JP2005255732A - Cyclic conjugated diene copolymer and manufacturing method for hydrogenate of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a hydrogenated cyclic conjugated diene copolymer excellent in impact resistance, heat resistance and transparency, and a resin molded product for optical applications made of the same. <P>SOLUTION: The manufacturing method for the hydrogenated cyclic conjugated diene copolymer comprises hydrogenating a random copolymer having a 1,2-linkage comprising 80-95 pts. wt. of a cyclic conjugated diene monomer and 5-20 pts. wt. of a linear conjugated diene monomer. The resin molded product for optical applications is made of the same. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a novel hydrogenated cyclic conjugated diene copolymer excellent in impact resistance, heat resistance and transparency and a method for producing each cyclic conjugated diene copolymer which is a precursor thereof.

  In recent years, resin optical materials that replace conventional glass have been widely used by taking advantage of the molding processability, light weight, and transparency of resin materials. Typical examples of the transparent resin material used for optics include polymethacrylic resin (PMMA) and polycarbonate resin (PC). However, since these are higher in hygroscopicity than glass, the surface accuracy of optical products is likely to change, and there is a great drawback that they are inferior in reliability as precision optical members. Further, PMMA has insufficient heat resistance, PC is slightly inferior in transparency, and birefringence, which is an optical distortion, is large, so that optical characteristics are not always sufficient. Therefore, there is a great demand for the development of a transparent resin molding material having both low hygroscopicity and heat resistance and excellent optical properties (transparency and low birefringence), and various new transparent resin materials are being studied.

  As the above-mentioned new transparent resin material, a cyclic polyolefin (Patent Document 1) using a polycyclic norbornene monomer has been proposed. Cyclic polyolefin materials using these polycyclic norbornene-based monomers have an amorphous structure having a softening temperature of about 120 to 160 ° C. by including a bulky five-membered ring structure in the polymer main chain skeleton. However, it has high industrial utility as a material having heat resistance and transparency. However, these various properties are not always sufficient in terms of impact resistance, even among mechanical properties such as rigidity and strength required for recent optical materials.

  Examples of improvements in cyclic polyolefin materials using these polycyclic norbornene monomers include hydrogenated cyclic olefin polymers obtained by polymerizing 1,3-cyclohexadiene monomers by anionic polymerization (Patent Document 2). It is done. These include a cyclohexane ring continuous structure having a unique polymer microstructure in the polymer main chain skeleton, and thus have an amorphous structure with a softening temperature exceeding 220 ° C., and have heat resistance and transparency. Both are possible. In addition, by utilizing the living property of anionic polymerization, which is a production method, a block polymer structure comprising a cyclohexane ring continuous structure block portion and a rubber component block portion comprising butadiene is realized, thereby realizing the above polycyclic norbornene-based unit. It is possible to greatly improve the impact resistance, which is the biggest problem of cyclic polyolefin using a monomer. However, the cyclic olefin copolymer having a block structure has a micro density gradient resulting from the micro phase separation structure as a result of the block structure, and is likely to cause scattering particularly for light of a short wavelength, Inferior to light transmittance.

Furthermore, a resin molding using a hydrogenated product of a monocyclic conjugated diene polymer or a monomer copolymerizable therewith has been proposed (Patent Document 3). However, there is no description of a random copolymer with a chain conjugated diene monomer.
Further, it is known that a cyclic conjugated diene polymer can be obtained from 1,3-cyclohexadiene monomer by coordination polymerization using a nickel complex (Patent Document 4). In recent years, an example of achieving high molecular weight in the copolymerization of 1,3-cyclohexadiene and 1,3-butadiene by the improvement of the nickel complex catalyst (Non-patent Document 1) has been reported, and the number average molecular weight is about 19000. A copolymer has been achieved. However, the polymer obtained from Non-Patent Document 1 has a structure having a repeating unit derived from a 1,3-cyclohexadiene monomer and a 1,3-butadiene monomer, although high molecular weight has been achieved. All of the structural parts composed of the repeating units derived from consist of 1,4-bonds. As a result, it is shown that the 1,4-bonded chain of the 1,3-cyclohexadiene part is a crystalline polymer. Has been. This polymer with high crystallinity of the 1,3-cyclohexadiene portion is extremely useful as a polyparaphenylene precursor, but it is not amorphous, so that it is sufficiently required for recent advanced optical materials, particularly optical films. It did not come to express the transparency.

Japanese Patent Publication No. 2-9612 JP 7-258362 A JP 2001-220448 A JP 2000-26581 A Polymer Papers, Vol. 59, no. 6 (2002)

  An object of the present invention is to provide a method for producing a novel hydrogenated cyclic conjugated diene copolymer excellent in balance between rigidity and impact resistance, strength, heat resistance and transparency, and a method for producing an optical resin molding comprising the same. Is to provide.

In order to solve the above-mentioned problems, the present inventors have repeated research on cyclic olefins, and have come up with a novel method for producing a hydrogenated cyclic conjugated diene copolymer.
That is, the present invention
(1) It consists of a repeating unit A derived from a cyclic conjugated diene monomer and a repeating unit B derived from a chain conjugated diene monomer. The repeating unit A and the repeating unit B have a random structure and are repeated. The unit A and / or the repeating unit B has a 1,2-bond, and the repeating unit A (x parts by weight) and the repeating unit B (y parts by weight) are 0.05 ≦ y / (x + y) ≦ 0.2. A method for producing a cyclic conjugated diene copolymer, characterized in that the cyclic conjugated diene monomer and the chain conjugated diene monomer are converted into an organic group 1 metal compound, an ether compound, and Cyclic conjugation characterized by polymerizing at a polymerization temperature ≦ 100 ° C. in a hydrocarbon compound solvent in the presence of a polymerization initiator combined with an amine compound and using at least one complete mixing reaction vessel Jie Method for producing a system copolymer.

(2) The method for producing a cyclic conjugated diene copolymer as described above, wherein the polymerization method is a continuous addition / continuous extraction method of a monomer and a polymerization initiator.
(3) At least 90% of the main chain and the side chain of the cyclic conjugated diene polymer in the presence of a hydrogenation catalyst in the cyclic conjugated diene copolymer obtained by the method of (1) or (2) above. A method for producing a hydrogenated cyclic conjugated diene copolymer obtained by hydrogenation.
(4) The cyclic conjugated diene copolymer according to any one of (1) to (2) above, wherein the cyclic conjugated diene is 1,3-cyclohexadiene and the chain conjugated diene is 1,3-butadiene, and It relates to a method for producing the hydrogenated cyclic conjugated diene copolymer described in 3).

  The hydrogenated cyclic conjugated diene polymer obtained by the method of the present invention is remarkably excellent in transparency and excellent in the balance between rigidity and impact resistance, strength, and heat resistance.

The present invention will be specifically described.
The cyclic conjugated diene monomer in the present invention is a 6-membered or higher cyclic conjugated diene constituted by a carbon-carbon bond. A preferable cyclic conjugated diene monomer is a 6- to 8-membered cyclic conjugated diene constituted by a carbon-carbon bond. 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 one type or two or more types as necessary. 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives are preferable, and 1,3-cyclohexadiene is particularly preferable.
The chain conjugated diene monomer in the present invention is a linear conjugated diene having 4 or more carbon atoms. Specific examples include chain conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Preferred are chain conjugated diene monomers having 4 to 5 carbon atoms, and examples include 1,3-butadiene and isoprene. Most preferred is 1,3-butadiene.

  In the present invention, in addition to the cyclic conjugated diene monomer and the chain conjugated diene monomer, other copolymerizable monomers may be used. The other copolymerizable monomer is a conventionally known monomer that can be polymerized by anionic polymerization. For example, styrene and o-methylstyrene, p-methylstyrene, tert-butylstyrene, 2,5-dimethylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, divinylbenzene, α-methylstyrene, etc. Styrene derivatives and vinyl naphthalene, vinyl pyridine, etc., polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methacrylonitrile, methyl vinyl ketone, methyl α-cyanoacrylate, ethylene oxide, propylene oxide, cyclic Examples include polar monomers such as lactones, cyclic lactams and cyclic siloxanes, and olefinic monomers such as ethylene. These monomers may be used alone or in combination of two or more as required. I do not care.

In the cyclic conjugated diene polymer that is a precursor of the hydrogenated cyclic conjugated diene copolymer of the present invention, the repeating unit A and / or the repeating unit B has a 1,2-bond. That the repeating unit A and / or the repeating unit B has a 1,2-bond can be confirmed by a peak appearing at a specific position on a chart obtained by ¹ H-NMR measurement. The peak seen at the position of 2.37 ppm peak due to the 1,2-bond of the repeating unit consisting of 2, and 4.75 to 5.25 ppm due to the 1,2-bonding of the repeating unit of B At least one of the peaks is confirmed. It is preferable that the repeating unit A and / or the repeating unit B have a 1,2-bond because the crystallinity is inhibited.

In the hydrogenated cyclic conjugated diene copolymer of the present invention, the recurring unit A and / or the recurring unit B has a 1,2-bond to suppress the crystallinity. It is speculated that it has a more transparent amorphous property.
In the hydrogenated cyclic conjugated diene copolymer in the present invention, the repeating unit A derived from the cyclic conjugated diene monomer may have a random structure with the repeating unit B derived from the chain conjugated diene monomer. is necessary.
Further, the hydrogenated cyclic conjugated diene copolymer of the present invention contains a repeating unit C derived from another copolymerizable monomer and can take a random structure with the repeating unit A and the repeating unit B. is there. In this case, it is preferable that the repeating unit A, the repeating unit B, and the repeating unit C have a random structure.

The weight ratio y / (x + y) of the repeating unit B to the repeating unit A + the repeating unit B is 0.05 ≦ y / (x + y) ≦ 0.2. More preferably, 0.1 ≦ y / (x + y) ≦ 0.2. When the repeating unit B is 5 to 20 parts by weight as a whole, the rigidity and transparency of the resulting resin are improved, and impact resistance is improved.
Furthermore, it is possible to copolymerize with a cyclic conjugated diene monomer and a chain conjugated diene monomer with respect to 100 parts by weight of the cyclic conjugated diene copolymer or hydrogenated cyclic conjugated diene copolymer of the present invention. Other monomers can be used at 30 parts by weight or less. Within this range, the surface hardness can be improved while maintaining the required impact resistance, which is preferable. From the balance of impact resistance and surface hardness, the particularly preferred range of the cyclic conjugated diene monomer and other monomers copolymerizable with the chain conjugated diene monomer is 25 parts by weight or less.

The number average molecular weight of the polymer chain in which the repeating unit A of the cyclic conjugated diene copolymer in the present invention has a random structure with the repeating unit B is 10,000 or more and 500,000 or less in terms of polystyrene average number molecular weight. Preferably, they are 20,000 or more and 200,000 or less, More preferably, they are 30,000 or more and 200,000 or less. When it is 10,000 or more, strength and impact resistance as a polymer material can be expressed. Moreover, if it is 500,000 or less, the solution viscosity at the time of solvent dissolution can be adjusted appropriately.
The polymerization method of the cyclic conjugated diene copolymer of the present invention will be described below.
The polymerization method of the cyclic conjugated diene copolymer of the present invention is an anionic polymerization method using a polymerization initiator in which an organic group 1 metal compound is combined with an ether compound and / or an amine compound in a hydrocarbon compound solvent.

  Examples of the hydrocarbon compound used in the polymerization solvent in the present invention include butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane, n-decane, cyclopentane, methylcyclohexane. Saturated hydrocarbon compounds having 4 to 10 carbon atoms such as pentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane, carbons such as benzene, toluene, xylene, ethylbenzene, cumene, tetralin An aromatic hydrocarbon compound having a number of 6 or more and 10 or less is included. These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, etc., and may be one kind or a mixture of two or more kinds as necessary. A more preferable solvent is a saturated hydrocarbon compound having 6 to 10 carbon atoms, and particularly preferable solvents are n-hexane, cyclohexane, methylcyclohexane, and decalin.

In the polymerization method of the cyclic conjugated diene copolymer of the present invention, examples of the group 1 metal of the organic group 1 metal compound used as the polymerization initiator include lithium, sodium, and potassium. Among these, lithium and sodium are preferable. . These organic group 1 metal compounds may be used alone or in combination of two or more as required.
The organic group 1 metal compound used as a polymerization initiator will be described below by taking the case of an organic lithium compound and an organic sodium compound as preferred organic metal compounds as examples.
The organic lithium compound and the organic sodium compound are conventionally known compounds containing one or two or more lithium atoms and sodium atoms bonded to an organic residue containing at least one carbon atom.

  Examples of the organic lithium compound include 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-lithio-1,3,3-trimethyl-butyl] benzene, cyclopentadienyl lithium, indenyl lithium, butadienyl dilithium, isoprenyl dilithium Or oligomers or polymer compounds containing a lithium atom in a part of the polymer chain, such as polybutadienyl lithium, polyisoprenyl lithium, and polystyryl lithium.

Organic sodium compounds include sodium atoms in some polymer chains such as sodium naphthalene, α-methylstyrene sodium living tetramer, n-amyl sodium or polybutadienyl sodium, polyisoprenyl sodium, and polystyryl sodium. And oligomers or polymer compounds.
Preferred organic lithium compounds are n-butyl lithium, sec-butyl lithium, tert-butyl lithium, cyclohexyl lithium, and 1,3-bis [1-lithio-1,3,3-trimethyl-butyl] benzene. Examples of the organic sodium metal compound include sodium naphthalene and α-methylstyrene sodium living tetramer.

The amount of the organic group 1 metal compound used as the polymerization initiator in the present invention varies depending on the target molecular weight and polymer structure, but is generally 2.0 × 10 6 as metal atoms per 1 kg of all monomers. ^-3 mol to 1.0 × 10 ⁻¹ mol, preferably 5.0 × 10 ⁻³ mol to 6.7 × 10 ⁻² mol.
Examples of the ether compound used in combination with the organic group 1 metal compound as a polymerization initiator in the polymerization reaction of the present invention include dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and 1,1-dimethoxycyclohexane. 1,1-diethoxycyclohexane, crown ether and the like. Preferred examples include tetrahydrofuran, ethylene glycol dimethyl ether, and 1,1-dimethoxycyclohexane. The most preferred ether compound is 1,1-dimethoxycyclohexane.

Examples of the amine compound used in combination with the organic group 1 metal compound as the polymerization initiator in the polymerization reaction of the present invention include N, N, N ′, N′-tetramethylethylenediamine (TMEDA), N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N, N ', N'-tetraethyl-1,2 -Ethanediamine, 1,4-diazabicyclo [2.2.2. And tertiary amines such as octane (DABCO), sparteine, trimethylamine, triethylamine and the like. Preferably, TMEDA can be mentioned.
These ether compounds and amine compounds may be used alone or in combination of two or more, or one or more of the ether compounds and one or more of the amine compounds may be used in combination.

The amount of the ether compound and / or amine compound used in the present invention is X / m, where X is the number of moles of the ether compound and / or amine compound used, and Y is the number of moles of the organic group 1 metal compound as the polymerization initiator. The value represented by Y is preferably 0.1 or more and 10 or less. If X / Y is 0.1 or more, the desired high molecular weight random copolymer can be obtained at a sufficient speed, and if it is 10 or less, there is little deactivation of the active terminal during polymerization and the number of polymers. The average molecular weight is preferable because it is easy to control. A more preferable range of X / Y is 0.2 or more and 5 or less.
The reaction temperature in the polymerization reaction of the present invention is set as required, but it is not more than 40 ° C. and not more than 100 ° C. from the point that the active terminal is hardly deactivated during the polymerization and a high molecular weight body can be easily obtained. It is essential. Furthermore, it is more preferable to carry out at 40 ° C. or more and 90 ° C. or less at which a high molecular weight product can be obtained more easily from the viewpoint of polymerization rate.

The monomer concentration in the polymerization reaction is represented by Y / (Y + Z), where Y is the total weight of all monomers and Z is the total weight of other components, and the value is 0.01 or more, 0 .50 or less is preferable. From the viewpoint of the polymerization rate, 0.01 or more is preferable, and 0.50 or less is preferable because stirring capable of maintaining the uniformity of the reaction solution is possible. More preferably, it is 0.10 or more and 0.35 or less, and particularly preferably 0.15 or more and 0.30 or less.
Since the time required for the polymerization reaction varies depending on the purpose or polymerization conditions, it cannot be particularly limited. However, it is usually within 48 hours, particularly preferably in the range of 30 minutes to 8 hours. .

The polymerization reaction is preferably carried out under an inert gas such as high purity nitrogen or high purity argon having a purity ≧ 99%, oxygen <1 ppm, carbon dioxide <1 ppm. During polymerization, even if several ppm of impurities (for example, water, oxygen, carbon dioxide gas, etc.) that inactivate the polymerization initiator and anion active terminal are mixed in the system, the polymerization rate is greatly reduced, which is not preferable. Therefore, it is necessary to pay particular attention to the contamination of impurities, and it is desirable that the polymerization system is always higher than the atmospheric pressure, and in order to maintain the raw material monomer and hydrocarbon compound solvent in the liquid phase within the above polymerization temperature range. Carry out in a sufficient pressure range.
When the necessary degree of polymerization is reached, the polymerization is terminated using a polymerization terminator in order to terminate the anion active terminal. As a polymerization terminator in this invention, the well-known polymerization terminator which deactivates an anion active terminal is employable. Preferable examples include water, alcohols having 1 to 20 carbon atoms, ketones, phenols, carboxylic acids, halogenated hydrocarbons, carbon dioxide, hydrogen, halogen gas, and the like. It is also possible to transfer the living polymer before the termination of polymerization to a reactor dedicated to termination of the reaction, and then terminate the polymerization using a polymerization terminator.

As the polymerization reaction, a batch method, an addition method, a batch-addition combination method, a continuous method, or the like can be used, but a continuous method is preferable.
That is, in the polymerization method of the cyclic conjugated diene copolymer of the present invention, a polymerization solvent, a polymerization initiator, ethers, amines, and monomers are appropriately partly and wholly added in advance to a reactor. Further, the order of addition, the timing of addition, and the rate of addition of each component thereafter can be selected as necessary. It is also possible to use a continuous addition / continuous extraction system in which a polymerization solvent, a polymerization initiator, ethers, amines, and monomers are introduced into a reaction tank at a certain ratio and discharged from the reaction tank at the same ratio. It is.

In addition, for the polymerization of the cyclic conjugated diene copolymer of the present invention, it is necessary to use at least one completely mixed reaction tank. Here, the complete mixing reaction tank is a reaction tank that is stirred to such an extent that the composition of monomers, polymerization solvent, polymerization initiator, ethers and amines in the lower, middle and upper parts of the reaction tank is uniform. It is.
The cyclic conjugated diene copolymer of the present invention comprises a polymer chain in which the repeating unit A has a random structure with the repeating unit B, and a polymer chain composed of a repeating unit derived from 1,3-butadiene as the repeating unit B. In the case of producing a hydrogenated product from a block copolymer, the molar amount of 1,2-bonds in the polymer chain composed of repeating units derived from 1,3-butadiene is the molar amount of 1,2-bonds. It is preferable to set it to 35 mol% or more and less than 85 mol% with respect to the total amount of 1,4-bond mol amounts. If it is this range, the block part after the hydrogenation of the polymer chain which consists of a repeating unit derived from 1,3-butadiene will not be an ethylene structure having crystallinity but will be amorphous and exhibit sufficient transparency. . More preferably, they are 35 mol% or more and 60 mol% or less, Especially preferably, they are 35 mol% or more and 50 mol% or less.

As a method for separating and recovering the cyclic conjugated diene copolymer of the present invention from the reaction solution, a method generally used when recovering the polymer from the reaction solution can be employed. For example, a steam coagulation method that evaporates and removes the polymerization solvent by directly contacting the reaction solution with water vapor, a method that precipitates the polymer by adding it to a poor solvent of the polymer that can be mixed with the polymerization solvent, and a thin reaction solution Examples of the method of heating above to distill off the solvent and the method of pelletizing while distilling off the solvent with an extruder equipped with a vent, and the properties of the cyclic conjugated diene copolymer and the solvent used It is possible to adopt an optimum method depending on the situation.
Furthermore, when it is necessary to obtain a high-purity cyclic conjugated diene copolymer in which the metals and amines contained in the polymerization initiator are extremely reduced, the metal ions in the cyclic conjugated diene copolymer solution Of water by solubilization with a suitable chelating agent and extraction and removal by AC contact with high-purity ion exchange water, removal of ionic impurities by ion exchange resin column, metal ion using carbon dioxide supercritical method And it is possible to carry out the low molecular amine removal method as required.

Further, during the separation and recovery of the cyclic conjugated diene copolymer of the present invention, known stabilizers and antioxidants are used in order to improve the thermal stability, stability against ultraviolet rays and flame retardancy of the copolymer. Specifically, various stabilizers such as phenol, organic phosphate, organic phosphite, amine, sulfur, silicon-containing, halogen, and the like, antioxidants, and flame retardants can be employed. As general addition amounts of these stabilizers, antioxidants, and flame retardants, a range of 0.001 to 5 parts by weight is selected with respect to 100 parts by weight of the copolymer.
The hydrogenated cyclic conjugated diene copolymer of the present invention is obtained by hydrogenating a part or all of the polymer main chain and side chain of the above cyclic conjugated diene copolymer using an appropriate hydrogenation catalyst. The resulting copolymer. The degree of hydrogenation is indicated by hydrogenation rate (mol%) = 100 × [1− (number of moles of unsaturated bonds after hydrogenation / number of moles of unsaturated bonds before hydrogenation)].

It is necessary that at least 90% of the unsaturated bonds in the main chain or side chain of the repeating unit A derived from the cyclic conjugated diene monomer be hydrogenated. When the hydrogenation rate is 90% or more, molecular cleavage due to high temperature heating or outdoor UV exposure is suppressed. A more preferable range of the hydrogenation rate is 95% or more, particularly preferably 98% or more, and most preferably 99% or more.
Furthermore, it is necessary that at least 90% of the unsaturated bonds in the main chain or side chain of the repeating unit B derived from the chain conjugated diene monomer be hydrogenated. When the hydrogenation rate is 90% or more, molecular cleavage caused by high-temperature heating or outdoor UV exposure is suppressed. A more preferable range of the hydrogenation rate is 95% or more, particularly preferably 98% or more, and most preferably 99% or more.

As the repeating unit C derived from a copolymerizable monomer, particularly when a repeating unit derived from a vinyl aromatic monomer is used, the hydrogenation rate of the unsaturated bond derived from the aromatic ring is 80% or more. More preferably, it is 90% or more, particularly preferably 95% or more, and most preferably 99% or more.
The hydrogenation reaction is carried out in a dilution system with a solvent in which the cyclic conjugated diene copolymer is sufficiently and sufficiently dissolved and is not hydrogenated. The working concentration is usually 5 wt% or more and 40 wt% or less. If it is 5 wt% or more, a sufficient hydrogenation rate can be obtained. Moreover, if it is 40 wt% or less, the viscosity is sufficiently low, and it is possible to sufficiently remove heat generated during hydrogenation. The hydrogenation temperature can be appropriately selected from 20 ° C to 180 ° C. Within this range, a sufficient hydrogenation rate can be obtained, and deterioration of the hydrogenation catalyst is not a problem, and selective hydrogenation of aromatic rings and nonconjugated unsaturated double bonds in the polymer chain is carried out. It is possible. The hydrogenation pressure varies depending on the type of hydrogenation catalyst, but can usually be selected appropriately from 0.5 MPa to 10 MPa.

The type and amount of the hydrogenation catalyst used in the present invention is not limited as long as the required hydrogenated polymer structure is obtained. Hydrogenation catalysts include Group 4, Group 6, Group 7, Group 8, Group 9, Group 10 metals, specifically titanium, zirconium, hafnium, molybdenum, iron, cobalt, nickel, rhenium, ruthenium, rhodium, palladium. It is possible to use a homogeneous hydrogenation catalyst or a heterogeneous hydrogenation catalyst containing at least one metal selected from platinum.
The homogeneous hydrogenation catalyst is an organometallic compound or metal complex of the above metal that is soluble in the reaction system. As a ligand of the metal complex, an appropriate element such as hydrogen, halogen, nitrogen compound, carboxylic acid, or 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. Moreover, it is possible to use together the organometallic compound of 1st group, 2nd group, 13th group, such as alkyl lithium, alkyl magnesium, and alkyl aluminum, as a reducing agent as needed.

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, Examples of titanium complexes include dicyclopentadienyl titanium dichloride, examples of ruthenium complexes include chlorohydridocarbonyltris (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, and dihydridocarbonyltris (triphenylphosphine) ruthenium. .
The amount of 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 preferably in the range of 1 wtppm to 2000 wtppm, more preferably in the range of 10 wtppm to 500 wtppm. It is. When the amount of the catalyst used is 1 wtppm or more and 2000 wtppm or less, a sufficient reaction rate can be obtained, coloring of the product does not become a problem, and it is not necessary to put much effort on separation and recovery of the catalyst metal. preferable.

The heterogeneous hydrogenation catalyst is a catalyst in which the metal or the metal oxide is supported on alumina, silica, activated carbon, barium sulfate, magnesium oxide, titania, or the metal powder or metal oxide powder itself. And is insoluble in the reaction system. As a method for the reaction, hydrogenation of the polymer solution and the heterogeneous hydrogenation catalyst powder as a dispersion can be performed. Alternatively, the heterogeneous hydrogenation catalyst is packed in a reaction tower, and the polymer solution is circulated and continuously hydrogenated. It is also possible to make it.
Examples of the metal used by being supported on a carrier include so-called noble metals among the above metals. Specific examples include rhenium, ruthenium, rhodium, palladium, platinum, and the like, but palladium is preferable because side reactions such as molecular cleavage are small. As the type of support, carbon, silica, and alumina are preferable from the viewpoint of hydrogenation activity, but alumina is particularly preferable when comprehensively considering catalyst recovery and recyclability after reaction, product color, and the like. Examples of heterogeneous catalysts other than noble metals include Raney nickel catalysts.

As a specific example of a catalyst in which a noble metal used for a heterogeneous hydrogenation catalyst is supported on a support, 2 wt% platinum alumina powder (support: alumina powder, specific surface area 80 to 100 m ² / g) (N.E. Chemcat ( 5 wt% palladium alumina powder (support: alumina powder, specific surface area 80-100 m ² / g) (manufactured by NEM Chemcat), 5 wt% palladium carbon powder (support: carbon powder, specific surface area) 900 to 1300 m ² / g, water-containing product) (manufactured by N.E. Chemcat Co., Ltd.), 5 wt% palladium silica-alumina powder (support: silica-alumina powder, specific surface area 400 to 600 m ² / g) (N.E.・ Chemcat Co., Ltd.), 5 wt% ruthenium alumina powder (carrier: alumina powder, specific surface area 80-100 m ² / g) (NEM Chemcat Co., Ltd.), 5 wt% rhenium alumina powder (carrier: alumina powder, specific surface area 80-100 m ² / g) (NEM Chemcat Co., Ltd.) can be mentioned. Specific examples of heterogeneous hydrogenation catalysts other than noble metals include so-called Raney nickel catalysts such as sponge nickel catalysts (trade names: R-100, R-200 manufactured by Nikko Rica Co., Ltd.). These are the steps of dissolving and removing the aluminum component in the nickel-aluminum alloy with an aqueous sodium hydroxide solution, that is, a process generally called development, and then from the water dispersion state to the methanol dispersion state, then the tetrahydrofuran dispersion state, and finally the hydrogenated 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 in the range of 0.1 wt% or more and 1000 wt% or less, preferably in the range of 0.5 wt% or more and 300 wt% or less, as the metal concentration with respect to the polymer present in the reaction system. More preferably, it is the range of 1.0 wt% or more and 150 wt% or less.
The reaction time varies depending on the reaction conditions such as the concentration of the reaction system, the amount of catalyst, the reaction temperature, and the target hydrogenation rate, but it can be completed within 1 to 24 hours. . Heterogeneous hydrogenation catalysts have a better product color than homogeneous catalysts, and can be easily reused after separation and recovery if the reaction system does not contain poisonous substances such as halogen, sulfur, and phosphorus. Therefore, it is industrially preferable to a homogeneous hydrogenation catalyst.

When it is necessary to obtain a high purity hydrogenated cyclic conjugated diene copolymer with extremely reduced hydrogenation catalyst metal, etc., metal ions in the hydrogenated cyclic conjugated diene copolymer solution are appropriately chelated. Extraction and removal by AC contact with high-purity ion exchange water after solubilization with an agent, removal of ionic impurities using ion exchange resin column, removal of metal ions and low molecular amines using carbon dioxide supercritical method The method can be implemented as needed.
Further, during the separation and recovery of the hydrogenated cyclic conjugated diene copolymer of the present invention, known stabilizers and antioxidants are used in order to improve the thermal stability, stability against ultraviolet rays and flame retardancy of the copolymer. Specifically, various stabilizers such as phenol, organic phosphate, organic phosphite, amine, sulfur, silicon-containing, halogen, etc., antioxidants, flame retardants can be employed. . As a general addition amount of these stabilizer, antioxidant, and flame retardant, a range of 0.001 to 5 parts by weight is usually selected with respect to 100 parts by weight of the copolymer.

The hydrogenated cyclic conjugated diene copolymer of the present invention can be molded by a usual method. Examples thereof include melt molding methods such as injection and extrusion, and cast film forming methods.
By using the melt molding method, it is possible to inexpensively produce molded bodies of all shapes corresponding to films, sheets, lenses, bags and the like. For example, a film having a thickness of 100 μm to 500 μm and a sheet having a thickness of 0.5 mm to 15 mm can be formed by extrusion molding. A lens having a diameter of 0.5 m or less can be molded from a microlens having a diameter of 10 μm or more using an injection molding machine.

  The cyclic diene copolymer and the hydrogenated cyclic diene copolymer of the present invention are prepared by using a solvent (the soluble solvent is a hydrocarbon solvent having 4 to 10 carbon atoms, an ether compound, a halogen-containing organic solvent, carbon The number of the ketone compounds is 6 or more and 10 or less, which may be one or two or more.) And dissolved by spin coating, dip coating, blade coating, roll coating, etc. After coating the material, it can be processed into a film by a known cast film forming method for obtaining a film by drying. Preferred solvents include cyclohexane, toluene, decalin, tetrahydrofuran, chloroform, cyclohexanone, and 1,1-dimethoxycyclohexane, and these may be one type or two types. A particularly preferred solvent is a mixed solvent of cyclohexane and 1,1-dimethoxycyclohexane.

By performing cast film formation from a solvent, it is possible to obtain a film having a surface smoothness higher than that of melt molding, a low birefringence, and a thickness of 0.1 μm or more and 500 μm or less. In the case of cast film formation, if the thickness of the film is thinner than 0.1 μm, the film strength becomes weak and handling becomes difficult. On the other hand, if the thickness of the film exceeds 500 μm, it takes time to dry the solvent, which is not preferable.
The above-mentioned crosslinking agent, reactive monomer, other crosslinking agent, curing accelerator, catalyst, thermal crosslinking agent, etc. are mixed when the above film or sheet is prepared. Crosslinking is possible by treating with an electron beam or the like. By crosslinking, the surface hardness of the film, so-called scratch resistance, and solvent resistance against organic solvents can be improved.

  Various molded articles obtained by the above method are excellent in light transmittance and excellent in balance between heat resistance, surface smoothness, surface hardness, and impact resistance, and thus can be used in various applications. Films, sheets, and molded articles typified by these advanced optical properties include lenses, aspherical lenses, Fresnel lenses, silver salt camera lenses, digital electronic camera lenses, video camera lenses, and projectors. Lens, photocopier lens, mobile phone camera lens, eyeglass lens, contact lens, aspheric pickup lens for digital optical disc device using blue light emitting diode, rod lens, rod lens array, micro lens, micro lens array, 120 Various lenses / various lens arrays, step index type / gradient index type / single mode type / multi-core type / polarization plane preserving type / side emission type optical fiber, automobile / train / ship, etc. / Aircraft / Space / The above optical fiber used in mobile objects such as space bases / satellite and the above optical fiber used in a thermal environment of 120 ° C. or higher, optical fiber adhesive, compact disk / magneto-optical disk / digital disk / blue light emitting diode Various disk substrates such as digital optical disks to be used, polarizing films for liquid crystals, light guide plates for liquid crystals for backlights and front lights, light diffusion plates for liquid crystals, light diffusion plates for liquid crystals in which fine particles having different refractive indexes are dispersed, and for liquid crystals Glass substrate substitute film, retardation film, retardation plate for liquid crystal, liquid crystal plate for mobile phone, retardation plate for organic electroluminescence, color filter for liquid crystal, antireflection film for flat panel display, touch panel substrate, transparent conductive Film, anti-reflection film, anti-glare film Substrate, electronic paper substrate, organic electroluminescence substrate, front protective plate for plasma display, anti-electromagnetic wave plate for plasma display, front protective plate for field emission display, light guide plate that diffuses the light of a specific part front using piezoelectric element , Prisms constituting polarizers and analyzers, diffraction gratings, endoscopes, endoscopes that guide high-energy lasers, camera mirrors or half mirrors represented by Dach mirrors, automotive headlight lenses, automotive Reflector for headlight, front protective plate for solar cell, window glass for housing, window glass for moving objects such as automobile / train / ship / aircraft / spacecraft / space base / satellite, antireflection film for window glass, semiconductor exposure Dust-proof film, protective film for electrophotographic photosensitive material, writing with ultraviolet light Embedded or rewritable semiconductor (EPROM, etc.) sealing material, light emitting diode sealing material, ultraviolet light emitting diode sealing material, white light emitting diode sealing material, SAW filter, optical band pass filter, second harmonic generation Body, Kerr effect generator, optical switch, optical interconnection, optical isolator, optical waveguide, surface light emitter using organic electroluminescence, surface light emitter in which semiconductor fine particles having an average particle diameter of 0.1 μm or less are dispersed, fluorescence Examples thereof include a phosphor in which a substance is dissolved / dispersed.

Further, the hydrogenated cyclic conjugated diene copolymer of the present invention can remarkably reduce the amount of various stabilizers used at the time of molding as compared with existing cyclic olefin resins, and transparency is required. It can also be applied to medical containers, sanitary containers, low-elution research containers and instruments, and highly safe tableware. Specific applications include research syringes, medical syringes, tubes, chemical solution storage containers, various proteins / amino acids / deoxyribonucleic acid / microtass substrates with low enzyme adsorption, and various proteins that require confirmation of internal conditions. / Amino acid / Deoxyribonucleic acid / Transparent chemical storage container with little adsorption amount, Chemical storage container without heat stabilizer / light stabilizer, Chemical storage bag, Various proteins / Amino acid / Deoxyribonucleic acid / Enzyme adsorption amount Transparent medical solution storage bag, infusion bag, resin baby bottle, resin baby bottle with less discoloration due to sterilization, transparent resin baby bottle not containing heat stabilizer / light stabilizer, transparent tableware for school children's meals, heat stabilizer / Transparent tableware for schoolchildren without light stabilizers, mineral water containers, reusable mineral water containers, reduced heat stabilizers / light stabilizers Such as reusable mineral water container and the like. For processing for these applications, it is possible to use a molding method using supercritical carbon dioxide gas described in JP-A-11-245256, JP-A-2000-263613, and the like.
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

<Purification of reagents used>
The cyclohexane solution of 1,3-cyclohexadiene, which is a cyclic conjugated diene monomer used in the present invention, and 1,3-butadiene, which is a chain conjugated diene monomer, and a hydrocarbon solvent are activated alumina (200 ° C. The product was purified by passing through a column packed with vacuum dried in a nitrogen atmosphere and then cooled under a nitrogen atmosphere. The organic group 1 metal compound used in the present invention was obtained by diluting a commercially available solution (for example, n-butyllithium solution of n-butyllithium manufactured by Wako Pure Chemical Industries, Ltd.) with a hydrocarbon solvent. As the amine compound used in the present invention, commercially available products (for example, tetramethylethylenediamine, redistilled grade, etc. manufactured by Aldrich Co., Ltd.) were used as they were. As the ether compound used in the present invention, commercially available dehydration grade products (for example, dimethoxyethane, dehydration grade, etc. manufactured by Aldrich Co., Ltd.) were used as they were. In addition, a commercially available product (for example, 1,1′-dimethoxycyclohexane manufactured by Wako Pure Chemical Industries, Ltd.) was used by distillation under a nitrogen atmosphere.

Moreover, the measurement used in the Example and the comparative example is as follows.
(1) Monomer conversion addition rate: A capillary column ULBON HR-20M manufactured by Shinwa Kagaku Co., Ltd. was attached to GC-1700 manufactured by Shimadzu Corporation, and the monomer conversion rate was determined. (Monomer conversion rate = 1-monomer concentration in the reactor / monomer concentration in the feed liquid) The monomer composition in the polymer was determined from the conversion rate obtained. (For example, monomer composition in polymer when monomers A and B are used (A: wt%) = 100 × (monomer A concentration in feed liquid × conversion rate of monomer A / (Determined by the monomer A concentration in the feed liquid × the conversion ratio of the monomer A + the monomer B concentration in the feed liquid × the conversion ratio of the monomer B))
(2) Molecular weight measurement: HLC-8020 manufactured by Tosoh Corporation was used for the molecular weight measurement of the polymerized polymer shown in Examples and Comparative Examples. The mobile phase was measured using chloroform at a column temperature of 40 ° C. About the polymer which does not melt | dissolve in chloroform, it measured using the high molecular laboratory PL-210 high temperature GPC. The mobile phase was measured using 1,2-dichlorobenzene at a column temperature of 130 ° C. The number average molecular weight and the weight average molecular weight were determined in terms of polystyrene.

(3) Nuclear magnetic resonance spectrum (NMR) measurement: DPX400 manufactured by Bruker was used to confirm the 1,2-bond and the hydrogenation rate. Deuterated chloroform or o-dichlorobenzene-d4 was used as a measurement solvent.
The peak seen at the peak top 2.37 ppm position due to the 1,2-bond of the repeating unit A and the peak seen in the range of 4.75-5.25 ppm due to the 1,2-bonding of the repeating unit B Observe and if either is observed, it is assumed to have a 1,2-bond.
(4) Glass transition temperature: Measured using a differential thermal analyzer (DSC7, manufactured by Perkin Elmer).
(5) Furthermore, various physical properties were measured using the obtained injection molded product of the resin.
Tensile properties conform to ASTM D638, flexural properties conform to ASTM D790, Izod impact strength conforms to ASTM D256, and total light transmittance conforms to JIS K-6714.

[Example 1]
(A): 1,3-cyclohexadiene (hereinafter referred to as CHD), (B): a 20 wt% cyclohexane solution of 1,3-butadiene (hereinafter referred to as BD), (C): cyclohexane, (D) : 0.234 mmol / g of cyclohexane solution of n-BuLi, (E): 2 wt% cyclohexane solution of TMEDA was prepared.
Using a feed pump, (A) 2.27 g / min, (B) 2.00 g / min, (C) 1.86 g / min, (D) 0.23 g / min and (E) 0.31 g / min. Min was sent to a stainless steel reaction tank (capacity 2 L) equipped with a stirrer. The inside of the reaction vessel was kept at 0.19 MPa and 50 ° C. After 3 hours from the start of liquid feeding, the reaction product started to be extracted from the reaction vessel at 6.67 g / min. The obtained polymer was dried after methanol precipitation, and ¹ H-NMR and DSC were measured. ¹ H-NMR confirmed the 1,2-bond of CHD and BD. In addition, it was confirmed from DSC that the glass transition temperature (Tg) is single and there is no other Tg or melting point, and the polymer obtained by this method is a random copolymer of CHD and BD. -It was found to be an amorphous polymer having a bond. Moreover, the conversion rate of CHD and BD was measured and the composition in a polymer was calculated | required.

1000 g of the polymer solution was transferred to a 5 L high-pressure reactor, and 10 g of Raney Ni was transferred using 1000 g of cyclohexane. The inside of the reactor was replaced with hydrogen, and a hydrogenation reaction was performed at 8 MPa and 160 ° C. for 6 hours. ^The hydrogenation rate was determined from ¹ H-NMR. The DSC of this hydride was measured to confirm a single Tg. Also in this case, it was confirmed that there was no other Tg or melting point, and it was found that hydrogenation (CHD / BD copolymer) was also a random copolymer. The molecular weight in terms of polystyrene (PS) was sufficiently high as weight average molecular weight (Mw) = 52,000 and number average molecular weight (Mn) = 30,000. The obtained hydride was molded into a dumbbell or the like at a mold temperature = 80 ° C. and a molding temperature = 250 ° C. using an injection molding machine, and the physical properties were measured. The results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was performed except that the amount of (B) fed was 0.6 g / min. PS conversion molecular weight of the obtained hydride was Mw = 58,000 and Mn = 32,000. A dumbbell or the like was molded from the obtained hydride using an injection molding machine at a mold temperature = 80 ° C. and a molding temperature = 270 ° C., and the physical properties were measured. The results are shown in Table 1.

[Example 3]
In place of the 2 wt% solution of TMEDA in (E), 1,1′-dimethoxycyclohexane (CHDA) was used, and the feed rates were (A) 2.00 g / min, (B) 9.56 g / min, (C ) 2.80 g / min, (D) 0.69 g / min and (E) (CHDA) 0.96 g / min. PS conversion molecular weight of the obtained hydride was Mw = 31,000 and Mn = 18,000. A dumbbell or the like was molded from the obtained hydride using an injection molding machine at a mold temperature = 50 ° C. and a molding temperature = 220 ° C., and the physical properties were measured. The results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the amount of (B) fed was 0.2 g / min. PS conversion molecular weight of the obtained hydride was Mw = 28,000 and Mn = 15,000. The obtained hydride was molded into a dumbbell and the like at a mold temperature = 80 ° C. and a molding temperature = 290 ° C. using an injection molding machine, and the physical properties were measured. The results are shown in Table 1. As is apparent from Table 1, when the BD content in the copolymer is less than 5 wt%, the Izod impact strength is remarkably inferior.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that the amount of (B) fed was 15.30 g / min. PS conversion molecular weight of the obtained hydride was Mw = 31,000 and Mn = 17,000. A dumbbell or the like was molded from the obtained hydride using an injection molding machine at a mold temperature = 40 ° C. and a molding temperature = 200 ° C., and the physical properties were measured. The results are shown in Table 1. As is apparent from Table 1, when the BD content in the copolymer exceeds 20 wt%, the total light transmittance is remarkably inferior and Tg is also greatly reduced.

  Since the hydrogenated cyclic conjugated diene polymer obtained by the method of the present invention is excellent in impact resistance, heat resistance and transparency, it can be widely used in various optical products including lenses.

Claims (4)

The repeating unit A is derived from a cyclic conjugated diene monomer and the repeating unit B is derived from a chain conjugated diene monomer. The repeating unit A and the repeating unit B have a random structure, and the repeating unit A and / Or the repeating unit B has a 1,2-bond, and the repeating unit A (x parts by weight) and the repeating unit B (y parts by weight) are 0.05 ≦ y / (x + y) ≦ 0.2. A method for producing a cyclic conjugated diene copolymer, characterized in that the cyclic conjugated diene monomer and the chain conjugated diene monomer are converted into an organic group 1 metal compound, an ether compound and / or an amine. Cyclic conjugation characterized in that polymerization is carried out at 40 ° C. ≦ polymerization temperature ≦ 100 ° C. in a hydrocarbon compound solvent in the presence of a polymerization initiator combined with the compound using at least one complete mixing reaction vessel The Method for producing emissions copolymer. The method for producing a cyclic conjugated diene copolymer according to claim 1, wherein the polymerization method is a continuous addition / continuous extraction system of a monomer and a polymerization initiator. The cyclic conjugated diene copolymer obtained by the method according to claim 1 or 2 in the presence of a hydrogenation catalyst, at least 90% of unsaturated bonds in the main chain and side chain of the cyclic conjugated diene polymer. A method for producing a hydrogenated cyclic conjugated diene copolymer obtained by hydrogenation. The cyclic conjugated diene copolymer according to any one of claims 1 to 2 and the cyclic conjugated diene copolymer according to any one of claims 1 to 2, wherein the cyclic conjugated diene is 1,3-cyclohexadiene and the chain conjugated diene is 1,3-butadiene. A method for producing a hydrogenated cyclic conjugated diene copolymer.