JPH07258362A - Novel polymer containing saturated cyclic molecular structural units - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant polymer by polymerizing a cyclic conjugated diene alone or together with monomers copolymerizable therewith to form a polymer having satd. cyclic molecular structural units with high-molecular chains represented by the specific formula. CONSTITUTION:A polymer having a number-average mol.wt. of 10,000-5,000,000 and satd. cyclic molecular structural units having polymer chains represented by the formula [wherein A is a cycloolefin unit; B is a cyclic conjugated diene unit; C is a linear conjugated diene unit; D is an arom. vinyl monomer unit; E is a polar monomer unit; F is an a-olefin unit; a to f are each the proportion (wt.%) of A to F, respectively, to the sum of amts. of A to F (a+b+c+d+e+f=100wt.%); 0.01<=a<=100; and 0<=b, c, d, e or f<100] is obtd. by adding a tert. amine-organolithium catalyst in an amt. of 1X10<-6>-1X10<-1>mol (in terms of metal atom) to an org.-solvent soln. contg. 1mol of monomer component comprising a cyclic conjugated diene (e.g. 1,3-cyclopentadiene) and monomers copolymerizable therewith, thermally polymerizing the monomer component. adding a polymn. stopper, and separating the resultant polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer having a saturated cyclic molecular structural unit and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, polymer chemistry has made progress through several innovations in order to meet the demands of diversifying markets. In particular, in the research of polymer materials intended for industrial materials, enormous research has been carried out to develop more excellent thermal and mechanical properties, and various and various materials and manufacturing methods have been proposed.

For example, many proposals have been made so far regarding conjugated diene polymers, and some of them have been widely used as important industrial materials.

As typical conjugated diene polymers, homopolymers such as polybutadiene and polyisoprene, butadiene-isoprene copolymers, styrene-butadiene copolymers, propylene-butadiene copolymers, styrene-isoprene copolymers. , Α-methylstyrene-butadiene copolymer, α-methylstyrene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer, isoprene-methyl methacrylate copolymer Blocks such as polymers, grafts, taper or random copolymers, and further hydrogenated polymers thereof are known as known materials, such as plastics, elastomers, machine parts, tires, belts, insulating agents, and adhesives. , Other resin modifiers, etc. Are used for various purposes and fields of application.

On the other hand, many proposals have hitherto been made regarding the method of polymerizing a conjugated diene polymer, which plays an extremely important role industrially.

In particular, a large number of polymerization catalysts which give a high cis 1,4-bond content have been studied and developed for the purpose of obtaining a conjugated diene polymer having improved thermal and mechanical properties. For example, catalyst systems based on alkali metal compounds such as lithium and sodium, or composite catalyst systems based on transition metal compounds such as nickel, cobalt, and titanium are known, and some of them are already known. It is industrially adopted as a polymerization catalyst for butadiene, butadiene, isoprene, etc. [End. Ing. Chem. , 48,784 (1
956), Japanese Patent Publication No. 37-8198, reference].

On the other hand, in order to achieve higher cis 1,4-bond content and excellent polymerization activity, rare earth metal compounds and I
~ A composite catalyst system composed of an organometallic compound of a group III metal has been researched and developed, and research on highly stereospecific polymerization has 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),].

Among these catalyst systems, a composite catalyst containing a neodymium compound and an organoaluminum compound as main components is
It has been confirmed that it has a high cis 1,4-bond content and an 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 the recent progress of industrial technology, the market demand for polymer materials has become more and more sophisticated, and higher thermal (melting point, glass transition temperature,
There is a strong demand for the development of polymer materials having thermal deformation temperature, etc.) and mechanical properties (tensile elastic modulus, bending elastic modulus, etc.).

As one of the most effective 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, a cyclic conjugated diene-based monomer is used. By homopolymerizing or copolymerizing the monomer and then hydrogenating it, a saturated cyclic molecular structural unit is introduced into the polymer chain of the conjugated diene polymer to obtain a polymer material having high thermal and mechanical properties. The research activities that one is trying to obtain have become popular.

However, in the prior art, butadiene,
For a monomer having relatively small steric hindrance such as isoprene, although a catalyst system showing a polymerization activity which is satisfied to some extent has been proposed, for a monomer having a large steric hindrance, that is, a cyclic conjugated diene monomer. No catalyst system having a sufficiently satisfactory polymerization activity has yet been found.
That is, in the prior art, it is difficult to homopolymerize a cyclic conjugated diene-based monomer and a sufficient high molecular weight polymer cannot be obtained, and in addition, it is necessary to optimize thermal and mechanical properties to meet various market demands. Even when an attempt was made to copolymerize with other monomers for the purpose of carrying out, only a low molecular weight substance of an oligomer level could be obtained.

Furthermore, when an attempt is made to introduce a saturated cyclic molecular structural unit into a polymer chain for the purpose of exhibiting the highest degree of thermal and mechanical properties, the carbon constituting the cyclic molecular structural unit is
The carbon double bond has a serious problem that the hydrogenation rate is extremely slow and it is extremely difficult to introduce a saturated cyclic molecular structural unit into the polymer.

That is, an excellent polymer having a saturated cyclic molecular structural unit that is sufficiently satisfactory as an industrial material has not yet been obtained, and this solution has been strongly desired.

J. Am. Chem. Soc. , 81 , 4
48 (1959), cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene, which is a cyclic conjugated diene-based monomer, using a composite catalyst composed of titanium tetrachloride and triisobutylaluminum, and a polymerization method thereof. It is disclosed.

The polymerization method described here requires not only a large amount of polymerization catalyst and a long reaction time, but also the molecular weight of the obtained polymer is extremely low, so that it has no industrial value. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

In addition, J. Polym. Sci. , Pt.
A, 2 , 3277 (1964) discloses a method for polymerizing a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene by various methods such as radical, cation, anion and coordination polymerization. However, in any of the polymerization methods described here, the molecular weight of the obtained polymer is extremely low and has no industrial value. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

British Patent Application No. 1,042,625 discloses a method for polymerizing a cyclohexadiene homopolymer by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst.

In the polymerization method disclosed herein, it is necessary to use 1 to 2% by weight of the catalyst with respect to the monomer, which is not only economically disadvantageous, but also the molecular weight of the obtained polymer is high. It will be extremely low. Furthermore, there is no suggestion or teaching about the possibility of obtaining a copolymer. On the other hand, with this polymerization method, it is difficult to remove the catalyst residue that remains in a large amount in the polymer, and the polymer obtained by this polymerization method has no commercial value. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

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 number average molecular weight of the polymer obtained here was 20,000 even though the polymerization reaction was continued for 5 weeks. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

Polym. Prepr. (Amer. C
hem. Soc. , Div. Polym. Chem. )
12 , 402 (1971), when 1,3-cyclohexadiene is polymerized using an organolithium compound as a catalyst, the limit of the number average molecular weight of cyclohexadiene homopolymer is 10,000 to 15,000. It has been disclosed, and the reason for this is that a polymerization reaction and a transfer reaction accompanied by abstraction of a lithium cation and a elimination reaction of lithium hydride occur at the same time. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

Die Makromoleculare
Chemie. , 163 , 13 (1973),
A cyclohexadiene homopolymer in which 1,3-cyclohexadiene is polymerized with 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.

Also disclosed is a hydrogenated cyclohexadiene homopolymer (polycyclohexane oligomer) which has been hydrogenated using a large excess of paratoluenesulfonyl hydrazide with respect to the carbon-carbon double bond of this polymer.

However, the hydrogenated polymer disclosed herein has an extremely low molecular weight, and the disclosed hydrogenation method has a serious disadvantage that it is economically disadvantageous because it is a stoichiometric reaction. Had. Therefore, the hydrogenation method disclosed herein has no industrial value, and the obtained polymer has no value as an industrial material.

[European Polymer]
J. , 9 , 895 (1973), a copolymer of 1,3-cyclohexadiene, butadiene, and isoprene using a π-allylnickel compound as a polymerization catalyst is described.

However, it is reported that the polymer obtained here is an oligomer having an extremely low molecular weight and has a single glass transition temperature suggesting a random copolymer. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units. Polymers Collection, Vol. Three
4, No. 5,333 (1977) describes a copolymer of 1,3-cyclohexadiene and acrylonitrile using zinc chloride as a polymerization catalyst. The alternating copolymer obtained here is an extremely low molecular weight oligomer. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units. J. Polym. Sci. , Poly
m. Chem. Ed. , 20 , 901 (1982), a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organic sodium compound as a catalyst is disclosed. The organic sodium compound used here is sodium naphthalene, and the dianion formed from radical anions serves as the polymerization initiation point in practice.

That is, the number average molecular weight of the cyclohexadiene homopolymer reported here is apparently 3
8,700, but the number average molecular weight is practically 19,3
Only 50 molecular chains grew in two directions from the polymerization initiation point.

The polymerization method disclosed herein is
It is a reaction at extremely low temperatures and has no industrial value. Furthermore, there is no teaching or suggestion as to the introduction of saturated cyclic molecular structural units.

Makromol. Chem. , 191 ,
2743 (1990) describes a method for polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. In the polymerization method described here, it is taught that transfer reaction accompanied by abstraction of lithium cation and elimination reaction of lithium hydride occur at the same time as the polymerization reaction, and the polymerization reaction is started using polystyryllithium as an initiator. Despite the fact that it was carried out, it was reported that the styrene-cyclohexadiene block polymer was not obtained at room temperature, and only the cyclohexadiene homopolymer was obtained.

Similarly, when polystyryllithium was used as an initiator and blocking was performed at -10 ° C., a block polymer of styrene-cyclohexadiene having a molecular weight of about 20,000 was obtained together with cyclohexadiene homopolymer in an extremely low yield. Has been done. However, the copolymer obtained here not only has a very small content of cyclohexadiene block, but also block copolymerization with a chain conjugated diene monomer, multiblock of triblock or more, and radial. There is no suggestion or teaching of blocks and the like, and no teaching or suggestion of introduction of a saturated cyclic molecular structural unit.

That is, in the prior art, a polymer having an excellent saturated cyclic molecule structural unit which is sufficiently satisfactory as an industrial material has not yet been obtained, and an industrially applicable polymerization method and saturated cyclic molecule are available. The method of introducing structural units was also unknown.

[0032]

DISCLOSURE OF THE INVENTION According to the present invention, the polymer main chain is composed of at least one saturated cyclic molecular structural unit, or at least one saturated cyclic molecular structural unit and at least one other copolymerizable therewith. It has a high number-average molecular weight and is excellent in thermal properties such as melting point, glass transition temperature, and heat distortion temperature and mechanical properties such as tensile modulus and flexural modulus. Provided is a combination and a method for producing the same.

[0033]

Means for Solving the Problems As a result of repeated research to solve the above problems, the present inventor has found that at least one cyclic conjugated diene-based monomer or at least one cyclic conjugated diene-based monomer and A mononuclear or polynuclear compound of an organometallic compound containing an organometal of Group IA of the Periodic Table and a complexing agent is preferably obtained by polymerizing or copolymerizing one or two or more monomers copolymerizable therewith. Polymerization or copolymerization in the presence of a catalyst composed of a polynuclear complex, and the carbon-carbon double bond site of the cyclic conjugated diene monomer unit of the resulting polymer is subjected to an addition reaction to give a saturated cyclic molecule. We have found a way to convert to structural units. As a result, we have succeeded in synthesizing a novel polymer having a saturated molecular structural unit, which has never been reported previously, and in addition to a part or all of a plurality of monomer units constituting a polymer chain, a saturated cyclic molecule. We have established the technology to introduce the structure in any proportion and form. The present invention has been completed based on these new findings.

That is, the present invention provides [1] a polymer having a polymer main chain represented by the following formula (I) and containing a saturated cyclic molecular structural unit.

[0035]

[Chemical 12] [In the formula (I), A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. ] (A): One or more monomer units selected from cyclic olefin monomer units. (B): One or more monomer units selected from cyclic conjugated diene monomer units. (C): One or more monomer units selected from chain conjugated diene monomer units. (D): One or more monomer units selected from vinyl aromatic monomer units. (E): One or more monomer units selected from polar monomer units. (F): One or more monomer units selected from ethylene and α-olefin monomer units.

A to f satisfy the following relationships.

A + b + c + d + e + f = 100, 0.001 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, 0 ≦ e <100, 0 ≦ f <100] The unit A is present in a proportion of 0.1 to 100 mol% with respect to the total number of moles of the monomer unit A and the monomer unit B, and the number average molecular weight of the polymer is 10,000.
~ 5,000,000.

[2] a + b = 100 and 0 <b, the monomer unit A is one or more monomer units selected from cyclic olefin monomer units, and the monomer unit B is The polymer according to [1], wherein is one or more monomer units selected from cyclic conjugated diene monomer units.

[3] a = 100 and the monomer unit A
The polymer according to [1], wherein is one or more monomer units selected from cyclic olefin monomer units.

[4] 0.001≤a + b <100 and 0.001≤a <100, and the monomer unit A is one or more monomers selected from cyclic olefin monomer units. The polymer according to [1], which is a unit and the monomer unit B is one or more monomer units selected from cyclic conjugated diene-based monomers.

[5] The polymer described in [4], which is a random copolymer.

[6] The polymer described in [4], which is an alternating copolymer.

[7] The polymer according to [4], which is a block copolymer having a block unit containing at least one monomer unit A.

[8] The block unit is a monomer unit A
The polymer according to [7], which is a block copolymer composed of only

[9] The polymer according to [7], which is a block copolymer in which the block unit further contains at least one monomer unit B.

[10] The block unit is a monomer unit A
And the polymer according to [9], which is a block copolymer composed of only the monomer unit B.

[11] The monomer unit A has the following formula (II)
Is at least one cyclic olefin-based monomer unit selected from the units represented by: and the monomer unit B is at least one cyclic conjugated diene-based unit selected from the units represented by the following formula (III): [1] which is a monomer unit
The polymer as described in any of [10].

[0048]

[Chemical 13]

[0049]

[Chemical 14] [12] The at least one cyclic olefinic monomer unit A is represented by the following formula (IV), and the at least one cyclic conjugated diene monomer unit B is represented by the following formula (V). The polymer according to [11].

[0050]

[Chemical 15]

[0051]

[Chemical 16] [13] The at least one cyclic olefin-based monomer unit A is a cyclohexene monomer unit having a 1,4-bond or a 1,2-bond, or a derivative thereof, or a cyclic olefin-based monomer unit. And having a carbon 6-membered ring structure bonded to it in the molecule, wherein the at least one cyclic conjugated diene monomer unit B is a 1,3-cyclohexadiene monomer unit or a derivative thereof, Alternatively, the polymer according to [11], which is a cyclic conjugated diene monomer unit and has a 6-carbon carbon ring structure bonded to the unit in the molecule.

[14] A method for producing a polymer containing a saturated cyclic molecular structural unit having a polymer main chain represented by the following formula (I):

[0053]

[Chemical 17] [In the formula (I), A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. ] (A): One or more monomer units selected from cyclic olefin monomer units. (B): One or more monomer units selected from cyclic conjugated diene monomer units. (C): One or more monomer units selected from chain conjugated diene monomer units. (D): One or more monomer units selected from vinyl aromatic monomer units. (E): One or more monomer units selected from polar monomer units. (F): One or more monomer units selected from ethylene and α-olefin monomer units.

A to f satisfy the following relationships.

A + b + c + d + e + f = 100, 0.001 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, 0 ≦ e <100, and 0 ≦ f <100 However, the monomer The unit A is present in a proportion of 0.1 to 100 mol% with respect to the total number of moles of the monomer unit A and the monomer unit B. The above-mentioned production method is (1) at least one cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith (chain conjugated diene). Based monomers, vinyl aromatic monomers, polar monomers, ethylene monomers, and α-olefin monomers) are polymerized to give the following formula (I ') A process for synthesizing a cyclic conjugated diene polymer having a polymer main chain:

[0056]

[Chemical 18] [In the formula (I ′), B ′, C, D, E and F represent monomer units constituting the polymer main chain, and B ′ to F may be arranged in any order. b ′ to f ′ represent wt% of each of the monomer units B ′ to F with respect to the total weight of the monomer units B ′ to F, and B ′ has the same meaning as B defined in formula (I). And each C, D, E, F has the same meaning as defined in formula (I).

B'-f 'satisfy the following relationship.

B + c + d + e + f = 100, 0.001≤b'≤100, 0≤c '<100, 0≤d'<100, 0≤e '<100, and 0≤f'<100] (2) Above The cyclic conjugated diene polymer is hydrogenated, halogenated, halogenated hydrogenated, sulfonated, hydrated, halohydrinated, alkylated, arylated at the carbon-carbon double bond site of the monomer unit B ′. When subjected to an addition reaction selected from the group consisting of oxidation, 0.1
˜100 mol% (based on the number of moles of the monomer unit B ′) is saturated, thereby converting 0.1 to 100 mol% of the monomer unit B ′ to the monomer unit A. The manufacturing method characterized by including :.

[15] The production method according to [14], wherein the addition reaction in the step (2) is a hydrogenation reaction.

[16] The block copolymerization is carried out by using the above-mentioned at least one cyclic conjugated diene-based monomer and at least one other monomer copolymerizable with the above-mentioned polymerization in the step (1). The production method according to [14] or [15], which produces a united body.

[17] The cyclic conjugated diene monomer unit B ′ is at least one cyclic conjugated diene monomer unit selected from the units represented by the following formula (III):

[0062]

[Chemical 19] Thereby, a polymer having a polymer main chain represented by the formula (I), and the monomer unit A in the formula (I) is at least one selected from the units represented by the following formula (II): The production method according to any one of [14] to [16], which comprises producing a polymer that is a monomer unit.

[0063]

[Chemical 20] [18] The cyclic conjugated diene monomer unit B ′ is
It is represented by the following formula (V),

[0064]

[Chemical 21] Thereby, the monomer unit A in the formula (I), which is a polymer having a polymer main chain represented by the formula (I), is at least one unit selected from the units represented by the following formula (IV). The production method according to [17], which comprises producing a polymer that is a monomer unit.

[0065]

[Chemical formula 22] [19] Performing the above-mentioned polymerization in the step (1) in the presence of a catalyst composed of a mononuclear, polynuclear or polynuclear complex of an organometallic compound containing a metal of Group IA of the periodic table and a complexing agent. The manufacturing method according to any one of [14] to [18], which is characterized.

[20] The production method according to [19], wherein the complexing agent contains an amine.

[21] The production method according to [19] or [20], wherein the catalyst is synthesized before the polymerization reaction. Is.

In the present invention, each monomer unit constituting the polymer is named according to the name of the monomer from which the monomer unit is derived. Therefore, for example, a “cyclic olefin-based monomer unit” means a constitutional unit of a polymer formed as a result of polymerizing a monomeric cyclic olefin, and its structure has two carbons of a cycloalkane. This is the molecular structure that serves as the binding site.

The novel polymer in the present invention is a polymer in which some or all of the plurality of monomer units constituting the polymer chain are saturated cyclic molecular structural units. More specifically, the polymer of the present invention is a polymer containing a saturated cyclic molecular structural unit having a polymer main chain represented by the above formula (I).

More specifically, part or all of the monomer units constituting the polymer chain are linked by a bond selected from 1,4-bonds, 1,2-bonds, etc., carbon-carbon 5
It is a polymer composed of a saturated cyclic molecular structural unit having a member ring or more.

More specifically, a homopolymer of a cyclic conjugated diene monomer, a copolymer of two or more cyclic conjugated diene monomers, or a cyclic conjugated diene monomer and a copolymer thereof. Contained in the copolymer with possible monomers, carbon-carbon double bond of the cyclic conjugated diene monomer unit is subjected to an addition reaction with respect to part or all of it, and the cyclic conjugated diene monomer is added. A polymer obtained by converting a body unit into a saturated cyclic molecular structure unit can be exemplified.

The preferred novel polymer of the present invention is a homopolymer of a cyclic conjugated diene monomer, a copolymer of two or more cyclic conjugated diene monomers, or a cyclic conjugated diene monomer and Exemplifying a polymer obtained by hydrogenating a part or all of carbon-carbon double bonds of a cyclic conjugated diene-based monomer unit contained in a copolymer with a copolymerizable monomer. You can

As the most preferable novel polymer, a polymer in which the saturated cyclic molecular structural unit contained in the polymer chain is a molecular structural unit having a cyclohexane ring can be exemplified.

The novel polymer of the present invention may be obtained by any production method, has the saturated cyclic molecular structural unit of the present invention, and is particularly preferably within the range of the number average molecular weight of the present invention. It is not subject to any other restrictions.

As a method for producing the novel polymer of the present invention, for example, a cyclic conjugated diene monomer is polymerized or copolymerized,
After the completion of the polymerization reaction, a method of converting the carbon-carbon unsaturated bond in the cyclic structure constituting the polymer chain into a saturated bond by performing an addition reaction on the carbon-carbon double bond remaining in the molecule . Alternatively, a method of polymerizing or copolymerizing a cyclic olefin-based monomer at the time of polymerization to introduce a saturated cyclic molecular structural unit can be exemplified.

The industrially most preferable production method of the novel polymer of the present invention is to polymerize or copolymerize a cyclic conjugated diene monomer, and after the completion of the polymerization reaction, the carbon-carbon diamine remaining in the molecule. This is a method in which a heavy bond is subjected to an addition reaction to convert it into a saturated cyclic molecular structural unit.

A preferred saturated cyclic molecular structural unit in the present invention is a molecular structural unit represented by the following formula (II), and more specifically, a 5-membered ring having a carbon-carbon single bond to form a 8-membered ring. It is a molecular structural unit having a saturated cyclic structure of a member ring.

[0078]

[Chemical formula 23] A particularly preferred saturated cyclic molecular structural unit is a molecular structural unit having a 6-membered cyclic structure, which is represented by the following formula (IV) and is bonded and formed by a carbon-carbon single bond.

[0079]

[Chemical formula 24] The saturated cyclic molecular structural unit of the present invention may be composed of carbon atoms and hydrogen atoms as represented by the above formulas (II) and (IV), or may be fluorine, chlorine, bromine, iodine. And the like, or one or more kinds such as an alkyl group and an aryl group, and one or more organic substituents.

As the organic substituent, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
A cyclohexyl group or (CHm) n [m is 0 to
Represents an integer of 2. n represents an integer of 1 or more. ] An aliphatic group such as a cyclic alkyl group represented by
Examples thereof include aromatic groups such as tolyl group, naphthyl group, cyclopentadienyl group, indenyl group and pyridyl group. These may be one kind or a mixture of two or more kinds.

In the present invention, a preferred saturated cyclic molecular structural unit is 5 to 8 composed of carbon atoms and hydrogen atoms.
It is a saturated cyclic molecular structural unit of a member ring, and the most preferred saturated cyclic molecular structural unit is a 6-membered saturated cyclic molecular structural unit composed of carbon atoms and hydrogen atoms, that is, a cyclohexane ring.

Examples of the preferred cyclic conjugated diene monomer unit in the present invention include a monomer unit derived from a cyclic conjugated diene having a 5-membered ring or more constituted by a carbon-carbon bond.

A more preferable cyclic conjugated diene-based monomer unit is a monomer unit represented by the following formula (III), which is derived from a cyclic conjugated diene having a 5- to 8-membered ring composed of carbon-carbon bonds. is there.

[0084]

[Chemical 25] A particularly preferred cyclic conjugated diene monomer unit is a monomer unit represented by the following formula (V), which is derived from a 6-membered cyclic conjugated diene composed of carbon-carbon bonds.

[0085]

[Chemical formula 26] For example, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-
Examples thereof include monomer units derived from cyclooctadiene and derivatives thereof. As a preferred cyclic conjugated diene-based monomer unit, a 1,3-cyclohexadiene monomer unit, a 1,3-cyclohexadiene derivative monomer unit or a cyclic conjugated diene-based monomer unit having a carbon 6-membered ring structure Can be exemplified in the molecule. The most preferred cyclic conjugated diene monomer unit is
It is a 1,3-cyclohexadiene monomer unit.

Other monomer units copolymerizable with the cyclic conjugated diene monomer unit of the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and 1,3. -Chain conjugated diene monomer unit derived from pentadiene, 1,3-hexadiene, styrene,
Vinyl aromatic mono-components derived from α-methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene, vinylpyridine, etc. Unit, methyl methacrylate,
A polar vinyl monomer unit derived from methyl acrylate, acrylonitrile, methyl vinyl ketone, methyl α-cyanoacrylate, etc. or a polar monomer derived from ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, cyclic siloxane, etc. Examples thereof include body units, ethylene monomer units, and α-olefin monomer units. These monomer units may be 1
It may be one kind or two or more kinds.

Further, various copolymerization modes are selected as required. For example, diblock, triblock, tetrablock, multiblock, radial block, star block, comb block block copolymerization, graft copolymerization, taper copolymerization, random copolymerization, alternating copolymerization, etc. may be exemplified. it can.

The content of the saturated cyclic molecular structural unit in the novel polymer of the present invention is not particularly limited because it is set variously depending on its intended use, but it is generally 0.001 to 1
It is in the range of 00 wt%, preferably 0.01 to 100
It is in the range of wt%, and particularly preferably 0.1 to 100 w
It is in the range of t%.

When the novel polymer of the present invention is used in applications and fields requiring high thermal and mechanical properties, the content of the saturated cyclic molecular structural unit is in the range of 1 to 100 wt%. Is preferred, particularly preferably in the range of 2 to 100 wt%, and most preferably in the range of 5 to 100 wt%.

The saturated cyclic molecular structural unit in the novel polymer of the present invention is 0.1 to the total number of moles of the saturated cyclic molecular structural unit and the cyclic conjugated diene monomer unit contained in the polymer.
Present in a proportion of ˜100 mol%.

The ratio of the saturated cyclic molecular structural unit to the total number of moles of the saturated cyclic molecular structural unit and the cyclic conjugated diene monomer unit contained in the polymer of the present invention is the saturation required for the intended use. Although it is not particularly limited because it is variously set depending on the required amount of the cyclic molecular structural unit, it is generally necessary to be in the range of 0.1 to 100 mol%, and it is in the range of 5 to 100 mol%. Things are preferable, 10
To 100 mol% is more preferable, and 20 to 20 mol% is more preferable.
Most preferably, it is in the range of 100 mol%.

When the novel polymer of the present invention is used in applications and fields in which particularly high thermal and mechanical properties are required,
The ratio of the saturated cyclic molecular structural unit to the total number of moles of the saturated cyclic molecular structural unit and the cyclic conjugated diene monomer unit is 5
It is preferably in the range of 0 to 100 mol%, 70 to 1
It is particularly preferable that the amount is in the range of 00 mol%, and 90 mol%
The above is most preferable in order to obtain particularly high thermal and mechanical properties.

The number average molecular weight of the novel polymer of the present invention is 1
It is in the range of 50,000 to 5,000,000. Also,
Considering industrial productivity, the number average molecular weight is desirably in the range of 15,000 to 5,000,000, preferably in the range of 20,000 to 3,000,000. More preferably, it is in the range of 3,000 to 2,000,000, and 30,000 to 1,000,
The range of 000 is particularly preferable. Most preferred is the range of 40,000 to 500,000.

When the number average molecular weight is 10,000 or less, it becomes a remarkably brittle solid or viscous liquid and its value as an industrial material becomes extremely low.

When the number average molecular weight is 5,000,000 or more, unfavorable results in industrial production such as long polymerization time and extremely high melt viscosity are brought about.

The number average molecular weight of the polymer in the present invention means that the polymer is dissolved in 1,2,4-trichlorobenzene, and G. P. It is the number average molecular weight in terms of standard polystyrene of polymer chains measured by C (gel permeation chromatography) method.

The novel polymer of the present invention is a block unit containing a saturated cyclic molecular structural unit as a part of the molecular structural unit constituting the polymer chain, or a block unit composed only of a saturated cyclic molecular structural unit. In the case of a block copolymer containing, it is possible to control the molecular weight of the block unit according to the purpose, but generally, at least 10 saturated molecular structural units are continuous in the block unit. It is preferable that 20 or more saturated molecular structural units are continuously bonded, and 30 or more saturated molecular structural units are continuously bonded. It is particularly preferable to improve the thermal / mechanical properties.

The novel polymer of the present invention is a copolymer containing a saturated cyclic molecular structural unit or a saturated cyclic molecular structural unit and a block unit composed of one or more monomer units copolymerizable therewith. As a production method in the case of a polymer, a block unit containing a cyclic conjugated diene monomer unit, or a block unit composed only of a cyclic diene monomer unit, and one or copolymerizable with this or It is possible to exemplify a method of combining two or more kinds of monomer units and further performing an addition reaction.

The following methods can be listed as specific embodiments of the method for producing the block copolymer of the present invention.

A block unit containing a cyclic conjugated diene-based monomer unit or a block unit composed of only a cyclic conjugated diene-based monomer unit is previously polymerized, and the polymer is polymerized from one end or both ends of the polymer. A method of polymerizing one or two or more kinds of monomers copolymerizable therewith, and further carrying out an addition reaction.

One or more kinds of monomers copolymerizable with the cyclic conjugated diene-based monomer are preliminarily polymerized, and the cyclic conjugated diene-based monomer and the necessary monomer are added from one end or both ends of the polymer. A method of polymerizing one or more monomers copolymerizable with the cyclic conjugated diene-based monomer according to the above, and further performing an addition reaction.

A block unit containing a cyclic conjugated diene-based monomer unit or a block unit composed of only a cyclic conjugated diene-based monomer unit is polymerized and then copolymerized with one or more of them. A method of polymerizing a monomer, further sequentially polymerizing a block unit containing a cyclic conjugated diene monomer unit or a block unit composed of only a cyclic conjugated diene monomer unit, and further performing an addition reaction .

A block unit containing a cyclic conjugated diene monomer unit or a cyclic conjugated diene monomer is prepared by previously polymerizing one or more monomers copolymerizable with the cyclic conjugated diene monomer. A method in which a block unit composed of only monomer units is polymerized, one or more monomers copolymerizable with a cyclic conjugated diene monomer are sequentially polymerized, and then an addition reaction is carried out.

A block unit containing a cyclic conjugated diene monomer unit or a block unit composed of only a cyclic conjugated diene monomer unit is polymerized and then copolymerized with one or more kinds thereof. The monomer is polymerized, and the polymer terminal is a conventionally known bifunctional or higher functional coupling agent (for example, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide). , Chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.), and further carry out an addition reaction.

A block unit containing a cyclic conjugated diene-based monomer unit or a block unit composed of only a cyclic conjugated diene-based monomer unit is preliminarily polymerized and end-modified at the polymer terminal. A method in which a functional group is introduced by reacting an agent, and then an addition reaction is carried out to bond with another polymer having a functional group to be bonded thereto.

A block unit containing a cyclic conjugated diene-based monomer unit or a block unit composed of only a cyclic conjugated diene-based monomer unit is polymerized and then copolymerized with one or more of them. A method in which a monomer is polymerized, a functional group is introduced by reacting a terminal modifier with a polymer terminal, and further an addition reaction is carried out to bond with another polymer having a functional group to be bonded thereto.

A method in which a cyclic conjugated diene-based monomer and one or more kinds of monomers different in polymerization rate and copolymerizable with each other are simultaneously polymerized and further subjected to an addition reaction.

A method in which a cyclic conjugated diene monomer and one or more kinds of monomers copolymerizable therewith are charged at different composition ratios and simultaneously polymerized, and an addition reaction is carried out.

The block unit containing the cyclic conjugated diene-based monomer unit is not particularly limited to contain one or two or more other monomer units copolymerizable therewith. .

Further, it is not particularly limited that the block unit containing one or more kinds of monomer units copolymerizable with the cyclic conjugated diene monomer contains the cyclic conjugated diene monomer unit. .

The most preferable block unit derived from the cyclic conjugated diene monomer in the present invention is
A block unit containing or composed of a molecular structural unit containing a cyclohexene ring.

The most preferable block unit containing a saturated cyclic molecular structural unit in the novel polymer of the present invention is a saturated product obtained by an addition reaction of a molecular structural unit containing a cyclohexene ring or a block unit composed of the above cyclohexene ring. Is a block unit containing or composed of a molecular structural unit containing a cyclohexane ring.

Preferred methods for producing a polymer containing a saturated cyclic molecular structural unit of the present invention include (1) at least one cyclic conjugated diene-based monomer, or at least one cyclic conjugated diene-based monomer and At least one other polymerizable monomer (chain conjugated diene monomer, vinyl aromatic monomer, polar monomer, ethylene monomer,
And selected from the group consisting of α-olefin monomers)
To synthesize a cyclic conjugated diene-based polymer having a polymer main chain represented by the following formula (I ′):

[0114]

[Chemical 27] [In the formula (I ′), B ′, C, D, E and F represent monomer units constituting the polymer main chain, and B ′ to F may be arranged in any order. b ′ to f ′ represent wt% of each of the monomer units B ′ to F with respect to the total weight of the monomer units B ′ to F, and B ′ has the same meaning as B defined in formula (I). And each C, D, E, F has the same meaning as defined in formula (I).

B'-f 'satisfy the following relationship.

B + c + d + e + f = 100, 0.001≤b'≤100, 0≤c '<100, 0≤d'<100, 0≤e '<100, and 0≤f'<100] (2) Above The cyclic conjugated diene polymer is hydrogenated, halogenated, hydrohalogenated, sulfonated, hydrated, halohydrinized, alkylated, arylated at the carbon-carbon double bond site of the monomer unit B ′. , Oxidation of the monomer unit B '.
1 to 100 mol% (based on the number of moles of the monomer unit B ') is saturated, thereby converting 0.1 to 100 mol% of the monomer unit B'to the monomer unit A. The method includes the step :.

In the production method of the present invention, the cyclic conjugated diene monomer is a cyclic conjugated diene having a 5-membered ring or more and composed of carbon-carbon bonds.

A preferred cyclic conjugated diene-based monomer is a 5- to 8-membered cyclic conjugated diene composed of carbon-carbon bonds.

Particularly preferred cyclic conjugated diene-based monomers are
It is a 6-membered cyclic conjugated diene composed of carbon-carbon bonds.

For example, 1,3-cyclopentadiene,
Examples thereof include 1,3-cyclohexadiene, 1,3-cyclooctadiene and derivatives thereof. Examples of preferred cyclic conjugated diene-based monomers include 1,3-cyclohexadiene, 1,3-cyclohexadiene derivative or cyclic conjugated diene having a carbon 6-membered ring structure bonded to it in its molecule. I can do things. The most preferred cyclic conjugated diene-based monomer is 1,3-cyclohexadiene.

As the other monomer copolymerizable with the cyclic conjugated diene monomer of the present invention, a conventionally known monomer which can be polymerized by anionic polymerization can be exemplified.

For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Chain conjugated diene-based monomers such as pentadiene and 1,3-hexadiene, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, divinyl Vinyl aromatic monomers such as benzene, vinylnaphthalene, diphenylethylene, vinyl pyridine, polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, and methyl α-cyanoacrylate, or ethylene oxide. Examples thereof include polar monomers such as propylene oxide, cyclic lactone, cyclic lactam, and cyclic siloxane, or ethylene and α-olefin-based monomers. These monomers may be used alone or in combination of two or more, if necessary.

Further, various copolymerization modes are selected as required. For example, diblock, triblock, tetrablock, multiblock, radial block, star block, comb block block copolymerization, graft copolymerization, taper copolymerization, random copolymerization, alternating copolymerization, etc. may be exemplified. it can.

When the novel polymer of the present invention is a polymer obtained by subjecting a cyclic conjugated diene-based polymer to an addition reaction, a cyclic conjugated diene-based monomer unit in the starting cyclic conjugated diene-based polymer is used. The content of is not particularly limited because it is set variously depending on its intended use, but it is generally in the range of 0.001 to 100 wt%, preferably in the range of 0.01 to 100 wt%. , Particularly preferably in the range of 0.1 to 100 wt%.

When the novel polymer of the present invention is used in applications and fields requiring high thermal and mechanical properties, the cyclic conjugated diene-based monomer in the cyclic conjugated diene-based polymer as a raw material is used. The content of the unit is preferably in the range of 5 to 100 wt%, particularly preferably in the range of 10 to 100 wt%, and most preferably in the range of 15 to 100 wt%.

In the method for producing a novel polymer of the present invention via the above-mentioned cyclic conjugated diene polymer having a polymer main chain represented by the following formula (I ′), the above cyclic conjugated diene polymer is In the step (1) of synthesis, it is preferable to use a polymerization catalyst having an anionic polymerization activity, particularly a living anion polymerization activity.

The polymerization catalyst preferably used is a complex compound composed of an organometallic compound containing a Group IA metal and a complexing agent, and the complex compound which is a polymerization active species is
A polymerization catalyst characterized by being a mononuclear, a polynuclear or a polynuclear complex, and more preferably a binuclear or a polynuclear complex.

Various catalyst systems having a living anion polymerization activity have been proposed in the past. In particular, an organometallic compound containing a Group IA metal or an organometallic compound containing a Group IA metal and a complexing agent has been proposed. Complex compounds are widely used as living anionic polymerization catalysts.

Among them, complex compounds of organometallic compounds containing a Group IA metal, especially alkyllithium (RL
A great deal of research has been carried out on complex compounds consisting of i) and TMEDA (tetramethylethylenediamine) as a complexing agent.

N. Y. Acad. Sci. 27,741
As taught in (1965), the polymerization active species in this complex is a mononuclear complex composed of alkyllithium represented by the following formula (VI) and TMEDA, that is, one atom of metal in one complex. It is said to be a complex containing.

[0131]

[Chemical 28] In the prior art, TM was added to the alkyl lithium aggregate.
When EDA is added, it is said that TMEDA reacts with alkyllithium to form a complex and separates the association between the alkyllithiums, and mononuclear active species are generated, so that effects such as improvement in polymerization activity are expressed. It was

Therefore, when the conventional polymerization catalyst is used, the metal cation is present alone at the end of the polymer chain growing in each free direction, and the monomer is approached from the free direction to cause the polymerization reaction. Have been suggested to progress.

On the other hand, this also teaches that in conventional polymerization catalysts, the control of the molecular structure of the polymer chain is governed by external factors such as the reaction temperature, so this control is extremely difficult. There is.

That is, the conventional living anionic polymerization catalyst does not have sufficient polymerization activity capable of being industrially adopted for a monomer having a large steric hindrance and difficult to polymerize, such as a cyclic conjugated diene monomer. Not only was the possibility of sufficient control of the polymer chain structure suggested or taught for other monomers as well.

The present inventors have found that when forming a complex compound of an organometallic compound containing a Group IA metal and a complexing agent, a complex structure that stabilizes the association between the organometallic compound containing a Group IA metal is improved. We have discovered a surprising fact, which is the most preferable as a polymerization active species, overturning the concept of the conventional living anionic polymerization catalyst, and completed the most preferable polymerization catalyst system used in the production method of the present invention.

In the most preferable polymerization method for obtaining the cyclic conjugated diene polymer which is the most preferable raw material of the novel polymer of the present invention, in the organometallic compound containing a Group IA metal in the periodic table as a polymerization catalyst, Mononuclear, polynuclear or polynuclear complex compounds are used.

More preferably, a complex compound that is a binuclear or polynuclear complex that stabilizes the association between the organometallic compounds containing a Group IA metal and retains the complex structure even in the presence of a monomer is used.

The characteristic feature of the polymerization method disclosed in the present invention is that the cyclic conjugation diene monomer itself, which has been considered unsolvable in the prior art, causes a rearrangement reaction due to the withdrawal of the group IA metal cation at the polymer terminal and the group IA. The elimination reaction of metal hydride is suppressed by complexing an organometallic compound containing a Group IA metal to protect the Group IA metal cation,
It is possible to achieve high molecular weight and copolymerization.

The binuclear complex used in the production method of the present invention means I contained in the complex compound which is a polymerization active species.
A metal atom is a complex compound associated with 2 atomic units, and a polynuclear complex is a complex compound associated with 3 atomic units or more.

The IA metal atom in the polynuclear complex used in the present invention may be associated with each other in units of 3 atomic units or more, and may be most selected depending on the kind and purpose of the organometallic compound having the IA metal atom, the complexing agent. A stable association state may be selected as appropriate.

In practice, the IA metal atoms in the polynuclear complex are preferably associated with each other in an amount of 3 to 20 atomic units.
It is particularly preferable that they are associated with 0 atomic unit, and most preferable that they are associated with 4 to 6 atomic unit for industrial implementation.

The polymerization catalyst used in the production method of the present invention is industrially applicable to a monomer having large steric hindrance and difficult to polymerize with a conventional catalyst system such as a cyclic conjugated diene monomer. Not only has a high polymerization activity, but also retains the complex structure in the presence of a monomer, and is a living anion polymerization, but the monomer is inserted into the complex that is a polymerization active species, as if it is a coordination polymerization type. Since the polymerization reaction progresses, the polymer chain structure can be sufficiently controlled not only for the cyclic conjugated diene-based monomer but also for other conventionally known monomers that can be anionically polymerized by conventional techniques. Is to have.

Group IA metals that can be used in the polymerization catalyst used in the production of the present invention are lithium, sodium, potassium, rubidium, cesium and francium, and preferred group IA metals are lithium, sodium and potassium. Can be illustrated, and lithium can be illustrated as a particularly preferable Group IA metal. They are,
One kind may be used or a mixture of two or more kinds may be used if necessary.

A preferable complex compound which is a polymerization catalyst used in the method of polymerizing the cyclic conjugated diene polymer in the step (1) of the above-mentioned production method is an organometallic compound containing the Group IA metal, that is, an organic lithium. Compound,
A complex compound of an organic sodium compound and an organic potassium compound, and a complex compound of an organic lithium compound can be exemplified as the most preferable complex compound.

The organolithium compound preferably used for the polymerization catalyst used in the step (1) of the above production method is
It is a compound containing one or more lithium atoms, which is bonded to an organic molecule or organic polymer containing at least one carbon atom. The organic molecules are C1 to C
20 alkyl groups, C2-C20 unsaturated aliphatic hydrocarbon groups, C5-C20 aryl groups, C3-C20 cycloalkyl groups, and C4-C20 cyclodienyl groups. The organolithium compound used for the polymerization catalyst is methyllithium, ethyllithium, n-propyllithium,
iso-propyllithium, n-butyllithium, se
c-Butyllithium, tert-butyllithium, pentyllithium, hexyllithium, allyllithium, cyclohexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadienyllithium, indenyllithium, butadienyldilithium, isoprenyldilithium. Etc. or polybutadienyl lithium,
Examples of the conventionally known oligomeric or polymeric organic lithium containing a lithium atom in a part of a polymer chain such as polyisoprenyllithium and polystyryllithium can be exemplified.

Methyllithium, ethyllithium, butyllithium, and cyclohexyllithium can be exemplified as preferable organic lithium compounds. As the most preferable organic lithium compound that can be industrially adopted, n-butyllithium can be exemplified.

The organometallic compound containing a Group IA metal used in the polymerization catalyst used in step (1) of the above-mentioned production method may be one kind or a mixture of two or more kinds, if necessary. Absent.

With regard to the compound (complexing agent) which forms a complex with the organometallic compound containing a Group IA metal, the kind and amount thereof are not particularly limited, and depending on the polymerization conditions, IA
The compound that most effectively protects the group metal cation may be appropriately selected.

More specifically, an organic compound having an electron donating ability to a Group IA metal is useful as a complexing agent, and for example, a non-shared electron capable of coordinating to an organometallic compound containing a Group IA metal. Polar groups in which a pair exists (RO-, R2N
-, RS-, 2-oxazoline group, etc .: R represents an alkyl group. The organic compound having a) can be exemplified.

Examples of more preferable organic compounds include amines, ethers, and thioethers.

These complexing agents may be one kind or a mixture of two or more kinds, if necessary.

From an industrial point of view, amines can be exemplified as preferable compounds that form a complex with an organometallic compound containing a Group IA metal.

That is, in the synthesis of the cyclic conjugated diene polymer in the step (1) of the above production method, IA
It is particularly preferable to use a complex compound synthesized from an organometallic compound containing a group metal and amines as a polymerization catalyst, and most preferably a complex compound synthesized from an organolithium compound and amines as a polymerization catalyst.

The amines which are the most preferable complexing agents in the polymerization catalyst used in the present invention are R1R2N which is a polar group having an unshared electron pair capable of coordinating with an organometallic compound containing a Group IA metal. -Group (R1 and R2 are each independently a hydrogen atom, a C1-C20 alkyl group, C2-
C20 unsaturated aliphatic hydrocarbon group, C5-C20 aryl group, C3-C20 cycloalkyl group, C4-C2
It is a cyclodienyl group of 0, or a multiple ring group having a 5- to 10-membered ring and containing at least one nitrogen, oxygen or sulfur as a hetero atom. Examples thereof include organic compounds or organic polymer compounds containing one or more).

Of these amines, the most preferred amines are tertiary (tertiary) amine compounds.

Preferred tertiary (tertiary) amine compounds are trimethylamine, triethylamine, dimethylaniline, diethylaniline, tetramethyldiaminomethane, tetramethylethylenediamine, tetramethyl-
1,3-propanediamine, tetramethyl-1,3-butanediamine, tetramethyl-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, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,5] 4,0] -7-undecene, 1,4,8,1
1-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine,
2,2'-bipyridyl, 4,4'-bipyridyl, 1,1
Examples thereof include 0-phenanthroline and hexamethylphosphoric triamide.

Particularly preferred tertiary amine compounds are:
Tetraethylethylenediamine (TEEDA), tetramethylethylenediamine (TMEDA), tetramethyldiethylenetriamine (TMEDTA), pentamethyldiethylenetriamine (PMDT), diazabicyclo [2,2,2] octane (DABACO), 2,2'-
Bipyridyl, 4,4'-bipyridyl, 1,10-phenanthroline, hexamethylphosphoric triamide (H
MPA) can be illustrated.

The most preferable tertiary amine compound that can be industrially employed is tetramethylethylenediamine (TM).
EDA) can be illustrated.

These compounds may be one kind or a mixture of two or more kinds, if necessary. Also, the combined use of amines and other complexing agents is not particularly limited, and a complexing agent that most effectively protects the Group IA metal cation may be appropriately selected according to the polymerization conditions.

The method for synthesizing the complex compound formed from the group IA metal-containing organometallic compound and amines, which is the polymerization catalyst used in the production of the polymer of the present invention, is not particularly limited and may be any necessary. A conventionally known technique can be adopted accordingly.

For example, a method in which an organometallic compound is dissolved in an organic solvent under an inert gas atmosphere and a solution of amines is added thereto. Alternatively, a method in which amines are dissolved in an organic solvent under an inert gas atmosphere and a solution of an organometallic compound is added thereto can be exemplified, and the method is appropriately selected as necessary.

A complex compound formed from an organometallic compound containing a Group IA metal and an amine, which is the most preferable polymerization catalyst in the polymerization method of the cyclic conjugated diene polymer which is the most preferable raw material of the novel polymer of the present invention. In the adjustment, when the amine compound molecule and the Group IA metal atom to be blended are M1 mol and M2 mol, respectively, the blending ratio of them is in the range of M1 / M2 = 1000/1 to 1/1000. It is advantageous that M1 / M2 = 100/1 to 1/100, and preferably M1 / M2 = 60/1 to 1/60, and M1 / M2 = 50/1 to 1 / A range of 50 is more preferable, a range of M1 / M2 = 30/1 to 1/30 is particularly preferable, and a range of M1 / M2 = 20/1 to 1/20 is high yield. rate The most preferable for obtaining a high molecular weight or copolymers.

If the compounding ratio of the amine compound molecule to the Group IA metal atom is outside the range of the present invention, not only is it economically disadvantageous, but the complex compound becomes unstable, and the transfer reaction or IA occurs simultaneously with the polymerization reaction. This leads to undesirable results such as side reactions such as elimination reaction of group metal hydride.

The polymerization catalyst used in the present invention, IA
A polymerization catalyst in which a complex compound of an organometallic compound containing a group metal, wherein the complex compound which is a polymerization active species is a binuclear or polynuclear complex, is used before the polymerization reaction, that is, when the monomer is in the reaction system. It is most preferable that it is formed before being added in order to maintain a stable complex structure.

When a tertiary amine compound is used as a complexing agent in the above polymerization catalyst, a complex compound represented by the following formula (VII) can be exemplified as a preferable polynuclear or polynuclear complex structure.

[(G) g · (J) j] k (VII) [G represents one or more kinds of organometallic compounds containing a Group IA metal. J represents one or more complexing agents. When k is 1, g is an integer of 2 or more and j is an integer of 1 or more. When k is 2 or more, both g and j are integers of 1 or more. As a typical polymerization catalyst used in the present invention, a complex compound composed of amine compound / organolithium compound = 1/4 (mol ratio) can be exemplified. More specifically, amine compound / methyl lithium, ethyl lithium,
A complex compound composed of organic lithium = 1/4 selected from butyllithium can be exemplified.

As the most preferable polymerization catalyst that can be industrially adopted, a polynuclear complex compound composed of TMEDA / n-BuLi = 1/4 can be exemplified.

As the polymerizable monomer in step (1) of the above-mentioned production method, not only the cyclic conjugated diene-based monomer of the present invention but also anionically polymerizable monomer by a conventionally known technique may be used. The type is not particularly limited.

For example, examples of the monomer other than the cyclic conjugated diene monomer include 1,3-butadiene, isoprene,
Chain conjugated diene monomers such as 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene , Vinyl aromatic monomers such as p-tert-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene and vinylpyridine, methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, Polar vinyl monomers such as α-methyl cyanoacrylate, ethylene oxide, propylene oxide,
Examples thereof include polar monomers such as cyclic lactones, cyclic lactams and cyclic siloxanes, and ethylene and α-olefin monomers. These monomers may be used alone or in combination of two or more, as required.

The mode of the polymer synthesized in the step (1) of the above-mentioned production method is not particularly limited because it can be selected variously according to need. For example, homopolymerization or block copolymerization of diblock, triblock, tetrablock, multiblock, radial block, star block, comb block, graft copolymerization, taper copolymerization, random copolymerization, alternating copolymerization, etc. Can be illustrated.

The polymerization method is also not particularly limited, and gas phase polymerization, bulk polymerization, solution polymerization or the like can be adopted. As the polymerization reaction system, for example, batch system, semi-batch system, continuous system, etc. are used. It is possible to

The polymerization catalyst used in the present invention may be used alone or in combination with other polymerization catalysts in the polymerization reaction, and if necessary, it may be carried on an inorganic compound such as silica or zeolite. It is not limited.

The method of polymerizing the cyclic conjugated diene polymer in the step (1) of the above-mentioned production method is carried out by using IA as the polymerization catalyst.
It is carried out in the presence of a complex compound of an organometallic compound containing a group metal, preferably by bulk polymerization or solution polymerization.

Polymerization solvents usable in the case of solution polymerization include butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane,
aliphatic hydrocarbons such as n-decane, cyclopentane,
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, diethyl ether, Ethers such as tetrahydrofuran can be exemplified.

These polymerization solvents may be used alone or, if necessary, as a mixture of two or more kinds.

The amount of the polymerization catalyst used in the present invention may be varied depending on the purpose, and therefore it is not particularly limited, but generally 1 × 10 ⁻⁶ mol as a metal atom per 1 mol of the monomer. To 1 × 10 ⁻¹ mol, preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻²
It can be carried out in the range of mol.

The polymerization temperature in the polymerization method of the present invention is set to various values depending on the needs, but is generally -100 to 150 ° C, preferably -80 to 120 ° C, particularly preferably -30 to 110. ° C, most preferably 0 to 1
It can be carried out in the range of 00 ° C. From an industrial point of view, it is advantageous to carry out the treatment at room temperature to 80 ° C.

The time required for the polymerization reaction is not particularly limited because it varies depending on the purpose or the polymerization conditions, but it is usually within 48 hours, particularly preferably in the range of 1 to 10 hours. To be done. The atmosphere of the polymerization system is nitrogen, argon, an inert gas such as helium,
In particular, a sufficiently dry inert gas is desirable.

Further, the pressure of the polymerization system is not particularly limited as long as it is within the pressure range sufficient for maintaining the monomer and the solvent in the liquid phase within the above-mentioned polymerization temperature range. Further, it is necessary to take care so that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the polymerization catalyst and the active terminal are not mixed in the polymerization system.

As a polymerization reaction system, 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 the cyclic conjugated diene polymer in the present invention, prior to the polymerization, a part or a combination of the catalyst components is preliminarily reacted or aged to synthesize a complex compound serving as a polymerization catalyst in advance. Placement is the preferred method for obtaining the polymers of the present invention.

In particular, the formation of the complex compound before the addition of the cyclic conjugated diene monomer is the most preferable method in the polymerization method of the present invention.

Depending on the conditions of these operations, it is possible to suppress side reactions, improve the polymerization activity, and narrow the molecular weight distribution.

The polymerization catalyst used in the method for polymerizing the cyclic conjugated diene polymer in the present invention may be one kind or a mixture of two or more kinds, if necessary.

As the polymerization terminator, a known polymerization terminator may be employed although it deactivates the polymerization active species of the polymerization catalyst of the present invention. Water and carbon number of 1 to 10 are preferable.
Are alcohols, ketones, polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.),
Examples thereof include phenol, carboxylic acid, halogenated hydrocarbon and the like.

The addition amount of the polymerization terminator is generally 0.001 to 10 relative to 100 parts by weight of the cyclic conjugated diene polymer.
Used in the wt part range. Further, it may be deactivated by bringing molecular hydrogen into contact with the active end of the polymer.

The novel polymer of the present invention can be produced by carrying out an addition reaction after the polymerization reaction of the cyclic conjugated diene polymer achieves a predetermined polymerization rate.

The addition reaction in the present invention is an addition reaction for a carbon-carbon double bond, which is carried out by a conventionally known technique. More specifically, hydrogen addition (hydrogenation reaction), halogen addition (halogenation reaction), hydrogen halide addition (halogenation reaction), sulfuric acid addition (sulfonation reaction), water addition ( Hydration reaction), addition of halohydrin (halohydrination reaction), alkyl group (alkylation reaction), addition of aryl group (arylation reaction), addition of oxygen or hydroxyl group (oxidation reaction), etc. can be exemplified.

Preferred addition reactions in the present invention are hydrogenation reaction, halogenation reaction for carbon-carbon double bond,
It is an alkylation reaction, more preferably a hydrogenation reaction or a halogenation reaction.

The most preferable addition reaction in the present invention is
It is an addition reaction of hydrogen to a carbon-carbon double bond, that is, a hydrogenation reaction.

As a form of the addition reaction in the present invention, a conventionally known technique can be used.

For example, the polymerization reaction is stopped by deactivating the polymerization catalyst, and an addition reaction catalyst such as a hydrogenation catalyst or a halogenation catalyst is added to the same reactor in which the polymerization reaction has been carried out to remove hydrogen or halogen. A method of manufacturing in batch by introducing.

The polymerization reaction was stopped by deactivating the polymerization catalyst, and the polymer solution was transferred to a reactor separate from the polymerization reaction,
A method for producing a semi-batch method by adding an addition reaction catalyst such as a hydrogenation catalyst or a halogenation catalyst into a reactor and introducing hydrogen or halogen.

A method of continuously producing by carrying out polymerization and addition reaction in a tube type reactor can be exemplified.

These can be appropriately selected and adopted according to the purpose and need.

When the novel polymer of the present invention is a polymer obtained by subjecting a cyclic conjugated diene-based polymer to an addition reaction, the cyclic conjugated diene-based monomer unit in the starting cyclic conjugated diene-based polymer is used. Carbon-carbon double bond constituting the, the saturation rate by the addition reaction is not particularly limited because it is variously set by the required amount of the saturated cyclic molecular structural unit required for its intended use, Generally 0.1-100
%, Preferably 1-100%, more preferably 5-100%, and more preferably 10%.
Is particularly preferably in the range of 20 to 10%.
Most preferably, it is in the range of 0%.

When the novel polymer of the present invention is used in applications and fields in which particularly high thermal and mechanical properties are required,
The carbon-carbon double bond constituting the cyclic conjugated diene-based monomer unit in the cyclic conjugated diene-based polymer as a raw material preferably has a saturation ratio by an addition reaction in the range of 50 to 100%, The range of 70 to 100% is particularly preferable, and the range of 90% or more is most preferable in order to obtain particularly high thermal and mechanical properties.

The most preferred novel polymer of the present invention is produced by carrying out a hydrogenation reaction after the polymerization reaction of the cyclic conjugated diene polymer has achieved a desired predetermined polymerization rate. It is a polymer.

When the novel polymer of the present invention is a hydrogenated polymer of a cyclic conjugated diene polymer, it is the most preferable polymer having high thermal and mechanical properties.

When the novel polymer of the present invention is a hydrogenated polymer of a cyclic conjugated diene polymer, it constitutes a cyclic molecular structural unit derived from the cyclic conjugated diene monomer in the cyclic conjugated diene polymer. The hydrogenation rate of the carbon-carbon double bond
Although it is not particularly limited because it is variously set depending on the required amount of the saturated cyclic molecular structural unit required for the intended use, it is generally in the range of 0.1 to 100%,
It is preferably in the range of 100%, more preferably in the range of 5 to 100%, particularly preferably in the range of 10 to 100%, and most preferably in the range of 20 to 100%.

When the novel polymer of the present invention is used in applications and fields in which particularly high thermal and mechanical properties are required,
The hydrogenation rate of the carbon-carbon double bond constituting the cyclic molecular structural unit derived from the cyclic conjugated diene-based monomer in the cyclic conjugated diene-based polymer as the raw material is in the range of 50 to 100%. Is preferred, with 70 to 100% being particularly preferred, and 90% or more being hydrogenated is most preferred in order to obtain particularly high thermal and mechanical properties.

The novel polymer of the present invention utilizes the carbon-carbon double bond existing in the polymer after partial hydrogenation as a chemical reaction site with a crosslinking agent or a compound having a functional group. Things are possible.

That is, the carbon remaining in the polymer
Depending on the purpose, it is also preferable to positively utilize the carbon double bond as a reaction site that does not chemically bond with a crosslinking agent or a compound having a functional group.

The hydrogenation reaction for obtaining the novel polymer of the present invention is carried out in the presence of a cyclic conjugated diene polymer and a hydrogenation catalyst in a hydrogen atmosphere.

The method of the hydrogenation reaction in the present invention is generally carried out by keeping the polymer solution at a predetermined temperature in an atmosphere of hydrogen or an inert gas, adding a hydrogenation catalyst with or without stirring, and then adding It is carried out by introducing hydrogen gas and pressurizing it to a predetermined pressure.

As the hydrogenation reaction system, a conventionally known technique can be adopted. For example, batch type, semi-batch type,
Either a continuous type or a combination thereof can be adopted.

The hydrogenation catalyst used in the present invention is not particularly limited in kind and amount as long as it is a catalyst which can obtain a hydrogenation rate for introducing a necessary saturated cyclic molecular structural unit, but is substantially Is a homogeneous hydrogenation catalyst or a heterogeneous hydrogenation catalyst containing at least one metal selected from Group IVB to VIII metals or rare earth metals in the periodic table, preferably a homogeneous hydrogenation catalyst, that is, Organometallic compounds or organometallic complexes selected from group IVA to VIII metals or rare earth metals that are soluble in a solvent are preferred, and organometallic compounds or organometallic complexes of group IVA or VIII metals are particularly preferred.

Organometallic catalysts which are these hydrogenation catalysts,
It is not particularly limited that the organometallic complex or the like is carried on an inorganic compound such as silica, zeolite or crosslinked polystyrene, or an organic polymer compound.

The metal contained in the hydrogenation catalyst used in the present invention includes titanium, zirconium, hafnium,
Chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium,
Palladium, osmium, iridium, platinum, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium can be exemplified, preferably titanium, zirconium, Hafnium, rhenium, cobalt, nickel, ruthenium, rhodium, palladium, cerium, neodymium, samarium, europium, gadolinium, and ytterbium can be exemplified.

Examples of industrially particularly preferable metals are titanium, cobalt, nickel, ruthenium, rhodium and palladium.

In the present invention, the most industrially preferable metals are titanium, cobalt and ruthenium.

In order for these metals to be soluble in a solvent, it is necessary that ligands such as hydrogen, halogen, nitrogen compounds and organic compounds are coordinated or bonded, and the combination is arbitrary. Although it can be selected, it is a preferable method to obtain a novel polymer of the present invention to select a combination that is soluble in at least a solvent.

Specific examples of the ligand include hydrogen, fluorine,
Organic compounds containing functional groups such as chlorine, bromine, nitric oxide, carbon monoxide or hydroxyl, ether, amine, thiol, phosphine, carbonyl, olefin, diene, or non-polar organic compounds containing no functional group It can be illustrated.

These hydrogenation catalysts may be used alone or in combination of two or more, if necessary, without any particular limitation.

The amount of the hydrogenation catalyst used in the present invention is appropriately selected depending on the hydrogenation conditions. Generally, the metal concentration is 1 to 50,000 pp relative to the polymer to be hydrogenated.
m is in the range, preferably 5 to 10,000 ppm, more preferably 10 to 5,000 ppm, and particularly preferably 15 to 1,000 ppm.

When the amount of the hydrogenation catalyst used is small, a sufficient reaction rate cannot be obtained. On the other hand, when the amount of the hydrogenation catalyst used is large, the reaction rate increases but separation and recovery of the catalyst becomes difficult. Not economical.

Further, it is preferable in the hydrogenation reaction of the present invention to use the hydrogenation catalyst of the present invention in combination with an organometallic compound of a Group IA to IIIA metal such as alkyllithium, alkylmagnesium or alkylaluminum, if necessary. Is the way.

Further details of the hydrogenation catalyst comprising an organometallic compound or an organometallic complex used in the present invention can be found in, for example, J. Am. Chem. So
c. , 85, 4014 (1963).

The solvent that can be used in the hydrogenation reaction of the present invention is preferably inert to the hydrogenation catalyst and soluble in the polymer and the hydrogenation catalyst.

Preferred solvents are n-pentane and n.
-Hexane, n-heptane, n-octane, iso-octane, n-nonane, aliphatic hydrocarbons such as n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin, Alicyclic hydrocarbons such as norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, halogenated hydrocarbons such as methylene chloride, dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, diethyl ether, The ethers such as tetrahydrofuran may be used alone or as a mixture containing them as a main component, and may be appropriately selected depending on the characteristics of the polymer to be hydrogenated or the conditions of the hydrogenation reaction.

From an industrial point of view, it is most preferable to use the same solvent as that used for the polymerization reaction, since it is economically advantageous to carry out the hydrogenation reaction subsequent to the polymerization reaction.

The concentration of the polymer solution in the hydrogenation reaction is not particularly limited, but it is usually preferably 1 to 90 wt%, more preferably 2 to 60 wt%, particularly preferably 5 to 40 wt%. Is.

When the concentration of the polymer solution is low, it is economically disadvantageous, and when the concentration is high, the viscosity of the polymer solution increases and the reaction rate decreases, which is not preferable.

The temperature of the hydrogenation reaction is usually in the range of 0 to 300 ° C, preferably 20 to 250 ° C, particularly preferably 30 to 200 ° C.

If the reaction temperature is too low, a large reaction rate cannot be obtained, while if the reaction temperature is too high, unfavorable results such as deactivation of the hydrogenation catalyst or deterioration of the polymer are obtained. Will be invited.

The pressure of the hydrogenation reaction system is usually 1 to 250 k.
g / cm ² G, preferably 2 to 200 kg
/ Cm ² G, more preferably 5 to 150 kg / cm ² G
Is.

If the pressure is too low, a sufficiently high reaction rate cannot be obtained. On the other hand, if the pressure is too high, the reaction rate increases, but an expensive pressure-resistant reaction apparatus is required, which is economical. is not. In addition, it may lead to undesirable results such as hydrogenolysis of the polymer.

The time required for the hydrogenation reaction is not particularly limited because it depends on the concentration of the polymer solution and the temperature and pressure of the reaction system, but it can usually be carried out for 5 minutes to 240 hours. .

After completion of the hydrogenation reaction, the hydrogenation catalyst may be used by a conventionally known means such as an adsorption separation method using an adsorbent, a washing removal method using water or a lower alcohol in the presence of an organic acid and / or an inorganic acid. Thus, it can be separated and recovered from the reaction solution.

In order to separate and recover the novel polymer of the present invention from the polymer solution, a conventionally known technique which is usually used when recovering a polymer from a polymer solution of a known polymer is adopted. You can

For example, a steam coagulation method of directly contacting the reaction solution with steam, a method of precipitating the polymer by adding a poor solvent for the polymer to the reaction solution, and a method of heating the reaction solution in a container to distill off the solvent. , It is possible to exemplify a method of pelletizing while distilling off the solvent with a vented extruder,
An optimum method can be adopted depending on the properties of the polymer and the solvent used.

The novel polymer of the present invention has a carboxyl group (maleic anhydride, maleic anhydride,
Itaconic anhydride, citraconic anhydride, acrylic acid, methacrylic acid, etc.), hydroxyl group, epoxy group (glycidyl methacrylate, glycidyl acrylate, etc.), amino group (maleimide, etc.), oxazoline group, alkoxy group (vinyl silane, etc.), isocyanate group, etc. It may be modified or crosslinked by adding the polar group of.

A heat stabilizer, depending on its purpose and use,
Antioxidants, UV absorbers, lubricants, nucleating agents, dyes, pigments,
Cross-linking agents, foaming agents, antistatic agents, anti-slip agents, anti-blocking agents, release agents, other polymeric materials, inorganic reinforcing agents, and other additives that are added or blended with general polymeric materials, reinforcing agents, etc. The inclusion of is also not particularly limited.

The novel polymer of the present invention may be used alone or as a composite with another polymer material / inorganic reinforced material / organic reinforced material, depending on its purpose / use.

Other polymer materials in the case where the novel polymer of the present invention is used as a composite can be selected from conventionally known organic polymers according to need.
The amount is not particularly limited.

For example, nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 11, nylon 12, nylon 46, nylon 66, nylon 61.
0, nylon 612, nylon 636, nylon 121
2 such as aliphatic polyamide, nylon 4T (T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I, nylon 12T, nylon 12I, nylon MXD6 (MXD: metaxylylenediamine), etc. Semi-aromatic polyamides, polyamide-based polymers such as copolymers and blends thereof, polyester-based polymers such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycarbonate (PC) and polyarylate (PAR) Polymer,
Polypropylene (PP), polyethylene (PE), ethylene-propylene rubber (EPR), polystyrene (PS
t) and other olefin polymers, polybutadiene (PB
d), polyisoprene (PIp), styrene-butadiene rubber (SBR) or conjugated diene polymers such as hydrides thereof, polyphenylene sulfide (PP)
S) and other thiol-based polymers, polyacetal (PO
M), ether-based polymers such as polyphenylene ether (PPE), acrylic resins, ABS resins, AS
Resin, polysulfone (PSF), polyether ketone (PEK), polyamide imide (PAI), etc. can be illustrated.

These organic polymers may be one kind or a mixture / copolymer of two or more kinds, if necessary.

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

The novel polymer of the present invention is used not only as a thermoplastic resin as an excellent industrial material but also as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin by adding a crosslinking agent as required. It can also be used as a curable resin such as a resin.

[0240]

The present invention will be described in more detail below with reference to Examples, Production Examples, Comparative Examples and Reference Examples, but the scope of the present invention is not limited to these Examples and is not construed. The chemicals used in this invention were of the highest purity available. A general solvent was degassed according to a conventional method, refluxed / dehydrated on an active metal in an inert gas atmosphere, and then distilled / purified.

The number average molecular weight is determined by dissolving the polymer in 1,2,4-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 Used as a Complex Compound of Organometallic Compound Containing Group IA Metal Used in Production Example) A required amount of tetramethylethylenediamine (TMEDA) under a dry argon atmosphere. Was dissolved in cyclohexane. This solution was cooled and maintained at -10 ° C, and n-BuL of a required amount of normal butyllithium (n-BuLi) was stored in a dry argon atmosphere.
The hexane solution was added slowly. After the start of dropping, the solution was cooled to -78 ° C to precipitate a white crystalline complex.

(Production Example 1) (Production Example 1 of cyclic conjugated diene homopolymer which is a raw material of the novel polymer of the present invention) A sufficiently dried 100 ml pressure-resistant glass bottle was stoppered and dried with argon according to a conventional method. The inside was replaced. After injecting 5.00 g of 1,3-cyclohexadiene and 5.00 g of toluene into the bottle, TMEDA
The polymerization catalyst adjusted at a ratio of / n-BuLi = 1/1 (mol ratio) was 0.080 mmo in terms of lithium atom.
1 was added and polymerization was carried out at room temperature for 5 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 polymer was obtained.

The yield of the polymer was 96.5 wt%.
The number average molecular weight of this polymer is 49,800, and the molecular weight distribution [weight average molecular weight / number average molecular weight (Mw / M
n)] was 1.51.

The glass transition temperature (Tg) measured by the DSC method was 89 ° C. (Production Example 2) (Production Example 2 of cyclic conjugated diene homopolymer which is a raw material of the novel polymer of the present invention) In the same manner as in Production Example 1 except that the polymerization catalyst was 0.040 mmol in terms of lithium atom. Polymerization was carried out.

The yield of the polymer was 98.5 wt%.
The number average molecular weight of this polymer was 64,300, and the molecular weight distribution (Mw / Mn) was 1.48.

The glass transition temperature (Tg) measured by the DSC method was 89 ° C. (Production Example 3) (Production Example 3 of cyclic conjugated diene homopolymer which is a raw material of the novel polymer of the present invention) TMEDA / n-BuLi = 1 /
The polymerization reaction was performed in the same manner as in Production Example 1 except that the polymerization catalyst adjusted at a ratio of 4 (mol ratio) was used and the toluene was changed to 10.0 g of cyclohexane.

The yield of the polymer was 98.9 wt%.
The number average molecular weight of this polymer was 121,800, and the molecular weight distribution (Mw / Mn) was 1.14.

The glass transition temperature (Tg) measured by the DSC method was 89 ° C. This polymer is molded by an injection molding machine set to a cylinder temperature of 300 ° C.,
A colorless and transparent test piece having a thickness of 3 mmt was obtained.

The tensile modulus (TM) of the molded product measured according to ASTM D638 is 4,020 MPa (1 MPa
= 10.19716 kgf / cm ² ). AS
Weighted 18.6 kg · f / c measured according to TMD648
The heat distortion temperature (HDT) at m ² was 102 ° C.

(Production Example 4) (Production Example 4 of cyclic conjugated diene-based copolymer which is a raw material for the novel polymer of the present invention) The inside of a sufficiently dried 5 l high pressure autoclave equipped with an electromagnetic induction stirrer was subjected to a conventional method. The atmosphere was replaced with dry nitrogen.

2400 g of cyclohexane and 4 of butadiene
00g was charged in the autoclave and TMEDA / n-
A polymerization catalyst adjusted at a ratio of BuLi = 1/4 (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. To this polymerization solution, 400 g of 1,3-cyclohexadiene was further added, and a polymerization reaction was carried out 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. After washing with methanol and vacuum drying at 80 ° C., a white polymer was obtained.

G. P. When the molecular weight of the polymer was measured by the C method, 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 polymer chain structure substantially equal to the charged composition of the monomers.

The glass transition temperature (Tg) on the high temperature side measured by the DSC method was 89 ° C.

(Production Example 5) (Production Example 5 of cyclic conjugated diene copolymer which is a raw material of the novel polymer of the present invention) The inside of a sufficiently dried 5 l high pressure autoclave equipped with an electromagnetic induction stirrer was subjected to a conventional method. The atmosphere was replaced with dry nitrogen.

2720 g of cyclohexane and 154 g of 1,3-cyclohexadiene were charged into the autoclave,
The polymerization catalyst adjusted at a ratio of TMEDA / n-BuLi = 1/4 (mol ratio) was 15.3 in terms of lithium atom.
6 mmol was added and a polymerization reaction was carried out at 40 ° C. for 5 hours.
To this polymerization solution, 326 g of butadiene was added, and 6
The polymerization reaction was carried out at 0 ° C. for 1 hour. After the completion of the polymerization reaction, 9.60 mmol of dichlorodimethylsilane was added, and the temperature was 65 ° C.
The polymer ends were coupled for 1 hour.

The polymer solution was poured into a large amount of a mixed solvent of methanol / hydrochloric acid to separate the polymer, which was washed with methanol and vacuum dried at 80 ° C. to obtain a white polymer.

G. P. When the molecular weight of the polymer was measured by the C method, the polymer showed a single peak, the number average molecular weight was 90,700, and the molecular weight distribution (Mw / Mn) was 1.39.

As a result of ¹ H-NMR measurement, it was confirmed that this polymer had a polymer chain structure substantially equal to the charged composition of the monomers.

The glass transition temperature (Tg) on the high temperature side measured by the DSC method was 89 ° C.

The softening temperature measured by the TMA method was 149 ° C., which was measured with a load of 50 g and a penetration temperature of 100 μm.

(Production Example 6) (Production Example 6 of cyclic conjugated diene copolymer which is a raw material of the novel polymer of the present invention) A sufficiently dried 100 ml pressure-resistant glass bottle was capped and dried with dry argon according to a conventional method. The inside was replaced. After injecting 2.50 g of 1,3-cyclohexadiene, 2.50 g of styrene, and 10.0 g of cyclohexane into the bottle, TMEDA / n-BuLi = 1/4 (m
The polymerization catalyst adjusted in the ratio of (ol ratio) was added in an amount of 0.08 mmol in terms of lithium atom and polymerized 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 further mixed with a large amount of a methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer.

The yield of the polymer was 74.8 wt%.
G. P. When the molecular weight of the polymer was measured by the C method,
The polymer shows a single peak with a number average molecular weight of 37,10
And the molecular weight distribution (Mw / Mn) was 1.53.

As a result of ¹ H-NMR measurement, it was confirmed that the polymer chain composition of this polymer was a composition derived from cyclohexadiene / styrene = 1 / 3.4.

The glass transition temperature (Tg) on the high temperature side measured by the DSC method was 89 ° C.

Example 1 (Novel Polymer 1 of the Present Invention) 1.0 g of the polymer obtained in Production Example 1 was charged into a sufficiently dried high pressure autoclave with an internal capacity of 180 ml equipped with an electromagnetic induction stirrer. The inside was dried by a conventional method and replaced with dry nitrogen.

After adding 100 ml of cyclohexane and dissolving the polymer by heating and stirring, Co (acac) ₃ 0.30 in cyclohexane was used as a hydrogenation catalyst.
mmol, triisobutylaluminum 1.80 mmo
The catalyst solution prepared from 1 was added.

The inside of the high-pressure autoclave was replaced with hydrogen gas, the temperature was raised to 180 ° C., and the hydrogen pressure was changed to 15 kg / cm.
^The hydrogenation reaction was carried out for 4 hours as ² G.

After cooling the autoclave to room temperature and replacing the inside with dry nitrogen, 10 ml of a 10 wt% methanol / cyclohexane mixed solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added. The catalyst was deactivated, and the polymer was separated with a large amount of a mixed solution of methanol / hydrochloric acid, washed with methanol, and vacuum dried at 80 ° C. to obtain a hydrogenated polymer.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight of this polymer is 53,
It was 400, and the molecular weight distribution (Mw / Mn) was 1.46.

The glass transition temperature measured by the DSC method was 219 ° C.

(Example 2) (New polymer 2 of the present invention) Hydrogen pressure was 85 kg / cm ^2.
The hydrogenation reaction was performed in the same manner as in Example 1 except that G was used.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight was 51,000 and the molecular weight distribution (Mw / Mn) was 1.39.

(Example 3) (Novel Polymer 3 of the Present Invention) The same procedure as in Example 1 was carried out except that 10.0 g of the polymer obtained in Production Example 1 and hydrogen pressure of 10 kg / cm ² G were used. The hydrogenation reaction was carried out.

The hydrogenation rate calculated by ¹ H-NMR was 99.6%.

The number average molecular weight was 53,900 and the molecular weight distribution (Mw / Mn) was 1.21.

(Example 4) (Novel Polymer 4 of the Present Invention) Hydrogen pressure was 40 kg / cm ^2.
The hydrogenation reaction was performed in the same manner as in Example 1 except that G was used.

The hydrogenation rate calculated by ¹ H-NMR was 100%.

The number average molecular weight was 52,400 and the molecular weight distribution (Mw / Mn) was 1.33.

Example 5 (Novel Polymer 5 of the Present Invention) As a hydrogenation catalyst, TiCl 2 in cyclohexane was used.
₂ (Cp) ₂ [Cp: cyclopentadienyl group]
0.30 mmol, triisobutylaluminum 1.8
Except that a catalyst solution adjusted to 0 mmol was added,
The hydrogenation reaction was carried out in the same manner as in Example 2.

The hydrogenation rate calculated by ¹ H-NMR was 90.0%.

The number average molecular weight was 50.300 and the molecular weight distribution (Mw / Mn) was 1.43.

(Example 6) (Novel Polymer 6 of the Present Invention) The hydrogenation catalyst was RuHCl (CO) [P (C ₆ H ₅ ).
_{3] 3} and then addition was performed a hydrogenation reaction in the same manner as in Example 2.

The hydrogenation rate calculated by ¹ H-NMR was 92.8%.

The number average molecular weight was 50,800 and the molecular weight distribution (Mw / Mn) was 1.41.

Example 7 (Novel Polymer 7 of the Present Invention) 200 g of the polymer obtained in the same manner as in Production Example 2 was charged into a sufficiently dried high pressure autoclave equipped with an electromagnetic induction stirrer having an internal capacity of 4 liters. The inside was dried by a conventional method and replaced with dry nitrogen.

Add 2.5 l of cyclohexane and heat.
After dissolving the polymer by stirring, as a hydrogenation catalyst,
Co (acac) ₃ 0.30 mm in cyclohexane
and a catalyst solution adjusted to 1.80 mmol of triisobutylaluminum was added.

After replacing the inside of the high-pressure autoclave with hydrogen gas and raising the temperature to 180 ° C., the hydrogen pressure was set to 30 kg / cm.
^The hydrogenation reaction was carried out for 6 hours as ² G.

After cooling the autoclave to room temperature and replacing the inside with dry nitrogen, 10 ml of a 10 wt% methanol / cyclohexane mixed solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added. The catalyst was deactivated, and the polymer was separated with a large amount of a mixed solution of methanol / hydrochloric acid, washed with methanol, and vacuum dried at 80 ° C. to obtain a hydrogenated polymer.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight of this polymer is 72,
And the molecular weight distribution (Mw / Mn) was 1.32.

The glass transition temperature measured by the DSC method was 220 ° C.

Example 8 (New Polymer 8 of the Present Invention) A hydrogenation reaction was carried out in the same manner as in Example 1 except that the polymer obtained in Production Example 3 was used.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight was 128,500 and the molecular weight distribution (Mw / Mn) was 1.16.

The glass transition temperature measured by the DSC method was 222 ° C. Cylinder temperature 3
Molding was performed by an injection molding machine set at 20 ° C. to obtain a colorless and transparent test piece having a thickness of 3 mmt.

The tensile modulus (TM) of the molded product measured according to ASTM D638 is 6,620 MPa (1 MPa
= 10.19716 kgf / cm ² ). AS
Weighted 18.6 kg · f / c measured according to TMD648
The heat distortion temperature (HDT) at m ² was 182 ° C.

Example 9 (Novel Polymer 9 of the Present Invention) A hydrogenation reaction was carried out in the same manner as in Example 1 except that 1.0 g of the polymer obtained in Production Example 4 was used.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight of this polymer is 72,
It was 100, and the molecular weight distribution (Mw / Mn) was 1.34.

The glass transition temperature on the high temperature side measured by the DSC method was 220 ° C.

(Example 10) (New polymer 10 of the present invention) A hydrogenation reaction was carried out in the same manner as in Example 7 except that 60.0 g of the polymer obtained in Production Example 5 and 2 l of cyclohexane were used. went.

The hydrogenation rate calculated by ¹ H-NMR was 100%. The number average molecular weight of this polymer is 10
1,800 and the molecular weight distribution (Mw / Mn) is 1.2.
It was 4.

The glass transition temperature on the high temperature side measured by the DSC method was 220 ° C.

The softening temperature measured by the TMA method was 238 ° C., which was measured with a load of 50 g and a penetration temperature of 100 μm.

(Example 11) (New polymer 11 of the present invention) A hydrogenation reaction was carried out in the same manner as in Example 1 except that 1.0 g of the polymer obtained in Production Example 6 was used.

The hydrogenation rate calculated by ¹ H-NMR was 100%.

The glass transition temperatures measured by the DSC method were 122 ° C. and 100 ° C.

However, the number average molecular weight of this polymer was 38,
It was 700 and the molecular weight distribution (Mw / Mn) was 1.35.

(Comparative Example 1) Polymerization was carried out in the same manner as in Production Example 1 except that the polymerization catalyst was 1.01 mmol in terms of lithium atom. The yield of the polymer was 99.1 wt%.

The number average molecular weight of this polymer was 4,700, and the molecular weight distribution (Mw / Mn) was 1.12.

This polymer was subjected to hydrogenation reaction in the same manner as in Example 1. ^The hydrogenation rate calculated by ¹ H-NMR was 100%. Since this oligomeric polymer was extremely fragile, it was damaged when taken out from the mold, and a molded product could not be obtained.

[0312]

INDUSTRIAL APPLICABILITY The novel polymer of the present invention has excellent thermal and mechanical properties due to the introduction of a saturated cyclic molecular structural unit in the polymer chain, and is used as a molded product. Since it has a sufficiently high molecular weight required for the purpose, it can be used in a wide range of applications as an industrial material.

This polymer can be copolymerized with other monomers at an arbitrary ratio according to the required thermal / mechanical properties (for example, from high heat resistance / high rigidity plastic to high heat resistance elastomer). It is possible to design a wide range of molecules according to the purpose and application (for example, from high heat resistance / high rigidity plastic to high heat resistance elastomer).

Accordingly, the novel polymer of the present invention can be used as an automobile part, an electric / electronic part, a film /
It can be used in a wide range of applications as industrial materials such as sheets and tubes.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum chart diagram of a cyclic conjugated diene polymer, which is a raw material for a novel polymer of the present invention, obtained in Production Example 3. The solvent used for measurement is 1,2-
The deuterated form of dichlorobenzene was used.

FIG. 2 is a ¹ H-NMR spectrum chart diagram of a cyclic conjugated diene-based polymer, which is a raw material for the novel polymer of the present invention, obtained in Production Example 4. A deuterated form of chloroform was used as a solvent at the time of measurement.

FIG. 3 shows the novel polymer of the present invention obtained in Example 8.
^{It is a} < ¹ > H-NMR spectrum chart figure. A deuterated body of 1,2-dichlorobenzene was used as a solvent at the time of measurement.

FIG. 4 shows the novel polymer of the present invention obtained in Example 9.
^{It is a} < ¹ > H-NMR spectrum chart figure. A deuterated body of 1,2-dichlorobenzene was used as a solvent at the time of measurement.

Claims (21)

[Claims] 1. A polymer containing a saturated cyclic molecular structural unit having a polymer main chain represented by the following formula (I). [Chemical 1] [In the formula (I), A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. ] (A): One or more monomer units selected from cyclic olefin monomer units. (B): One or more monomer units selected from cyclic conjugated diene monomer units. (C): One or more monomer units selected from chain conjugated diene monomer units. (D): One or more monomer units selected from vinyl aromatic monomer units. (E): One or more monomer units selected from polar monomer units. (F): One or more monomer units selected from ethylene and α-olefin monomer units. a to f satisfy the following relationships. a + b + c + d + e + f = 100, 0.001 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, 0 ≦ e <100, 0 ≦ f <100] where the monomer unit A is The polymer is present in a proportion of 0.1 to 100 mol% with respect to the total number of moles of the monomer unit A and the monomer unit B, and the number average molecular weight of the polymer is 10,000.
~ 5,000,000. 2. A + b = 100 and 0 <b, the monomer unit A is one or more monomer units selected from cyclic olefin monomer units, and the monomer unit B is The polymer according to claim 1, which is one kind or two or more kinds of monomer units selected from cyclic conjugated diene monomer units. 3. The polymer according to claim 1, wherein a = 100 and the monomer unit A is one or more monomer units selected from cyclic olefin monomer units. 4. 0.001 ≦ a + b <100, and 0.
001 ≦ a <100, the monomer unit A is one or more kinds of monomer units selected from cyclic olefin-based monomer units, and the monomer unit B is a cyclic conjugated diene-based monomer. The polymer according to claim 1, which is one or more monomer units selected from the group consisting of: 5. The polymer according to claim 4, which is a random copolymer. 6. The polymer according to claim 4, which is an alternating copolymer. 7. The polymer according to claim 4, which is a block copolymer having a block unit containing at least one monomer unit A. 8. The polymer according to claim 7, which is a block copolymer in which the block unit is composed of only the monomer unit A. 9. The polymer according to claim 7, which is a block copolymer in which the block unit further contains at least one monomer unit B. 10. The polymer according to claim 9, which is a block copolymer in which the block unit is composed of only a monomer unit A and a monomer unit B. 11. The monomer unit A is at least one cyclic olefin-based monomer unit selected from the units represented by the following formula (II), and the monomer unit B is represented by the following formula (I
11. At least one cyclic conjugated diene monomer unit selected from the units represented by II).
The polymer according to any one of 1. [Chemical 2] [Chemical 3] 12. The at least one cyclic olefin-based monomer unit A is represented by the following formula (IV), and the at least one cyclic conjugated diene-based monomer unit B is:
The polymer according to claim 11, which is represented by the following formula (V). [Chemical 4] [Chemical 5] 13. The cyclohexene monomer unit, wherein the at least one cyclic olefin monomer unit A has a 1,4-bond or a 1,2-bond, or a derivative thereof, or a cyclic olefin monomer unit. A body unit having a 6-membered carbon ring structure bonded to it in the molecule, wherein at least one cyclic conjugated diene monomer unit B is 1,
The polymer according to claim 11, which is a 3-cyclohexadiene monomer unit or a derivative thereof, or a cyclic conjugated diene monomer unit having a 6-membered carbon ring structure bonded thereto in the molecule. 14. A method for producing a polymer containing a saturated cyclic molecular structural unit having a polymer main chain represented by the following formula (I), wherein: [In the formula (I), A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. ] (A): One or more monomer units selected from cyclic olefin monomer units. (B): One or more monomer units selected from cyclic conjugated diene monomer units. (C): One or more monomer units selected from chain conjugated diene monomer units. (D): One or more monomer units selected from vinyl aromatic monomer units. (E): One or more monomer units selected from polar monomer units. (F): One or more monomer units selected from ethylene and α-olefin monomer units. a to f satisfy the following relationships. a + b + c + d + e + f = 100, 0.001 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, 0 ≦ e <100, and 0 ≦ f <100 However, the monomer unit A is It exists in a proportion of 0.1 to 100 mol% based on the total number of moles of the monomer unit A and the monomer unit B. The above-mentioned production method is (1) at least one cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith (chain conjugated diene) Based monomers, vinyl aromatic monomers, polar monomers, ethylene monomers, and α-olefin monomers) are polymerized to give the following formula (I ') A process for synthesizing a cyclic conjugated diene-based polymer having a polymer main chain: [In the formula (I ′), B ′, C, D, E and F represent monomer units constituting the polymer main chain, and B ′ to F may be arranged in any order. b ′ to f ′ represent wt% of each of the monomer units B ′ to F with respect to the total weight of the monomer units B ′ to F, and B ′ has the same meaning as B defined in formula (I). And each C, D, E, F has the same meaning as defined in formula (I). b ′ to f ′ satisfy the following relationship. b + c + d + e + f = 100, 0.001 ≦ b ′ ≦ 100, 0 ≦ c ′ <100, 0 ≦ d ′ <100, 0 ≦ e ′ <100, and 0 ≦ f ′ <100] (2) The above cyclic conjugated diene The system polymer comprises hydrogenation, halogenation, halogen hydrogenation, sulfonation, hydration, halohydrination, alkylation, arylation, and oxidation at the carbon-carbon double bond site of the monomer unit B '. When subjected to an addition reaction selected from the group, the monomer unit B ′ of 0.1
˜100 mol% (based on the number of moles of the monomer unit B ′) is saturated, thereby converting 0.1 to 100 mol% of the monomer unit B ′ to the monomer unit A. The manufacturing method characterized by including :. 15. The production method according to claim 14, wherein the addition reaction in step (2) is a hydrogenation reaction. 16. The block copolymer, wherein the polymerization in step (1) is carried out using at least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith. The manufacturing method according to claim 14 or 15, which manufactures. 17. The cyclic conjugated diene monomer unit B ′ is at least one cyclic conjugated diene monomer unit selected from the units represented by the following formula (III): ] Thereby, a polymer having a polymer main chain represented by the formula (I), and the monomer unit A in the formula (I) is at least one selected from units represented by the following formula (II): The production method according to any one of claims 14 to 16, which comprises producing a polymer that is a monomer unit. [Chemical 9] 18. The cyclic conjugated diene-based monomer unit B ′ is represented by the following formula (V): Thereby, the monomer unit A in the formula (I), which is a polymer having a polymer main chain represented by the formula (I), is at least one unit selected from the units represented by the following formula (IV). The production method according to claim 17, wherein a polymer which is a monomer unit is produced. [Chemical 11] 19. The above-mentioned polymerization in step (1) is carried out in the presence of a catalyst comprising a mononuclear, polynuclear or polynuclear complex of an organometallic compound containing a metal of Group IA of the periodic table and a complexing agent. The manufacturing method according to any one of claims 14 to 18, wherein: 20. The method of claim 1, wherein the complexing agent comprises an amine.
9. The manufacturing method according to 9. 21. The method according to claim 19 or 20, wherein the catalyst is synthesized before the polymerization reaction.