KR100235083B1 - Novel polymerization catalyst - Google Patents

Abstract

A novel polymerization catalyst is disclosed which contains a heteronuclear or multinuclear complex of an organometallic compound containing a metal belonging to group IA of the periodic table with a complexing agent. The catalyst of the present invention is useful for the preparation of cyclic conjugated diene polymers containing one or more cyclic conjugated diene monomer units or containing one or more cyclic conjugated diene monomer units and one or more types of comonomers. Since the mold conjugated diene polymer has a high number average molecular weight, it is not only excellent in thermal properties but also in mechanical properties. The catalyst of the present invention not only obtains the desired high degree of polymerization but also has excellent catalytic activity capable of efficiently and efficiently carrying out a living anion polymerization capable of block copolymerizing the cyclic conjugated diene monomer and one or more types of the comonomer.

Description

New Polymerization Catalysts {NOVEL POLYMERIZATION CATALYST}

So far, several proposals have been made regarding conjugated diene polymers. Some of the polymers produced by such proposed techniques are widely used as commercially important materials.

Representative examples of known conjugated diene polymers include homopolymers such as polybutadiene and polyisoprene; Butadiene-isoprene copolymer, styrene-butadiene copolymer, propylene-butadiene copolymer, styrene-isoprene copolymer, α-methylstyrene-butadiene copolymer, α-methylstyrene-isoprene copolymer, acrylonitrile-butadiene copolymer, Blocks such as acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer, copolymers of graft, taper and random arrangement; And hydrogenated polymers derived from them. Such polymers are used for various purposes in various fields. For example, such conventional polymers include plastics; Elastic body; Parts for machines, tires and belts; Insulator; glue ; It has been used as a modifier for other resins and the like.

For example, in the field of thermoplastic elastomers, agglomerate phases (ie, hard segments) of polymer blocks with Tg (glass transition temperature) above room temperature, and elastic phases (ie soft segments) of polymer blocks with Tg below room temperature. Block copolymers containing polymer chains composed of these are conveniently used.

Representative examples of such block copolymers include styrene-butadiene (isoprene) -styrene block copolymers and their hydrogenation products.

In addition, in order to improve various properties of the styrene-butadiene (isoprene) -styrene block copolymer or its hydrogenation product (eg, heat resistance, flowability and adhesion), the block copolymer or its hydrogenation product and another polymer such as Block copolymers or hydrogenated polymers thereof are widely used in the form of polystyrene, polyolefin, polyphenylene ether or styrene-butadiene diblock copolymers, or block copolymer compositions obtained by blending hydrogenated products thereof.

On the other hand, various proposals have been made regarding the preparation of conjugated diene polymers which are very important from a commercial standpoint.

In particular, in order to obtain conjugated diene polymers with improved thermal mechanical properties, various studies have been conducted to develop polymerization catalysts capable of producing conjugated diene polymers having a high cis-1,4-bond content.

For example, catalyst systems mainly comprising alkali metal compounds such as lithium or sodium, and complex catalyst systems mainly comprising transition metal compounds such as nickel, cobalt or titanium have been proposed. Some of these catalyst systems have already been used to carry out commercial scale polymerization of butadiene, isoprene and the like (see, eg, End. Ing. Chem., 48, 784 (1956) and Japanese Patent Publication No. 37- 8198).

On the other hand, in order to achieve higher cis-1,4-bond content and good polymerization activity, a complex catalyst system comprising an organometallic compound and a rare earth metal compound containing a metal belonging to Groups I, II or III of the periodic table is developed. Many studies have been conducted to accomplish this. In addition, intensive studies on highly stereospecific polymerization have been made in conjunction with the study of these catalyst systems. See, eg, J. Polym. Sci., Polym. Chem. Ed., 18, 3345 (1980); Sci, Sinica., 2/3, 734 (1980); Makromol. Chem. Suppl, 4, 61 (1981); Federal Republic of Germany Patent Application No. 2,848,964; Rubber Chemical Technology., 58, 117 (1985)].

Among these composite catalyst systems, it was confirmed that composite catalysts mainly comprising neodymium compounds and organoaluminum compounds have not only the ability to provide the desired polymer of high cis-1,4-bond content, but also have excellent polymerization activity. Therefore, this kind of complex catalyst has already been used commercially as a catalyst for polymerization of butadiene and the like [see, for example, Makromol. Chem., 94, 119 (1981); Macromolecules, 15, 230 (1982)].

However, with the remarkable development of recent technology in this field, the development of polymer materials with more improved properties, in particular good thermal properties (melting point, glass transition temperature and heat deformation temperature) and excellent mechanical properties (tensile and flexural modulus) There was a strong demand for

As one of the most practical ways to meet this need, techniques for improving the structure of polymer chains in polymers of conjugated diene monomers in order to obtain polymeric materials with good thermal mechanical properties (comparatively small steric hindrances (e.g. butadiene Or a monomer having isoprene) and a monomer having large steric hindrance (for example, a monomer having a cyclic conjugated diene monomer) is attempted.

Regarding the homopolymerization or copolymerization of monomers having relatively small steric hindrance (for example butadiene or isoprene), catalyst systems with somewhat satisfactory polymerization activity have been successfully developed. However, in the single polymerization or copolymerization of monomers having large steric hindrance (for example, cyclic conjugated diene monomers), a catalyst system having satisfactory polymerization activity has not yet been developed.

In other words, even the single polymerization of the cyclic conjugated diene is difficult by the prior art, and it is not possible to obtain a homopolymer having a desired high molecular weight. Moreover, attempts to copolymerize cyclic conjugated dienes with monomers other than these cyclic conjugated dienes have shown that in order to obtain polymers having optimal thermal mechanical properties to meet a variety of commercial needs, the material obtained has only low molecular weight. The oligomer of was not successful with the result.

As is apparent from the above, in all prior art, it was not possible to obtain cyclic conjugated diene polymers with satisfactory properties. Therefore, there has been a strong demand for the development of high molecular weight cyclic conjugated diene polymers that can meet commercial needs.

J. Am. Chem. Soc., 81, 448 (1959) describes cyclohexades obtained by polymerizing 1,3-cyclohexadiene (a representative example of cyclic conjugated diene monomers) using a complex catalyst comprising titanium tetrachloride and triisobutylaluminum. Diene homopolymers and methods of polymerization thereof are disclosed. However, the polymerization method disclosed in this prior art document is disadvantageous in that a large amount of catalyst must be used, the polymerization reaction must be carried out for a long time, and the obtained polymer is extremely low molecular weight. Thus, the polymers obtained by the techniques of this prior art document have no commercial value.

In addition, J. Polym. Sci., Pt. A, 2,3277 (1964) discloses a process for preparing cyclohexadiene homopolymers in which polymerization of 1,3-cyclohexadiene is carried out by various polymerization methods such as radical polymerization, cationic polymerization, anionic polymerization and coordination polymerization. . However, the polymers obtained in all the methods disclosed in these prior art documents have only very low molecular weights. Thus, the polymers obtained by the techniques of this prior art document have no commercial value.

British Patent Application No. 1,042,625 discloses a process for the preparation of cyclohexadiene homopolymers in which polymerization of 1,3-cyclohexadiene is carried out using a large amount of organolithium compounds as catalysts.

In the polymerization process disclosed in British Patent Application No. 1,042,625, the catalyst should be used in an amount as high as 1-2 wt% based on the total weight of the monomers. Thus, this method is economically disadvantageous. In addition, the polymer obtained by this method has only very low molecular weight. Moreover, there is no teaching or suggestion regarding the obtaining of copolymers in this prior art document. In addition, the process of this prior art document contains a large amount of catalytic moieties because the polymer obtained is very difficult to remove from the polymer and therefore the polymer obtained by this process has the disadvantage of lacking commercial value.

J. Polym. Sci., Pt. A, 3, 1553 (1965) discloses cyclohexadiene homopolymers obtained by polymerizing 1,3-cyclohexadiene using organolithium compounds as catalyst. However, in this prior art document, the polymerization reaction must last for 5 weeks and the polymer obtained has a number average molecular weight of only about 20,000 or less.

Polym. Prepr. (Amer. Chem. Soc., Div. Polym. Chem.) 12, 402 (1971) shows the cyclohexadiene single obtained when the polymerization of 1,3-cyclohexadiene is carried out using an organolithium compound as a catalyst. It shows that the upper limit of the number average molecular weight of a polymer is only 10,000-15,000. This document also teaches that the reason for this low molecular weight is that, along with the polymerization reaction, a transition reaction and a removal reaction of lithium hydride caused by the removal of the lithium cation present at the polymer end occur.

Die Makromolekulare Chemie., 163, 13 (1973) discloses cyclohexadiene homopolymers obtained by polymerizing 1,3-cyclohexadiene using large amounts of organolithium compounds as catalysts. However, the polymers obtained in these prior art documents are oligomers having a number average molecular weight of only 6,500.

European Polymer J., 9, 895 (1973) discloses copolymers obtained by copolymerizing 1,3-cyclohexadiene with butadiene and / or isoprene using π-arylnickel compounds as polymerization catalysts. .

However, the polymers obtained in these prior art documents are oligomers with extremely low molecular weights. In addition, polymers of this prior art document have been reported to have a single glass transition temperature, suggesting that the polymer is a random copolymer structure.

Kobunshi Ronbun-shu (Collection of Papers on Polymers), Vol. 34, No. 5, 333 (1977) discloses a method for synthesizing a copolymer of 1,3-cyclohexadiene and acrylonitrile using zinc chloride as a polymerization catalyst. However, the alternating copolymers obtained in these prior art documents are oligomers with extremely low molecular weights.

J. Polym. Sci., Polym. Chem. Ed., 20, 901 (1982) discloses cyclohexadiene homopolymers obtained by polymerizing 1,3-cyclohexadiene using organic sodium compounds as catalysts. The organic sodium compound used in this prior art document is sodium naphthalene, and the radical anions derived from sodium naphthalene form two anions (dianions) that serve as polymerization initiation sites.

This means that although the cyclohexadiene homopolymer reported in this document has an apparent number average molecular weight of 38,700, in practice the single polymer is only a combination of two polymer chains, each having a number average molecular weight of 19,350, each of which It extends in two different directions from the polymerization initiation site.

In addition, in the polymerization method disclosed in this document, the polymerization reaction needs to be carried out at extremely low temperature. Thus, the techniques of this prior art document have no commercial value.

Makromol. Chem. 191, 2743 (1990) discloses a process for polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. This prior art document discloses that not only the transition reaction caused by the removal of lithium cations present at the polymer end with the polymerization reaction, but also the reaction of removing lithium hydride violently occurs. Furthermore, although the polymerization is carried out using polystyryllithium as the polymerization initiator, it has been reported that the styrene-cyclohexadiene block copolymer cannot be obtained at room temperature, and the obtained product is only a cyclohexadiene homopolymer.

Furthermore, this prior art document reports that when the polymerization reaction is carried out at -10 ° C., a styrene-cyclohexadiene block copolymer having a molecular weight of about 20,000 is obtained in very low yield with a cyclohexadiene homopolymer. .

However, the content of cyclohexadiene block in the obtained copolymer is extremely low. Moreover, this prior art document not only describes cyclohexadiene block copolymers with chain conjugated diene monomers, but also multiblock cyclohexadiene copolymers having three or more block arrangements, or radial block copolymers of cyclohexadiene. No teaching or presentation is given.

As easily understood above, it was not possible to obtain cyclic conjugated diene copolymers with good properties that could be satisfactorily used as industrial materials in all prior art. Needless to say, polymerization catalysts of such cyclic conjugated diene copolymers are not known.

Summary of the Invention

In this situation, the inventors may contain one or more types of cyclic conjugated diene monomer units, or derived from one or more types of monomers other than one or more types of cyclic conjugated diene monomer units and the aforementioned cyclic conjugated diene monomers. As cyclic conjugated diene polymers containing monomer units (these other monomers are copolymerizable with cyclic conjugated diene monomers), the number average molecular weight of such cyclic conjugated diene polymers is high, e.g., melting point, glass transition temperature and In addition to having good thermal properties with regard to heat deflection temperature, it is also widely and intensively to develop new polymerization catalysts useful for the preparation of cyclic conjugated diene polymers, which have good mechanical properties such as high tensile modulus and high flexural modulus. Phosphorus study was performed. As a result, the inventors have successfully developed novel polymerization catalysts capable of preparing polymers as mentioned above. Not only can this catalyst achieve the desired high degree of polymerization, but it can also carry out living anionic polymerization effectively and efficiently, which can block copolymerize the cyclic conjugated diene monomer with at least one other monomer copolymerizable with it. Has excellent catalytic activity. By such a novel polymerization catalyst, a novel cyclic conjugated diene polymer that has not been reported for the first time can be synthesized. In addition, the novel polymerization catalyst produces a cyclic conjugated diene polymer wherein monomer units derived from the cyclic conjugated diene monomer are introduced as a part or all of the monomer units constituting the main chain of the polymer, in a predetermined ratio and in a predetermined arrangement. Do it. The present invention has been completed based on this new finding.

It is therefore an object of the present invention to provide useful new polymerization catalysts which can produce polymers such as those mentioned above. Not only can this catalyst achieve the desired high degree of polymerization, but it can also carry out living anionic polymerization effectively and efficiently, which can block copolymerize the cyclic conjugated diene monomer with at least one other monomer copolymerizable with it. Has excellent catalytic activity.

In the present invention, there is provided a polymerization catalyst containing a heterogeneous or multinuclear complex of a complexing agent and an organometallic compound containing a metal belonging to group IA of the periodic table.

The present invention relates to novel polymerization catalysts. More specifically, the present invention relates to a polymerization catalyst containing a heteronuclear or multinuclear complex of an organometallic compound containing a metal belonging to group IA of the periodic table and a complexing agent. The catalyst of the present invention contains one or more types of cyclic conjugated diene monomer units or monomer units derived from one or more types of cyclic conjugated diene monomer units and one or more types of monomers other than the above-mentioned cyclic conjugated diene monomers. (These other monomers are copolymerizable with the cyclic conjugated diene monomer.) It is useful for the preparation of a novel cyclic conjugated diene polymer, wherein the number average molecular weight of the cyclic conjugated diene polymer is high, for example, a melting point, It is a novel cyclic conjugated diene polymer which not only has excellent thermal properties in glass transition temperature and heat deformation temperature but also has excellent mechanical properties such as high tensile modulus and high flexural modulus, which is also described in the above-mentioned excellent cyclic conjugated diene polymer. It is involved in the manufacturing method. The novel polymerization catalyst of the present invention not only can achieve the desired high degree of polymerization, but also can effectively and efficiently block copolymerize the cyclic conjugated diene monomer with at least one other monomer copolymerizable with the living anion. It has excellent catalytic activity to perform the polymerization (living anionic polymerization).

In the attached drawing:

1 is a chart obtained in Example 3 measured using deuterated form of 1,2-dichlorobenzene as a solvent, showing the ¹ H-NMR spectrum of the cyclic conjugated diene homopolymer;

2 is a chart showing the viscoelastic spectrum of the cyclic conjugated diene homopolymer obtained in Example 9;

3 is a chart obtained in Example 20 measured using a deuterated form of chloroform as solvent, showing the ¹ H-NMR spectrum of the cyclic conjugated diene copolymer;

4 is a chart obtained in Example 24 measured using a deuterated form of chloroform as a solvent, showing the ¹ H-NMR spectrum of the cyclic conjugated diene copolymer;

FIG. 5 is a chart obtained in Example 27 measured using deuterated form of chloroform as solvent, showing ¹ H-NMR spectrum of cyclic conjugated diene copolymer; FIG.

6 is a chart obtained in Example 29 measured using a deuterated form of 1,2-dichlorobenzene as solvent, showing the ¹ H-NMR spectrum of the cyclic conjugated diene block copolymer composition;

7 shows a GPC chart of a cyclic conjugated diene block copolymer composition obtained in Example 29;

8 shows the DMA spectrum of the cyclic conjugated diene block copolymer composition obtained in Example 29;

9 is a chart obtained in Example 30 measured using a deuterated form of 1,2-dichlorobenzene as solvent, showing the ¹ H-NMR spectrum of the cyclic conjugated diene block copolymer composition;

10 shows a GPC chart of a cyclic conjugated diene block copolymer composition obtained in Example 30; And

11 shows a chart showing the DMA spectrum of the cyclic conjugated diene block copolymer composition obtained in Example 31.

For easy understanding of the present invention, the important features and various aspects of the present invention are listed below.

1. A polymerization catalyst containing a heteronuclear or multinuclear complex of an organometallic compound containing a metal belonging to group IA of the periodic table with a complexing agent.

2. The polymerization catalyst according to the above 1, wherein the complexing agent contains an amine.

3. The polymerization catalyst according to the above 1 or 2, which is used to prepare a cyclic conjugated diene polymer containing a main chain represented by the following formula (I):

[Formula I]

[Wherein, A to E are monomer units constituting the main chain in which monomer units A to E are arranged in an arbitrary order, and l to p are monomer units A based on the total weight of monomer units A to E, respectively. Weight% of ˜E; At this time,

A is selected from the group consisting of cyclic conjugated diene monomer units,

B is selected from the group consisting of chain conjugated diene monomer units,

C is selected from the group consisting of vinyl aromatic monomer units,

D is selected from the group consisting of polar monomer units, and

E is selected from the group consisting of ethylene monomer units and α-olefin monomer units; And

l to p satisfy the following conditions:

l + m + n + o + p = 100,

0.5 ≤ l ≤ 100,

0 ≤ m <100,

0 ≤ n <100,

0 ≦ o <100, and

0 ≦ p <100.

In the present invention, the monomer unit of the polymer is used in the same way as the nomenclature and the term “unit” is used without changing the name of the basic monomer from which the monomer unit is derived. For example, the term “cyclic conjugated diene monomer unit” is a monomer unit formed in a polymer obtained by polymerization of a cyclic conjugated diene monomer, in which a cycloolefin corresponding to a cyclic conjugated diene monomer is substituted at two carbon atoms of its skeleton. It means that the bond has a formed molecular structure.

As mentioned above, the cyclic conjugated diene polymer obtained using the catalyst of the present invention is a polymer containing a main chain composed of some or all of monomer units derived from the cyclic conjugated diene monomer.

Representative examples of the cyclic conjugated diene polymer of the present invention are polymers containing a main chain composed of only one or more monomers selected from the group consisting of cyclic conjugated diene monomer units, and cyclic conjugated diene monomer units and copolymerized with the conjugated diene monomers. And polymers containing a main chain composed of at least one monomer unit selected from the group consisting of monomer units derived from at least one comonomer.

More specific examples of cyclic conjugated diene polymers include homopolymers of cyclic conjugated diene monomers, copolymers of two or more types of cyclic conjugated diene monomers, and copolymerization with one or more cyclic conjugated diene monomers and the cyclic conjugated diene monomers. Copolymers of one or more comonomers.

Most preferred examples of the cyclic conjugated diene polymer include a polymer containing a main chain composed of at least one monomer unit selected from the group consisting of cyclic conjugated diene monomer units having a cyclohexene ring in its molecular structure.

In the present invention, the term "cyclic conjugated diene monomer" means a cyclic conjugated diene having a ring structure of five or more rings.

It is preferable that the cyclic conjugated diene monomer is a cyclic conjugated diene having a 5 to 8 membered carbon ring structure. More preferably, the cyclic conjugated diene monomer is a cyclic conjugated diene having a 6-membered carbon ring structure.

Examples of cyclic conjugated diene monomers include derivatives from 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and derivatives thereof. Preferred examples of the cyclic conjugated diene monomers include 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives, or cyclic conjugated diene monomers having a 6-membered carbon ring structure bonded therein. Of these, 1,3-cyclohexadiene is most preferred.

In the present invention, examples of the comonomer copolymerizable with the cyclic conjugated diene monomer include monomers that can be polymerized by anionic polymerization.

Examples of such monomers include chain conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene; Vinyl aromatic monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-t-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene and vinylpyridine; Polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone and methyl α-cyanoacrylate; Polar monomers such as ethylene oxide, propylene oxide, lactones, lactams and cyclosiloxanes; Ethylene monomers; And α-olefin monomers. Each of these monomers may be used alone or in combination.

In the present invention, the copolymer of the above-mentioned comonomer and the cyclic conjugated diene monomer may be in any arrangement. For example, the copolymer can be a diblock, triblock, tetrablock, multiblock, radial block copolymer, graft copolymer, tapered copolymer, random copolymer or alternating copolymer.

In the cyclic conjugated diene polymer, the monomer units derived from one or more comonomers copolymerizable with the cyclic conjugated diene monomer may be monomer units formed by subsequent polymerization such as hydrogenation, halogenation, and the like.

In the cyclic conjugated diene polymer, the content of the cyclic conjugated diene monomer unit is not particularly limited and may vary depending on the intended use of the polymer. However, the content of the cyclic conjugated diene monomer unit is generally 0.1 to 100% by weight, preferably 0.5 to 100% by weight, more preferably 1, based on the weight of the main chain of the cyclic conjugated diene polymer. It is in the range of -100 weight%.

Moreover, in order to obtain a cyclic conjugated diene polymer that can be used in a field in which the polymer needs to have excellent thermomechanical properties, the content of the cyclic conjugated diene monomer unit in the cyclic conjugated diene polymer is the main component of the cyclic conjugated diene polymer. Based on the weight of the chain, it is recommended to be in the range of 5 to 100% by weight, more preferably 10 to 100% by weight, most preferably 15 to 100% by weight.

In order to obtain a cyclic conjugated diene polymer that can be used as a material for mechanical parts and the like, the number average molecular weight of the polymer is preferably in the range of 25,000 to 5,000,000. From the point of view of production rate in producing such a polymer on a commercial scale, the number average molecular weight of the polymer is from 25,000 to 3,000,000, more preferably from 30,000 to 2,000,000, even more preferably from 35,000 to 1,000,000, most preferably from 40,000 to 500,000. It is recommended to be in range.

When the cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention contains a main chain composed only of one or more monomer units selected from the group consisting of cyclic conjugated diene monomer units, the number average molecular weight of the polymer is assayed from standard polystyrene. The value obtained using the curve is preferably 40,000 or more.

If the number average molecular weight of such a polymer is less than 40,000, the polymer is significantly brittle, resulting in extremely low commercial value of the polymer. In terms of production rate for producing such polymers on a commercial scale, the number average molecular weight of the polymer is 40,000 to 5,000,000, more preferably 40,000 to 2,000,000, even more preferably 40,000 to 1,000,000, most preferably 40,000 to 500,000. It is recommended to be in range.

In a cyclic conjugated diene polymer prepared using a polymerization catalyst of the present invention in which the main chain is composed of only one or more monomer units selected from the group consisting of cyclic conjugated diene monomer units, the molecular weight of the polymer may be controlled or In order to obtain in the form, the ends of the plurality of polymer chains are dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, A combined arrangement can be assumed using two or more conventional functional coupling agents such as titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, or esters.

Prepared using a polymerization catalyst of the present invention which is a copolymer containing at least one monomer unit selected from the group consisting of cyclic conjugated diene monomer units and monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer. For the cyclic conjugated diene polymer, there is no particular limitation on the molecular weight, and the molecular weight of the polymer can be appropriately selected depending on the intended use of the polymer.

However, the number average molecular weight of the polymer, converted into values obtained using the calibration curve of standard polystyrene, is generally from 25,000 to 5,000,000, preferably from 25,000 to 3,000,000, more preferably from 30,000 to 2000,000, even more preferably from 35,000. It is recommended to be in the range of -1,000,000, most preferably 40,000-500,000.

When the number average molecular weight of such a polymer is less than 25,000, the polymer produced using the polymerization catalyst of the present invention becomes a remarkably brittle solid material or viscous liquid, and the commercial value of the polymer as an industrial material becomes extremely low.

On the other hand, when the number average molecular weight of the polymer is 5,000,000 or more, the polymer is disadvantageous in various commercial aspects. For example, such a high molecular weight cyclic conjugated diene copolymer takes a long time to polymerize, and has a disadvantage in that the melt viscosity of the obtained polymer becomes high.

In the present invention, the number average molecular weight of the polymer is converted into a value obtained using the calibration curve of standard polystyrene.

When the cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention is a cyclic conjugated diene block copolymer containing a plurality of different polymer blocks in its polymer chain, the polymer block is made from only one or more cyclic conjugated diene monomers. A polymer block composed of derived monomer units, a polymer block composed of monomer units derived from one cyclic conjugated diene monomer and monomer units derived from one or more types of comonomers copolymerizable with the cyclic conjugated diene, or a ring It may be a polymer block composed of monomer units derived from one or more comonomers copolymerizable with the type conjugated diene monomer. For various purposes, different types of polymer blocks can be designed and polymerized. By appropriately selecting and combining such polymer blocks, it is possible to obtain cyclic conjugated diene block copolymers having properties suitable for the intended use.

In the present invention, when some or all of the polymer blocks contain a monomer unit selected from the group consisting of cyclic conjugated diene monomer units, the thermal mechanical properties of the cyclic conjugated diene block copolymer prepared using the polymerization catalyst of the present invention. To improve this, the polymer block contains a continuous arrangement of at least 10 cyclic conjugated diene monomer units, preferably at least 20 cyclic conjugated diene monomer units, more preferably at least 30 cyclic conjugated diene monomer units. It is recommended to do

As a polymerization method of a cyclic conjugated diene block copolymer prepared using the polymerization catalyst of the present invention, a block unit polymer containing monomer units derived from at least one cyclic conjugated diene monomer, at least one cyclic conjugated diene Block unit polymers containing monomer units derived from monomers and monomer units derived from one or more types of comonomers copolymerizable therewith, and monomer units derived from one or more types of comonomers copolymerizable with cyclic conjugated diene monomers. Preparing a block unit polymer containing; Selecting an appropriate combination of such block unit polymers; Mention may be made of the process comprising polymerizing-bonding combinations of block unit polymers together to obtain cyclic conjugated diene block copolymers having properties suitable for the intended use of the polymers. If the carbon-carbon double bond contained in the molecular structure of the cyclic conjugated diene monomer unit is not saturated by hydrogenation or the like, the cyclic conjugated diene block copolymer can undergo a hydrogenation reaction or the like if necessary.

Specific examples of preferred embodiments of the polymerization process using the catalyst of the present invention include the following manner.

One aspect of the method comprises forming a block unit polymer containing monomer units derived from one or more cyclic conjugated diene monomer units by polymerization, or block unit polymers derived solely from cyclic conjugated diene monomer units; Polymerizing the unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer, wherein the comonomer is continuously bonded to one or both ends of the block unit polymer by polymerization. If necessary, the obtained block copolymer can be subjected to a hydrogenation reaction or the like.

Another aspect of this method is to polymerize one or more types of comonomers copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; Polymerization of the block unit polymer with at least one type of cyclic conjugated diene monomer and optionally at least one type of comonomer copolymerizable with the cyclic conjugated diene monomer, wherein the cyclic conjugated diene monomer and any of the comonomers are polymerized Continuously coupled to one or both ends of the. If necessary, the obtained block copolymer can be subjected to a hydrogenation reaction or the like.

Another aspect of the method comprises forming a block unit polymer containing monomeric units derived from at least one type of cyclic conjugated diene monomer by polymerization, or a block unit polymer derived solely from cyclic conjugated diene monomers; Polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a polymer; Continuously bonding to the obtained polymer by polymerizing a block unit polymer containing monomer units derived from at least one cyclic conjugated diene monomer or a block unit polymer derived solely from cyclic conjugated diene monomers. If necessary, the obtained block copolymer can be subjected to a hydrogenation reaction or the like.

A further aspect of this method is to polymerize one or more types of comonomers copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; Polymerizing the block unit polymer with a block unit polymer containing a monomer unit derived from at least one cyclic conjugated diene monomer unit or a block unit polymer derived from only a cyclic conjugated diene monomer; Continuously bonding to the obtained polymer by polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer. If necessary, the obtained block copolymer can be subjected to a hydrogenation reaction or the like.

Another further aspect of the process is the formation of a block unit polymer containing monomeric units derived from a cyclic conjugated diene monomer on one paper by polymerization, or a block unit polymer derived solely from cyclic conjugated diene monomers; Polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a polymer; The end of the polymer chain of the obtained polymer is a known coupling agent having at least 2-functional groups (e.g., dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide , Chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, or esters). If necessary, the obtained block copolymer can be subjected to a hydrogenation reaction or the like.

Another further aspect of the process is the formation of a block unit polymer containing monomeric units derived from a paper-like cyclic conjugated diene monomer by polymerization, or just a block unit polymer derived from cyclic conjugated diene monomers; Hydrogenation of functional block unit polymers (if required) by introducing functional groups using terminal modifiers (ethylene oxide, propylene oxide, cyclohexene oxide, carbon dioxide, or acid chloride) at one or both ends of the block unit polymer And the like); And combining the obtained functional block unit polymer with another polymer having a functional group that can be bonded to the functional group of the polymer. Examples of such other polymers include polyamides, polyesters, polyketones, polyimides, polysulfides, polysulfones, polystyrenes and polyolefins.

Another further aspect of the process is the formation of a block unit polymer containing monomeric units derived from a cyclic conjugated diene monomer on one paper by polymerization, or a block unit polymer derived solely from cyclic conjugated diene monomers; Polymerizing this block unit polymer with at least one comonomer capable of copolymerizing with a cyclic conjugated diene monomer to obtain a polymer; At one or both ends of the obtained polymer, a functional group can be introduced by using a terminal modifier (ethylene oxide, propylene oxide, cyclohexene oxide, carbon dioxide, or acid chloride) to carry out a hydrogenation reaction of the functional polymer (if necessary). ); And combining the obtained functional polymer with another polymer having a functional group that can be bonded to the functional group of the polymer.

Another further aspect of the process involves polymerizing one or more types of comonomers capable of copolymerizing cyclic conjugated diene monomers with one or more types of conjugated monomers having a different polymerization rate than the cyclic conjugated diene monomers. Obtaining coalescing. If necessary, the obtained block copolymer can undergo a hydrogenation reaction or the like.

Another additional aspect of the method involves polymerizing the cyclic conjugated diene monomer with at least one comonomer copolymerizable therewith, where the ratio of the cyclic conjugated diene monomer to at least one conjugated monomer is inconsistent. . If necessary, the obtained block copolymer can undergo a hydrogenation reaction or the like.

In the cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention, the block unit polymer containing at least one monomer unit selected from the group consisting of cyclic conjugated diene monomer units is one species copolymerizable with the cyclic conjugated diene monomer. The monomer unit derived from the above comonomer may be further included.

In addition, the block unit polymer containing monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer may further include at least one monomer unit selected from the group consisting of cyclic conjugated diene monomer units. have.

In the cyclic conjugated diene polymer prepared by using the polymerization catalyst of the present invention, a monomer unit derived from one or more cyclic conjugated diene monomers, and a block unit polymer comprising such monomer units, the monomer comprising a cyclohexene ring Most preferably, the unit is used and a block unit polymer comprising monomer units comprising a cyclohexene ring or composed of each monomer unit containing a cyclohexene ring.

In the cyclic conjugated diene monomer unit contained in all or part of the monomer units constituting the main chain of the cyclic conjugated diene polymer produced using the polymerization catalyst of the present invention, preferred examples are represented by the following formula (II), Most preferred is represented by the following formula (III):

[Formula II]

[Wherein, x is an integer of 1 to 4, each R ¹ is independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, a C _{5 to} C ₂₀ aryl group , C ₃ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cyclodienyl group or a 5-10 membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a hetero atom, each R ² independently represents a hydrogen atom, a halogen atom, C ₁ ~C ₂₀ alkyl group, C ₂ ~C ₂₀ unsaturated aliphatic hydrocarbon group, C ₅ ~C ₂₀ aryl group, C ₃ ~C ₂₀ cycloalkyl group, C ₄ ~C ₂₀ cycloalkyl cyclopentadienyl group, or one as a hetero atom A 5-10 membered heterocyclic group having at least nitrogen, oxygen or sulfur atoms, or each R ² is independently a bridge in which two R ² groups together are represented by the formula — (CR ³ ₂ ) _y — where R is ³ has the same meaning as defined for R ^1, y is 1, Which represents a bond or a group which forms a is an integer of 10), the carbon only formula (II) - carbon double bond is not hydrogenated;

[Formula III]

[Wherein each R ² is as defined for Formula (II)].

In the formulas (II) and (III), the alkyl group has 2 to 10 carbon atoms, the unsaturated aliphatic hydrocarbon group has 2 to 10 carbon atoms, the aryl group has 5 to 10 carbon atoms, and the cycloalkyl group has 5 It is preferred to have from 10 to 10 carbon atoms, the cyclodienyl group to have 5 to 10 carbon atoms, and the heterocyclic group to have a 5 to 8 membered ring structure.

Specific examples of the substituents R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, cyclopentyl and cyclo Hexyl group, vinyl group, phenyl group, tolyl group, naphthyl group, cyclopentadienyl group, indenyl group, pyridyl group, and piperidyl group.

In order to obtain a cyclic conjugated diene block copolymer used as a thermoplastic elastomer or a special high impact transparent resin, or to obtain a composition containing such a block copolymer, the block copolymer has one or more agglomerated phases (blocks) It contains the above elastic phase (block), and these two types of blocks need to form a microdomain structure. Aggregated phases in the polymer chain of such block copolymers act as physical crosslinking points at temperatures lower than Tg, causing the block copolymer to become elastic. On the other hand, at a temperature higher than Tg or Tg, the flocculated phase is fluidized to impart fluidity to the block copolymer. Therefore, in the latter case it is possible to injection mold or recycle the block copolymer.

As mentioned above, the preferred form of the cyclic conjugated diene block copolymer prepared using the polymerization catalyst of the present invention is at least two Y blocks and conjugated diene monomer units each containing at least one cyclic conjugated diene monomer unit A. Triblock or higher copolymers containing one or more Z blocks mainly composed of B chains.

Another preferred form of the cyclic conjugated diene block copolymer prepared using the polymerization catalyst of the present invention is mainly composed of one Y block and conjugated diene monomer unit B chains containing at least one cyclic conjugated diene monomer unit A It is a copolymer of two or more blocks containing one Z block.

In addition, block copolymers prepared using the polymerization catalysts of the present invention, as mentioned above, in (a) the aforementioned triblock or higher copolymer and (β) the above-mentioned diblock or higher air in another aspect of the present invention. It can be used to provide a cyclic conjugated diene copolymer composition containing the copolymer.

In the cyclic conjugated diene block copolymer composition containing the block copolymers (α) and (β), the Y blocks and Z blocks contained in the block copolymers (α) and (β) of each component form a microdomain structure. I found an amazing fact.

In the cyclic conjugated diene block copolymer composition, the Y blocks form an aggregated phase (ie, hard segments) and the Z blocks form an elastomeric phase (ie, soft segments).

As mentioned above, the cyclic conjugated diene block copolymer which can be used as component (α) in the cyclic conjugated diene block copolymer composition is a triblock or more containing main chain composed of two or more Y blocks and one or more Z blocks. Copolymer, which is prepared using the polymerization catalyst of the present invention.

Three or more blocks each containing two or more polymer blocks (Y blocks) mainly composed of cyclic conjugated diene monomer units or derivatives thereof, and one or more polymer blocks (Z blocks) mainly composed of chain conjugated diene monomers or derivatives thereof Examples of the cyclic conjugated diene block copolymer which can be used as component (α) which is a copolymer include linear block copolymers represented by the following formula (IV) and radial block copolymers represented by the following formula (V), respectively:

(Y-Z) r, Y- (Z-Y) q, and Z- (Y-Z) r (IV)

(Wherein q is an integer of 1 or more, and each r is an integer of 2 or more)

[(Z-Y) q] rX, [(Y-Z) q] rX,

[(Z-Y) q-Z] rX, and [(Y-Z) q-Y] rX (V)

Wherein each q and each r are as defined above; X is independently a residue of a multifunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, or epoxidized soybean oil, or the present invention Residues of the polymerization catalyst).

In addition, the cyclic conjugated diene block copolymer which can be used as the component (α) may have a different arrangement from that represented by the formulas (IV) and (V).

For example, the block copolymer can have an asymmetric radial block, graft block, star block and comb block arrangement. In particular, in order to obtain a cyclic conjugated diene block copolymer composition which can be used as a thermoplastic elastomer or a special high impact transparent resin, as in the case of the block copolymers represented by the formulas (IV) and (V), The block copolymer needs to contain two or more Y blocks.

As long as the cyclic conjugated diene block copolymer composition contains the block copolymer as mentioned above as component (α), the copolymer composition has the formula ZYZ, i.e., the formula (IV) Z- (YZ) wherein r is 1 The triblock copolymer represented by r may be further contained.

There is no particular limitation on the content of such copolymers in block copolymer compositions in which the copolymer cannot act as a physical crosslinking point (such as the triblock copolymer mentioned above represented by the formula ZYZ), and the intended use of the block copolymer composition. Depending on the content of the copolymer can be appropriately selected. However, in order to obtain satisfactory mechanical properties, it is desirable that the content of such copolymers be less than 70% by weight based on the weight of the copolymer composition.

There is no particular limitation on the form of bonding between the block copolymer as component (α) and the block copolymer as component (β). For example, the block copolymers (α) and (β) may be directly bonded to each other by carbon-carbon bonds. Alternatively, if desired, the block copolymers (α) and (β) are bonded to one another via residues of difunctional or polyfunctional coupling agents (such as dimethyldichlorosilane or methylene chloride), or ether crosslinks, ester crosslinks Or by conventional covalent bonds such as amide crosslinking, imide crosslinking, or carbonate crosslinking.

The radial block copolymer represented by the formula [(YZ) q] rX, [(YZ) qY] rX, or [(ZY) qZ] rX (wherein q is an integer of 1 or more and r is an integer of 2 or more) is thermoplastic. It can be used as an elastic body. On the other hand, a radial block copolymer represented by [(Z-Y) q] rX can be used as an elastomer only if q is an integer of 2 or more (and r is an integer of 2 or more).

In the cyclic conjugated diene block copolymer composition, each radial block copolymer of the above formula need not have the same structural composition. For example, the radial block copolymer represented by [(YZ) q] rX in the formula (V) may be selected from the following formulas (YZ) ₄ X, (YZ) ₃ X, (YZ) ₂ It may be present in the form of a mixture of block copolymers represented by X and (YZ), respectively.

The cyclic conjugated diene block copolymer as component (α) in the cyclic conjugated diene block copolymer composition is a block copolymer containing at least a portion of the main chain of a copolymer composed of two or more Y blocks and one or more Z blocks. Therefore, the block copolymer need not contain only Y block and Z block.

For example, the cyclic conjugated diene block copolymer that can be used as component (α) is a structure represented by YZUY, YUZY or ZYUY (wherein the U block is composed of monomer units copolymerizable with Y block and Z block). And one or more monomer units or derivatives thereof selected from the group consisting of: a). Examples of monomer units copolymerizable with Y blocks and Z blocks include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinyl Vinyl aromatic monomers such as naphthalene, diphenylethylene and vinylpyridine; Polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone and methyl α-cyanoacrylate; Polar monomers such as ethylene oxide, propylene oxide, lactones, lactams and cyclic siloxanes; Ethylene monomers; And α-olefin monomers. Furthermore, cyclic conjugated diene monomers or derivatives thereof and / or chains such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene or 1,3-hexadiene Conjugated diene monomers may be copolymerized into Ublocks. Alternatively, the block copolymer may contain a plurality of different polymer blocks, such as for example U blocks, V blocks, W blocks and the like. In the above, each monomer unit such as a V block, a W block, etc. is selected from the same monomer units used in the U block but arranged in a different arrangement from the U block. The arrangement of such block copolymers, which are component (α) containing three or more polymer blocks, is not limited to the linear block arrangement, which is the case for the formulas indicated above. For example, the block copolymer can have an arrangement of radial blocks, star blocks or comb blocks.

The content of component (α) in the cyclic conjugated diene block copolymer composition may be appropriately selected within the range of 5 to 95% by weight, preferably 15 to 85% by weight. When the content of component (α) is less than 5% by weight, it is not possible to obtain a copolymer composition having satisfactory mechanical properties (such as breaking tensile strength and elongation at break) that can be used as a thermoplastic elastomer or a special high impact transparent resin. On the other hand, when the content of component (α) is 95% by weight or more, the copolymer composition exhibits special performance in particular in mechanical properties, but the processability and fluidity deteriorate.

The cyclic conjugated diene block copolymer that can be used as component (β) in the cyclic conjugated diene block copolymer composition is composed of one Y block and one mainly composed of monomer units derived from one or more cyclic conjugated diene monomers or derivatives thereof. It is a diblock copolymer containing one Z block mainly composed of monomer units derived from the conjugated diene monomer or derivatives thereof. That is, the cyclic conjugated diene block copolymer as component (β) is a Y-Z diblock copolymer.

Y-Z diblock copolymer as component (β) preferably has a Y / Z weight ratio of 3/97 to 97/3. In addition, the Y / Z weight ratio of component (β) may or may not be the same as the block copolymer of component (α).

The content of Y-Z diblock copolymer as component (β) in the cyclic conjugated diene block copolymer composition may be appropriately selected within the range of 95 to 5% by weight, preferably 85 to 15% by weight. When the content of the Y-Z diblock copolymer as component (β) is less than 5% by weight, the processability and fluidity of the copolymer composition are deteriorated. On the other hand, when the content of the YZ diblock copolymer as component (β) is 95% by weight or more, the processability of the copolymer composition is greatly improved, but satisfactory mechanical properties that can be used as a thermoplastic elastomer or a special high impact transparent resin (break tensile) Copolymer compositions with strength and elongation at break) cannot be obtained.

In the cyclic conjugated diene block copolymer composition obtained using the catalyst of the present invention, the molecular weight of each component (α) and (β) is not particularly limited and may be appropriately adjusted according to the intended use of the composition. . However, the number average molecular weights of the components (α) and (β) in terms of values obtained using the calibration curve of standard polystyrene are generally 1,000 to 1,000,000, preferably 10,000 to 500,000, and more preferably 20,000 to 400,000. .

Molecular weight distribution of each component (α) and (β) The value of, and Represents a weight average molecular weight and a number average molecular weight, respectively) in the range of 1.01 to 10, preferably 1.05 to 7, more preferably 1.1 to 5.

Although the molecular weights of components (α) and (β) can be appropriately selected within the above-mentioned ranges, in general, the molecular weight of each component is adjusted so that the molecular weight of component (α) is greater than the molecular weight of component (β). .

In the cyclic conjugated diene block copolymer composition, the molecular weight of the Y block contained in each component (α) and (β), which is composed of some or all of monomer units derived from one or more cyclic conjugated diene monomers or derivatives thereof, It may be appropriately adjusted according to the intended use of the. In general, the Y block is preferably composed of a contiguous arrangement of at least 20 monomer units, more preferably at least 30 monomer units, most preferably at least 50 monomer units. Each component of two or more Y blocks in component (α) may be the same or different. For example, when component (α) is a triblock copolymer having a Y—Z—Y structure, each Y block may have a different length to form an asymmetric block copolymer.

In the cyclic conjugated diene block copolymer composition, the content of the Y block (ie, the polymer block mainly composed of monomer units derived from one or more cyclic conjugated diene monomers or derivatives thereof) in each of the components (α) and (β) is It is not particularly limited and may be appropriately selected depending on the intended use of the composition. However, the content of the Y blocks in each of the components (α) and (β) is selected in the range of 3 to 97% by weight, preferably 10 to 85% by weight, based on the weight of the composition.

In particular, in order to obtain a block copolymer composition that can be used as the thermoplastic elastomer, it is preferable that the content of the Y block is in the range of 10 to 50% by weight based on the weight of the copolymer composition. In order to obtain a block copolymer composition that can be used as a special high impact transparent resin, it is preferable that the content of the Y block is in the range of 65 to 90% by weight based on the weight of the copolymer composition.

If necessary in the cyclic conjugated diene block copolymer composition, the Y blocks contained in each of the components (α) and (β) may further contain monomer units derived from one or more comonomers capable of copolymerizing with the cyclic conjugated diene monomer. It may contain. Generally, the Y block will contain monomeric units derived from one or more comonomers capable of copolymerizing with the cyclic conjugated diene monomer in an amount of up to 80% by weight, preferably up to 50% by weight, based on the weight of the Y block. Can be.

Preferred examples of the cyclic conjugated diene monomer used to form the Y block include those mentioned above as examples of the cyclic conjugated diene monomer used in the preparation of the cyclic conjugated diene polymer using the polymerization catalyst of the present invention.

If the Y block contains one or more monomer units selected from the group consisting of cyclic conjugated diene monomer units and comonomer units derived from one or more comonomers capable of co-polymerizing with it, the Y block may be, for example, random, block It may have any conventional arrangement, such as alternating or tapered arrangement.

Preferred examples of comonomers that can be used to introduce comonomer units into the Y block include styrene and α-methylstyrene.

On the other hand, examples of the chain conjugated diene monomer used to form the Z block contained in each component (α) and (β) of the cyclic conjugated diene block copolymer composition include 1,3-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene are mentioned. Among these, 1,3-butadiene and isoprene are particularly preferable.

If desired, the Z block, which is predominantly composed of chain conjugated diene monomer units, may further contain monomer units derived from one or more comonomers that can copolymerize with the chain conjugated diene monomer.

When the Z block contains a chain conjugated diene monomer unit and a monomer unit derived from one or more comonomers copolymerizable therewith, the Z block may be, for example, in a random, block, alternating or tapered arrangement. It may have a known arrangement.

There is no particular limitation on the content of comonomer units derived from comonomers that can copolymerize with the chain conjugated diene monomer in the Z block. However, the content of the comonomer in the Z block is generally at most 50% by weight, preferably at most 30% by weight.

Specific examples of the comonomer copolymerizable with the chain conjugated diene monomer include styrene and α-methylstyrene.

When 1,3-butadiene is used as the chain conjugated diene monomer to form a Z block, the polybutadiene block is formed into a Z block. In the microstructure of the polybutadiene block, cis- and trans-1,4- bonds and vinyl-1,2- bonds are present in the polybutadiene block. There is no particular limitation on the ratio of these bonds. However, the vinyl-1,2-bond content is generally controlled within the range of 10 to 90 mole percent.

As mentioned above, the Z block is a soft segment (elastomer phase). Therefore, the glass transition temperature (Tg) of the Z block is preferably less than room temperature in order to obtain a cyclic conjugated diene block copolymer composition that can be used as a thermoplastic elastomer. If the Z block contains too much 1,2-bonds, the Tg of the Z block becomes undesirably high, degrading the properties of the elastomer under low temperature conditions. Therefore, it is preferable that the 1,2-bond content is in the range of 10 to 80 mol%.

There is no particular limitation on the method for preparing the cyclic conjugated diene block copolymer composition, and known methods can be used.

For example, the process for preparing the cyclic conjugated diene block copolymer composition of the present invention may include melt-kneading or solution-mixing separately polymerized components (α) and (β); A method of continuously supplying a monomer and a catalyst to the polymer solution; Preparing a Y-Z diblock living polymer and partially coupling the polymer; And combinations thereof.

From a commercial point of view, the most preferred method is to prepare a Y-Z diblock living polymer by living anion polymerization and then couple a portion of the active end of the living polymer.

In this method, cyclic conjugated diene block copolymers containing different kinds of polymer blocks can be obtained by varying the equivalent ratio of the concentration of active end to functional group of the coupling agent to control the coupling ratio.

The cyclic conjugated diene block copolymer composition may contain a cyclic conjugated diene homopolymer and / or a chain conjugated diene homopolymer.

Such cyclic conjugated diene homopolymers and / or chain conjugated dienes single having compatibility with each of the Y blocks and Z blocks (ie, cyclic conjugated diene block copolymers) contained in each component (α) and (β) Polymers are sometimes added to act as plasticizers. The content of the cyclic conjugated diene homopolymer and / or the chain conjugated diene homopolymer in the copolymer composition is preferably 40% by weight or less, more preferably 20% by weight or less and most preferably 10% by weight or less.

Preferred examples of the cyclic conjugated diene block copolymer composition include a copolymer composition containing a combination of the following components (α) and (β):

(α) Y-Z-Y or [(Y-Z) q] rX copolymer

Wherein q is an integer of 1 or more and each r is an integer of 2 or more; X is a residue of a multifunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, or epoxidized soybean oil, or the present invention Is a residue of a polymerization catalyst); And

(β) Y-Z Diblock Copolymer

(In the above, components (α) and (β) are present in amounts of 5 to 95% by weight and 95 to 5% by weight, based on the total weight of components (α) and (β), respectively.

The novel polymerization catalysts of the present invention have anionic polymerization activity, in particular living anionic polymerization activity.

The polymerization catalyst of the present invention is a complex containing an organometallic compound containing a metal (Group IA metal) belonging to the Group IA of the periodic table and a complexing agent.

Such complexes, which are polymeric active species, have a binuclear or multinuclear complex structure.

Up to now, various catalysts having living anionic polymerization activity have been proposed. For example, organometallic compounds containing Group IA metals or complexes of complexing agents with them are already widely used as living anionic polymerization catalysts.

Among these complexes of organometallic compounds containing Group IA metals, extensive research has been carried out, particularly with regard to complexes of alkyllithium (R-Li) and TMEDA (tetramethylethylenediamine) as complexing agents.

N. Y. Acad. Sci. 27,741 (1965) is a polymerizable active species, which has a mononuclear alkyllithium-TMEDA complex structure of formula (VI) shown below, characterized in that it contains one metal element in one complex. It says:

(Wherein R represents a C ₁ to C ₂₀ alkyl group).

In the prior art, when TMEDA is added to the molecular system in which the alkyllithium is associated, TMEDA reacts with the alkyllithium to form a complex, thereby destroying the association of the alkyllithium molecules, thus forming mononuclear active species and forming an alkyllithium type catalyst. It has been shown to bring an improvement in the polymerization activity of the.

Therefore, when a conventional polymerization catalyst is used, there is one metal cation at each end of the polymer chains growing in any direction, and monomers arrive alone from any direction at these ends each containing a single metal cation. It was proposed that the polymerization reaction proceed.

Illuminated from a different angle, this suggests that when conventional polymerization catalysts are used, the molecular structure of the polymer chain is influenced by external factors such as reaction temperature, making it extremely difficult to control the molecular structure of the polymer chain.

That is, conventional living anionic polymerization catalysts do not have satisfactory polymerization activity for use for commercial scale practice of polymerization of monomers with large steric hindrance, and therefore are difficult to polymerize cyclic conjugated diene monomers and the like. Moreover, no prior art teaches or suggests that when such conventional anionic polymerization catalysts are used, the polymer chain structure can be satisfactorily controlled.

The inventors have found surprising facts against conventional recognition of living anionic polymerization catalysts. That is, the present inventors surprisingly provide a polymerizable active species having excellent complex structure capable of self-stabilizing the association of the organometallic compound molecules containing the Group IA metal with respect to the complex of the organometallic compound containing the Group IA metal and the complexing agent. Found to be most effective. On the basis of this new finding, polymerization catalysts which have been most preferably used in the process of the present invention have been successfully developed.

The novel polymerization catalyst of the present invention is a complex of a complexing agent and an organometallic compound containing a Group IA metal in which the polymerization active species of the complex has a heteronuclear or multinuclear complex structure.

More specifically, the polymerization catalyst used in the present invention is a heteronuclear or multinuclear complex of an organometallic compound containing a Group IA metal, which can self-stabilize the association of the organometallic compound molecules, and even in the presence of a monomer, It has a complex structure that can hold itself.

In the present invention, the term “dinuclear complex” means a complex of an organometallic compound containing a Group IA metal in which two atoms of the Group IA metal are associated together to form an associative unit. “Multinuclear complex” means a complex of organometallic compounds containing a Group IA metal in which three or more atoms of the Group IA metal are associated together to form an associative unit.

In multinuclear complexes in which three or more atoms of the Group IA metal of the present invention are associated together, the associative form of the atoms may vary depending on the organometallic compound, the type of complexing agent, and the intended use of the complex, the most stable associative form. May be appropriately selected.

In the present invention, the Group IA metal in the multinuclear complex is preferably present in the form of an association of 3 to 20 metal atoms, more preferably 3 to 10 metal atoms. From a commercial standpoint, it is most preferred that the Group IA metal in the multinuclear complex is in the form of an association of 4 to 6 metal atoms. The polymerization catalyst of the present invention not only has satisfactory polymerization activity capable of polymerizing monomers that are difficult to polymerize due to steric hindrance, such as cyclic conjugated diene monomers, on a commercial scale, but also has its own complex structure in the presence of monomers to be polymerized. Has the ability to sustain The polymerization reaction using the polymerization catalyst of the present invention is a living anion polymerization reaction. Nevertheless, however, since the reaction proceeds with the specific structure of the catalyst of the present invention, such as coordination polymerization, the monomer to be polymerized is inserted into the complex as the polymerization active species in the coordination polymerization. Therefore, even when the catalyst of the present invention is used for the polymerization of other known monomers that can be polymerized by anionic polymerization, the molecular structure of the obtained polymer can be satisfactorily controlled.

Examples of Group IA metals that can be used as the polymerization catalyst of the present invention include lithium, sodium, potassium, rubidium, cesium and francium. Of these, lithium, sodium and potassium are preferred, and lithium is particularly preferred.

The complex used as the polymerization catalyst of the present invention is a complex of an organometallic compound containing a Group IA metal. Preferred examples of such complexes include dinuclear or multinuclear complexes of organolithium compounds, organosodium compounds or organopotassium compounds. Of these, dinuclear or polynuclear complex compounds of organolithium compounds are most preferred.

The organolithium compound which can preferably be used as the polymerization catalyst of the present invention is a compound containing at least one lithium atom bonded to an organic molecule containing at least one carbon atom or bonded to an organic polymer. Examples of such organic molecules include C _{1 to} C ₂₀ alkyl groups, C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon groups, C _{5 to} C ₂₀ aryl groups, C _{3 to} C ₂₀ cycloalkyl groups and C _{4 to} C ₂₀ cyclodienyl groups Can be. Examples of the organolithium compound that can be used in the polymerization catalyst of the present invention include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, pentyllithium and hexyl Lithium, aryl lithium, cyclohexyl lithium, phenyl lithium, hexamethylene di lithium, cyclopentadienyl lithium, indenyl lithium, butadienyl di lithium, and isoprenyl di lithium.

As long as a stable association can be formed, there are no particular restrictions on the type of organolithium compound. Representative examples of such organolithium compounds include methyllithium, ethyllithium, n-butyllithium, s-butyllithium, t-butyllithium and cyclohexyl lithium. Of these, n-butyllithium is most preferred from a commercial point of view.

In the present invention, each organometallic compound containing the above-mentioned Group IA metal may be used alone or in combination if necessary.

There is no particular limitation on the kind of the compound (complexing agent) which is coordinated with the organometallic compound containing a Group IA metal to form the polymerization catalyst of the present invention. However, in order to form dinuclear or multinuclear complexes that can maintain their structure even in the presence of monomers to be polymerized, it is necessary to allow the compound to form stable associations between organometallic compounds containing Group IA metals. .

More specifically, an organic compound capable of donating electrons to the Group IA metal of the Group IA metal containing metal so that a stable association can be formed between the organ metal compounds containing the Group IA metal is used as the complexing agent. Can be. Examples of such organic compounds include polar groups [RO-, R ₂ N-, RS-, or 2-oxazoline groups (here, R having an unshared electron pair that can coordinate with an organometallic compound containing a Group IA metal). And an alkyl group)] may be mentioned.

Examples of such organic compounds containing polar groups include amines, ethers and thioethers.

The above-mentioned compounds may be used alone or in combination if necessary as complexing agents.

In commercial terms, amines are most preferred complexing agents to be used with organometallic compounds containing Group IA metals to form binary or multinuclear complexes.

Specifically, in the polymerization catalyst of the present invention, it is particularly preferable that a heteronuclear or polynuclear complex is formed from a complex generator such as an IA metal-containing organometallic compound and an amine, and a heteronuclear or multinuclear complex is formed from an organolithium compound and an amine. Most preferred.

Examples of amines most preferably used as complexing agents capable of forming the polymerization catalyst of the present invention include one or more R ¹ R ² N-groups, wherein each of R ¹ and R ² is independently a hydrogen atom, C _{1 to} C ₂₀ alkyl group, C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, C _{5 to} C ₂₀ aryl group, C _{3 to} C ₂₀ cycloalkyl group, C _{4 to} C ₂₀ cyclodienyl group, or a hetero atom, at least one nitrogen, oxygen or The organic compound and organic polymer containing the 5-10 membered ring heterocyclic group containing a sulfur atom are mentioned. The group is a polar group having a lone pair of electrons capable of coordinating with an organometallic compound containing a Group IA metal.

Of these amines, tertiary amines are most preferred.

Examples of tertiary amines include 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 [5,4,0] -7-undecene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra Decane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine, 2,2'-bipyridyl, 1,10-phenanthroline, hexamethylphosphoric triamide The.

Among them, tetraethylethylenediamine (TEEDA), tetramethylethylenediamine (TMEDA), tetramethyldiethylenetriamine (TMEDTA), pentamethyldiethylenetriamine (PMDT), diazabicyclo- [2,2,2] More preferred are octane (DABACO), 2,2'-bipyridyl, 1,10-phenanthroline, and hexamethylphosphoric triamide (HMPA).

Of these, tetramethylethylenediamine (TMEDA) is most preferred from a commercial point of view.

The amines mentioned above may be used alone or in combination if necessary. The amine can also be used in combination with other types of complexing agents. When combining amines with other types of complexing agents, suitable combinations are selected that allow the intermolecular association of organometallic compounds containing Group IA metals to be stabilized.

There is no particular limitation in the method for synthesizing the heteronuclear or multinuclear complex which is the most preferred polymerization catalyst of the present invention obtained by reaction of an organometallic compound containing a Group IA metal with an amine. Synthesis can be performed by conventional methods.

Examples of such known techniques include a method of dissolving an organometallic compound in an organic solvent in an atmosphere of inert gas, and adding an amine solution in an organic solvent thereto; Then, there is a method of dissolving an amine in an organic solvent under an atmosphere of inert gas and adding an organometallic compound solution thereto. In these methods, a preferred method can be appropriately selected.

When preparing a heteronuclear or multinuclear complex, which is the most preferred polymerization catalyst of the present invention, from the reaction of an amine metal-containing organometallic compound with an amine, the molar ratio of the IA metal contained in the amine and the organometallic compound may be used as desirable.

The molar ratio is preferably M ₁ / M ₂ = 60/1 to 1/60, more preferably M ₁ / M ₂ = 50/1 to 1/50, even more preferably M ₁ / M ₂ = 30 / 1 to 1/30, most preferably M ₁ / M ₂ = 20/1 to 1/20.

In the above, M ₁ is the molar amount of the amine, M ₂ is the molar amount of the Group IA metal contained in the organometallic compound.

When the above-mentioned molar ratio M ₁ / M ₂ is within the above defined range, stable dinuclear or multinuclear complexes can be obtained, which can be advantageously used to prepare polymers or copolymers in high yield.

If the molar ratio M ₁ / M ₂ is out of the above defined range, it is expensive to prepare the complex, and because the complex is unstable, such as undesirable transition reaction or removal reaction of hydride of group IA metal at the same time as polymerization reaction There may also be several disadvantages of side reactions.

In order to maintain a stable complex structure of the polymerization catalyst by itself, a heteronuclear or polynuclear complex of an organometallic compound containing a Group IA metal as the polymerization active species before the start of the polymerization reaction, that is, before adding the cyclic conjugated diene monomer to the reaction system, It is most preferable to manufacture the polymerization catalyst of this invention which contains. When the complexing agent used when preparing the polymerization catalyst of the present invention is a tertiary amine, the preferred form of the heteronuclear or polynuclear complex has a structure represented by the following formula (VII):

[(G) g. (J) j] k (VII)

Wherein G is at least one organometallic compound containing a Group IA metal; J is at least one complexing agent; k is an integer of at least 1; and when k is 1, g represents an integer of at least 2 j represents an integer of 1 or more, and when k is an integer of 2 or more, g and j each represent an integer of 1 or more).

Representative polymerization catalysts of the invention include complexes containing amines and organolithium compounds such that the molar ratio of amine to organolithium is 1/4 to 1/1. More specific examples of the polymerization catalyst of the present invention include an organolithium compound selected from the group consisting of amine and methyllithium, ethyllithium and n-butyllithium such that the molar ratio of amine to organolithium compound is 1/2 to 1/1. And complexes.

In commercial terms, most preferred are multinuclear complexes containing TMEDA and n-butyllithium (n-BuLi) such that the molar ratio of TMEDA to n-BuLi is from 1/2 to 1/1.

The polymerization catalyst of the present invention can be used not only for the polymerization of cyclic conjugated diene monomers but also for the polymerization of other monomers that can be polymerized by anionic polymerization.

Examples of monomers other than the cyclic conjugated diene monomers include chains such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Type conjugated diene monomers; Vinyl aromatic monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-t-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene, and vinylpyridine; Polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, and methyl α-cyanoacrylate; Polar monomers such as ethylene oxide, propylene oxide, lactones, lactams, and cyclic siloxanes; And α-olefin monomers. The monomers mentioned above may be used alone or in combination if necessary.

There is no particular limitation on the arrangement of the polymer obtained using the polymerization catalyst of the present invention, and the arrangement of the polymer may be appropriately selected. Examples of polymer arrangements include homopolymers; Block copolymers such as diblock, triblock, tetrablock, multiblock, radial block, star block, or comb block copolymer; Graft copolymers; Tapered copolymers; Random copolymers; And alternating copolymers.

There is no special restriction | limiting in the polymerization method using the polymerization catalyst of this invention, As an example, a gaseous-phase polymerization method, a bulk polymerization method, or solution polymerization method is mentioned. Moreover, the polymerization reaction can be carried out in various ways such as batchwise, semibatchwise, or continuously.

In carrying out the polymerization reaction, the polymerization catalyst of the present invention may be used alone or in combination with other types of polymerization catalysts. In addition, if necessary, the polymerization catalyst of the present invention may be supported by an inorganic compound such as silica or zeolite.

By using the catalyst of the present invention, undesirable side reactions at the polymer ends, such as transition reactions caused by extraction of Group IA metal cations present at the polymer ends and removal reactions of lithium hydride (side reactions are cyclic conjugated dienes By suppressing the occurrence of the monomer itself), it is possible for the first time to polymerize or copolymerize a cyclic conjugated diene monomer into a homopolymer or copolymer having a high degree of polymerization.

When using the polymerization catalyst of the present invention to obtain a cyclic conjugated diene polymer, in order to improve the fluidity or other properties of the polymer, the catalyst is used in combination with an organometallic compound containing a Group IA metal which does not complex with the complexing agent. Can also be.

The polymerization process for producing the cyclic conjugated diene polymer using the polymerization catalyst of the present invention can be carried out by bulk polymerization or solution polymerization in the presence of a polymerization catalyst.

Examples of the polymerization solvent used for the solution polymerization include aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, and n-decane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; And ethers such as diethyl ether and tetrahydrofuran.

These polymerization solvents may be used alone or in combination if necessary.

In the polymerization process using the polymerization catalyst of the present invention, the amount of the polymerization catalyst is not particularly limited and may vary depending on the intended use of the polymer to be used. However, polymerization catalysts are generally expressed in moles of metal atoms per mole of monomer or monomers, ranging from 1 × 10 ⁻⁶ moles to 1 × 10 ⁻¹ moles, preferably from 5 × 10 ⁻⁶ moles to 5 × 10 ⁻² moles It can be used in an amount of.

In the polymerization method using the polymerization catalyst of the present invention, the polymerization reaction temperature may vary depending on other polymerization conditions. However, the polymerization reaction temperature is generally -100 to 150 ° C, preferably -80 to 120 ° C, more preferably -30 to 110 ° C, and most preferably 0 to 100 ° C. In commercial aspect, the polymerization reaction temperature is advantageously in the range from room temperature to 80 ° C.

In the polymerization method using the polymerization catalyst of the present invention, the polymerization reaction time is not particularly limited, and the polymerization reaction time may vary depending on the intended use of the polymer and other polymerization reaction conditions. However, polymerization reaction time generally does not exceed 48 hours, Preferably it is 1 to 10 hours. It is also preferable to carry out the polymerization reaction under an atmosphere of inert gas such as nitrogen, argon or helium. Particular preference is given to using well-dried inert gases.

The pressure in the polymerization reaction system is not particularly limited, and a wide range of pressures can be selected as long as the pressure keeps the monomer or monomers and the solvent in a liquid state at a polymerization temperature within the above-mentioned range. In addition, care must be taken to prevent impurities such as water, oxygen and carbon dioxide from inactivating the active end of the polymerization catalyst or polymer into the polymerization reaction system.

In a polymerization process for producing a cyclic conjugated diene polymer using the catalyst of the present invention, a complex to be used as a polymerization catalyst is prepared by pre-reacting (and optionally aging) a portion or all of each component of the catalyst with each other prior to the start of the polymerization reaction. It is preferable to synthesize.

In particular, in the polymerization method using the polymerization catalyst of the present invention, it is most preferable to make a complex (as a polymerization catalyst) before adding the cyclic conjugated diene monomer to the reaction system.

If the complex is made before the addition of the cyclic conjugated diene monomer to the reaction system, side reactions are suppressed, thereby improving the polymerization activity of the catalyst and obtaining various advantages in that the obtained polymer has a narrow molecular weight distribution.

In the polymerization process for preparing the cyclic conjugated diene polymer, the above-mentioned catalysts may be used alone or in combination if necessary.

In the polymerization method for producing the cyclic conjugated diene polymer using the polymerization catalyst of the present invention, when a predetermined degree of polymerization is reached, conventional additives may be added to the polymerization reaction system. Examples of such conventional additives include halogen gas, carbon dioxide, carbon monoxide, alkylene oxide, alkylene sulfides, isocyanate compounds, imino compounds, aldehyde compounds, ketone compounds, thioketone compounds, esters, lactones, amido group containing compounds, Terminal modifiers such as urea compounds or acid anhydrides; Terminal-branching agents such as polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyanhydrides, polyesters, polyhalides or metal halides; Dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, zirconocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxy Coupling agents such as refined soybean oil or esters; Polymerization inhibitors; Polymerization stabilizers; And antioxidants.

In the polymerization process using the catalyst of the present invention, conventional polymerization stabilizers and antioxidants can be used. Examples thereof include phenolic, organic phosphate, organic phosphite, amine and sulfur type polymerization stabilizers and antioxidants.

The amount of each stabilizer and antioxidant added is generally from 0.001 to 10 parts by weight per 100 parts by weight of the cyclic conjugated diene polymer.

As the polymerization terminator, any known polymerization terminator may be used as long as the polymerization active species of the polymerization catalyst of the present invention can be inactivated. Preferred examples of polymerization terminators include water, C ₁ -C ₁₀ alcohols, ketones, polyhydric alcohols (such as ethylene glycol, propylene glycol, or glycerol), phenols, carboxylic acids, and halogenated hydrocarbons.

The amount of the polymerization terminator added is generally from 0.001 to 10 parts by weight per 100 parts by weight of the cyclic conjugated diene polymer. The polymerization terminator may be added before or simultaneously with the addition of the stabilizer and / or the antioxidant. Alternatively, the active end of the polymer can be inactivated by contacting the active end with molecular hydrogen.

Separation and recovery of the cyclic conjugated diene polymer from the polymerization reaction mixture can be carried out using conventional methods commonly used to recover conventional polymers from the polymerization reaction mixture containing them. Such conventional methods include steam-condensation, in which the polymerization reaction mixture is brought into direct contact with steam; Adding a poor solvent of a polymer to the polymerization reaction mixture to precipitate the polymer; Heating the polymerization reaction mixture in a polymerization reactor to distill off the solvent; And a method of obtaining a pelletized polymer by extruding the polymerization reaction mixture using an extruder having a vent and distilling off the solvent through the vent. The most suitable method can be selected depending on the nature of the solvent used and the cyclic conjugated diene polymer to be obtained.

If necessary, the cyclic conjugated diene polymer prepared using the catalyst of the present invention may undergo a hydrogenation reaction, a halogenation reaction, or the like. Moreover, the cyclic conjugated diene polymer prepared using the catalyst of the present invention can also be modified or crosslinked by adding polar groups by conventional techniques. Examples of such polar groups include carboxyl groups (derived from maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic anhydride, methacrylic anhydride, etc.), hydroxyl groups, epoxy groups (glycidyl methacrylate, glycidyl) Derived from acrylate, etc.), amino group (derived from maleimide, etc.), oxazoline group, alkoxy group (derived from vinyl compound containing alkoxysilane group, etc.), and isocyanate group.

In addition, additives used in conventional polymeric materials can be used depending on the intended use of the polymer. Examples of such additives include heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, nucleating agents, colorants, pigments, crosslinkers, foaming agents, antistatic agents, antislip agents, antiblocking agents, mold release agents, other polymeric materials, and inorganic reinforcing materials. .

The cyclic conjugated diene polymer prepared using the polymerization catalyst may be in single form or in complex form with other polymeric materials, inorganic or organic reinforcing materials, depending on the intended use of the polymer.

When the cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention is used in a complex form with other polymers, such other polymer materials may be appropriately selected from conventionally known organic polymers. There is no particular limitation on the type and amount of organic polymer.

Examples of such organic polymers include aliphatic polyamides such as nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 636 and nylon 1212. ; Partially aromatic polyamides such as nylon 4T (T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I, nylon 12T, nylon 12I and nylon MXD6 (MXD: methacrylicylenediamine); Amide polymers such as copolymers or blends of the aforementioned aliphatic polyamides or partially aromatic polyamides; Polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycarbonate (PC) and polyacrylate (PAR); Olephine polymers such as polypropylene (PP), polyethylene (PE), ethylene-propylene rubber (EPR), and polystyrene (PSt); Conjugated diene polymers such as polybutadiene (PBd), polyisoprene (PIp), styrene-butadiene rubber (SBR), or hydrides thereof; Thiol polymers such as polyphenylene sulfide (PPS); Ether polymers such as polyacetals such as polyoxymethylene (POM) and polyphenylene ether (PPE); Acrylic resins; ABS resin; AS resin; Polysulfone (PSF); Polyether ketone (PEK) and polyamideimide (PAI).

These organic polymers may be used alone or in the form of a mixture or a copolymer thereof, if necessary.

Examples of inorganic reinforcing materials include glass fibers, glass wool, carbon fibers, talc, mica, ulastonite, kaolin, montmorillonite, titanium whiskers and rock wool. Examples of the organic reinforcing material include aramid, polyimide, liquid crystalline polyester (LCP), polybenzoimidazole and polybenzothiazole.

The cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention can be used as an excellent industrial material such as plastics, thermoplastic elastomers, other resin modifiers and the like. If necessary, a crosslinking agent may be added to the cyclic conjugated diene polymer prepared using the polymerization catalyst of the present invention to provide a cured resin such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or the like.

The invention will be described in more detail with reference to the following examples, comparative examples and reference examples, but are not given to limit the scope of the invention.

In Examples, Comparative Examples and Reference Examples, chemicals of high purity are used among those that are commercially available. The solvent is treated by a known method before using a commercially available solvent. That is, the solvent is degassed, dehydrated by reflux in an activated substance under an atmosphere of inert gas, and then purified by distillation.

To determine the number average molecular weight of the polymer, the polymer was dissolved in 1,2,4-trichlorobenzene, and the resulting solution was subjected to gel permeation chromatography (GPC) using a calibration curve obtained using standard polystyrene. Measure the molecular weight. The GPC apparatus used what was manufactured and marketed by Water Assoc. Co., USA.

Example 1

(Preparation of Novel Polymerization Catalyst of the Present Invention which is a Binary or Multinuclear Complex of Organometallic Compound Containing Group IA Metal)

In an atmosphere of dry argon gas, a predetermined amount of tetramethylethylenediamine (TMEDA) is dissolved in cyclohexane. The resulting solution is cooled and kept at -10 ° C. The n-hexane solution of n-butyllithium (n-BuLi) is then slowly added dropwise to the cyclohexane solution of TMEDA in an amount such that the molar ratio of TMEDA / n-BuLi is 1/4 in the atmosphere of dried argon gas. The mixture obtained after the start of addition of the n-hexane solution of n-BuLi is slowly cooled to -78 ° C. As a result, a tetranuclear complex having a molar ratio of TMEDA / n-BuLi of 1/4 is obtained in the form of white crystals. The structure is estimated as [(TMEDA). (N-BuLi) ₄ ] _∞ .

Example 2

(Preparation of Novel Polymerization Catalyst of the Present Invention which is a Binary or Multinuclear Complex of Organometallic Compound Containing Group IA Metal)

In an atmosphere of dry argon gas, a predetermined amount of tetramethylethylenediamine (TMEDA) is dissolved in cyclohexane. The resulting solution is cooled and kept at -10 ° C. Thereafter, an n-hexane solution of n-butyllithium (n-BuLi) is slowly added dropwise to the cyclohexane solution of TMEDA in an amount such that the molar ratio of TMEDA / n-BuLi is 1/1 under an atmosphere of dried argon gas. The mixture obtained after the start of addition of the n-hexane solution of n-BuLi is slowly cooled to -78 ° C. As a result, a binuclear complex having a molar ratio of TMEDA / n-BuLi of 1/1 is obtained in the form of white crystals. The structure is estimated as [(TMEDA) ₂ · (n-BuLi) ₂ ].

Comparative Example 1

(Polymerization using conventional catalyst system)

The well-dried 100 ml Schlenk test tubes are cleaned with dried argon gas according to conventional methods. 5.00 g of 1,3-cyclohexadiene and 10.0 g of cyclohexane are charged into a Schlene test tube. The temperature of the obtained cyclohexane solution of 1,3-cyclohexadiene is maintained at room temperature, and n-hexane solution of n-BuLi is added to 0.04 mmol amount of cyclohexane solution in the amount of lithium atoms to obtain a mixture. .

After the addition of n-BuLi, the color characteristic of the cyclohexadienyl anion rapidly disappeared from the mixture to give the desired polymer.

Comparative Example 2

(Polymerization using a catalyst that does not contain a binary or multinuclear complex of an organometallic compound containing a Group IA metal)

The well-dried 100 ml shren test tubes are washed with dried argon gas according to a conventional method. 5.00 g of 1,3-cyclohexadiene, 10.0 g of cyclohexane and 0.01 mmol of TMEDA are charged to a Schlene test tube. The temperature of the obtained cyclohexane solution of 1,3-cyclohexadiene and TMEDA was maintained at room temperature, and the n-hexane solution of n-BuLi was added to a 0.04 mmol amount of cyclohexane solution in the amount of lithium atoms to prepare a mixture. To obtain.

After the addition of n-BuLi, the color characteristic of the cyclohexadienyl anion rapidly disappeared from the mixture to give the desired polymer.

Comparative Example 3

(Polymerization using a catalyst that does not contain a binary or multinuclear complex of an organometallic compound containing a Group IA metal)

Substantially the same procedure as in Comparative Example 2 was repeated except that the amount of TMEDA was changed to 0.04 mmol.

After the addition of n-BuLi, the color characteristic of the cyclohexadienyl anion rapidly disappeared from the mixture to give the desired polymer.

Comparative Example 4

(Polymerization using a catalyst that does not contain a binary or multinuclear complex of an organometallic compound containing a Group IA metal)

The procedure was substantially the same as in Comparative Example 2 except that the amount of TMEDA was changed to 0.40 mmol.

After the addition of n-BuLi, the color characteristic of the cyclohexadienyl anion rapidly disappeared from the mixture to give the desired polymer.

Example 3

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

The well-dried 100 ml shren test tubes are cleaned with dried argon gas according to conventional methods. 5.00 g of 1,3-cyclohexadiene and 10.0 g of cyclohexane are charged into a Schlene test tube. The temperature of the obtained cyclohexane solution of 1,3-cyclohexadiene was maintained at room temperature, and the polymerization catalyst obtained in the same manner as in Example 1 was added to the 0.04 mmol amount cyclohexane solution in terms of the amount of lithium atoms. And the polymerization reaction is carried out for 5 hours. After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixture of methanol and hydrochloric acid was added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to finally give a white polymer mass.

In the polymerization catalyst used above, the lithium atom is present in an amount as large as 4 equivalents per 1 equivalent of TMEDA. Nevertheless, each lithium atom acts as the same active site for polymerization, extending the polymerization chain by living anionic polymerization. As a result, the number average molecular weight is as high as 121,800 The ratio (used as a criterion of molecular weight distribution) was obtained with a yield of 98.9% by weight of cyclohexadiene homopolymer of 1.14.

From the above facts, it was confirmed that in the polymerization reaction system, the polymerization catalyst of the present invention maintains its complex structure and the polymer extends the polymer chain by performing the polymerization on the multinuclear complex.

The glass transition point (Tg) of the obtained polymer was measured at 137 degreeC by the DSC method. The polymer was injection molded at a cylinder temperature of 300 ° C. to obtain a colorless transparent test specimen having a thickness of 3 mm.

The tensile modulus (TM) of the test specimen was measured at 4,020 MPa (1 MPa = 10.19716 kgf / cm ² ) according to ASTM D 638. The heat deflection temperature (HDT) of the test specimen was measured at 102 ° C. at a load of 18.6 kgf / cm ² according to ASTM D648.

Example 4

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

Subsequently, the same procedure as in Example 3 was repeated except that a mixed solvent of 1.00 g of toluene and 9.00 g of cyclohexane was used as the polymerization solvent.

The yield of the obtained polymer is 98.7% by weight, the number average molecular weight is 101,900 The ratio (used as a criterion of the molecular weight distribution) was 1.21.

Example 5

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

Substantially the same procedure as in Example 3 was repeated except that the amount of polymerization catalyst was converted to 0.08 mmol in terms of the amount of lithium atoms.

The yield of the obtained polymer is 98.5% by weight, the number average molecular weight is 61,400 The ratio (used as a criterion of molecular weight distribution) was 1.18.

Example 6

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

The same procedure as in Example 5 was repeated except that a mixed solvent of 2.00 g of toluene and 18.0 g of cyclohexane was used as the polymerization solvent, and the polymerization temperature was changed to 60 ° C.

The yield of the obtained polymer is 72.5% by weight, the number average molecular weight is 43,700 The ratio (used as a criterion of the molecular weight distribution) was 1.27.

Example 7

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

Substantially the same procedure as in Example 5 was repeated except that the polymerization solvent was changed to 20.0 g of cyclohexane, the polymerization temperature was changed to 40 ° C., and the amount of the polymerization catalyst was changed to 0.06 mmol in terms of the amount of lithium atoms.

The yield of the obtained polymer was 99.8% by weight, the number average molecular weight is 83,800. The ratio (used as a criterion of the molecular weight distribution) was 1.16.

Example 8

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

A well dried 100 ml pressure-resistant glass bottle with a sealing stopper is cleaned with dried argon gas according to conventional methods. 5.00 g of 1,3-cyclohexadiene and 5.00 g of toluene are charged into a glass bottle. Thereafter, the polymerization catalyst obtained in substantially the same manner as in Example 2 was added to a toluene solution of 1,3-cyclohexadiene obtained in an amount of 0.080 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out at room temperature for 5 hours. Perform. After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer was washed with methanol and then dried under reduced pressure at 80 ° C. to finally obtain a white polymer mass.

The yield of the obtained polymer is 96.5% by weight, its number average molecular weight is 49,800, The ratio (used as a criterion of the molecular weight distribution) was 1.51.

Example 9

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

Substantially the same procedure as in Example 8 was repeated except that the amount of polymerization catalyst was converted to 0.040 mmol in terms of the amount of lithium atoms.

The yield of the obtained polymer is 98.5% by weight, the number average molecular weight is 64,300 The ratio (used as a criterion of molecular weight distribution) was 1.48.

The viscoelastic behavior of the obtained polymer was measured by the following method.

The polymer is molded to produce test specimens approximately 2 mm thick.

For the storage modulus (E ') and the loss modulus (E' ') of the test specimens, the changes of E' and E '' with temperature change were respectively measured under the following conditions: FT Rheospectoler DVE / V4, Rheological Commercially available, USA).

Length (Span): approx. 18 mm

Measurement temperature: 30 to 150 ° C

Temperature rise rate: 3 ℃ / min

Frequency: 35 Hz

The change of E 'and E' 'with the change in temperature is shown in FIG. 2 with the change of the loss factor (tan δ: tan δ is defined by the ratio E' '/ E') with temperature.

Example 10

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

The same procedure as in Example 8 was repeated except that cyclohexane was used as the polymerization solvent instead of toluene.

The yield of the obtained polymer is 98.8% by weight, the number average molecular weight is 49,300 The ratio (used as a criterion of the molecular weight distribution) was 1.28.

Example 11

(Synthesis of cyclic conjugated diene homopolymers using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

The procedure is substantially the same as in Example 9, except that cyclohexane is used as the polymerization solvent instead of toluene.

The yield of the obtained polymer is 99.1% by weight, the number average molecular weight is 61,700 The ratio (used as a criterion of molecular weight distribution) was 1.29.

Example 12

(Synthesis of cyclic conjugated diene homopolymers having a number average molecular weight of less than 40,000 using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

4.02 g of 1,3-cyclohexadiene and 4.30 g of toluene are charged to a glass bottle. Thereafter, the polymerization catalyst obtained in substantially the same manner as in Example 2 was added to a toluene solution of 1,3-cyclohexadiene obtained in an amount of 0.101 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out at room temperature for 2 hours. Perform.

The yield of the obtained polymer is 98.9% by weight, the number average molecular weight thereof is 38,800, The ratio (used as a criterion of the molecular weight distribution) was 1.17.

Example 13

(Synthesis of cyclic conjugated diene homopolymers having a number average molecular weight of less than 40,000 using dinuclear or multinuclear complexes of organometallic compounds containing Group IA metals according to the invention as polymerization catalysts)

Substantially the same procedure as in Example 12 was repeated except that the polymerization temperature was changed to 50 ° C.

The yield of the obtained polymer is 99.8% by weight, the number average molecular weight is 39,200 The ratio (used as a criterion of the molecular weight distribution) was 1.19.

Comparative Example 5

(Polymerization using conventional catalyst system)

A well dried 100 ml pressure-resistant glass bottle with a sealing stopper is cleaned with dried argon gas according to conventional methods. 4.02 g of 1,3-cyclohexadiene and 4.30 g of toluene are charged to a glass bottle. Thereafter, 1.01 mmol of n-BuLi was added to a toluene solution of 1,3-cyclohexadiene obtained as a polymerization catalyst, and the polymerization reaction was carried out at 50 ° C. for 8 hours. After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C.

The yield of the obtained polymer is 95.9% by weight, the number average molecular weight thereof is only 16,800, The ratio (used as a criterion of molecular weight distribution) was 1.87.

This polymer was yellowish in color and very brittle so that no molded product could be produced from the polymer.

Comparative Example 6

(Polymerization using conventional catalyst system)

Substantially the same procedure as in Comparative Example 5 was repeated except that the amount of n-BuLi was changed to 0.101 mmol.

The catalyst of Comparative Example 6 is present in an amount of 1/10 as compared to the catalyst of Comparative Example 5. High molecular weight polymers were not obtained. The yield of the obtained polymer was as low as 45.6% by weight, the number average molecular weight is 12,500, The ratio (used as a criterion of molecular weight distribution) was 2.05. The polymer was yellowish.

Examples 14-19

(Polymerization using the polymerization catalyst of the present invention, which is a complex of an organometallic compound containing an IA metal with an amine compound / organic metal compound ratio and an amine compound)

Polymerization catalysts having various TMEDA / n-BuLi molar ratios as described in Table 1 were prepared under an atmosphere of dried argon gas. The polymerization reaction was carried out in substantially the same manner as in Example 3, except that these catalysts were used alone and the amount of cyclohexane was changed to 5.0 g.

The results of Examples 14 to 19 are shown in Table 1.

TMEDA / n-BuLi Yield (wt%) Example 14 2/1 58.6 Example 15 1/1 98.4 Example 16 1/2 97.7 Example 17 1/4 99.5 Example 18 1/8 69.2 Example 19 1/16 35.5

Comparative Example 7

(Polymerization using a conventional polymerization system)

Substantially the same procedure as in Example 3 was repeated except changing the polymerization catalyst to n-BuLi (mixing ratio of TMEDA / n-BuLi: 0/1) and changing the amount of cyclohexane to 5.0 g. As a result, no polymerization reaction occurred, and the desired polymer was not obtained.

Example 20

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

A well dried 100 ml pressure-resistant glass bottle with a sealing stopper is cleaned with dried argon gas according to conventional methods. 2.31 g of isoprene and 5.00 g of toluene are charged into a glass bottle. Thereafter, the polymerization catalyst obtained in substantially the same manner as in Example 2 was added to the toluene solution of isoprene obtained in an amount of 0.08 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out at room temperature for 4 hours. Thereafter, 2.72 g of 1,3-cyclohexadiene was added to the polymerization reaction system, and then the polymerization reaction was further performed at room temperature for 4 hours. After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer was washed with methanol and then dried in vacuo at 80 ° C. to obtain a white isoprene-cyclohexadiene diblock copolymer.

The yield of the obtained copolymer was 97.6% by weight, the number average molecular weight thereof was 38,200 as measured by GPC. The obtained chromatogram showed a single peak. The ratio (used as a criterion of molecular weight distribution) was 1.22.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was confirmed that the polymer chain of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers filled in the glass bottle.

Example 21

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

The procedure is substantially the same as in Example 20, except that the amount of isoprene is changed to 2.50 g and the amount of 1,3-cyclohexadiene is changed to 2.50 g.

The yield of isoprene-cyclohexadiene diblock copolymer was 98.8% by weight, and its number average molecular weight measured by GPC was 34,400. The obtained chromatogram showed a single peak. The ratio (used as a criterion of molecular weight distribution) was 1.31.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was confirmed that the polymer chain of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers filled in the glass bottle.

Example 22

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

The same procedure as in Example 20 was repeated except that the polymerization temperature was changed to 50 ° C.

The yield of isoprene-cyclohexadiene diblock copolymer was 98.0 wt%, and its number average molecular weight measured by GPC was 30,700. The obtained chromatogram showed a single peak. The Mw / Mn ratio (used as a criterion of molecular weight distribution) was 1.20.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was confirmed that the polymer chain of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers filled in the glass bottle.

Comparative Example 8

(Polymerization using conventional catalyst system)

Except that n-BuLi was used as the polymerization catalyst, substantially the same procedure as in Example 22 was repeated. The polymer obtained was an isoprene homopolymer.

Example 23

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

Subsequently, the same procedure as in Example 20 was repeated except that 1,3-cyclohexadiene was polymerized and then copolymerized with isoprene.

The yield of isoprene-cyclohexadiene diblock copolymer was 98.5 wt% and its number average molecular weight measured by GPC was 36,200. The obtained chromatogram showed a single peak. The ratio (used as a criterion of molecular weight distribution) was 1.32.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was confirmed that the polymer chain of the copolymer had substantially the same monomer unit ratio as that of the monomers filled in the glass bottles.

Comparative Example 9

(Polymerization using conventional catalyst system)

Substantially the same procedure as in Example 23 was repeated except that n-BuLi was used as the polymerization catalyst. The polymer obtained was a cyclohexadiene homopolymer.

Example 24

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

A well dried 5 liter high pressure autoclave equipped with an electromagnetic induction stirrer is cleaned with dried nitrogen gas according to conventional methods. 2,400 g of cyclohexane and 400 g of butadiene are charged to the autoclave. Thereafter, a polymerization catalyst prepared such that the molar ratio of TMEDA / n-BuLi is 1/4 is added to the cyclohexane solution of 25.6 mmol amount butadiene in terms of the amount of lithium atoms, and the polymerization reaction is performed at 60 ° C. for 1 hour. . Thereafter, 400 g of 1,3-cyclohexadiene was added to the obtained polymerization reaction system, and then the polymerization reaction was further performed at 40 ° C for 6 hours. After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer was washed with methanol and then dried under reduced pressure at 80 ° C. to obtain a white butadiene-cyclohexadiene diblock copolymer.

The number average molecular weight measured by GPC of the obtained copolymer was 44,100. The obtained chromatogram showed a single peak. The ratio (used as a criterion of molecular weight distribution) was 1.36.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was found that the polymer chains of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers charged to the autoclave.

The obtained copolymer was charged into a mold and compression molded at 180 ° C. to obtain a sample having a thickness of 3 mm.

The tensile modulus (TM) of the samples measured according to ASTM D638 was 680 MPa (1 MPa = 10.19716 kgf / cm ² ). Tensile elongation (TE) was at least 500%.

Example 25

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

A well dried 5 liter high pressure autoclave equipped with an electromagnetic induction stirrer is cleaned with dried nitrogen gas according to conventional methods. 2720 g of cyclohexane and 154 g of 1,3-cyclohexadiene are charged to the autoclave. Thereafter, a polymerization catalyst prepared such that the molar ratio of TMEDA / n-BuLi is 1/4 is added to the cyclohexane solution of 15.36 mmol amount of 1,3-cyclohexadiene in terms of the amount of lithium atoms, and the polymerization reaction is carried out at 40 ° C. Run for 5 hours at. Thereafter, 326 g of butadiene was added to the obtained polymerization reaction system, and then the polymerization reaction was further performed at 60 ° C for 1 hour. After completion of the polymerization reaction, 9.6 mmol of dichlorodimethylsilane as a coupling agent was added to the obtained polymerization reaction mixture, and the reaction was further performed at 65 ° C for 1 hour to couple the ends of the polymer formed in the polymerization reaction mixture.

Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer was washed with methanol and then dried under reduced pressure at 80 ° C. to obtain a white cyclohexadiene-butadiene triblock copolymer.

The number average molecular weight measured by GPC of the obtained copolymer was 69,700. The obtained chromatogram showed a single peak. The ratio (used as a criterion of the molecular weight distribution) was 1.39.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was found that the polymer chains of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers charged to the autoclave.

The obtained copolymer was charged into a mold and compression molded at 220 ° C. to obtain a colorless transparent test sample having a thickness of 3 mm.

The tensile modulus (TM) of the sample measured substantially according to ASTM D638 was 6.57 MPa (1 MPa = 10.19716 kgf / cm ² ), except that the measurement was performed under conditions of 300% elongation. Tensile elongation (TE) was at least 500%.

Example 26

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

Substantially the same procedure as in Example 25 was repeated except that 3.80 mmol of tetrachlorosilane was used instead of dichlorodimethylsilane as the coupling agent.

The number average molecular weight measured by GPC of the obtained cyclohexadiene-butadiene radial block copolymer was 120,500. The obtained chromatogram showed a single peak. The ratio (used as a criterion of the molecular weight distribution) was 1.57.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was found that the polymer chains of the copolymer had a monomer unit ratio substantially equal to the ratio of monomers charged to the autoclave.

The obtained copolymer was charged into a mold and compression molded at 220 ° C. to obtain a colorless transparent test sample having a thickness of 3 mm.

The tensile modulus (TM) of the test specimens measured substantially according to ASTM D638, except that the measurements were performed under conditions of 300% elongation, was 7.06 MPa (1 MPa = 10.19716 kgf / cm ² ). Tensile elongation (TE) was at least 500%.

Example 27

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

A well dried 100 ml pressure-resistant glass bottle with a sealing stopper is cleaned with dried argon gas according to conventional methods. 2.50 g of 1,3-cyclohexadiene, 2.50 g of styrene and 10.0 g of cyclohexane are charged into a glass bottle. Thereafter, the polymerization catalyst obtained in substantially the same manner as in Example 1 was added to the obtained cyclohexane solution of 1,3-cyclohexadiene and styrene obtained in an amount of 0.08 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out. Run at room temperature for 4 hours.

After a predetermined time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the polymerization reaction system to terminate the polymerization reaction. Thereafter, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the obtained polymerization reaction mixture to separate the formed polymer. The separated polymer was washed with methanol and then dried in vacuo at 80 ° C. to obtain a white cyclohexadiene-styrene copolymer.

The yield of the obtained copolymer was 74.8% by weight, the number average molecular weight thereof was 37,100 as measured by GPC. The obtained chromatogram showed a single peak. The ratio (used as a criterion of the molecular weight distribution) was 1.53.

The polymer chain structure of the copolymer was determined by ¹ H-NMR. It was confirmed that the polymer chain of the obtained copolymer had a structural composition corresponding to the molar ratio (1 / 3.4) of cyclohexadiene monomer / styrene monomo in the vial.

Example 28

(Synthesis of cyclic conjugated diene copolymer using a polymerization catalyst of the present invention containing a monomer unit derived from a cyclic conjugated diene monomer and a monomer unit derived from a monomer copolymerizable with a cyclic conjugated diene monomer)

Substantially the same procedure as in Example 27 was repeated except that a mixed solvent of 9 g of cyclohexane and 1 g of toluene was used as the polymerization solvent.

0.5 hours and 1 hour after the start of the polymerization reaction, each copolymerization test specimen was obtained from the polymerization reaction mixture. For the test specimens obtained, each molecular weight was measured by GPC. The chromatogram of each of the test specimens showed a single peak. The number average molecular weights of the copolymers obtained 0.5 hours and 1 hour after the start of the polymerization reaction were 16,100 and 33,800, respectively. Copolymer test specimen The ratios (used as a criterion for molecular weight distribution) were 1.28 and 1.21, respectively.

The polymer chain structure of the copolymer test specimen was determined by ¹ H-NMR. The polymer chains of the copolymers obtained 0.5 and 1 hour after the start of the polymerization reaction each have a tapered block arrangement, corresponding to the molar ratio (1 / 4.9 and 1 / 2.9) of the charged cyclohexadiene monomer / styrene monomer. It was confirmed that each had a structural composition.

Example 29

(Preparation of Cyclic Conjugated Diene Block Copolymer Composition)

A well-dried 5 liter high pressure reaction vessel equipped with an electromagnetic induction stirrer is cleaned with dried nitrogen gas according to a conventional method.

2,060 g of cyclohexane and 154 g of 1,3-cyclohexadiene are charged to the autoclave. Thereafter, a polymerization catalyst prepared such that the molar ratio of TMEDA / n-BuLi is 1/1 is added to the cyclohexane solution of 25.6 mmol amount of 1,3-cyclohexadiene in the amount of lithium atoms, and the polymerization reaction is carried out at 35 ° C. Run for 4 hours at. The conversion of 1,3-cyclohexadiene was determined to be 97.8% by gas chromatography.

After adding a sample of the polymerization reaction mixture to methanol, the molecular weight of the polymer formed in the sample was measured by GPC. The color of the polymerization reaction mixture was dark yellow. From this color it was confirmed that the reaction was carried out by living anionic polymerization.

Thereafter, 990 g of a 33 wt% solution of butadiene in cyclohexane is added to the polymerization reaction mixture remaining in the autoclave, and the polymerization reaction is further performed at 60 to 70 ° C for 1 hour. The obtained polymerization reaction mixture sample was added to methanol to measure the molecular weight of the polymer formed in the sample by GPC.

The color of the resulting polymerization reaction mixture was yellow, the same color as that of polybutadienyllithium. From this color it was confirmed that the reaction was carried out by living anionic polymerization.

After completion of the intended polymerization reaction, dimethyldichlorosilane was added to the polymerization reaction mixture as a coupling agent in an amount of 1/2 equivalents per 1 equivalent of lithium atoms in the catalyst, followed by stirring at 70 ° C for 1 hour.

Thereafter, a sample of the obtained polymerization reaction mixture was added to methanol, and then the molecular weight of the polymer formed in the sample was measured by GPC. The resulting polymerization reaction mixture was colorless. Thus, it was confirmed that the active end of the polymer was inactivated by the reaction with the coupling agent.

From the GPC chart of the polymer sample taken in the above three steps, it was confirmed that the peaks of the GPC chart shifted toward the higher molecular weight step by step in the order of the three steps mentioned above. This indicates that the polymerization reaction was carried out by living anionic polymerization and the desired cyclic conjugated diene block copolymer composition was formed.

From the ratio of the peak areas in the GPC chart of the obtained block copolymer composition, the block copolymer composition is 55 wt% polycyclohexadiene-polybutadiene-polycyclohexadiene triblock copolymer and 55 wt% polycyclohexadiene. It was confirmed that the polybutadiene diblock copolymer was composed.

The sheet was obtained after the solvent was distilled off from the polymerization reaction mixture. The sheet obtained from the copolymer composition was filled into a mold and then compression molded at 220 ° C. to obtain a test specimen. Using this test specimen, various properties of the block copolymer composition were evaluated by the following method.

<Evaluation method>

(1) molecular weight

The number average molecular weight of the block copolymer composition was measured by GPC in terms of a value obtained using a calibration curve of standard polystyrene.

(2) Structural Composition and Microstructure:

The structural composition ratio and the microstructure of the block copolymer composition were measured by ¹ H-NMR (400 MHz; GX-400 FT-NMR: commercially available from JEOL, Japan). 32 fold integration using 10 w / v% deuterated form of dichlorobenzene as solvent for quantitative determination.

(3) viscoelastic behavior:

For the storage modulus (E ') and the loss modulus (E' ') of the block copolymer composition, the changes of E' and E '' according to temperature change were respectively determined under the conditions shown in Table 2 below. Instrument, commercially available, USA). The change of the E 'value with the change in temperature is shown in FIG. 8 with the change of the loss factor (tan δ: tan δ is defined by the E' '/ E' ratio) with the temperature change.

(4) surface hardness:

Surface hardness (JIS A) was measured at 25 ° C.

(5) Tensile strength at break (Tb) (kgf / cm ² ) and elongation at break (E1) (%)

Test specimens 20 mm long x 3 mm wide x 3 mm thick are prepared by compression molding. For the test specimens, the tensile strength at break and the elongation at break were measured by performing a tensile test at 25 ° C. and a head speed of 20 mm / min according to JIS K6301.

(6) Softening point (℃)

Softening points were measured with a TMA 100 (manufactured and sold by Seiko Instruments, Japan) using a 100 μm needle under a load of 10 g.

(7) tensile modulus:

The tensile modulus (TM) of the test specimen was measured substantially in accordance with ASTM D638, except that the measurement was performed under conditions of 300% elongation. The obtained value [300% Ms (kgf / cm ² )] is shown in Table 3.

Example 30

(Preparation of Cyclic Conjugated Diene Block Copolymer Composition)

Substantially the same procedure as in Example 29 was repeated except that tetrachlorosilane was used as coupling agent in an amount of 1/4 equivalent per 1 equivalent of lithium atom in the catalyst.

From the ratio of the peak area of the GPC chart of the obtained block copolymer composition, the block copolymer composition is 62% by weight of the radial block copolymer [(polycyclohexadiene-polybutadiene) _x SiCl _4-x (where x is 2 to 4) and 38% by weight of polycyclohexadiene-polybutadiene diblock copolymer.

The sheet was obtained after the solvent was distilled off from the polymerization reaction mixture. The obtained sheet was filled into a mold and then compression molded at 220 ° C. to obtain a test specimen. Using this test specimen, various properties of the block copolymer composition were evaluated in substantially the same manner as in Example 29.

Example 31

(Preparation of Cyclic Conjugated Diene Block Copolymer Composition)

A well dried 5 liter high pressure autoclave equipped with an electromagnetic induction stirrer is cleaned with dried nitrogen gas according to conventional methods.

2,060 g of cyclohexane and 77 g of 1,3-cyclohexadiene are charged into the autoclave. Thereafter, a polymerization catalyst prepared such that the molar ratio of TMEDA / n-BuLi is 1/1 is added to the cyclohexane solution of 1,3-cyclohexadiene in an amount of 25.6 mmol in terms of the amount of lithium atoms, and the polymerization reaction is 35 At 3 ° C. for 3 hours. Conversion of 1,3-cyclohexadiene was determined to 96.5% by gas chromatography.

Thereafter, 800 g of a 33 wt% solution of butadiene in cyclohexane is added to the polymerization reaction mixture remaining in the autoclave, and the polymerization reaction is further performed at 60 to 70 ° C for 1 hour. The conversion of butadiene was determined to 100% by gas chromatography.

Thereafter, 77 g of 1,3-cyclohexadiene is added to the polymerization reaction mixture, and the polymerization reaction is further performed at 35 ° C for 3 hours. Conversion of 1,3-cyclohexadiene was determined to 93.3% by gas chromatography.

After a predetermined time, the methyl alcohol was added to the polymerization reaction mixture obtained as a polymerization terminator in an amount of 0.8 equivalent moles per 1 equivalent of the lithium atom in the catalyst, followed by stirring at 70 ° C. for 1 hour, thereby forming a living formed in the polymerization reaction mixture. The active end of the polymer was inactivated.

The sheet was obtained after the solvent was distilled off from the polymerization reaction mixture. The obtained sheet was filled into a mold and then compression molded at 220 ° C. to obtain a test specimen. Using this test specimen, various properties of the block copolymer composition were evaluated in substantially the same manner as in Example 29.

Comparative Example 10

(Preparation of conventional conjugated diene block copolymer composition)

Substantially the same procedure as in Example 29 was repeated except that styrene was used instead of 1,3-cyclohexadiene to obtain a block copolymer composition.

The sheet was obtained after the solvent was distilled off from the polymerization reaction mixture. The obtained sheet was filled into a mold and then compression molded at 220 ° C. to obtain a test specimen. Using this test specimen, various properties of the block copolymer composition were evaluated in substantially the same manner as in Example 29.

Comparative Example 11

(Preparation of conventional conjugated diene block copolymer composition)

Except that styrene was used instead of 1,3-cyclohexadiene, substantially the same procedure as in Example 31 was repeated to obtain a block copolymer composition.

The sheet was obtained after the solvent was distilled off from the polymerization reaction mixture. The obtained sheet was filled into a mold and then compression molded at 220 ° C. to obtain a test specimen. Using this test specimen, various properties of the block copolymer composition were evaluated in substantially the same manner as in Example 29.

Table 3 shows various properties measured for the block copolymer compositions obtained in Examples 29 to 31 and Comparative Examples 10 and 11. Table 4 shows the results of the ¹ H-NMR spectrum.

The novel polymerization catalyst of the present invention has a high activity capable of polymerizing the cyclic conjugated diene monomer, and it is possible not only to obtain a high yield of polymer even with a relatively small amount of catalyst, but also by using a conventional catalyst. It can be used to synthesize high molecular weight polymers and copolymers that can never be produced. The polymerization catalyst of the present invention can also be usefully used as a living anion polymerization catalyst for obtaining a polymer having a desired structure, so that the catalyst can be widely used to prepare a conventional polymer by living anion polymerization.

Claims (3)

A polymerization catalyst containing a heteronuclear or multinuclear complex of an organometallic compound containing a metal belonging to group IA of the periodic table with a complexing agent. The polymerization catalyst according to claim 1, wherein the complexing agent contains an amine. The polymerization catalyst according to claim 1 or 2, which is used to prepare a cyclic conjugated diene polymer containing a main chain represented by the following formula (I): [Formula I] [Wherein, A to E are monomer units constituting the main chain in which monomer units A to E are arranged in an arbitrary order, and l to p are monomer units A based on the total weight of monomer units A to E, respectively. Weight% of ˜E; At this time, A is selected from the group consisting of cyclic conjugated diene monomer units, B is selected from the group consisting of chain conjugated diene monomer units, C is selected from the group consisting of vinyl aromatic monomer units, D is selected from the group consisting of polar monomer units, and E is selected from the group consisting of ethylene monomer units and α-olefin monomer units; And 1 to p satisfy the following conditions: l + m + n + o + p = 100, 0.5 ≤ l ≤ 100, 0 ≤ m <100, 0 ≤ n <100, 0 ≦ o <100, and 0 ≦ p <100.