, as long as the pressure is sufficient to maintain the monomer and the solvent in the liquid phase in the above-mentioned polymerization temperature range. Further, it is necessary to take care that impurities such as water, oxygen, carbon dioxide, etc., which inactivate the polymerization catalyst and the active terminal, do not enter into the polymerization system. As the polymerization reaction format, a conventionally known technique can be adopted. For example, a batch system, a semi-batch system, or a continuous system can be used.

In the method for polymerizing a cyclic conjugated diene-based copolymer of the present invention, prior to polymerization, some or all of the catalyst components are preliminarily reacted or aged to synthesize a complex compound to be a polymerization catalyst in advance. Preparing is a preferred method for obtaining the polymer of the present invention. In particular, the fact that the complex compound is formed before the monomer is added is the most preferable method in the polymerization method of the present invention. Depending on the conditions of these operations, side reactions are suppressed,
It is also possible to achieve effects such as improvement in polymerization activity and narrowing of the molecular weight distribution.

In the method for polymerizing a cyclic conjugated diene copolymer of the present invention, a known terminal modifier (halogen gas, carbon monoxide, ethylene oxide, propylene oxide) may be used, if necessary, after the polymerization reaction has achieved a predetermined polymerization rate. Such as alkylene oxides, alkylene sulfides, isocyanate compounds, imino compounds, cyclohexene oxide, carbon dioxide, acid chlorides, aldehyde compounds, ketone and thioketone compounds, esters, lactones, amide-containing compounds, urea compounds, etc.); Agents (carbon tetrachloride, titanium tetrachloride, silicon tetrachloride, tin tetrachloride, chloroform, bromoform, titanocentrichloride, zirconocentrichloride, methyltrichlorosilane,
Methyltribromosilane, epoxidized soybean oil and the like, polyepoxide, polyisocyanate, polyimine, polyaldehyde, polyketone, polyanhydride, polyester, polyhalide and other compounds), coupling agent (dimethyldichlorosilane, dimethyldibromosilane,
Titanocene dichloride, zirconocene dichloride,
Methylene chloride, methylene bromide, etc.)
The addition of a polymerization stabilizer, an antioxidant and the like is not particularly limited. These terminal modifiers or terminal branching agents may be used alone or in combination of two or more.

Conventionally known stabilizers and antioxidants can be employed as they are.
Organic phosphates, organic phosphites, amines,
It is possible to employ various stabilizers such as sulfur type and antioxidants. The amount of the stabilizer and the antioxidant is generally 0.00.0 parts by weight based on 100 parts by weight of the cyclic conjugated diene copolymer.
Used in the range of 01 to 10 parts by weight. As the polymerization terminator, a known polymerization terminator that deactivates the polymerization active species of the polymerization catalyst of the present invention can be used. Preferred are water, alcohols having 1 to 10 carbon atoms, ketones,
Examples include polyhydric alcohols (such as ethylene glycol, propylene glycol, and glycerin), phenol, carboxylic acids, and halogenated hydrocarbons. The amount of the polymerization terminator added is generally about 100% of the cyclic conjugated diene copolymer.
It is used in a range of 0.001 to 10 wt part with respect to t part. The polymerization terminator may be added before adding the stabilizer and the antioxidant, or may be added simultaneously with the stabilizer and the antioxidant. The polymer may be deactivated by bringing molecular hydrogen into contact with the active terminal of the polymer.

In order to separate and recover the cyclic conjugated diene-based copolymer of the present invention from a polymer solution, a conventionally known technique usually used when recovering a polymer from a polymer solution of a known polymer is used. Can be adopted. For example, a steam coagulation method in which a reaction solution is brought into direct contact with steam; a method in which a polymer poor solvent is added to the reaction solution to precipitate the polymer; a method in which the reaction solution is heated in a vessel to distill off the solvent; attached while distilling off the solvent in an extruder can be exemplified a method of carrying up to pelletization, it can be employed the best method depending on the cyclic conjugated diene copolymer and the nature of the solvent used.

If necessary, the cyclic conjugated diene copolymer of the present invention may be hydrogenated, halogenated, or the like, or a carboxyl group (maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic acid , Methacrylic acid, etc.), a hydroxyl group, an epoxy group (glycidyl methacrylate, glycidyl acrylate, etc.), an amino group (maleimide, etc.), an oxazoline group, an alkoxy group (vinyl silane, etc.), a polar group such as an isocyanate group, and modification or crosslinking. It may be.

In addition, a heat stabilizer depending on its purpose and application,
Antioxidants, ultraviolet absorbers, lubricants, nucleating agents, dyes, pigments,
Additives, reinforcing agents, etc. added to or blended with general polymer materials, such as crosslinking agents, foaming agents, antistatic agents, anti-slip agents, anti-blocking agents, release agents, other polymer materials, inorganic reinforcing materials, etc. Is not particularly limited. The cyclic conjugated diene-based copolymer of the present invention may be used alone or in accordance with the purpose and use of the polymer, other polymer materials, inorganic reinforcing materials, and the like.
It can be used as a composite with an organic reinforcing material.

When the cyclic conjugated diene-based copolymer of the present invention is used as a composite, other polymer materials can be selected from conventionally known organic polymers as necessary. -The amount is not limited. For example, aliphatic polyamides such as nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 636, nylon 1212; and nylon 4T (T: terephthalic acid), nylon 4I
(I: isophthalic acid), nylon 6T, nylon 6I,
Nylon 12T, Nylon 12I, Nylon MXD6
(MXD: metaxylylenediamine) semi-aromatic polyamide and the like; these copolymers, polyamide polymers such as blends, polybutylene terephthalate (PB
T), polyethylene-based polymers such as polyethylene terephthalate (PET), polycarbonate (PC), polyarylate (PAR); polypropylene (PP), polyethylene (PE), ethylene-propylene rubber (EP
R), olefin polymers such as polystyrene (PSt); polybutadiene (PBd), polyisoprene (PI
p), conjugated diene copolymers such as styrene-butadiene rubber (SBR) or hydrides thereof; thiol polymers such as polyphenylene sulfide (PPS); ethers such as polyacetal (POM) and polyphenylene ether (PPE) Polymer; or acrylic resin, ABS resin, AS resin, polysulfone (PS
F), polyetherketone (PEK), polyamideimide (PAI) and the like. These organic polymers may be one kind or, if necessary, a mixture or copolymer of two or more kinds.

As the inorganic reinforcing material, glass fiber, glass wool, carbon fiber, talc, mica, wollastonite, kaolin, montmorillonite, titanium whisker, rock wool, etc., and as the organic reinforcing material, aramid, polyimide, liquid crystal polyester ( L
CP), polybenzimidazole, polybenzothiazole and the like.

The cyclic conjugated diene copolymer of the present invention can be used not only as an excellent industrial material as a modifier for plastics, thermoplastic elastomers and other resins, but also, if necessary, with a crosslinking agent. Depending on the circumstances, it can be used as a curable resin such as a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin.

[0058]

The present invention will be described in more detail with reference to the following Examples, Production Examples, Comparative Examples and Reference Examples, but the scope of the present invention is not limited to these Examples. The chemicals used in the present invention were of the highest purity available. The general solvent was degassed according to a conventional method, refluxed and dehydrated on an active metal under an inert gas atmosphere, and then distilled and purified. The number average molecular weight is 1
Dissolved in 2,4-trichlorobenzene; P. The values in terms of standard polystyrene measured by the C (gel permeation chromatography) method are shown.

(Reference Example 1) (Preparation example of polymerization catalyst which is a complex compound of an organometallic compound containing a Group IA metal used in this production example) Under dry argon atmosphere, required amount of tetramethylethylenediamine (TMEDA) Was dissolved in cyclohexane.
This solution was cooled and maintained at −10 ° C., and a required amount of normal butyl lithium (n-BuL
The n-hexane solution of i) was added slowly. After the dropwise addition was started, the solution was cooled to −78 ° C. to precipitate a white crystalline complex.

(Comparative Example 1) <Polymerization Example 1 with Conventional Catalyst System> The inside of a 100 ml Schlenk tube sufficiently dried according to a conventional method was replaced with dry argon. 5.00 g of 1,3-cyclohexadiene and 10.0 g of cyclohexane were injected into a Schlenk tube. Keeping the temperature of the solution at room temperature, n-B
To a solution of uLi in n-hexane, 0.04 mmol as a lithium atom was added. Immediately after the addition of n-BuLi, the color of the cyclohexadienyl anion disappeared, and the polymer was not recovered. (Comparative Example 2) <Polymerization Example 1 when stable complex compound of organometallic compound containing Group IA metal is not formed> The inside of a 100 ml Schlenk tube sufficiently dried according to a conventional method was replaced with dry argon. 5.00 g of 1,3-cyclohexadiene, 10.0 g of cyclohexane, TMED
0.01 mmol of A was injected into the Schlenk tube. While maintaining the temperature of the solution at room temperature, 0.04 mmol of an n-BuLi n-hexane solution was added in terms of lithium atoms. Immediately after the addition of n-BuLi, the color of the cyclohexadienyl anion disappeared, and the polymer was not recovered.

(Comparative Example 3) <Polymerization Example 2 when a stable complex compound of an organometallic compound containing a Group IA metal is not formed> Comparative Example 2 except that TMEDA was changed to 0.04 mmol.
A polymerization reaction was carried out in the same manner as described above. Immediately after the addition of n-BuLi, the color of the cyclohexadienyl anion disappeared, and the polymer was not recovered. (Comparative Example 4) <Polymerization Example 3 when stable complex compound of organometallic compound containing Group IA metal is not formed> Comparative Example 2 except that TMEDA was set to 0.40 mmol.
A polymerization reaction was carried out in the same manner as described above. Immediately after the addition of n-BuLi, the color of the cyclohexadienyl anion disappeared, and the polymer was not recovered.

(Example 1) <Polymerization Example 1 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene-based copolymer 1 of the present invention> Stoppered 100ml pressure-resistant glass bottle,
The inside was replaced with dry argon according to a conventional method. After injecting 2.31 g of isoprene and 5.00 g of toluene into the bottle, 0.08 mmol of a polymerization catalyst adjusted at a ratio of TMEDA / n-BuLi = 1/1 (molar ratio) in terms of lithium atoms was added, Polymerization was performed at room temperature for 4 hours.
The polymerization solution was further added with 1,3-cyclohexadiene.
72 g was added, and polymerization was carried out at room temperature for 4 hours. After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid. After washing with methanol and vacuum drying at 80 ° C., a white isoprene / cyclohexadiene diblock copolymer was obtained. The yield of the polymer was 97.6 wt%. G. FIG. P. When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak and the number average molecular weight was 3
8,200, and the molecular weight distribution (Mw / Mn) is 1.2.
It was 2. As a result of ¹ H-NMR measurement, it was confirmed that this polymer had a structure of a polymer chain substantially equal to the charged composition of the monomer.

(Example 2) <Polymerization Example 2 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene-based copolymer 2 of the present invention> A polymerization reaction was carried out in the same manner as in Example 1, except that the amount was changed to 0.50 g and 2.50 g of 1,3-cyclohexadiene. The yield of the isoprene / cyclohexadiene diblock copolymer was 98.8% by weight. G. FIG. P.
When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak, the number average molecular weight was 34,400, and the molecular weight distribution (Mw / Mn) was 1.31. ¹
As a result of measuring the H-NMR, it was confirmed that this polymer had a constitution of a polymer chain substantially equal to the charged composition of the monomer.

(Example 3) <Polymerization Example 3 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene copolymer 3 of the present invention> A polymerization reaction was carried out for 4 hours in the same manner as in Example 1 except that the temperature was changed to 50 ° C. The yield of the isoprene / cyclohexadiene diblock copolymer was 98.0% by weight. G. FIG. P. When the molecular weight of the polymer was measured by the method C, the polymer showed a single peak, and the number average molecular weight was 30,
700 and the molecular weight distribution (Mw / Mn) was 1.20. As a result of measuring ¹ H-NMR, this polymer was
It was confirmed that the composition of the polymer chain was almost equal to the charged composition of the monomer.

(Comparative Example 5) <Polymerization Example 2 with Conventional Catalyst System> A polymerization reaction was carried out in the same manner as in Example 3, except that the polymerization catalyst was changed to n-BuLi. The obtained polymer was an isoprene homopolymer.

(Example 4) <Polymerization Example 4 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene copolymer 4 of the present invention> 1,3 A polymerization reaction was carried out in the same manner as in Example 1 except that cyclohexadiene was polymerized first and isoprene was additionally added. The yield of the cyclohexadiene / isoprene diblock copolymer was 98.5% by weight. G. FIG. P. When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak, the number average molecular weight was 36,200, and the molecular weight distribution (Mw / Mn) was 1.32. ¹ H-NM
As a result of measurement of R, it was confirmed that this polymer had a structure of a polymer chain substantially equal to the charged composition of the monomer.

Comparative Example 6 Polymerization Example 3 Using Conventional Catalyst System A polymerization reaction was carried out in the same manner as in Example 4 except that the polymerization catalyst was changed to n-BuLi. The obtained polymer was a cyclohexadiene homopolymer.

(Example 5) <Polymerization Example 5 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene-based copolymer 5 of the present invention> The interior of the 5 l high-pressure autoclave with the electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane and 400 g of butadiene were charged in an autoclave, and TMEDA / n-BuLi = 1/4.
The polymerization catalyst adjusted at a ratio of (mol ratio) was added in an amount of 25.6 mmol in terms of lithium atom, and a polymerization reaction was performed at 60 ° C. for 1 hour. 400 g of 1,3-cyclohexadiene was further added to the polymerization solution, and a polymerization reaction was performed at 40 ° C. for 6 hours. After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid. , Washed with methanol and vacuum dried at 80 ° C to give white butadiene /
A cyclohexadiene diblock copolymer was obtained. G. FIG.
P. When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak, the number average molecular weight was 44,100, and the molecular weight distribution (Mw / Mn) was 1.36.
As a result of ¹ H-NMR measurement, it was confirmed that this polymer had a structure of a polymer chain substantially equal to the charged composition of the monomer. The polymer was filled in a mold at 180 ° C. and compression-molded to prepare a test piece having a thickness of 3 mm. AS
Tensile modulus (T) of the molded body measured according to TM D638
M) is 680 MPa and the tensile elongation (TE) is 50
0% or more.

(Example 6) <Polymerization Example 6 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene-based copolymer 6 of the present invention> The interior of the 5 l high-pressure autoclave with the electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2,720 g of cyclohexane, 1,3-cyclohexadiene 15
4 g is charged in an autoclave, and TMEDA / nB
15.36 mmol of a polymerization catalyst adjusted at a ratio of uLi = 1/4 (mol ratio) was added in terms of lithium atom,
The polymerization reaction was performed at 40 ° C. for 5 hours. 326 g of butadiene was further added to the polymerization solution, and a polymerization reaction was performed at 60 ° C. for 1 hour. After the completion of the polymerization reaction, 9.60 mmol of dichlorodimethylsilane was added, and the polymer terminals were coupled at 65 ° C. for 1 hour.

The polymer solution was poured into a large amount of a mixed solvent of methanol / hydrochloric acid to separate the polymer. The polymer was washed with methanol, dried at 80 ° C. in vacuo, and obtained as white cyclohexadiene /
A butadi entry block copolymer was obtained. G. FIG. P. When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak, the number average molecular weight was 69,700, and the molecular weight distribution (Mw / Mn) was 1.39. ¹ H-N
As a result of measuring MR, this elastomeric polymer was
It was confirmed that the composition of the polymer chain was almost equal to the charged composition of the monomer. This polymer was filled in a mold at 220 ° C. and compression-molded to prepare a 3 mm-thick test piece. The 300% stretched state tensile modulus (TM) of the colorless and transparent molded article measured according to ASTM D638 is 6.5.
It was 7 MPa. The tensile elongation (TE) was 500% or more.

(Example 7) <Polymerization Example 7 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene copolymer 7 of the present invention> Dichlorodimethylsilane Was carried out in the same manner as in Example 6 except that 3.80 mmol of tetrachlorosilane was added instead of G. FIG. P. When the molecular weight of the cyclohexadiene / butadiene radial block copolymer was measured by Method C, the polymer showed a single peak, the number average molecular weight was 120,500, and the molecular weight distribution (Mw
/ Mn) was 1.57. As a result of ¹ H-NMR measurement, it was confirmed that this polymer had a structure of a polymer chain substantially equal to the charged composition of the monomer. This polymer was filled in a mold at 220 ° C. and compression-molded to a thickness of 3 μm.
mmt test pieces were prepared. The tensile elastic modulus (TM) in a 300% stretched state of the colorless and transparent molded article measured according to ASTM D638 was 7.06 MPa. The tensile elongation (TE) was 500% or more.

(Example 8) <Polymerization Example 8 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene-based copolymer 8 of the present invention> Stoppered 100ml pressure-resistant glass bottle,
The inside was replaced with dry argon according to a conventional method. After injecting 2.50 g of 1,3-cyclohexadiene, 2.50 g of styrene and 10.0 g of cyclohexane into the bottle, the polymerization catalyst obtained in Example 1 was added with 0.08 mmol in terms of lithium atom, Polymerization was performed at room temperature for 4 hours.
After completion of the polymerization reaction, BHT [2,6-bis (t-butyl)
-4-methylphenol] The reaction was stopped by adding a 10 wt% methanol solution, the polymer was further separated with a large amount of a mixed solvent of methanol / hydrochloric acid, and washed with methanol.
Vacuum drying was performed at 0 ° C. to obtain a white cyclohexadiene / styrene copolymer. The yield of the polymer was 74.8% by weight. G. FIG. P. When the molecular weight of the polymer was measured by Method C, the polymer showed a single peak and the number average molecular weight was 3
7,100 and a molecular weight distribution (Mw / Mn) of 1.5
It was 3. As a result of ¹ H-NMR measurement, the composition of the polymer chain of this polymer was as follows: cyclohexadiene / styrene =
It was confirmed that the composition was derived from 1 / 3.4.

(Example 9) <Polymerization Example 8 when the complex compound of an organometallic compound containing a Group IA metal of the present invention is used as a polymerization catalyst and cyclic conjugated diene copolymer 8 of the present invention> A polymerization reaction was carried out in the same manner as in Example 8, except that the mixed solvent of 9 g of cyclohexane and 1 g of toluene was used. After 0.5 hour, sampling after 1 hour,
G. FIG. P. When the molecular weight of the polymer was measured by the method C,
The polymer shows a single peak and the number average molecular weight is 1
6,100, 33,800 and the molecular weight distribution (Mw /
Mn) were 1.28 and 1.21. ¹ H-NMR
As a result, the composition of the polymer chain of this polymer was found to be cyclohexadiene / styrene = 1 / 4.9 and 1 respectively.
/2.9 was confirmed to be a tapered block copolymer.

(Preparation Example 1) <Polymerization Example 9 and a Cyclic Conjugated Diene-Based Homopolymer When the Complex Compound of an Organometallic Compound Containing a Group IA Metal of the Present Invention was Used as a Polymerization Catalyst> The inside of a 100 ml Schlenk tube was replaced with dry argon. 5.00 g of 1,3-cyclohexadiene and 10.0 g of cyclohexane were injected into a Schlenk tube. Keep the temperature of the solution at room temperature, TM
To the polymerization catalyst synthesized at a ratio of EDA / n-BuLi = 1/4, 0.04 mmol in terms of lithium atom was added, and polymerization was performed at room temperature for 5 hours. After completion of the polymerization reaction, BH
The reaction was stopped by adding a 10 wt% methanol solution of T [2,6-bis (t-butyl) -4-methylphenol], and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and washed with methanol. , And vacuum dried at 80 ° C to obtain a white polymer.

Despite the presence of 4 equivalents of lithium atoms per equivalent of TMEDA, a polymer chain grows by living anion polymerization using each lithium atom as an equivalent polymerization active site, and has a number average molecular weight of 121,800 and a molecular weight distribution. (M
A cyclohexadiene homopolymer having (w / Mn) 1.14 was obtained in a yield of 98.9% by weight. The glass transition temperature (Tg) measured by the DSC method was 89 ° C. This polymer was molded by an injection molding machine set at a cylinder temperature of 300 ° C. to obtain a colorless and transparent 3 mmt thick test piece. The tensile modulus (TM) of the molded body measured according to ASTM D638 is 4,020 MPa (1 MP
a = 10.19716 kgf / cm ² ). AS
Weight 18.6kg ・ f / c measured according to TMD648
The heat distortion temperature (HDT) at m ² was 102 ° C.

[0076]

The novel 6-membered cyclic conjugated diene copolymer of the present invention has excellent thermal and mechanical properties, and is required for use as a molded article. It has a sufficiently high molecular weight and can be copolymerized with other monomers in any ratio and form according to the required thermal and mechanical properties. It can be used in a wide range of fields as useful industrial materials such as elastomers. Additionally the cyclic conjugated diene copolymer of the present invention, as a complex alone, or other resin materials and inorganic materials in accordance with the purpose and application, automobile parts, electric and electronic parts, such as a film sheet tube Can be used for a wide range of applications. The polymerization process of the present invention, 6
It has a high degree of polymerization activity for cyclic conjugated diene monomers composed of a membered ring, and a polymer can be obtained in high yield with a small amount of catalyst,
In addition, since it is possible to produce a high molecular weight polymer and a copolymer which has never been obtained in the past, it can be industrially widely used as a method for producing a cyclic conjugated diene-based copolymer comprising a 6-membered ring. .

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum chart of a cyclic conjugated diene-based copolymer of the present invention obtained in Example 1. As a solvent at the time of measurement, a deuterated form of chloroform was used.

FIG. 2 is a ¹ H-NMR spectrum chart of the cyclic conjugated diene-based copolymer of the present invention obtained in Example 5. As a solvent at the time of measurement, a deuterated form of chloroform was used.

FIG. 3 is a ¹ H-NMR spectrum chart of the cyclic conjugated diene-based copolymer of the present invention obtained in Example 8. As a solvent at the time of measurement, a deuterated form of chloroform was used.

FIG. 4 is a ¹ H-NMR spectrum chart of the cyclic conjugated diene homopolymer obtained in Production Example 1. A deuterated 1,2-dichlorobenzene was used as a solvent during the measurement.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 232/06 C08F 4/46 C08F 297/00-297/06

Claims (7)

(57) [Claims] 1. A copolymer in which a repeating unit constituting a polymer chain contains a molecular structural unit derived from a cyclic conjugated diene monomer, wherein the polymer chain is represented by the following formula (I). A cyclic conjugated diene copolymer. Embedded image [Formula (I) represents a composition formula of a polymer. (A) to (D) represent molecular structural units constituting the polymer main chain. 1 to p represent wt% of each molecular structural unit contained in the polymer chain. The number average molecular weight of the polymer is 25,000 to 5,000,000
Range. (A): a molecular structural unit derived from one or more monomers selected from the cyclic conjugated diene monomers represented by the following formula (2) . Embedded image [In the formula (2), R represents a hydrogen atom or an alkyl
Group, alkenyl group, aryl group, cycloalkyl group,
At least one selected from a chromodienyl group and a heterocyclic group
Species of organic substituents. However, double bonds are not hydrogenated
No. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): a molecular structural unit derived from one or more monomers selected from vinyl aromatic monomers. (D): a molecular structural unit derived from one or more monomers selected from polar monomers. (E): a molecular structural unit derived from one or more monomers selected from ethylene and α-olefin monomers. However, 1 + m + n + o + p = 100, 0.5 ≦ 1
<100, 0 ≦ m <100, 0 ≦ n <100, 0 ≦ o <
100, 0 ≦ p <100, 0 <m + n + o + p <100
It is. ] 2. The cyclic conjugated diene-based block copolymer according to claim 1, having a block unit containing a molecular structural unit derived from the cyclic conjugated diene-based monomer. 3. The cyclic structure according to claim 1, wherein the molecular structural unit constituting the polymer chain contains a block unit consisting only of a molecular structural unit derived from a cyclic conjugated diene-based monomer. Conjugated diene copolymer. 4. The cyclic conjugated diene-based monomer is a 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative or a cyclic conjugated diene having a carbon-carbon 6-membered ring structure in a molecule thereof. The cyclic conjugated diene copolymer according to any one of claims 1 to 3. 5. A polymer chain comprising a repeating unit containing a molecular structural unit derived from a cyclic conjugated diene monomer is a copolymer represented by the following formula (I), Is polymerized by using a complex compound of an organic metal compound containing a Group IA metal as a catalyst. Embedded image [Formula (I) represents a composition formula of a polymer. (A) to (D) represent molecular structural units constituting the polymer main chain. 1 to p represent wt% of each molecular structural unit contained in the polymer chain. polymerization
The number average molecular weight of the body is between 25,000 and 5,000,000
Range. (A): a molecular structural unit derived from one or more monomers selected from the cyclic conjugated diene monomers represented by the following formula (2) . Embedded image [In the formula (2), R represents a hydrogen atom or an alkyl
Group, alkenyl group, aryl group, cycloalkyl group,
At least one selected from a chromodienyl group and a heterocyclic group
Species of organic substituents. However, double bonds are not hydrogenated
No. (B): a molecular structural unit derived from one or more monomers selected from linear conjugated diene monomers. (C): a molecular structural unit derived from one or more monomers selected from vinyl aromatic monomers. (D): a molecular structural unit derived from one or more monomers selected from polar monomers. (E): a molecular structural unit derived from one or more monomers selected from ethylene and α-olefin monomers. However, 1 + m + n + o + p = 100, 0.5 ≦ 1
<100, 0 ≦ m <100, 0 ≦ n <100, 0 ≦ o <
100, 0 ≦ p <100, 0 <m + n + o + p <100
It is. ] 6. A copolymer of a cyclic conjugated diene monomer and one or more monomers copolymerizable therewith with a complex compound of an organometallic compound containing a Group IA metal as a catalyst. A method for polymerizing a cyclic conjugated diene-based copolymer according to any one of claims 1 to 5 , characterized in that: 7. A copolymer of a cyclic conjugated diene monomer and one or more monomers copolymerizable therewith with a complex compound containing a Group IA metal and an amine as a catalyst. The method for polymerizing a cyclic conjugated diene-based copolymer according to claim 6, wherein