JP2002371117A - Cyclic conjugate diene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic resin having excellent heat resistance, transparency, nonhygroscopicity and chemical resistance with excellent casting workability, and to provide a copolymerization method for the resin. SOLUTION: The cyclic conjugated diene copolymer has (A) a molecular unit derived from a cyclic conjugate diene monomer and (B) a second molecular unit derived from an α-substituted vinyl aromatic monomer, and has a random structure. An another copolymer is obtained by hydrogenation or epoxidation of the above copolymer. An another method for producing the above copolymer comprises copolymerization between the cyclic conjugated diene monomer and the α-substituted vinyl aromatic monomer by living anionic copolymerization process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, transparency,
The present invention relates to a novel cyclic polyolefin-based resin having non-hygroscopicity, chemical resistance and excellent workability.

[0002]

2. Description of the Related Art General-purpose polyolefin materials represented by polyethylene, polypropylene and the like are excellent in chemical resistance such as acid resistance and base resistance, and are non-hygroscopic. A general-purpose polyolefin-based material is a thermoplastic resin and is excellent in recyclability, and has extremely high industrial use value as a plastic structural material. However, these general-purpose polyolefin-based materials cannot be used in applications that require both heat resistance and transparency. For example, the melting temperature of general crystalline polypropylene is at most 170 ° C., and the transparency is poor. In order to improve the heat resistance of general-purpose polyolefins, generally, the degree of crystallinity can be raised. However, those having high crystallinity have poorer transparency than those having low crystallinity, and have a problem that they cannot be used for applications requiring both heat resistance and transparency.

As an improvement of polyolefin-based materials, cyclic polyolefins using polycyclic norbornene-based monomers (Japanese Patent Publication No. 2-9612, Japanese Patent Application Laid-Open No. 60-168708, and Japanese Patent Publication No. 8-26124) have been proposed. Have been. Cyclic polyolefin materials using these polycyclic norbornene monomers have an amorphous structure having a softening temperature of about 160 ° C. by including a bulky 5-membered ring structure in the polymer main chain skeleton, and are used for general-purpose polyolefins. It has high industrial utility value as a material having higher heat resistance and transparency. However, these various properties have not always been sufficient as heat resistance, rigidity, hardness and impact resistance required for transparent materials in recent years.

As an improvement of a cyclic polyolefin material using these polycyclic norbornene monomers, a cyclic olefin polymer obtained by polymerizing a 1,3-cyclohexadiene monomer by anionic polymerization (for example, WO94-2803)
No. 8, WO94-29359, JP-A-7-2
47321, JP-A-7-258318, JP-A-7-247323, JP-A-7-247405,
JP-A-7-258362). These include a cyclohexane ring continuous structure having a unique polymer microstructure in the main chain skeleton of the polymer, resulting in 220
It has an amorphous structure with a softening temperature exceeding ℃,
It enables both heat resistance and transparency, and has high rigidity and hardness. In addition, the heat resistance is impaired by realizing a block polymer structure comprising a cyclohexane ring continuous structure block portion and a rubber component block portion made of butadiene, isoprene, etc. by utilizing the living property of anionic polymerization which is a production method. It also makes it possible to greatly improve the impact resistance.

However, since it has a cyclohexane ring continuous structure inevitably having a unique polymer microstructure, the dissolvable solvent is practically limited to decahydronaphthalene having a high boiling point, and high properties are required. In the solvent casting method, which is indispensable for producing an optical film, it is extremely difficult to remove the solvent, and there is a major problem in its moldability.

[0006]

An object of the present invention is to provide a novel cyclic polyolefin resin having high heat resistance, transparency, non-hygroscopicity, chemical resistance and excellent processability. And a method for producing the same.

[0007]

Means for Solving the Problems The present inventor has conducted studies on cyclic olefins to solve the above-mentioned problems, and has invented a novel cyclic polyolefin resin. That is, the present invention provides: [1] a cyclic conjugated diene-based copolymer represented by the following formula (1):

[0008]

Embedded image

[Formula (1) represents a composition formula of a polymer.
(A), (B), and (C) represent each molecular structural unit constituting the polymer main chain. l, m, and n represent wt% of each molecular structural unit contained in the polymer main chain. (A): a molecular structural unit derived from a cyclic conjugated diene-based monomer (the molecular structural unit may be one type or two or more types). (B): a molecular structural unit derived from an α-substituted vinyl aromatic monomer (the molecular structural unit may be one type or two or more types). (C): a molecular structural unit derived from another copolymerizable monomer (the molecular structural unit may be one type or two or more types). However, the bonding structure between (A) and (B) is a random structure, l + m + n = 100, and 0.1 ≦ l / m ≦
9, 0 ≦ n ≦ 90, and the number average molecular weight of the polymer is 5,000 to 500,000. [2] A random polymer structure comprising (A) a molecular structural unit derived from a cyclic conjugated diene monomer and (B) a molecular structural unit derived from an α-substituted vinyl aromatic monomer. A cyclic conjugated diene-based copolymer according to [1], wherein the cyclic conjugated diene-based copolymer according to [1], comprising: The molecular structural unit may be one type or two or more types), [3] the polymer main chain of the cyclic conjugated diene-based copolymer according to [1] or [2], and a polymer A hydrogenated cyclic conjugated diene-based copolymer obtained by hydrogenating at least a part of a side chain; [4] a polymer main chain of the cyclic conjugated diene-based copolymer according to [1] or [2]; Epoxy obtained by epoxidation of at least a part of non-conjugated double bond of molecular side chain A cyclic conjugated diene-based polymer, [5] a hydrogenated cyclic conjugated diene-based copolymer of [3], wherein at least a part of a non-conjugated double bond of a polymer main chain and a polymer side chain is epoxidized Epoxidized hydrogenated cyclic conjugated diene-based polymer, [6] using at least a cyclic conjugated diene-based monomer and an α-substituted vinyl aromatic-based monomer as raw material monomers in a hydrocarbon compound solvent, A method for producing a cyclic conjugated diene-based polymer, wherein the polymerization is carried out in the presence of a polymerization initiator in which a group 1 organometallic compound and an ether compound are combined;
It is.

The present invention will be specifically described. The cyclic conjugated diene-based monomer in the present invention is a cyclic conjugated diene having 6 or more membered rings constituted by carbon-carbon bonds.
Preferred cyclic conjugated diene-based monomers are 6- to 8-membered cyclic conjugated dienes constituted by carbon-carbon bonds.
A particularly preferred cyclic conjugated diene monomer is a 6-membered cyclic conjugated diene. Specific examples include 1,3-cyclohexadiene, 1,3-cyclooctadiene, and derivatives thereof. These monomers may be used alone or in combination of two or more as necessary. Particularly preferred are 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives.

The α-substituted vinyl aromatic monomer in the present invention includes vinyl aromatic monomers in which the α-position is substituted with a hydrocarbon group such as an alkyl group or an aryl group, and derivatives thereof. I can do it. Specifically, α-methylstyrene, 1,2-dimethylstyrene, 1,1-diphenylethylene, 2,4-diphenyl-4-methyl-1-
Pentene and 1,3-diisopropenylbenzene. These monomers may be used alone or in combination of two or more as necessary.

The other copolymerizable monomer in the present invention is a conventionally known monomer which can be polymerized by anionic polymerization. For example, 1,3-butadiene, isoprene,
Chain conjugated diene monomers such as 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, styrene, o-methylstyrene, p-methylstyrene, tert-butylstyrene , 2,5-dimethylstyrene, o-methoxystyrene, divinylbenzene, vinylnaphthalene, vinylpyridine and the like, vinyl aromatic monomers excluding α-substituted vinyl aromatic monomers,
Methyl methacrylate, methyl acrylate, acrylonitrile, methacrylonitrile, methyl vinyl ketone, α-
Polar vinyl monomers such as methyl cyanoacrylate, ethylene oxide, propylene oxide, cyclic lactone,
Examples include polar monomers such as cyclic lactams and cyclic siloxanes, as well as ethylene and α-olefin monomers, and these monomers may be used alone or in combination of two or more as necessary. .

The cyclic conjugated diene-based copolymer of the present invention comprises a molecular structural unit derived from a cyclic conjugated diene-based monomer and α
-It is essential that the molecular structural unit derived from the substituted vinyl aromatic monomer has a random structure. Further, α- of a molecular structural unit derived from a cyclic conjugated diene-based monomer
The weight ratio 1 / m to the molecular structural unit derived from the substituted vinyl aromatic monomer is 0.1 or more and 9 or less. l
If / m is smaller than 0.1, the composition ratio of the molecular structural units derived from the α-substituted vinyl aromatic monomer increases, which is too brittle and is not preferable as an optical material. If it exceeds 9, the molecular structural unit derived from the cyclic conjugated diene-based monomer is too long, so that it is difficult to develop sufficient solvent solubility. 0.6 ≦ due to the balance between heat resistance and solvent solubility
It is preferable that 1 / m ≦ 5.

The number average molecular weight of the cyclic conjugated diene copolymer in the present invention is 5,000 to 500,000, preferably 10,000 to 200,000, in terms of polystyrene equivalent average molecular weight. If it is less than 5000, the strength and impact resistance of the polymer material cannot be sufficiently exhibited. On the other hand, if it is larger than 500,000, the solution viscosity at the time of dissolving the solvent is too high, which is not practical. The cyclic conjugated diene-based copolymer of the present invention comprises at least (A) a molecular structural unit derived from a cyclic conjugated diene-based monomer;
A molecular structural unit derived from a substituted vinyl aromatic monomer is a copolymer randomly polymerized.

The cyclic conjugated diene-based copolymer of the present invention comprises:
(A) a random polymer structural unit composed of a molecular structural unit derived from a cyclic conjugated diene-based monomer and (B) a molecular structural unit derived from an α-substituted vinyl aromatic-based monomer; C) It is possible to have a polymer block structure composed of a polymer structural unit composed of a molecular structural unit derived from other copolymerizable monomers. In particular, when a molecular structural unit derived from a chain conjugated diene-based monomer is selected as the molecular structural unit derived from the (C) other copolymerizable monomer, heat resistance and solvent solubility are maintained. , Impact resistance can be greatly improved. The polymer block structure can be selected as needed, such as a diblock structure or a triblock structure.

In the formula (1), n, which is wt% of the molecular structural unit derived from (C) and other copolymerizable monomers, has a different desired value depending on the required product characteristics. It is possible to select between 90 and 90. When used for products that do not require impact resistance and place emphasis on the balance between heat resistance and surface hardness, the value of n is 0 or more and 1
It is preferred to select less than zero. It is more preferably 0 or more and 1 or less, and the film surface hardness after film formation is the highest, and the practically important scratch-resistant property is the best.

When used for products in which the balance between heat resistance and impact resistance is more important than surface hardness, the value of n is preferably selected from 10 to 90. When n is greater than 90, it comprises (A) a molecular structural unit derived from a cyclic conjugated diene-based monomer and (B) a molecular structural unit derived from an α-substituted vinyl aromatic-based monomer. Since the compatibility between the random polymer structural unit and the polymer structural unit composed of the molecular structural unit derived from (C) other copolymerizable monomer is increased, and the phase separation structure is hardly generated, heat resistance is obtained. And impact resistance are difficult to balance. From the viewpoint of the balance between heat resistance and impact resistance, a more preferable value of n is 15 or more and 80 or less. In this region, it is possible to exhibit the best impact resistance while maintaining transparency and necessary heat resistance. It is possible.

The cyclic conjugated diene copolymer of the present invention has a structure in which a part or all of the polymer main chain and side chains are hydrogenated using a suitable hydrogenation catalyst after completion of the polymerization reaction. Is possible. Hydrogenation suppresses molecular cleavage caused by exposure to ultraviolet light at the time of high temperature heating or outdoors of the copolymer,
Environmental resistance is improved. The type and amount of the hydrogenation catalyst used in the present invention are not limited as long as the catalyst can obtain a required hydrogenated polymer structure. Group 4 as hydrogenation catalyst,
Group 6, 7, 8, 9 and 10 metals, specifically titanium, zirconium, hafnium, molybdenum, iron, cobalt, nickel, rhenium, ruthenium, rhodium,
It is possible to use a homogeneous or heterogeneous hydrogenation catalyst containing at least one metal selected from palladium and platinum.

The homogeneous hydrogenation catalyst is an organometallic compound or a metal complex of the above metal which is soluble in the reaction system. As the ligand of the metal complex, an appropriate element such as hydrogen, halogen, nitrogen compound, carboxylic acid, or an organic compound can be arbitrarily selected. Specific examples of the ligand include hydrogen, fluorine, chlorine, bromine, nitric oxide, carbon monoxide, and compounds such as hydroxyl, ether, amine, thiol, phosphine, carbonyl, olefin, and various dienes. I can do it. If necessary, an organic metal compound of Group 1, Group 2, or Group 13 such as alkyl lithium, alkyl magnesium, and alkyl aluminum can be used in combination as a reducing agent.

Specific examples of the homogeneous hydrogenation catalyst include nickel naphthenate, nickel octoate, nickel acetyl acetate, nickel chloride, nickel carbonyl, nickelocene, cobalt naphthenate, cobalt octoate,
Cobalt acetyl acetate, cobalt chloride, cobalt carbonyl, dicyclopentadienyl titanium dichloride as a titanium complex, chlorohydridocarbonyl tris (triphenylphosphine) ruthenium as a ruthenium complex, dichlorotris (triphenylphosphine)
Ruthenium and dihydridocarbonyltris (triphenylphosphine) ruthenium can be exemplified.

The amount of the homogeneous hydrogenation catalyst used in the present invention is appropriately selected depending on the hydrogenation conditions, but the metal concentration relative to the polymer is not less than 1 wtppm and not more than 2000 wtpp.
m or less, more preferably 10 wtpp
m or more and 500 wtppm or less. When the amount of the catalyst used is 1 wtppm or more and 2000 wtppm or less, a sufficient reaction rate can be obtained, the coloring of the product does not become a problem, and there is no need to put great effort into the separation and recovery of the catalyst metal. preferable.

The reaction temperature varies depending on the catalyst used, but is preferably in the range of 60 ° C. to 180 ° C., more preferably 80 ° C. to 160 ° C. Temperature 6
If it is 0 ° C. or higher, a sufficient reaction rate can be obtained, and if it is 180 ° C. or lower, there is no problem of catalyst deterioration. A heterogeneous hydrogenation catalyst is one in which the above metal or an oxide of the above metal is supported on alumina, silica, activated carbon, barium sulfate, magnesium oxide, titania, or the like, or the above metal powder or metal oxide powder itself Which is insoluble in the reaction system. As a reaction method, it is possible to hydrogenate the polymer solution and the heterogeneous catalyst powder as a dispersion, or to pack the heterogeneous catalyst in a reaction tower and continuously hydrogenate while flowing the polymer solution. is there.

As the metal to be supported on a carrier,
Among the above metals, so-called noble metals are mentioned. Specific types include rhenium, ruthenium, rhodium, palladium, platinum and the like, but palladium is preferred because of less side reactions such as molecular cleavage. As the type of the carrier, carbon and silica are preferable from the viewpoint of hydrogenation activity, but catalyst recovery and recyclability after the reaction,
Alumina is most preferable when the color of the product is considered comprehensively. Examples of the heterogeneous catalyst other than the noble metal include a Raney nickel catalyst.

As a specific example of a catalyst in which a noble metal used for a heterogeneous hydrogenation catalyst is supported on a carrier, a noble metal catalyst manufactured by NE Chemcat Co., Ltd. [2 wt% platinum alumina powder (carrier: alumina powder, Specific surface area 80-100m
² / g), 5 wt% palladium alumina powder (carrier: alumina powder, specific surface area: 80 to 100 m ² / g), 5 wt%
% Palladium carbon powder (carrier: carbon powder, specific surface area: 900 to 1300 m ² / g, water-containing product), 5 wt% palladium silica / alumina powder (carrier: silica / alumina powder, specific surface area: 400 to 600 m ² / g), 5 wt%
Ruthenium alumina powder (carrier: alumina powder, specific surface area: 80 to 100 m ² / g), 5 wt% rhenium alumina powder (carrier: alumina powder, specific surface area: 80 to 100 m ²⁾
/ G)].

As a kind of the noble metal, palladium is preferable because there are few side reactions such as molecular cleavage. Further, as a specific example of the heterogeneous hydrogenation catalyst other than the noble metal, a sponge nickel catalyst (trade name: R-100, manufactured by Nikko Rika Co., Ltd.)
R-200). These are steps of dissolving and removing the aluminum component in the nickel-aluminum alloy with an aqueous sodium hydroxide solution, i.e., a step generally called development, from an aqueous dispersion state to a methanol dispersion state, then to a tetrahydrofuran dispersion state, and finally to a hydrogenation solvent dispersion After replacing the solvent to the state, it is added to the reaction system.

The amount of the heterogeneous hydrogenation catalyst used is 0.1 wt% as a metal concentration with respect to the polymer present in the reaction system.
As described above, the range is 1000 wt% or less, preferably 0.5 wt% or more and 300 wt% or less, and more preferably 1.0 wt% or more and 150 wt% or less. The reaction temperature is in the range of 20 ° C. to 240 ° C., preferably 90 ° C. to 180 ° C. The temperature can be changed as needed during the reaction, and the unsaturated double bond in the polymer main chain and polymer side chain is hydrogenated at a temperature of 20 ° C or higher and lower than 140 ° C. The aromatic ring of the side chain of the polymer can be hydrogenated in the range of not lower than ℃ and not higher than 240 ° C. Reaction temperature 20
C. or higher is preferred from the viewpoint of the reaction rate. Also,
When the temperature is 240 ° C. or lower, the catalyst is not deteriorated, and the activity is not remarkably reduced at the time of reuse after recovery, which is preferable.

The reaction time varies depending on the reaction conditions, such as the concentration of the reaction system, the amount of catalyst, and the reaction temperature, and the value of the target hydrogenation rate as a product. It is possible. Heterogeneous hydrogenation catalysts have a better product hue than homogeneous catalysts, and are easy to reuse after separation and recovery if the reaction system does not contain poisonous substances including halogens, sulfur, phosphorus, etc. Therefore, it is industrially preferable to a homogeneous hydrogenation catalyst.

After completion of the polymerization reaction or the hydrogenation reaction, the cyclic conjugated diene-based copolymer of the present invention is prepared by using a suitable peroxide with one of the unsaturated double bonds present in the polymer main chain and side chains. It is possible to take a structure in which part or all of the structure is modified with an epoxy group. By performing the epoxy modification, the wettability of the film surface after cast molding can be changed. This greatly improves the adhesion with an inorganic film typified by an ITO transparent electrode. By crosslinking the epoxy group, the surface hardness of the film, that is, the so-called scratch resistance can be improved.

Specific examples of the peroxide used in the epoxy modification reaction include aqueous hydrogen peroxide, peracetic acid, perbenzoic acid, m-
Chloroperbenzoic acid can be exemplified, particularly preferably peracetic acid,
It is possible to exemplify m-chloroperbenzoic acid. These react equimolarly with unsaturated double bonds in the polymer main chain and polymer side chains, and quantitatively modify the unsaturated double bonds into epoxy groups. Therefore, when the double bond in the polymer is completely epoxy-modified, the molar amount of the peroxide is equal to or slightly greater than the molar number of the double bond. If a double bond is to be left partially in anticipation of participating in crosslinking, a peroxide having a mole number equal to the mole number of the double bond to be epoxidized may be used.

The solvent used in the epoxy modification reaction is not particularly limited as long as the copolymer of the present invention can be dissolved before and after the reaction. Specific examples include organic solvents such as cyclohexane, decalin, and toluene, and halogen-containing organic solvents such as chloroform, dichloromethane, and carbon tetrachloride. From the viewpoint of safety, the halogen-containing organic solvent alone or an appropriate organic solvent is used. A mixed solvent of a halogen-containing organic solvent is desirable. Also, if necessary, water,
Additives such as sodium bicarbonate can be added. The reaction temperature is from 20 ° C. to 100 ° C. in view of the reaction rate.
It is preferable to carry out at a temperature of not more than ° C.

The epoxidized cyclic conjugated diene copolymer of the present invention can have a crosslinked structure by using an appropriate crosslinking agent. As a crosslinking agent, a dicarboxylic anhydride, an amine compound, a polyamidoamine compound, a reactive monomer, and other crosslinking agents can be selected as necessary,
If necessary, a curing accelerator such as a peroxide or an organic phosphorus compound may be used in combination. Specific examples of dicarboxylic acids include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and anhydride. Maleic acid, trimellitic anhydride, chlorendic anhydride, alkenyl succinic anhydride, dodecel succinic anhydride and the like can be mentioned. When crosslinking is performed using these acid anhydrides, triphenylphosphine can be used as a curing accelerator.

As a specific example of the amine compound, diethylene
Triamine, triethylenetetramine, tetraethylene
Pentamine, dimethylaminopropylamine, dibutyl
Aminopropylamine, hexamethylenediamine, m-
Phenylenediamine, p, p ^,-Diaminodiphenyle
Tan, p, p^,-Diaminodiphenyl sulfone, metaki
And cilenediamine. Polyamidoamine compound
Specific examples of the product include various polyamides and polyamidoamines.
Adducts.

Specific examples of the reactable monomer include methyl methacrylate, cyclohexyl methacrylate, methyl acrylate, and the like. When crosslinking is performed with these, perbutyl O and perbutyl H manufactured by NOF Corporation are used as curing accelerators. Etc. can be used. Specific examples of other crosslinking agents include aluminum trisethyl acetoacetate, stannous octylate, and polymercaptan.

Hereinafter, a method for polymerizing the cyclic conjugated diene copolymer of the present invention will be described. The method for polymerizing a cyclic conjugated diene copolymer of the present invention is an anionic polymerization method using a polymerization initiator obtained by combining a group 1 organometallic compound / ether compound in a hydrocarbon compound solvent. The hydrocarbon compound used in the polymerization solvent in the present invention includes butane, n-
Pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane,
C 4-10 saturated hydrocarbon compounds such as methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane, and C6-10 aromatics such as benzene, toluene, xylene, ethylbenzene, cumene and tetralin Group hydrocarbon compounds. These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like, and may be one kind or a mixture of two or more kinds as necessary.
Particularly preferred solvents are saturated hydrocarbon compounds such as cyclohexane, methylcyclohexane and decalin.

In the method for polymerizing a cyclic conjugated diene copolymer of the present invention, the Group 1 metal of the Group 1 organometallic compound used as a polymerization initiator includes lithium, sodium and potassium. Sodium is preferred. These may be one kind or two or more kinds as necessary. 1 used as a polymerization initiator
The group organometallic compound will be described below by taking as an example a case of an organic lithium compound and an organic sodium compound which are preferable organometallic compounds.

The organic lithium compound and the organic sodium compound are conventionally known compounds containing one or more lithium atoms and sodium atoms bonded to an organic residue containing at least one carbon atom, respectively. . As the organic lithium compound, for example, methyl lithium, ethyl lithium, n-propyl lithium, iso-
Propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, allyl lithium, cyclohexyl lithium, phenyl lithium, hexamethylene dilithium, 1,3-bis [1-lithium-1, [3,3-trimethyl-butyl] benzene, cyclopentadienyllithium, indenyllithium, butadienyldilithium, isoprenyldilithium, etc., or polymers such as polybutadienyllithium, polyisoprenyllithium, polystyryllithium Oligomers or polymer compounds containing a lithium atom in a part of the chain are mentioned.

Examples of the organic sodium compound include naphthalene sodium, α-methylstyrene sodium living tetramer, n-amyl sodium or polybutadienyl sodium, polyisoprenyl sodium, and polystyryl sodium. An oligomer containing an atom or a high molecular compound can be used. Preferred organic lithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, cyclohexyllithium, 1,3-bis [1
-Lithio-1,3,3-trimethyl-butyl] benzene, and preferable organic sodium metal compounds include naphthalene sodium and α-methylstyrene sodium living tetramer.

Group 1 organic compound which is a polymerization initiator in the present invention
The amount of metal compound used depends on the desired molecular weight, polymer structure
Depends on each, but generally 1kg of total monomer
2 × 10 as metal atom^-3From 4 × 10^-1mol range
And preferably 5 × 10 ^-32 × 10 from mol^-1m
ol range. Polymerization reaction of the present invention
In combination with group 1 organometallic compounds as polymerization initiators
As the ether compound used in combination,
Ether compounds containing one or more oxygen atoms, such as
Methyl ether, diethyl ether, isopropyl ether
Ter, tetrahydrofuran, tetrahydropyran, dime
Toxiethylene glycol, diethoxyethylene glyco
, Dioxane, trioxane, 2,2-bis (2-
Oxolanyl) propane, 1,1-dimethoxycyclo
Xanone and the like can be exemplified.

In the present invention, the required amount of the ether compound varies depending on the kind of the ether and the composition of the intended polymer. Assuming that the weight of the ether compound is X and the total weight of the cyclic conjugated diene monomer and the α-substituted vinyl aromatic monomer to be used is Y, in the case of an ether having one oxygen atom in the molecule, X The value represented by / Y is preferably 0.55 or more and 1000 or less. X / Y is 0.
If it is 55 or more, the desired high molecular weight random copolymer can be obtained at a sufficient speed. If it is more than 1000, the deactivation of the active terminal during the polymerization cannot be ignored,
It becomes difficult to control the number average molecular weight of the polymer. A more preferable range of X / Y is 0.60 or more and 500 or less, particularly preferably 0.70 or more and 250 or less.

In the case of an ether having two or more oxygen atoms in the molecule, the value represented by X / Y is 0.025
It is preferably at least 100. X / Y is 0.
If it is 025 or more, the desired high molecular weight random copolymer can be obtained at a sufficient speed. If it is larger than 100, the deactivation of the active terminal during polymerization cannot be ignored,
It becomes difficult to control the number average molecular weight of the polymer. A more preferable range of X / Y is 0.03 or more and 50 or less, particularly preferably 0.035 or more and 25 or less.

A monodentate coordinating amine can be further added to the Group 1 metal organic compound which is a polymerization initiator used in the present invention. The purpose of use of the amines is to dissociate the group 1 metal organic compound which is a polymerization initiator having an association structure in a polymerization solution, and to end the initiation reaction with the monomer very quickly. It is possible to narrow the molecular weight distribution. Specific examples of amines include triethylamine. It can be used in a molar ratio of 0 or more to 1 or less with respect to the Group 1 metal element.

The polymerization temperature in the polymerization reaction of the present invention is set as required, but is generally -30 ° C. or higher and 10
0 ° C. or less, the active terminal is hardly deactivated during polymerization,
It is preferable because a high molecular weight product can be obtained. From the viewpoint of the polymerization rate, it is more preferable to carry out the reaction at 0 ° C or higher and 80 ° C or lower. Monomer concentration in the polymerization reaction, the total weight of all monomers is Y ', and the total weight of other components is Z,
Y ′ / (Y ′ + Z), whose value is 0.01 or more,
It is preferably 0.50 or less. From the viewpoint of the polymerization rate, it is preferably 0.01 or more. If it exceeds 0.50, the viscosity of the reaction solution is too high, and it is difficult to stir to keep the inside of the reactor uniform. The preferred monomer concentration is 0.05 or more, 0.40 or less, more preferably 0.1
0 or more, 0.35 or less, particularly preferably 0.15 or more,
0.30 or less.

The time required for the polymerization reaction varies depending on the purpose and the polymerization conditions and cannot be particularly limited. However, it is usually within 48 hours, particularly preferably 30 minutes to 8 hours. Is done. All polymerization reactions are carried out under an inert gas such as high-purity nitrogen or high-purity argon having a purity of 99.9999%, oxygen of less than 0.2 ppm, and carbon dioxide of less than 1.0 ppm. During the polymerization, even if a few ppm of impurities (for example, water, oxygen, carbon dioxide gas, etc.) that inactivate the polymerization initiator or the anionic active terminal are mixed into the system, it is not preferable because the polymerization rate is greatly reduced. Therefore, it is necessary to pay special attention to the contamination of impurities, it is desirable that the polymerization system is always higher than the atmospheric pressure, and it is necessary to keep the monomer and hydrocarbon compound solvent in the liquid phase in the above-mentioned polymerization temperature range. Perform in a sufficient pressure range.

When the required degree of polymerization is reached, the polymerization is terminated by using a polymerization terminator to terminate the anionic active terminal. As the polymerization terminator in the present invention, a known polymerization terminator that deactivates anionic active terminals can be used. Preferred are water, having 1 to 20 carbon atoms.
Alcohols, ketones, phenols, carboxylic acids,
Examples thereof include halogenated hydrocarbons, carbon dioxide, hydrogen, and halogen gas. It is also possible to transfer the living polymer before the termination of the polymerization to a reactor dedicated to the termination of the reaction, and thereafter terminate the termination by using a polymerization terminator.

The type of the polymerization reaction is a lump-in type, a follow-up type,
It is also possible to use a partial lump-and-addition combination type or a continuous type. That is, in the method for polymerizing a cyclic conjugated diene-based copolymer of the present invention, a polymerization solvent, a polymerization initiator, an amine, and a monomer are appropriately added as necessary, and a part and the entire amount thereof is added to a reactor in advance. The order of addition of each component and the timing of addition can be appropriately selected as needed.

As the method for separating and recovering the cyclic conjugated diene copolymer of the present invention from the reaction solution, a technique generally used when recovering a polymer from the reaction solution can be adopted. For example, a steam coagulation method of evaporating and removing a polymerization solvent by directly contacting a reaction solution with water vapor, a method of adding a poor solvent of a polymer that can be mixed with a polymerization solvent to precipitate a polymer, and forming the reaction solution into a thin film. And a method in which the solvent is distilled off by heating after heating, a method in which the solvent is distilled off with a vented extruder, and a process in which pelletization is performed, and the like, and the properties of the cyclic conjugated diene copolymer and the solvent used. It is possible to adopt an optimal method according to the conditions.

Further, when it is necessary to obtain a high-purity cyclic conjugated diene copolymer in which the amount of metals, amines, hydrogenation catalyst metals and the like contained in the polymerization initiator is extremely reduced, the cyclic conjugated diene-based copolymer may be used. A method in which metal ions in a copolymer solution are water-solubilized with a suitable chelating agent and then extracted and removed by AC contact with high-purity ion-exchanged water, a method for removing ionic impurities using an ion-exchange resin column, carbon dioxide It is possible to implement a method for removing metal ions and low molecular amines using a supercritical method as necessary.

When the cyclic conjugated diene-based copolymer of the present invention is separated and recovered, a known stabilizer and an antioxidant are used to improve the thermal stability, stability against ultraviolet rays and the like and flame retardancy of the copolymer. It is possible to employ various stabilizers such as phenol-based, organic phosphate-based, organic phosphite-based, amine-based, sulfur-based, silicon-containing, and halogen-based agents, antioxidants, and flame retardants. is there. Typical amounts of these stabilizers, antioxidants and flame retardants include
With respect to 100 parts by weight of the cyclic conjugated diene copolymer, 0.0
A range from 01 to 5 parts by weight is selected.

The cyclic diene copolymer of the present invention may be dissolved in a solvent (for example, a hydrocarbon solvent having 4 to 10 carbon atoms, an ether compound, a halogen-containing organic solvent, or a solvent having 6 to 10 carbon atoms). Is a ketone compound.
More than species may be used. ), Coated on a substrate by a suitable coating method such as spin coating, dip coating, blade coating, roll coating, etc., and then processed into a film by a known cast film forming method of obtaining a film by drying. . Preferred dissolvable solvents include cyclohexane, toluene, decalin, tetrahydrofuran, chloroform, cyclohexanone. By performing cast film formation from a solvent that can be dissolved,
It is possible to obtain a film having an excellent balance of heat resistance, surface hardness and impact resistance, high surface smoothness, and low birefringence.

Applications of these films having high optical properties include electronic materials such as glass substrates for liquid crystals, organic electroluminescent substrates, optical waveguides, electronic paper substrate materials, organic semiconductor substrates, and gene diagnostic chips. Examples of medical material applications that require optical detection, such as substrates and substrates for various microtasks.

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the cyclic conjugated diene monomer and the hydrocarbon compound solvent used in the present invention are obtained by adding calcium hydride. After refluxing in a high-purity argon atmosphere for 12 hours, a product purified by distillation was used. The α-substituted vinyl aromatic monomer is extracted with a 0.5N sodium hydroxide solution to remove the polymerization inhibitor, washed with water until the pH becomes neutral, dehydrated with anhydrous sodium sulfate, and then subjected to a high-purity argon stream. The one subjected to vacuum distillation purification under the following was used. The ether compound was obtained by adding sodium metal and benzophenone under a high-purity argon atmosphere, refluxing all day and night, and then purifying by distillation.

The measurements used in the examples and comparative examples are as follows. The <gas chromatography (GC) Measurement> Shimadzu ^GC-14, ββ, - and the oxy dipropionate nitrile using packed column to the column packing. The moving layer was He, the column temperature was 90 ° C., and the injection and detector temperatures were 200 ° C. Ethylbenzene was used as an internal standard in determining the actual conversion of each component. <Gel permeation chromatography (GPC)
Measurement> The sampled butadiene moiety polymer, the polymer after polymerization shown in all Examples and Comparative Examples, the number average molecular weight measurement and the weight molecular weight distribution measurement of the epoxidized polymer exemplified in Example 8 were measured using a Showdex column. (K-80
Tosoh HLC-8 with 2, 804, 805)
A 020 type device was used. The measurement was performed under the conditions of a tetrahydrofuran mobile phase and a column temperature of 40 ° C. The molecular weight was calculated as a polystyrene-converted molecular weight from a calibration curve created from the elution time of a standard polystyrene sample.

The polymers after hydrogenation exemplified in Comparative Examples 2 and 3 have extremely low solubility in tetrahydrofuran,
Measurement with C-8020 was not possible. Therefore, the measurement was performed using PL-210 high-temperature GPC manufactured by Polymer Laboratory. The mobile phase is o-dichlorobenzene and the column temperature is 13
Performed at 0 ° C. <Measurement method of glass transition temperature> DSC manufactured by Seiko Denshi Co., Ltd.
200 was used. The measurement was carried out under the conditions of a sample weight of 10 to 15 mg, a nitrogen stream (60 mL / min), and a heating rate of 10 ° C / min. <Method for Measuring Microstructure of Sampled Butadiene Portion Polymer> The measurement was performed using an NMR apparatus JEOL-EX270. Deuterated chloroform was used as the measuring solvent, and the concentration was 12.5.
mg / 0.5 mL of chloroform was measured at room temperature. The method for calculating the 1,2-structure ratio of all butadiene moieties to all double bonds is based on an experimental method for polymer synthesis (Chemical Dojinsha, Experimental Example 22).
5, p51), the following formula (2) was employed.

[0054]

(Equation 1)

In the formula, I _(4.60 to _5.05) is 4.60 of NMR.
Integrated area in the range from to 5.05 ppm. I _{(5.05-6.00 )}
Is an integrated area in the range of NMR 5.05 to 6.00 ppm. x is the 1,2-structure ratio of the butadiene moiety to all double bonds. <Method of measuring hydrogenation ratio> Ultraviolet absorbance analysis and NMR apparatus (JEOL-EX270, measurement conditions: measurement solvent o-dichlorobenzene-d4, concentration 12.5 mg / 0.5 mL)
-Dichlorobenzene-d4, measured at 135 ° C.) to determine the hydrogenation rate. The ratio of the unreacted monomer was determined by gas chromatography, and the composition ratio of the molecular structural units constituting the polymer was determined from the ratio and the amount of the charged monomer. Next, the residual benzene ring in the polymer was determined from ultraviolet absorbance analysis, and the hydrogenation rate of α-MS was determined.

The composition ratio of the molecular structural units constituting the polymer,
1,2-structure ratio of butadiene moiety to all double bonds, α
With the MS hydrogenation rate as a constant, the values were calculated for CHD and the butadiene double bond, assuming that there is no special selectivity between the 1,2-structure and the 1,4-structure. . <Method of measuring epoxidation ratio> NMR apparatus (JEOL-E
X270, measurement solvent: deuterated chloroform, concentration 12.5m
g / 0.5 mL of deuterated chloroform), the areas of two hydrogen atoms in the 1,3-cyclohexane-derived part after the epoxy reaction and two hydrogen atoms in the epoxy group were determined. Next, the area obtained by dividing the area of two hydrogens of the epoxy group by the area obtained by adding both of them was defined as the epoxidation ratio. The number-average molecular weight and weight-average molecular weight distribution of the epoxidized modified product showed values in terms of standard polystyrene measured by GPC (gel permeation chromatography).

[0057]

Example 1 A Teflon (registered trademark) -coated stirrer was placed in each of three 100 mL pressure-resistant glass bottles, heated and dried at 120 ° C. for 24 hours, and then immersed in cyclohexane to remove plasticizers. (Manufactured by K.K.) and stoppered with a crown. Then, using a vacuum line, 0.02
The interior was sufficiently purged with argon by repeatedly performing pressure reduction to mmHg and purging with high-purity argon five times.
Subsequently, using a glass syringe purged with nitrogen and substituted with nitrogen, cyclohexane, tetrahydrofuran, α-methylstyrene (hereinafter referred to as α-MS), and 1,3-cyclohexadiene (hereinafter referred to as CHD) are shown in Table 1. A predetermined amount was added and mixed well. Next, a predetermined amount of a 1.62 N n-butyllithium hexane solution was added with a syringe while stirring at room temperature (20 ° C.) to initiate polymerization. 3 after the start
It was immersed in a 0 ° C. oil bath, stirring was continued, and the polymerization reaction was continued.

The reaction system immediately turned red-orange immediately after the dropwise addition of the n-butyllithium solution, and thereafter maintained a constant color tone and color density until the end of the reaction. As a known fact, the color of the living anion of α-MS is magenta, while the color of the living anion of CHD is lemon yellow. Assuming block polymerization, α-MS reacts first,
Assuming that CHD is subsequently polymerized, the color of the reaction system should initially change to magenta and then rapidly to lemon yellow. Also, assuming block polymerization in the reverse order, the reaction system should change color in the exact reverse order. These assumptions are inconsistent with experimental facts. Therefore, it is clear that the polymerization reaction is not proceeding in a block manner but is polymerizing randomly.

After 5.5 hours, 0.1 mL of methanol was added to stop the polymerization reaction. Immediately after the termination, a part of the reaction solution was sampled to determine the conversion ratio of CHD and α-MS. As a result, the conversion of each monomer was sufficiently high. Thereafter, about 2 mL of the reaction solution was diluted twice with cyclohexane, poured into 50 mL of acetone, and vigorously stirred to obtain a polymer precipitate. After the precipitate was separated by filtration, the precipitate was further washed with acetone and then sufficiently dried with a vacuum drier to obtain a polymer powder. GPC measurement was performed on the polymer powder to determine a number average molecular weight and a weight average molecular weight distribution.

As the molecular weight, a value almost equal to the set number average molecular weight set from the n-butyllithium amount and the monomer amount was obtained, and the molecular weight distribution was a single peak. From these facts, it becomes clear that each monomer is independently polymerized and two types of polymers are not generated, and in consideration of the fact that block polymerization is denied,
It can be said that this further supports that the polymerization proceeds randomly. Next, Run 1, which is the highest molecular weight in Table 1, was used.
A solubility test was performed using three samples. The test solvents described in Table 5 were used. First, 1 g of a polymer is collected in a 50 mL vial, 4 g of a solvent is added, and 20 wt.
% Polymer solution was prepared. Then, the mixture was stirred and shaken by hand while being placed in a water bath at 50 ° C. The solution was permeated for approximately 30 minutes, and when the temperature returned to room temperature, the dissolved state of the solution was evaluated. When a gel state, a cloudy state, and a solid residue were recognized, it was determined that dissolution was impossible.

When the solution was not completely dissolved, the solution was diluted with the same solvent to prepare a 10 wt% solution, and the solution was again stirred and shaken at 50 ° C., and the dissolved state was evaluated according to the same standard. If it was not completely dissolved, it was diluted again to prepare a 5 wt% solution, and after the same dissolution operation, solubility was confirmed. The evaluation score was determined as follows.
The sample dissolved under the 0% condition was evaluated as ○, the sample dissolved under the 5% condition was evaluated as Δ, and the sample not dissolved under the 5% condition was evaluated as ×. Table 5 shows the results. From this result, it is clear that the compound is extremely soluble in various solvents.

On the other hand, the CHD polymer (Comparative Example 2) and the CHD block polymer (Comparative Example 3) disclosed in JP-A-7-258318 are not easily dissolved in various solvents at room temperature. This fact also indicates that α-MS and CHD are randomly copolymerized, the continuous structure of the cyclohexane ring is cleaved at α-MS monomer units, and the solubility is improved. Further, Tg was measured using DSC, and the Tg was 1
It was confirmed that only one point was measured around 70 ° C. This also supports that the copolymerization is not block copolymerization but random copolymerization.

[0063]

[Example 2] In the same manner as in Example 1, 10 was replaced with dry argon.
Prepare five 0 mL pressure bottles, each with cyclohexane 2
7 g, 9.5 g of tetrahydrofuran, α-MS 3.1
g, CHD 9.6 g. 0.1 at room temperature (20 ° C).
1.04 mL of a cyclohexane solution of an equimolar mixture of 8N 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added to initiate polymerization. Thereafter, the polymerization was continued at 10 to 15 ° C., and at a predetermined time from 15 to 240 minutes shown in Table 2, the polymerization was stopped with each 0.2 mL of methanol, and the time course of the conversion of each monomer, The polymer composition up to each time was determined. Polymer powder was obtained in the same manner as in Example 1, and the average molecular weight and the time course of the molecular weight distribution were determined. As a result, the number average molecular weight is about 40,000 in the final 240 minute polymerized product.
It was clarified that a polymer showing a single peak was obtained in a state where the conversion of each monomer was high, and that the time course of CHDwt% in the polymer was almost constant. Further, only one Tg measured by DSC was measured at 156 ° C.

From the total conversion and the polymerization time obtained from the weighted average of each monomer and the time course of the value of [-Ln (1-total conversion)], an almost linear relationship is established. It was found that the polymerization rate was almost a first-order reaction. In addition, since there is a proportional relationship between the number average molecular weight and the total conversion, it is clear that the polymerization proceeds in a living manner. 240 more obtained
A solubility test was conducted on the polymer powder after the polymerization in the same manner as in Example 1. Table 5 shows the results. It was easily soluble in various organic solvents such as cyclohexane, tetrahydrofuran, and chloroform, and a high concentration could be adjusted in various solvents.

[0065]

[Embodiment 3] In the same manner as in Embodiment 1, dry argon was replaced with 10
Prepare five 0 mL pressure bottles, each with cyclohexane 2
5.5 g, tetrahydrofuran 12.2 g, α-MS
5.3 g and CHD 7.9 g were added. At room temperature (20 ° C)
0.8-defined 1,3-bis [1-lithium-1,3,3
-Trimethyl-butyl] benzene / triethylamine equimolar mixture in 1.04 mL of cyclohexane,
The polymerization was started. Thereafter, the polymerization was continued at 10 to 15 ° C., and the polymerization was stopped with 0.2 mL of methanol for a predetermined time from 15 to 240 minutes shown in Table 3, and the conversion of each monomer over time, The polymer composition up to time was determined. A polymer powder was obtained in the same manner as in Example 1,
C was used to determine the average molecular weight and the time course of the molecular weight distribution. As a result, a polymer showing a single peak with a number average molecular weight of about 40,000 was obtained at a high conversion rate, and CHD wt% in the polymer was obtained.
Has also been found to be almost constant. From the DSC measurement, Tg was measured at only one point at 162 ° C.

As in Example 2, since the polymerization rate is a first-order reaction, and the number-average molecular weight is proportional to the total conversion, it is clear that the polymerization proceeds in a living manner. Was. Further, a solubility test was performed in the same manner as in Example 1. Table 5 shows the results. The polymer powder after polymerization for 240 minutes was easily soluble in various organic solvents such as cyclohexane, tetrahydrofuran and chloroform. As described above, by mixing the cyclic conjugated diene monomer and the α-substituted aromatic monomer from Examples 2 and 3, and selecting appropriate polymerization conditions, a random polymer having a wide composition can be obtained. It became clear that it was.

[0067]

Example 4 A Teflon (registered trademark) -coated stirrer was placed in a 100 mL pressure-resistant glass bottle, heated and dried at 120 ° C. for 24 hours, then stoppered with Viton rubber, and stoppered with a crown. Next, the inside was sufficiently purged with dry argon by repeatedly performing the pressure reduction to 0.02 mmHg and the replacement with argon five times using a vacuum line. Then, dry thoroughly and use a glass syringe purged with nitrogen to obtain cyclohexane 29.37.
g, 2,2-bis (2-oxolanyl) propane 0.3
7 g and 2.47 g of α-MS were added, and the temperature was raised to 40 ° C. Thereafter, 0.56 mL of a 1.62 N hexane solution of n-butyllithium was added to initiate polymerization. CH immediately after starting
D dropping was started and 7.77 g was added over 55 minutes. Immediately after the start of the polymerization, the reaction system was purplish red. Immediately after the start of the dropping of CHD, the reaction system turned slightly bright orange, and maintained a constant color tone and color density for 3 hours. After 3 hours, the polymerization reaction was
Stopped with mL of methanol. CHD conversion is 100
%, And the conversion of α-MS was 99.4%.

As a result of GPC measurement, the number average molecular weight was 110
It was a single peak with a molecular weight distribution of 1.6.
Furthermore, the polymer powder after polymerization was easily soluble in various organic solvents such as cyclohexane, tetrahydrofuran and chloroform. Further, when a solubility test was carried out in the same manner as in the other examples, the polymer powder after polymerization was easily soluble in various organic solvents such as cyclohexane, tetrahydrofuran and chloroform. From this fact, it was clarified that the polymerization can be performed at a temperature condition of 40 ° C. or higher, and that a necessary polymer can be obtained from ether compounds other than tetrahydrofuran by selecting appropriate conditions.

[0069]

COMPARATIVE EXAMPLE 1 Dry air was replaced with 10 in the same manner as in Example 1.
Two 0 mL pressure bottles were prepared for adjusting the monomer mixture, and two bottles were used for polymerization. Then CH in the mixing bottle
Two types of D / α-MS monomer mixture (7.0 g / 3.0)
g, 9.0 g / 1.0 g). Next, N 2, N 2 ^, N 3,.
1.25 mL of N ^, -tetramethylethylenediamine,
Next, 0.62 mL of 1.62 N n-butyllithium hexane solution was added, and the mixture was stirred for 5 minutes. To each pressure-resistant bottle for polymerization, 10 g of the prepared mixed monomer was added, and polymerization was started. Then immerse in a 40 ° C oil bath,
Stirring was continued.

The reaction system having any monomer composition showed a red-purple anion color immediately after the addition of the monomer, and the terminal of the initiator was α-
It turned out that it changed to the methylstyrene anion terminal. In addition, disappearance of the anion coloration was not observed throughout the reaction, and almost no inactivation of the active terminal itself was observed. On the other hand, almost no increase in the viscosity of the reaction system was observed,
It was not apparent that the polymer polymerization was progressing. 2
After an hour, the reaction was stopped with 0.1 mL of methanol. About 2 mL of each reaction solution was poured into 50 mL of acetone and methanol poor solvent, respectively. Although slight turbidity was observed in each of the mixed solutions, a sufficient amount of the polymer required for the analysis was not polymerized, so that it was not possible to collect by filtration and perform the subsequent analysis.

From this fact, it is apparent that the polymer having the object of the present invention cannot be obtained from the initiator having a special complex structure disclosed in JP-A-7-258318. That is, the polymer of the present invention is essentially different from a cyclic olefin polymer in which the molecular structural unit composed of a cyclic conjugated diene monomer has a special polymer microstructure as disclosed in JP-A-7-258318. It is clear that their polymer microstructures are different.

[0072]

Example 5 A 5 L high pressure reactor was thoroughly dried with dry nitrogen,
Deoxygenation was performed. Next, 1811 g of cyclohexane and 575 g of tetrahydrofuran were added as reaction solvents, and the internal temperature was cooled to 5 ° C. while stirring. 0.8
To a solution of 19.75 g of a cyclohexane solution of an equimolar mixture of 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added, and α-MS was added.
151 g and 454 g of CHD were sequentially added. The temperature during the reaction was controlled between 5 ° C and 15 ° C. After 11 hours, the reaction was stopped with 0.7 g of methanol. After the reaction, the conversion of CHD was 94.8%, α-MS was 77.8%, and the total conversion was 89.
8%, Tg was 160 ° C.

Then, the polymer solution 1355 was dried under dry nitrogen.
g, and dilute with 1367 g of cyclohexane.
After mixing with 550 g (average particle size: 40 μm) of 5% palladium-supported alumina powder manufactured by A-Chemcat, the mixture was added to the 5 L high-pressure reactor again. The internal gas is sufficiently replaced with high-purity nitrogen and then high-purity hydrogen, and the inside of the reactor is 80 kgf / c.
It was in m ^2. Thereafter, while maintaining the hydrogen pressure, the temperature inside the reactor was gradually increased, and after reaching 180 ° C., the reaction was continued for 4 hours. After cooling the internal temperature to room temperature,
5% palladium alumina powder was removed using a pressure filter using a μm PTFE membrane filter.
The polymer solution after filtration was poured into acetone four times the total volume to carry out precipitation and recovery. The recovered polymer was dried in a vacuum drier to remove the residual solvent. Various characterizations of the obtained polymer were performed, and the results are shown in Table 4. The solvent solubility test was performed based on the same evaluation method as in Example 1. Table 5 shows the results.

[0074]

Example 6 A 5 L high pressure reactor was thoroughly dried with dry nitrogen,
Deoxygenation was performed. Next, 1755 g of cyclohexane, 21.3 g of tetrahydrofuran, 1,3
-Add 148.5 g of butadiene (hereinafter referred to as BD),
The internal temperature was raised to 40 ° C. while stirring. 0.
18.36 g of a cyclohexane solution of an equimolar mixture of 8N 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added to initiate polymerization. The polymerization temperature was controlled from 40 ° C. to 45 ° C., and stirring was continued for 1 hour. After 1 hour, cooling was started, and the internal temperature of the reactor was rapidly cooled to 5 ° C. At this time, a part of the reaction solution was sampled.

Next, tetrahydrofuran 60 in a completely dry state
8.6 g was added, and 110 g of α-MS and 341 g of CHD were added in this order. The temperature during the reaction was controlled between 5 ° C and 15 ° C. After 12 hours, the reaction was stopped with 1.6 g of methanol.
The conversion of the butadiene polymer sampled on the way is 1
00%. For the sampled butadiene polymer, the reaction solution was added to a 20-fold volume of methanol for reprecipitation and recovery, and the polymer was obtained by drying under reduced pressure. The conversion of CHD is 93.1.
% And α-MS were 83.3%. Tg was measured at two points, -44 ° C on the low temperature side and 157 ° C on the high temperature side.

Then, the polymerization solution 1350 was dried under dry nitrogen.
g) and diluted with 1365 g of cyclohexane.
5% palladium alumina powder 5 manufactured by A-Chemcat
After mixing with 50g (average particle size 40μm), 5L high pressure reaction
Added to the vessel again. High-purity nitrogen and then high-purity hydrogen are sufficient
The internal gas is replaced with 80 kgf / cm ^Two
I made it. After that, while maintaining the hydrogen pressure, gradually
The temperature was raised to 180 ° C and the reaction was continued for 4 hours.
Was. After cooling the internal temperature to room temperature, 0.2 μm under nitrogen
Pressurized filter using PTFE membrane filter
To remove 5% palladium alumina powder. filtration
Pour the polymer solution after that into 4 times the total volume of acetone,
Precipitation recovery was performed. The recovered polymer is dried in a vacuum dryer
And the residual solvent was removed. Various characters of the obtained polymer
The kartization was performed and the results are shown in Table 4. Also
The solvent solubility test was performed based on the same evaluation method as in Example 1.
did. Table 5 shows the results.

[0077]

Comparative Example 2 First, a 5 L high-pressure reactor was sufficiently dried with dry nitrogen and deoxygenated. Decalin 315 as a reaction solvent
^{0g, N, N, N,} , N, - tetramethylethylenediamine 2.54g was added to the reactor. Then at room temperature.
16.66 g of a cyclohexane solution of an equimolar mixture of 8N 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added. The temperature inside the reactor was raised to 40 ° C., 350 g of CHD was added,
The polymerization was started. After 6 hours, 2 mL of methanol was added to terminate the polymerization. After the reaction, the conversion of CHD was 94.9.
%, Tg was 140 ° C.

Then, the polymerization solution 1300 was dried under dry nitrogen.
and Nikko Rica Co., Ltd. dispersed in 1350 g of decalin
And a sponge nickel catalyst (equivalent to R-100), and the mixture was added again to the 5 L high-pressure reactor. The internal gas is sufficiently replaced by high-purity nitrogen and then high-purity hydrogen, and the inside of the reactor is cooled to 8%.
The pressure was set to 0 kgf / cm ² . Thereafter, while maintaining the hydrogen pressure, the internal temperature of the reactor was gradually increased, and the reaction was continued for 8 hours after reaching 160 ° C. After cooling the internal temperature to room temperature, the sponge nickel catalyst was removed with a pressure filter using a 0.2 μm PTFE membrane under nitrogen to obtain a transparent polymer solution. The polymer solution after filtration was poured into acetone four times the total volume to carry out precipitation and recovery. The recovered polymer was dried in a vacuum drier to remove the residual solvent. Various characterizations of the obtained polymer were performed, and the results were shown in Table 4.
It was shown to. The solvent solubility test was performed based on the same evaluation method as in Example 1. Table 5 shows the results.

[0079]

Comparative Example 3 A 10 L high pressure reactor was sufficiently dried with dry nitrogen and deoxygenated. Decalin 600 as reaction solvent
^{7g, N, N, N,} , N, - tetramethylethylenediamine 2.2mL was added to the reactor. Then at room temperature.
79.3 mL of a cyclohexane solution of an equimolar mixture of 8N 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added. The temperature inside the reactor was raised to 60 ° C., and 270 g of BD was added to initiate polymerization. Immediately after the start, cooling of the reactor was started and the internal temperature was maintained at 60 ° C. After 25 minutes, sampling of the butadiene portion was performed, and then the temperature inside the reactor was set to 40 ° C. Further ^{N, N, N,, N} , - tetramethylethylenediamine 9.
0 mL was added followed by 632 g of CHD after 5 minutes. Four hours after the start of the polymerization, 9.5 mL of heptanol was added to stop the polymerization. The conversion of CHD after the reaction was 9
It was 5.7%. Tg was measured at two points, and the low temperature side was -4.
The temperature was 6 ° C and the high temperature side was 132 ° C.

Then, the polymerization solution 1300 was dried under dry nitrogen.
g and sponge nickel catalyst (equivalent to R-100) manufactured by Nikko Rica Co., Ltd. dispersed in 1350 g of decalin, and added to a 5 L high-pressure reactor. The internal gas is sufficiently replaced with high-purity nitrogen and then high-purity hydrogen, and the inside of the reactor is
kgf / cm ² . Then, while maintaining the hydrogen pressure,
The temperature inside the reactor was gradually increased, and after reaching 160 ° C., the reaction was continued for 8 hours. After cooling the internal temperature to room temperature, the sponge nickel catalyst was removed with a 0.2 μm PTFE membrane under nitrogen to obtain a transparent polymer solution. The polymer solution after filtration was poured into acetone four times the total volume to carry out precipitation and recovery. The recovered polymer was dried in a vacuum drier to remove the residual solvent.

Various characterizations of the obtained polymer were carried out, and the results are shown in Table 4. The solvent solubility test was performed based on the same evaluation method as in Example 1. Table 5 shows the results. As is clear from Tables 4 and 5, Examples 5 and 6 have significantly improved solubility in solvents before and after hydrogenation as compared with Comparative Examples 2 and 3, respectively. . Further, after hydrogenation, the glass transition temperature is 200 ° C. or higher, and the required heat resistance is sufficiently satisfied.

[0082]

Example 7 A 5 L high-pressure reactor was thoroughly dried with dry nitrogen,
Deoxygenation was performed. Then, as a reaction solvent, cyclohexane 1500 g, tetrahydrofuran 900 g, α-MS
365 g was added, and the internal temperature was reduced to 20 ° C. while stirring.
I made it. Then, a cyclohexane solution of an equimolar mixture of 0.8 N 1,3-bis [1-lithium-1,3,3-trimethyl-butyl] benzene / triethylamine was added.
g was added to initiate polymerization. Thereafter, 243 g of CHD was gradually added to the reaction system over 1 hour. The temperature during the reaction was controlled between 18 ° C and 23 ° C. After 7.5 hours from the start of the polymerization, the reaction was stopped with 0.7 g of methanol. After the reaction, the conversion of CHD was 97.7%, the α-MS was 95.7%, and the total conversion was 96.5%.

This polymer solution was poured into acetone four times the total volume to carry out precipitation and recovery. The recovered polymer was dried in a vacuum drier to remove the residual solvent. The polymer after recovery had a Tg of 173 ° C. and a number average molecular weight of 42,000.
10 g of recovered polymer (molar number of double bonds in polymer: 50 m
mol) was added to a 500 mL flask, and after sufficiently replacing with nitrogen, 50 mL of chloroform was added to dissolve. Then, 15.1 g of m-chloroperbenzoic acid (hygroscopic product, purity 69 to
75%, the number of moles as a pure product of 60 to 66 mmol) was dissolved in 50 mL of chloroform, and added dropwise to the polymer solution at room temperature. At the same time as the dropwise addition, heat was generated in the reaction system, and the internal temperature rose. When heat generation was almost completed, the temperature was raised to 50 ° C. After 6 hours, the reaction system was cooled and poured into 1200 mL of acetone to precipitate a polymer. Then, the polymer was separated by suction filtration. Thereafter, the entire amount of the polymer separated by filtration was redissolved in 100 mL of chloroform, and poured again into 1200 mL of acetone to precipitate the polymer. The polymer was collected by filtration again and dried under reduced pressure at room temperature.

After drying, the glass transition temperature of the polymer, GPC
Measurement and measurement of the epoxidation ratio by NMR were performed. T
g was 238 ° C., the number average molecular weight was 51,000, and the epoxidation ratio was 99%. The solvent solubility test was performed by the same evaluation method as in Example 1. Table 5 shows the results. The epoxidized polymer was easily dissolved in toluene, xylene, cyclohexanone, and chloroform. As a result of producing a film from the dissolved polymer by a casting method, a transparent film having excellent surface smoothness could be obtained.

[0085]

Comparative Example 4 The same procedure as in Example 1 was repeated except that the atmosphere was replaced with dry argon.
Prepare a 00 mL round bottom flask and add
g, 2.40 g of tetrahydrofuran (weight of tetrahydrofuran / weight of all monomers = 0.02), styrene 72.0
g, 48.0 g of CHD. While stirring at room temperature, 3.40 mL of a 1.06 N secondary butyllithium cyclohexane solution was added at room temperature (20 ° C.) to initiate polymerization. The reaction system immediately turned reddish purple of the styrene terminal anion. After the start, the reaction system was immersed in a water bath at 25 ° C. to perform polymerization.

Four minutes after the initiation of the polymerization, the reddish purple color of the styrene terminal anion rapidly changed to lemon yellow of the CHD terminal anion. Thereafter, in the reaction system, the turbidity gradually increased, and at the same time, the coloration of lemon yellow became lighter. Forty minutes later, after the reaction system became cloudy, the reaction was stopped with 0.2 mL of methanol. Immediately after the termination, a part of the reaction solution was sampled to determine the conversion of styrene and CHD. The conversion of styrene was 100%, and the conversion of CHD was 69.7%. About 2 mL of the reaction solution was collected, diluted twice with cyclohexane, and poured into 50 mL of isopropyl alcohol.
By vigorous stirring, a polymer precipitate was obtained.

The polymer precipitate was separated by filtration, washed again with isopropyl alcohol, and sufficiently dried with a vacuum dryer to obtain a polymer powder. GPC measurement of this polymer powder showed a single peak with the number average molecular weight of 39,100 and the weight average molecular weight distribution of 1.27. The solubility test was performed as in Example 1. The results are shown in Table 5,
It is apparent that the solubility is clearly lower than that of the examples, and it is understood that it is difficult to prepare a film having excellent surface smoothness.

This is because, as can be seen from the sudden change in the color of the reaction system from reddish purple at the styrene end to lemon yellow at the CHD end, styrene polymerizes preferentially in the early stage of polymerization, and thereafter CHD is polymerized. This is because it has polystyrene and poly CHD blocks. The rapid increase in turbidity of the reaction system also supports the fact that the reaction system has a CHD block that is hardly dissolved in cyclohexane. From the above facts, when the polymerization of styrene and CHD is carried out under the condition of tetrahydrofuran weight / total monomer weight = 0.02, it is impossible to obtain a random polymer of styrene and CHD. This is because the polymerization active terminal of styrene is more easily reacted with styrene than CHD. Also, when the amount of tetrahydrofuran used is increased, the polymerization rate of styrene becomes faster than the polymerization rate of CHD increases, so that block polymerization proceeds more easily.

On the other hand, in the case of the present invention, since the polymerization active terminal of α-MS is sterically bulky and has a ceiling temperature near room temperature, even if the amount of ether is increased, α-MS terminal is
The polymerization reaction to -MS is suppressed. For this reason, CHD preferentially reacts from the α-MS terminal over α-MS of the same type. Therefore, it is possible to adjust the polymerization rate of CHD to the polymerization rate of α-MS by selecting an appropriate amount of ether used and polymerization conditions. For this reason, polymerization of a random copolymer excellent in solubility became possible.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

According to the present invention, the cyclic conjugated diene-based copolymer is
It is an olefin resin that combines high heat resistance, transparency, non-hygroscopicity, chemical resistance, and excellent castability.
It is very useful in industry. Further, the polymerization method of the present invention makes it possible to obtain a desired random copolymer from a conjugated diene-based cyclic olefin monomer and an α-substituted vinyl aromatic-based monomer using anionic polymerization. It was done.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/00 C08F 232/00 F term (Reference) 4J011 HA03 HB14 HB22 4J015 DA02 EA03 4J100 AA00R AA02R AB00R AB01P AB02R AB03P AB04R AB07R AB16R AE03R AL03R AM02R AM04R AQ12R AR16Q AR18Q AS01R AS02R AS03R AS04R BA05R CA04 CA05 CA31 DA01 FA08 FA19 FA30 HA04 HA05 HA29 HA53 HB34 HC36 HE41 JA32 JA35 JA43 JA51

Claims (6)

[Claims] 1. A cyclic conjugated diene copolymer represented by the following formula (1). Embedded image [Formula (1) represents a composition formula of a polymer. (A),
(B) and (C) represent each molecular structural unit constituting the polymer main chain. l, m, and n represent wt% of each molecular structural unit contained in the polymer main chain. (A): a molecular structural unit derived from a cyclic conjugated diene-based monomer (the molecular structural unit may be one type or two or more types). (B): a molecular structural unit derived from an α-substituted vinyl aromatic monomer (the molecular structural unit may be one type or two or more types). (C): a molecular structural unit derived from another copolymerizable monomer (the molecular structural unit may be one type or two or more types). However, the bonding structure between (A) and (B) is a random structure, l + m + n = 100, and 0.1 ≦ l / m ≦
9, 0 ≦ n ≦ 90, and the number average molecular weight of the polymer is 5,000 or more and 500,000 or less. ] 2. A random polymer comprising (A) a molecular structural unit derived from a cyclic conjugated diene-based monomer and (B) a molecular structural unit derived from an α-substituted vinyl aromatic-based monomer. 2. The cyclic conjugated diene-based copolymer according to claim 1, wherein the cyclic conjugated diene-based copolymer has a structural unit and a polymer structural unit composed of a molecular structural unit derived from (C) another copolymerizable monomer. The number of the molecular structural units may be one or two or more.) 3. A hydrogenated cyclic conjugated diene copolymer obtained by hydrogenating at least a part of a polymer main chain and a polymer side chain of the cyclic conjugated diene copolymer according to claim 1 or 2. Coalescing. 4. An epoxidation wherein at least a part of a non-conjugated double bond of a polymer main chain and a polymer side chain of the cyclic conjugated diene-based copolymer according to claim 1 or 2 is epoxidized. Cyclic conjugated diene polymer. 5. An epoxidized hydrogenated cyclic structure obtained by epoxidizing at least a part of non-conjugated double bonds of a polymer main chain and a polymer side chain of the hydrogenated cyclic conjugated diene-based copolymer according to claim 3. Conjugated diene polymer. 6. A group 1 organometallic compound and an ether compound in a hydrocarbon compound solvent using at least a cyclic conjugated diene monomer and an α-substituted vinyl aromatic monomer as raw material monomers. A method for producing a cyclic conjugated diene-based polymer, wherein the polymerization is carried out in the presence of a polymerization initiator obtained by combining the above.