JP3333045B2 - Cyclic diene block copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a specific ratio of (a) at least two cyclic conjugated diene-based blocks and at least one
Block copolymer having a linear conjugated diene-based block such as 1,3-butadiene or isoprene; and (b) a diblock copolymer having a cyclic conjugated diene-based block and a linear conjugated diene-based block. To a novel cyclic conjugated diene-based block copolymer composition.

[0002]

2. Description of the Related Art Numerous proposals have been made on conjugated diene-based polymers, mainly as elastomers, thermoplastic elastomers and special transparent resins for improving the impact resistance of tires, belts and resins. Widely used for adhesives, films, containers and the like. Representative conjugated diene polymers include polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, α-methylstyrene-butadiene copolymer, and α-methylstyrene. -Isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer, isoprene-methyl methacrylate copolymer, and hydrogenated polymers thereof are known. .

On the other hand, as a molecular structural unit constituting a polymer chain, a polymer block having a Tg higher than room temperature (constrained phase) is provided at both ends, and a polymer block having a Tg lower than room temperature (rubber phase) is interposed therebetween. Block copolymers such as styrene-butadiene (or isoprene) -styrene block copolymers and hydrogenated polymers thereof are widely used as thermoplastic elastomers in many applications such as injection molding and resin modification. Further, polystyrene, polyolefin, polyphenylene ether, styrene-butadiene diblock copolymer, hydrogenated product thereof, and the like were blended with the styrene-butadiene (or isoprene) -styrene block copolymer and hydrogenated polymer thereof. Block copolymer compositions are widely used to improve various physical properties such as heat resistance, fluidity, and adhesive properties of styrene-butadiene (or isoprene) -styrene block copolymers and hydrogenated polymers thereof.

However, with recent advances in industrial technology, market requirements for polymer materials have become increasingly sophisticated, and higher thermal properties (melting point, glass transition point, softening point) and mechanical properties ( Development of a polymer material having tensile modulus, flexural modulus, high-temperature mechanical properties, etc.) has been strongly desired. One of the powerful means to solve this problem is to copolymerize not only monomers with relatively small steric hindrance such as butadiene and isoprene but also monomers with large steric hindrance, that is, cyclic monomers. Research activities to improve the structure of the polymer chain of the conjugated diene-based polymer by further hydrogenation as necessary to obtain a polymer material with advanced thermal and mechanical properties It has become popular.

However, it is not only difficult to homopolymerize or copolymerize the cyclic conjugated diene monomer, but also for the purpose of remarkably exhibiting the characteristics caused by introducing the cyclic conjugated diene monomer into the polymer chain. Attempts to block copolymerize a cyclic conjugated diene monomer have been studied, but a cyclic conjugated diene-based block copolymer has not yet been obtained, and this solution has been strongly desired.

In British Patent Application No. 1,042,625, 1,3,3 a large amount of butyllithium is used as a polymerization catalyst.
A process for the preparation of cyclohexadiene is disclosed. The production method disclosed herein is based on the method of
% Of the catalyst must be used, which is not only economically difficult but also the resulting cyclohexadiene homopolymer.
Has a low molecular weight. Furthermore, there is no suggestion or disclosure about the possibility of obtaining a copolymer.

[0007] Makromol. Chem. , 191 ,
2743 (1990) describes a method for polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. In the polymerization method described here, it is taught that a transfer reaction accompanied by a lithium cation abstraction reaction and a lithium hydride elimination reaction occur considerably at the same time as the polymerization reaction, and the polymerization is carried out using polystyryllithium as an initiator. In spite of the fact that it was carried out, it was reported that at room temperature, a styrene-cyclohexadiene block polymer was not obtained, but only a cyclohexadiene homopolymer was obtained. Similarly, when blocking is performed at −10 ° C. using polystyryllithium as an initiator, a styrene-cyclohexadiene block polymer having a molecular weight of about 20,000 is obtained together with a cyclohexadiene homopolymer. No disclosure or suggestion is made of a block, a multi-block over a tri-block, a radial block, or the like.

[0008] European Polymer
J. , 9 , 895 (1973), describe a copolymer of 1,3-cyclohexadiene, butadiene, and isoprene using a π-allyl nickel compound as a polymerization catalyst. It is reported that the polymer obtained here has a single glass transition temperature suggesting a random polymer, and no block copolymer has been obtained. 34 (5), 333 (1977) describes a copolymer of 1,3-cyclohexadiene and acrylonitrile using zinc chloride as a polymerization catalyst. The polymer is an alternating copolymer, not a block copolymer.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a novel cyclic diene block copolymer comprising the following specific ratios which improve the processability and fluidity of the novel cyclic diene block copolymer, and (a) a molecular structure constituting a polymer chain. As a unit, at least 2 units partially or entirely composed of a cyclic conjugated diene monomer or a derivative thereof
Having at least one block and at least one block composed of a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer. (B) a cyclic diene-based diblock copolymer composed of a block partially or wholly composed of a cyclic conjugated diene monomer or a derivative thereof and a block mainly composed of a conjugated diene monomer or a derivative thereof And (a) 5 to 95% by polymerization,
(B) 5 to 95% by weight, provided that (a) + (b) = 100%
And a novel cyclic diene-based block copolymer composition.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have developed a novel cyclic conjugated diene-based block copolymer composition which has not been reported before, This block copolymer composition was confirmed to be a cyclic conjugated diene-based block copolymer composition having excellent rubber properties, impact properties and processability in a wide temperature range from low to high temperatures, and completed the present invention. .

That is, the present invention relates to [1] (a) as a part or all of the molecular structural units constituting the polymer chain, a part or all of which is represented by the following general formula (1):
At least two block units (A blocks) composed of the cyclic conjugated diene monomer represented by (2) or a derivative thereof, and mainly a linear conjugated diene monomer or a linear conjugated diene monomer Having at least one block unit (hereinafter referred to as B block) composed of a monomer having a number average molecular weight of 1,000 to 1,000,000
Wherein the weight ratio of / B is in the range of 3/97 to 97/3, and (b) A
-B diblock copolymer, each having a composition ratio of (a) 5 to 95% by weight, and (b) 5 to 95% by weight.
A cyclic diene-based block copolymer composition characterized in that the weight percentage is (where (a) + (b) = 100 percentage).

[0012]

Embedded image (However, n is a value selected from an integer from 1 to 4)

[0013]

Embedded image (However, n is a value selected from an integer from 1 to 4)

[2] In the preferred block copolymer composition comprising the components (a) and (b), a part or all of the monomers constituting the A block are 1,3-cyclohexadiene;
A 1,3-cyclohexadiene derivative or a cyclic conjugated diene monomer having a 6-membered ring structure in its molecule;
The monomer constituting the block is 1,3-butadiene and / or
Or the cyclic diene-based block copolymer composition which is isoprene or a monomer mainly composed of 1,3-butadiene and / or isoprene. [3] The cyclic diene which cyclic structure diene block copolymer is represented by A-B-A or _{[(A-B) n]} m X preferred (a) in the block copolymer composition Block copolymer composition. (Where m is an integer of 2 or more, n is an integer of 1 or more, and X represents a residue of a polyfunctional coupling agent or a residue of an initiator such as a polyfunctional organic alkali metal compound).

The thermoplastic elastomer or the special transparent resin (composition) having impact resistance is composed of at least two constrained phases (blocks) and at least one rubber phase (block), and both blocks are separated by microphase. There is a need to. When the constrained phase is below its Tg, the molecule having such a structure acts as a physical cross-linking point, and exhibits elastomeric elasticity. Above the Tg of the hard segment, the constrained phase also flows,
Injection molding and recycling become possible.

In the present invention, the fact that the A block and the B block of the block copolymer constituting (a) and (b) in the composition surprisingly microphase-separated was discovered, and based on this, intensive studies were conducted. As a result, the present invention has been completed. The block A forms the constrained phase (hard segment) in the present invention, and the block B forms the rubber phase (soft segment).

In the present invention, the cyclic conjugated diene-based block copolymer of the component (a) refers to a cyclic conjugated diene monomer or a cyclic conjugated diene monomer or a part thereof or all of the molecular structural units constituting the polymer chain. A block unit composed of at least two block units composed of derivatives (hereinafter referred to as A block) and a monomer composed mainly of a linear conjugated diene monomer or a linear conjugated diene monomer (hereinafter referred to as B block) block)
Is a cyclic conjugated diene-based block copolymer having at least one Examples of such a copolymer include a linear block copolymer represented by the following general formula (Formula 5) and a radial block copolymer represented by the following general formula (Formula 6).

[0018]

(AB) _a , A- (BA) _b , B- (AB) _c (where a and c are 2 or more and b is an integer of 1 or more)

## STR6 ## [(BA) _n ] _mx , [(AB) _n ]
_{m X, [(B-A} ) n -B] m X, [(A-B) n -
A] _m X (where m is an integer of 2 or more, and n is an integer of 1 or more. X
Represents a residue of a polyfunctional coupling agent or a residue of an initiator of a polyfunctional organic alkali metal compound.) In addition, an asymmetric radial type, a graft block type and the like can be exemplified.

In particular, when the block copolymer composition of the present invention is used as a thermoplastic elastomer or a special transparent resin having impact resistance, the molecular structural unit constituting the polymer chain of the block copolymer (a) is preferred. Needs to have two or more A blocks shown in the general formula (Chem. 5 and 6) in the molecule. If such a molecule is contained, a =
1, a block copolymer in which c = 1, that is, BA-
A B triblock copolymer or the like may be contained. In this case, the amount of the copolymer that does not contribute to the physical crosslinking can be used according to each application even if it is contained in an arbitrary ratio in the entire block copolymer. Less than 70 weight percent is preferred. The connection point between the A block and the B block of the block copolymer of the component (a) and the component (b) may be such that the cyclic conjugated diene monomer and the linear conjugated diene monomer are directly bonded. Residues of functional coupling agents (eg, dimethyldichlorosilane, methylene chloride, etc.), ester bonds, amide bonds, carbon
They may be connected by a bond or the like.

The general formula [(AB) _n ] _m X,
The radial block copolymer represented by [(AB) _n -A] _m X (where m is an integer of 2 or more and n is an integer of 1 or more) becomes a thermoplastic elastomer, but has a general formula [( BA) _n ] _m X, [(BA) _n
-B] radial block copolymer represented by _m X composition is a thermoplastic elastomer - the need for n is an integer of 2 or more to become a (where m is an integer of 2 or more). These radial block copolymers need not all have the same composition. For example, [(AB) _n ] _{m of the} general formula (Formula 6)
X is (AB) ₄ X, (AB) ₃ X, (AB) ₂ X
And a mixture of any composition of (AB).

In the present invention, the cyclic conjugated diene-based block copolymer as the component (a) refers to a copolymer in which a part or all of the molecular structural units constituting the polymer chain is composed of at least two A block units and at least one It is not necessary that the block copolymer is composed of only A and B blocks because it is a block copolymer composed of B block units. Therefore, for example, AB
-CA, ACBA, BACA (however, C
The block is a block unit composed of a monomer copolymerizable with the A and B monomer blocks and a derivative thereof, for example, a vinyl aromatic hydrocarbon monomer such as styrene or α-methylstyrene; methyl methacrylate , Acrylonitrile, ethylene oxide, propylene oxide and other polar monomers; cyclic lactone, cyclic siloxane and other cyclic compound monomers) are also included in the present invention. Of course, the C block may be copolymerized with a cyclic conjugated diene or a derivative thereof and / or a linear conjugated diene or a derivative thereof. Further, a plurality of different types of blocks (C, D, E...) May be included. D, E, F
... The monomers constituting the block are the same as the definition of the monomers constituting the C block. The copolymer having three or more types of blocks may take any form such as a radial type, a star type, a comb type, and a graft block type as well as the linear type.

The ratio of the component (a) in the block copolymer composition comprising the components (a) and (b) of the present invention is 5
To 95 weight percent.
If the ratio of the component (a) is less than 5% by weight, good mechanical properties (such as breaking strength and breaking elongation) as a thermoplastic elastomer or a special transparent resin having impact resistance cannot be expected, which is not preferable. When the ratio exceeds 95% by weight, the performance properties, particularly mechanical properties, are good, but the effect of improving processability and fluidity may not be exhibited.

The component (b) in the block copolymer composition of the present invention comprises a block composed entirely or partially of a cyclic conjugated diene monomer or a derivative thereof and a linear conjugated diene monomer or a linear conjugated diene monomer. Cyclic diene-based diblock copolymer comprising a block mainly composed of a monomer mainly composed of a conjugated diene monomer, that is, an AB diblock copolymer.

In the AB diblock copolymer, A /
The weight ratio of B is 3/97 to 97/3, and the weight ratio of A / B may be the same as or different from the ratio of the component (a) in the block copolymer. The cyclic diene-based block copolymer composition of the present invention may be produced by blending each of the components (a) and (b). A process for producing the block copolymer composition of the present invention by polymerizing the AB block by anionic polymerization and coupling a part of the AB block can be mentioned. In this method, (a) and ( b) The weight ratio of A / B in the components becomes equal. The proportion of the AB diblock copolymer (b) in the block copolymer composition is from 5 to 95% by weight. If this ratio is less than 5% by weight, the effect of improving processability and fluidity may be reduced. If the content is more than 95% by weight, the processability and the like are greatly improved, but the mechanical properties (breaking strength, breaking elongation, etc.) as thermoplastic elastomer and special transparent resin having impact resistance are improved.
Is not preferred because it is lost.

The molecular weight of each of the components (a) and (b) in the block copolymer composition of the present invention is variously set depending on the purpose, but is generally 1000 as a number average molecular weight (Mn). To 1,000,000, preferably 10,000 to 500,000, and more preferably 20,000 to 400,000. The molecular weight distribution (Mw / Mn, where Mw is a weight average molecular weight) is 1.01 to 10, preferably 1.05 to 7, and particularly preferably 1.1 to 5. The molecular weights of the components (a) and (b) are arbitrarily set within the above range, but according to the later-described preferred production examples of block copolymer compositions, the molecular weights are in the order of (a)> (b). .

The A block in the components (a) and (b) constituting the block copolymer composition of the present invention, ie, a monomer mainly composed of a cyclic conjugated diene monomer or a derivative thereof, Although it is possible to adjust the molecular weight of the monomer, it is generally preferable that the monomer is constituted by continuously binding at least 20 monomers, and more than 30 monomers Are more preferably bonded, and more preferably 50 or more monomers are bonded. The length of the A block in the component (a) is
They may be the same or different. For example, in the case of ABA, the length of each terminal A block is changed depending on the purpose,
It may be symmetric or asymmetric.

The A block in the components (a) and (b) constituting the block copolymer composition of the present invention, ie, a monomer mainly composed of a cyclic conjugated diene monomer or a derivative thereof. The weight is not particularly limited because it is set variously according to the purpose.
~ 97% by weight, preferably 10 ~ 85% by weight
Can be set in the cent range. In particular, when used as a thermoplastic elastomer, this value is preferably in the range of 10 to 50% by weight, and when used as a special transparent resin having excellent impact resistance, it is suitably set in the range of 65 to 90% by weight. Is done. Such a cyclic conjugated diene monomer or a derivative thereof is a cyclic conjugated diene having 5 or more membered rings constituted by carbon-carbon bonds, preferably 1,3 or more.
-Cyclopentadiene, 1,3-cyclohexadiene,
Examples thereof include 1,3-cyclopeptadiene, 1,3-cyclooctadiene and derivatives thereof, and particularly preferable ones are 1,3-cyclohexadiene and 1,3.
A cyclohexadiene derivative or a cyclic conjugated diene having a six-membered ring structure in the molecule.

The A block in the components (a) and (b) constituting the block copolymer composition of the present invention, that is, "part or all is composed of a cyclic conjugated diene monomer or a derivative thereof. The meaning of "part or all" of the "block unit" is not limited to the case where the cyclic conjugated diene monomer or its derivative is only included, but other monomers copolymerizable with these cyclic conjugated diene monomer or its derivative. Means that the copolymer block may be used.
Examples of the copolymerizable monomer include, for example, conventionally known monomers that can be polymerized by anionic polymerization.

These include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,
Linear conjugated diene monomers such as 1,3-pentadiene and 1,3-hexadiene, styrene, α-methylstyrene,
o-methylstyrene, p-methylstyrene, p-tert-
Vinyl aromatic hydrocarbon monomers such as butylstyrene, 1,3-dimethylstyrene, divinylbenzene, diphenylethylene, vinylnaphthalene, vinylanthracene, and vinylpyridine; methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, Various polar monomers such as a polar vinyl monomer such as α-methyl methyl cyanoacrylate and a cyclic compound monomer such as ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam and cyclic siloxane can be exemplified. Of course, cyclic conjugated dienes and cyclic conjugated diene derivatives can also be copolymerized. These monomers may be one kind or a mixture of two or more kinds. Of these, styrene and α-methylstyrene are preferred. These copolymerizable monomers can be used in the A block in an amount of preferably not more than 80% by weight, more preferably not more than 50% by weight. These copolymerizable monomers in the A block may be distributed in the molecular chain by random or alternating copolymerization, or may be distributed in a tapered manner even if a partial block is formed. It does not matter.

The linear conjugated diene monomer constituting the B block in the components (a) and (b) constituting the block copolymer composition of the present invention is a pair of a conjugated carbon-carbon dimer. A linear diolefin having a heavy bond;
-Butadiene, isoprene, 2,3-dimethyl-1,3
-Butadiene, 1,3-cyclopentadiene, 1,3-
Hexadiene is exemplified, and 1,3-butadiene and isoprene are particularly preferred. Further, a block unit composed of a monomer mainly composed of a linear conjugated diene monomer constituting the B block may be a conventionally known block unit which can be copolymerized with the linear conjugated diene monomer, if necessary. Means a block unit obtained by copolymerizing the above monomers.

Examples of monomers capable of anionic copolymerization with these linear conjugated diene monomers include, for example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, , 3-dimethylstyrene, divinylbenzene, diphenylethylene, vinylnaphthalene, vinylanthracene, vinylpyridine and other vinyl aromatic hydrocarbon monomers; methyl methacrylate,
Examples thereof include polar monomers such as methyl acrylate, acrylonitrile, methyl vinyl ketone, and α-methyl methyl cyanoacrylate, and cyclic compound monomers such as ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, and cyclic siloxane. Of course, cyclic conjugated dienes,
Cyclic conjugated diene derivatives can also be copolymerized. These monomers may be one kind or a mixture of two or more kinds. Of these, styrene and α-methylstyrene are preferred. These copolymerizable monomers can be used in the B block in an amount of preferably 50% by weight or less, more preferably 30% by weight or less. These copolymerizable monomers in the B block are converted into B by random or alternating copolymerization.
It may be distributed in a block molecular chain, may form a partial block, or may be distributed in a tapered shape.

When 1,3-butadiene is used as the linear conjugated diene monomer constituting the B block, a polybutadiene block is formed. The polybutadiene has 1,4 bonds of cis and trans and 1,2 bonds of vinyl, and the ratio thereof is variously changed depending on polymerization conditions, and is not particularly limited. In anionic polymerization using a complex of an alkali metal compound as an initiator, which is a preferable method for producing a diene-based block copolymer composition, the ratio of 1,2 bonds is 10 to 80 mol% in the B block.

Since the B block serves as a soft segment (rubber phase) of the block copolymer of the present invention, particularly when used as a thermoplastic elastomer, the glass transition temperature (T
g) is preferably lower than room temperature. In this case, if the 1,2 bond of butadiene in the B block becomes too large, T
Since g increases and the low-temperature performance of the elastomer deteriorates, it is better to control the amount of 1 and 2 bonds to about 10 to 70 mol%.

For the production of the cyclic conjugated diene block copolymer composition of the present invention, living anionic polymerization using a specific initiator (complex of an alkali metal compound) is suitably used. The complex of an alkali metal compound which is an initiator used in a preferred production example in the present invention is a complex compound of an alkali metal, that is, an organometallic compound containing a Group IA metal in the periodic table. Preferably, it is a polynuclear or polynuclear complex compound of an organometallic compound.

The Group IA metals usable in the present invention are lithium, sodium, potassium, rubidium, cesium, and francium. Preferred Group IA metals include lithium, sodium, and potassium, and are particularly preferable. Lithium can be exemplified as the Group IA metal. The preferred alkali metal compound used in the present invention is an organic compound containing the Group IA metal, that is, an organic lithium compound, an organic sodium compound,
A complex compound of an organic potassium compound is particularly preferable, and a complex compound of an organic lithium compound is particularly preferable. The organic lithium compound is an organic lithium compound in which one or more lithium atoms are bonded in a molecule, such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-lithium. -Butyllithium, allyllithium,
Phenyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium and the like. These may be used alone or in combination of two or more.

As the compound which forms a complex with an organometallic compound containing a Group IA metal, a polar group (RO—, R ₂ N—,
RS-, 2-oxazoline group and the like: R represents an alkyl group). More preferred compounds include amines, ethers, and thioethers.
Ters can be exemplified, and tertiary amines are particularly preferred. Particularly preferred tertiary amine compounds include trimethylamine, triethylamine, tetramethylethylenediamine (TMED
A), diazobicyclo [2,2,2] octane (DAB
CO). These compounds are 1
It can be a species or, if necessary, a mixture of two or more species.

The method for synthesizing the complex compound of an organometallic compound containing a Group IA metal is not particularly limited.
Conventionally known methods and techniques can be adopted. For example, a method of dissolving an organometallic compound in an organic solvent and adding a solution of a compound serving as a ligand thereto, or dissolving a compound serving as a ligand in an organic solvent and adding a solution of the organometallic compound thereto And the like. The preferred production method of the present invention is carried out by bulk polymerization or solution polymerization in the presence of an alkali metal compound as a polymerization initiator. The production of the block copolymer consists of a block unit mainly composed of a cyclic diene monomer or a derivative thereof, and a linear conjugated diene monomer or a linear conjugated diene monomer copolymerizable therewith. By combining block units composed of monomers mainly composed of

For example, a block unit composed of a cyclic diene monomer or a derivative thereof is subjected to living anionic polymerization in advance using these initiators, and a linear conjugate is obtained from one or both ends of the polymer. A method of sequentially feeding and polymerizing a diene monomer or a derivative thereof, or a method in which a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer is prepared in advance. Living anion polymerization is performed, and a cyclic diene-based monomer or a derivative thereof can be polymerized from one end or both ends of the polymer. If necessary, feed a cyclic diene monomer or its derivative monomer or a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer sequentially. Can polymerize a triblock or multiblock copolymer.

A block unit composed of a cyclic diene monomer or a derivative thereof is previously subjected to living anion polymerization using these initiators, and a linear conjugated diene monomer is obtained from one end of the polymer. [(AB) _n ] _{m + 2} X by polymerizing a monomer of the compound or a derivative thereof and coupling the active terminal thereof with a suitable coupling agent.
(Where m is 0 or an integer of 1 or more and n = 1. X is a residue of a polyfunctional coupling agent such as silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, or a polyfunctional organic alkali metal compound) (Representing the residue of the initiator).

Further, a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer is subjected to living anion polymerization in advance, and a cyclic diene monomer is added from one end of the polymer. [(BA) _n ] _m X (where m is an integer of 2 or more, n = 1) by polymerizing the compound or its derivative and coupling the active terminal thereof with an appropriate coupling agent. X represents, for example, the residue of a polyfunctional coupling agent such as silicon tetrachloride, tin tetrachloride, or epoxidized soybean oil or the residue of an initiator such as a polyfunctional organic alkali metal compound). You can make a union.

The polyfunctional coupling agent may be any known one and is not particularly limited. For example, halides such as dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, and tin tetrachloride; Examples include epoxy compounds such as soybean oil and esters, and esters.

The process for producing the block copolymer composition according to the present invention comprises blending the components (a) and (b) obtained individually by the above-mentioned polymerization method at a composition ratio within the range of the present invention, respectively. The components (a) and / or (b) obtained alone are blended with the composition obtained in (1) and melted by a suitable melt kneading machine such as an extruder, a roll, a Banbury mixer, and a Labo Plastomill. In addition to the blending method obtained by blending, a method in which a monomer and a catalyst are sequentially fed during the above polymerization, or a method in which an AB diblock living polymer is prepared in advance and partially coupled, and It is divided into the direct method obtained by these combinations. In consideration of economy, the latter method is advantageous, and the latter method is preferably employed.

The preferred production method for obtaining the block copolymer composition of the present invention is solution polymerization, but usable solvents include butane, pentane, n-hexane, isohexane, isopentane, heptane, octane and isooctane. Hydrocarbons, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; ethers such as diethyl ether and tetrahydrofuran Can be exemplified. These alone are 2
A mixture of more than one species may be used.

As a particularly preferred production method for producing the cyclic diene block copolymer composition of the present invention, AB diblock living polymer is polymerized in advance by living anion polymerization, and the active terminal is partially coupled. Is the way. In this case, the cyclic diene block copolymer composition having different block chains can be obtained by changing the concentration of the active terminal and the equivalent ratio of the functional group of the coupling agent to control the coupling ratio.

Further, the block copolymer composition of the present invention may contain a cyclic diene homopolymer and / or a linear diene homopolymer. Such a cyclic diene homopolymer and / or chain diene homopolymer is compatible with the A block and the B block in the cyclic diene block copolymers (a) and (b), respectively, and functions as a plasticizer. In some cases, it is preferably 40% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

The following combinations are exemplified as particularly preferred compositions of the block copolymer composition of the present invention. (A) ABA or [(AB) _n ] _m X (where m is an integer of 2 or more, and n is an integer of 1 or more. X
Represents a residue of a polyfunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, or a residue of an initiator such as a polyfunctional organic alkali metal compound. ) AB diblock copolymer The composition ratio of the constituent components of this composition is (a) 5-9, respectively.
5% by weight and (b) 5 to 95% by weight (provided that (a) + (b) = 100%).

The amount of the polymerization initiator used in the preferred production method for obtaining the block copolymer composition of the present invention can be varied depending on the purpose and cannot be limited. 1 × 10
^Over 5 ～1X10 ^{- 1} mole% - in the range of St, preferably 1x10 ^over 4 ～1X10 ^{- 2} mole% - can be implemented in cents range. The polymerization temperature in the preferred method for producing the block copolymer composition of the present invention is set to variously different ones as necessary, but is generally from -100 ° C to 1 ° C.
It can be carried out at a temperature of 50 ° C, preferably -80 ° C to 100 ° C, particularly preferably -50 ° C to 80 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, particularly preferably 1 to 10 hours. Further, it is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen, argon or helium. The polymerization pressure is not particularly limited, as long as the polymerization is performed at a pressure sufficient to maintain the monomer and the solvent in the liquid phase in the above-mentioned polymerization temperature range. Further, care must be taken to prevent impurities such as water, oxygen, carbon dioxide and the like, which inactivate the initiator and the active terminal, from being mixed into the polymerization system. The polymerization system can be used in any of a batch system, a continuous system, and a semi-batch system.

Further, prior to the polymerization, in the presence of a cyclic conjugated diene monomer and / or a monomer copolymerizable therewith,
Preliminary reaction or aging of some or all of the initiator components, preferably in the absence of, to prepare a complex compound in advance is a method for suitably obtaining the block copolymer and the composition of the present invention. Is a preferred means. Depending on the conditions of these operations, the polymerization activity is improved, and undesirable side reactions (chain transfer, elimination of active metal species) can be prevented as much as possible. As a result, effects such as narrowing of the molecular weight distribution can be achieved. is there. After the polymerization reaction has reached a predetermined reaction rate, if necessary, in addition to the known coupling agent as described above, a terminal modifying agent or a terminal branching agent, further a polymerization terminator, a polymerization stabilizer, an antioxidant Is added to the reaction system.
The addition of these at this stage is effective in preventing the polymer from undergoing oxidative deterioration or thermal deterioration when the solvent is removed in the next step.

Examples of the terminal modifying agent include known compounds capable of reacting with the active terminal of ordinary living anionic polymerization. These include alkylene oxides such as halogen gas, carbon dioxide, carbon monoxide, ethylene oxide and propylene oxide, alkylene sulfides, isocyanate compounds, imino compounds, aldehyde compounds, ketone and thioketone compounds, esters, lactones, and amide-containing groups. Examples include compounds, urea compounds, acid anhydrides, acid chlorides, and the like. Examples of the terminal branching agent include compounds such as polyepoxide, polyisocyanate, polyimine, polyaldehyde, polyketone, polyanhydride, polyester, and polyhalide, carbon tetrachloride, titanium tetrachloride, silicon tetrachloride, chloroform, bromoform, titanocent chloride, Zirconic trichloride, methyltrichlorosilane, methyltribromosilane, epoxidized soybean oil and the like. These compounds are
Two or more functional groups may be contained in the molecule. These terminal modifiers or terminal branching agents may be used alone or in combination of two or more.

As the stabilizer and antioxidant, any of the conventionally known stabilizers may be used, and various stabilizers such as phenol, organic phosphate, organic phosphite, amine and sulfur can be used. The known antioxidants are used. The stabilizer is generally used in the range of 0.001 to 10 parts by weight based on 100 parts by weight of the block copolymer composition. As the polymerization terminator, a known terminator which can deactivate the active terminal of the organometallic compound complex which is a preferable initiator can be used.
Alcohols, ketones, polyhydric alcohols (ethylene glycol, propylene glycol, glycerin), phenol, hindered phenol which is also an antioxidant, acid, ketone, halogenated Hydrocarbons, amines and mixtures thereof. These are generally used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer and the composition. The terminating agent may be added before adding the stabilizer, or may be added simultaneously with the stabilizer. Alternatively, deactivation may be performed by bringing molecular hydrogen into contact with the active terminal.

Next, the solvent is removed from the polymer solution, but a known desolvation method in the production of an ordinary conjugated diene polymer may be used, for example, a method of evaporating the solvent by heating, or dispersing the solution in warm water. And steam is blown to evaporate the solvent (steam stripping method), a method of adding a large amount of a precipitant such as methanol to separate the solvent from the solvent, a method of drying the solution under vacuum, After evaporating a part of the solvent, a method of further removing the solvent with a vented extruder can be adopted. The cyclic diene-based block copolymer composition obtained in the present invention, if necessary,
Part or all of the B block part, further all of the B block part and part or all of the A block part can be hydrogenated.

[0052]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. The chemicals used in the present invention were of the highest purity available. The general solvent was degassed, refluxed over the active metal and then distilled.

<Evaluation Method> [Molecular Weight] The number average molecular weight of the block copolymer was expressed as a value in terms of polystyrene by the GPC method. [Composition and microstructure] The composition and microstructure of the block copolymer are ¹ H-NMR.
(400 MHz: GX-400 FT-NM manufactured by JEOL
R) was performed 32 times in 10 W / V% d-dichlorobenzene solvent and quantified. [Viscoelastic Behavior] The temperature change and tan δ of the dynamic storage elastic modulus (E ′) of the block copolymer were measured using a DMA spectrometer (983 DMA manufactured by DuPont Instruments) under the conditions shown in Table 1. did.

[0054]

[Table 1]

[Surface hardness] JIS A hardness was measured at 25 ° C. [Breaking strength (kg · f / cm ² ), breaking elongation (%)] According to JIS K6301, length 20 mm x width 3 mm x
Using a compression molded piece having a thickness of 3 mm, a tensile test was performed at 25 ° C. under a condition of a head speed of 20 mm / min. [Softening temperature (° C)] Using TMA100 manufactured by SEIKO Electronics Co., Ltd., load 50g
It was measured at a penetration temperature of 100 μm.

(Production Example) The alkali metal complex compound as the polymerization catalyst used in this example was prepared by adding an equivalent mole of a tertiary amine (TMEDA) to n-butyllithium and coordinating. Example 1 2060 g of cyclohexane and 154 g of 1,3-cyclohexadiene were added to a 5-liter autoclave equipped with a stirrer and sufficiently purged with nitrogen, and n was used as a polymerization initiator.
25.6 mmol of a metal complex compound synthesized from -butyllithium and TMEDA was added, and polymerized at 35 ° C for 4 hours. The addition ratio of 1,3-cyclohexadiene determined by gas chromatography was 97.8%. At this time, a part of the polymer solution was extracted into methanol and subjected to GPC measurement. The color of the polymer solution was deep yellow, confirming that the reaction was proceeding by living polymerization.

Next, 990 g of a 33% by weight solution of butadiene in cyclohexane was added.
Polymerized for hours. Further, at this time, a part of the polymer solution was withdrawn into methanol and subjected to GPC measurement. Since the color of the polymer solution was the same yellow as that of polybutadienyl lithium, it was confirmed that the reaction was progressing by living polymerization.

Next, ｎ with respect to n-butyl lithium
Add equivalent mole of dimethyldichlorosilane and add
Stirring was performed for hours. At this time, a part of the polymer solution was extracted into methanol and subjected to GPC measurement. Since the color of the polymer solution was colorless, it was confirmed that the active terminal was deactivated by reacting with the coupling agent. The solvent was evaporated, and the obtained sheet was compression-molded at 220 ° C and subjected to various physical property tests. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer.

[0059]

[Table 2]

FIG. 1 shows a GPC chart of components sequentially extracted.
Show A peak on the high molecular weight side for each sequence
Thus, it was confirmed that the polymerization had progressed by living anionic polymerization, and that the desired cyclic diene-based block copolymer composition had been produced. From the area ratio of this GPC, the composition of this composition was such that the polycyclohexadiene-polybutadiene-polycyclohexadiene block copolymer was 45% by weight and the polycyclohexadiene-polybutadiene diblock copolymer was 55% by weight. Was confirmed. Further, ¹ H-NM of this block copolymer composition
The R (400 MHz) spectrum is shown in FIG. 5.0-
A signal derived from an olefinic proton was observed at around 6.4 ppm. Table 3 shows the assignment of each signal.

[0061]

[Table 3] In addition, DM of this cyclic diene-based block copolymer composition
The A spectrum (E ′ and tan δ) is shown in FIG.

Example 2 The same procedure as in Example 1 was carried out except that 1/4 equivalent mole of tetrachlorosilane was used as the coupling agent with respect to the charged n-BuLi. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer composition. The GPC char of the cyclic diene-based block copolymer composition before and after the addition of the coupling agent.
FIG. 4 shows the ¹ H-NMR spectrum after coupling, and FIG. 6 shows the DMA chart after coupling. From the GPC peak area, the composition of this block copolymer composition was (polycyclohexadiene-polybutadiene) _x SiCl _{4 -x} (x = integer from 2 to 4) radial block copolymer at 62 weight percent, It was confirmed that the cyclohexadiene-polybutadiene diblock copolymer was 38% by weight.

Example 3 2060 g of cyclohexane and 77 g of 1,3-cyclohexadiene were added to the autoclave of Example 1, and a metal complex compound synthesized from n-butyllithium and TMEDA as a polymerization initiator 25. 6 mmol was added and polymerized at 35 ° C. for 3 hours. The addition ratio of 1,3-cyclohexadiene determined by gas chromatography was 96.5%. Then, a 33% by weight solution of butadiene in cyclohexane was
0 g was added, and polymerization was carried out at 60 to 70 ° C. for 1 hour. Similarly, the addition ratio of butadiene was determined to be 1 by gas chromatography.
00 percent was confirmed.

Then, 1,3-cyclohexadiene was added to 77
g was added and polymerized at 35 ° C. for 3 hours. The addition ratio of 1,3-cyclohexadiene in this sequence was 93.3% by gas chromatography. The active end of the living polymer was used as a terminator with 0.8 equivalent mol of methyl alcohol based on n-BuLi charged.
Inactivated at 0 ° C. for 1 hour. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer composition.

(Comparative Example 1) The procedure of Example 1 was repeated except that styrene was used instead of 1,3-cyclohexadiene. Molecular weight of the obtained block copolymer composition
Table 2 summarizes the composition and various physical properties.

(Comparative Example 2) The same procedure as in Example 3 was carried out except that styrene was used instead of 1,3-cyclohexadiene. Molecular weight of the obtained block copolymer composition
Table 2 summarizes the composition and various physical properties.

[0067]

The cyclic diene block copolymer composition of the present invention comprises an A block composed of a part or all of a cyclic diene monomer or a derivative thereof, and a linear block copolymerizable with the A block. A novel block copolymer composition containing a monomer block (B block) mainly composed of a conjugated diene monomer or a linear conjugated diene monomer in an arbitrary unit. That is, in addition to excellent heat-resistant mechanical properties having a cyclic conjugated diene-based polymer, it is possible to combine various properties required for a polymer material, and in some cases, a stabilizer, an ultraviolet absorber, a light stabilizer, Additives such as fillers, hydrogenate a part or all of the olefinic double bond, and modify the terminal modification, functionalization, etc. to obtain special impact-resistant resins and thermoplastic elastomers. −
Not only as a simple substance, but also for the purpose of modifying other polymer materials such as polyamide, polyester, polyether, polyphenylene sulfide, polyolefin, etc., such as automobile parts, electric / electronic parts, films, sheets, etc. Can be used for a wide range of applications.

[Brief description of the drawings]

FIG. 1 shows GPC of the block copolymer obtained in Example 1.
It is a chart.

FIG. 2 shows ¹ H- of the block copolymer obtained in Example 1.
It is an NMR spectrum.

FIG. 3 shows a DMA of the block copolymer obtained in Example 1.
It is a spectrum.

FIG. 4 shows GPC of the block copolymer obtained in Example 2.
It is a chart.

FIG. 5 shows ¹ H- of the block copolymer obtained in Example 2.
It is an NMR spectrum.

FIG. 6 shows a DMA of the block copolymer obtained in Example 3.
It is a spectrum.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 53/00

Claims (3)

(57) [Claims] 1. (a) As a part or all of the molecular structural units constituting the polymer chain, a part or the whole is a cyclic conjugated diene monomer or a cyclic conjugated diene monomer represented by the following general formulas (1) and (2): A block unit composed of at least two block units (hereinafter referred to as A block) composed of a derivative thereof, and a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer (hereinafter referred to as a block unit) B block) and a number average molecular weight of 1,000 to 100,000
0, wherein the weight ratio of A / B is in the range of 3/97 to 97/3, comprising: a cyclic diene-based block copolymer; and (b) an AB diblock copolymer, The composition ratio is (a) 5 to 95% by weight,
(B) 5-95% by weight (however, (a) + (b)
= 100%). The cyclic diene-based block copolymer composition characterized in that: Embedded image (However, n is a value selected from integers from 1 to 4) (However, n is a value selected from an integer from 1 to 4) 2. A cyclic conjugated diene monomer in which part or all of the monomer constituting the A block is 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative, or a 6-membered ring structure in the molecule thereof. The monomer according to claim 1, wherein the monomer constituting the B block is 1,3-butadiene and / or isoprene, or a monomer mainly composed of 1,3-butadiene and / or isoprene. A cyclic diene block copolymer composition. 3. The structure of the cyclic diene block copolymer (a) is represented by A-B-A or _{[(A-B) n]} m X, cyclic diene according to claim 1 or 2, wherein Block copolymer composition. (Where m is an integer of 2 or more, n is an integer of 1 or more, and X represents a residue of a polyfunctional coupling agent or a residue of a polyfunctional organic alkali metal compound initiator)