WO1996016090A1 - Polymere ameliore de dienes cycliques conjugues et procede pour le fabriquer - Google Patents

Polymere ameliore de dienes cycliques conjugues et procede pour le fabriquer Download PDF

Info

Publication number
WO1996016090A1
WO1996016090A1 PCT/JP1995/002362 JP9502362W WO9616090A1 WO 1996016090 A1 WO1996016090 A1 WO 1996016090A1 JP 9502362 W JP9502362 W JP 9502362W WO 9616090 A1 WO9616090 A1 WO 9616090A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
cyclic conjugated
monomer
complexing agent
monomer units
Prior art date
Application number
PCT/JP1995/002362
Other languages
English (en)
Japanese (ja)
Inventor
Itaru Natori
Tomonari Watanabe
Hideyuki Yamagishi
Miyuki Kazunori
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Priority to GB9705274A priority Critical patent/GB2307238B/en
Priority to DE19581790T priority patent/DE19581790T1/de
Priority to KR1019970702284A priority patent/KR100208316B1/ko
Publication of WO1996016090A1 publication Critical patent/WO1996016090A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/048—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers, conjugated dienes and polar monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type

Definitions

  • the present invention relates to an improved cyclic conjugated polymer and a method for producing the same. More specifically, the present invention provides a polymer main chain comprising at least one kind of cyclic conjugated monomer unit, or at least one kind of cyclic conjugated monomer unit, and At least one other monomer unit capable of being copolymerized, and the cyclic conjugated diene monomer unit is composed of 1,2-bonds and 1,4-bonds in the polymer main chain. Cyclic conjugated genus that is linked, has a relatively high 1,2-bond / 1,4 bond molar ratio, has a relatively narrow molecular weight distribution, and has improved thermal and mechanical properties. It relates to a polymer. The present invention also relates to an industrially advantageous method for producing such an excellent conjugated gen-based polymer using a specific catalyst.
  • conjugated gen-based polymers such as polybutadiene and polyisoprene have a high degree of freedom in the design of polymer chains and a high degree of material properties.
  • Numerous proposals have been made since the control is relatively easy, and some of them have been widely used as important industrial materials.
  • the cyclic conjugated diene monomer is difficult to homopolymerize, and it is difficult to obtain a sufficient high molecular weight polymer. Even if the copolymerization with other monomers is attempted for the purpose of optimizing the mechanical properties to meet various market requirements, it is possible to obtain only a low molecular weight substance such as an oligomer. Was not done.
  • the polymerization method described here not only requires a large amount of a polymerization catalyst and a long reaction time, but also has a very low molecular weight and has no industrial value. .
  • the molecular weight of the obtained polymer is extremely low and has no industrial value.
  • the polymerization method disclosed herein requires a catalyst as much as 1 to 2% by weight based on the monomer, which is not only economically disadvantageous but also makes the obtained polymer The molecular weight will be very low. Furthermore, there is no suggestion or teaching as to the possibility of obtaining a copolymer. On the other hand, in this polymerization method, it is difficult to remove a large amount of catalyst residue remaining in the polymer, and the polymer obtained by this polymerization method has no commercial value.
  • 1,3-cyclohexaene was polymerized with an organic lithium compound as a catalyst. It has been disclosed.
  • the polymer obtained here had a limit of number average molecular weight of 2000, although the polymerization reaction was continued for 5 weeks.
  • the polymer obtained here is a very low molecular weight oligomer and has a single glass transition temperature that is indicative of a random copolymer. .
  • the mouth mouth hexagen homolog reported here Although the number average molecular weight of the polymer is apparently 38,700, the molecular chain having a number average molecular weight of 19,350 actually grows only in a linear direction from the polymerization initiation point. .
  • the polymerization method disclosed herein is a reaction at an extremely low temperature and has no industrial value.
  • Makromo 1 Chem., 191, 2743 (1990) describes a method for polymerizing 1,3-cyclohexadiene using polystyrene-lithium as a polymerization initiator. In the polymerization method described here, it is taught that at the same time as the polymerization reaction, a rearrangement reaction involving the extraction of lithium cations and a elimination reaction of lithium hydride occur quite simultaneously. Despite the polymerization reaction using lithium as the initiator, no block copolymer of styrene-cyclohexadiene was obtained at room temperature, and only xadiene homopolymer was obtained at the bicyclium at room temperature. Is reported to have been c
  • a monomer unit derived from a cyclic conjugated dimeric monomer is partially or entirely contained in a polymer main chain.
  • anion polymerization preferably living anion polymerization, is carried out under an industrially advantageous production condition in an arbitrary ratio.
  • the present invention was completed by establishing a technology for introducing and introducing a derived monomer unit into the main chain through 1,2-linkage and 1,4-linkage.
  • a complex obtained by reacting a group IA metal-containing organometallic compound with a complexing agent (first complexing agent) in the polymerization of a cyclic conjugated diene monomer and a further complex In the prior art, when a mixture of a complexing agent (second complexing agent) (the first complexing agent and the second complexing agent may be the same or different) is used as a polymerization catalyst, Only the transfer reaction by extraction of the group IA metal cation from the polymer terminal and the elimination reaction of the group IA metal hydride by the cyclic conjugated gen-based monomer itself, which were considered unsolvable, are suppressed only.
  • the polymerization catalyst shows excellent polymerization activity even at a high temperature of about 40 ° C. to about 70 ° C.
  • the cyclic conjugated diene monomer has 1,2-bond and 1,4
  • a cyclic conjugated polymer linked by a bond (and at a relatively high 1,2 bond ratio) can be produced industrially advantageously, and the resulting polymer has a molecular weight distribution
  • the present invention has been found to have narrow and excellent thermal and mechanical properties, and has completed the present invention.
  • an organometallic compound containing a Group IA metal and a complexing agent such as an amide compound, an ether compound, or a metal alkoxide often form a highly reactive complex. It has been known and is used as an effective reaction agent in the organic synthesis reaction of monomers.
  • a mixture of a complex obtained by reacting an organometallic compound containing a Group IA metal with a first complexing agent and a second complexing agent is used as a polymerization catalyst.
  • the catalyst can maintain a thermally stable solid state without causing side reactions such as metallization.
  • a mixture of this complex (of an organometallic compound containing a Group IA metal and a first complexing agent) and a second complexing agent is used as a polymerization catalyst to form a cyclic conjugated diene monomer.
  • the living conjugate polymerization reaction of the cyclic conjugated gen-based monomer does not proceed even under high temperature conditions, the molecular weight distribution of the obtained polymer is narrow, and the cyclic conjugated gen-based monomer is It is said that the cyclic conjugated polymer with excellent thermal properties (glass transition temperature, thermal deformation temperature, etc.) can be obtained because the monomer is linked into the polymer main chain with a high 1,2-bond ratio.
  • the present invention was completed by discovering the most favorable facts industrially.
  • one object of the present invention is to have a narrow molecular weight distribution and excellent thermal properties (melting point, glass transition temperature, heat deformation temperature, etc.) and mechanical properties (tensile elastic modulus, flexural modulus, etc.) It is an object of the present invention to provide an improved cyclic conjugated polymer having the following.
  • Another object of the present invention is to be able to polymerize a cyclic conjugated monomer which has been considered difficult to polymerize due to large steric hindrance.
  • An object of the present invention is to provide a method for industrially advantageously producing the above-mentioned excellent cyclic conjugated polymer, which is effective for linking in a polymer main chain at a 2-bond ratio.
  • FIG. 1 (a) is a structural explanatory view of a cyclohexadiene monomer unit having a 1,2-bond.
  • FIG. 1 (b) is an explanatory view of the structure of a cyclohexadiene monomer unit having 1,4 single bonds.
  • FIG. 2 is a 2D (two-dimensional) NMR spectrum chart of the polycyclohexene obtained in Example 22 measured by the H—HCOSY method.
  • a cross-talk is observed in H (hydrogen) bonded to the carbon atom adjacent to the carbon atom bonded by the olefin bond.
  • FIG. 3 is a 2D (two-dimensional) NMR spectrum chart of the polycyclohexene obtained in Example 22 measured by the H—HCOSY method. Cross-linked to H (hydrogen) bonded to the carbon atom bonded by a olefin bond in each cyclohexadiene monomer unit constituting the high molecular backbone of polycyclohexadiene A peak is observed.
  • FIG. 3 is an NMR spectrum diagram.
  • FIG. 3 is an NMR spectrum diagram.
  • FIG. 8 is a 1 H-NMR spectrum diagram of n—BuLi used in Comparative Example 8.
  • FIG. 10 is a 1 H-NMR spectrum diagram of the cyclohexadiene homopolymer obtained in Example 22.
  • FIG. 11 is a 1 H-NMR spectrum diagram of the hydrogenated cyclohexagene homopolymer obtained in Example 24.
  • FIG. 12 is a 1 H-NMR spectrum chart of the polycyclohexene-polysoprene-polycyclohexene-trib-opened copolymer obtained in Example 38. is there.
  • FIG. 13 shows the 1 H-NMR spectrum chart of the hydrogenated polyhexadiene-polysoprene-polycyclohexa- gen-tri-lipid copolymer obtained in Example 44.
  • FIG. FIG. 14 is a 1 H—NMR spectrum diagram of the polyhexahexene-polystyrene-polyhexahexene reblock copolymer obtained in Example 47. is there.
  • FIG. 15 is a 1 H-NMR spectrum chart of the polycyclohexene-polybutadiene-polycyclohexadiene triblock copolymer obtained in Example 57.
  • FIG. 16 shows the 1 H-NMR spectrum chart of the hydrogenated polyhexadiene-polystyrene-polycis-mouth hexagently block copolymer obtained in Example 70.
  • the polymer is linked into the polymer main chain by a bond, and the molar ratio of 1,2-bond / ⁇ 1,4 bond is in the range of 40/60 to 90/10.
  • a cyclic conjugated gen system characterized in that the number average molecular weight is in the range of 500 to 5, 000, 0000 A polymer is provided.
  • a to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order.
  • To e represent wt% of each of the monomer units A to E with respect to the total weight of the monomer units A to E.
  • A One or more monomer units selected from cyclic conjugated diene monomer units.
  • B One or more monomer units selected from chain conjugated diene monomer units.
  • E Ethylene, a—One or more monomer units selected from monomer units.
  • a to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order.
  • a to e represent wt% of each of the monomer units A to E with respect to the total weight of the monomer units A to E.
  • A One or more monomer units selected from cyclic conjugated diene monomer units.
  • B One or more monomer units selected from chain conjugated diene monomer units.
  • E One or more monomer units selected from ethylene and ⁇ -olefin monomer units.
  • the number average molecular weight of the above polymer is in the range of 500 to 5,000,
  • a production method characterized by polymerizing in the presence of a catalyst.
  • a to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order.
  • a to e represent wt% of each of the monomer units A to E with respect to the total weight of the monomer units A to E.
  • A One or more monomer units selected from cyclic conjugated diene monomer units.
  • B One or more monomer units selected from chain conjugated diene monomer units.
  • E Ethylene, ⁇ -olefin monomer units selected from — or two or more monomer units. a to e satisfy the following relationship.
  • cyclic conjugated polymer according to any one of the above items 2 to 4, which is at least a block copolymer of a triblock.
  • At least at least two or more monomer units A At least one jib mouth with at least one block unit and at least one block unit consisting of at least one monomer unit selected from monomer units B to E 5.
  • Two block units X containing at least one monomer unit A, and at least one kind of unit selected mainly from monomer units B and E. It is a block copolymer of a triblock having one block unit Y composed of monomer units, and having a weight ratio of XZY in the range of 199 to 99Z1.
  • Previous Item 6 The cyclic conjugated diene polymer according to item 5.
  • the structure of the block copolymer of at least the above triblock is X— (Y—X) P , (X ⁇ Y) q , Y ⁇ (X ⁇ Y) Y,
  • P is an integer of 1 or more, and q is an integer of 2 or more.
  • X and Y have the same meaning as defined above. ]
  • Each R 1 is independently a hydrogen atom, a halogen atom, C 1, to C 2 .
  • Unsaturated aliphatic hydrocarbon group C 5 ⁇ C 2 Q of ⁇ Li Lumpur group, C 3 ⁇ C 2.
  • a linking group or group such that two R 2 form ⁇ CR ⁇ ⁇ ⁇ (R 3 has the same meaning as R 1, and n is an integer from 1 to 10) Is shown. ]
  • the monomer unit A is at least one kind of cyclic conjugated monomer unit selected from the monomer units represented by the following formula (III).
  • the monomer unit A is a 1,3-cyclopentadiene monomer unit, a 1,3-cyclohexadiene monomer unit, a 1,3-cyclopentadiene monomer unit and the like.
  • the monomer unit A is 1,3-cyclohexadiene monomer 15.
  • a to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order.
  • To e represent wt% of each of the monomer units A to E with respect to the total weight of the monomer units A to E.
  • A One or more monomer units selected from cyclic conjugated diene monomer units.
  • B One or more monomer units selected from chain conjugated diene monomer units.
  • E One or more monomer units selected from ethylene and ⁇ -olefin monomer units.
  • the number average molecular weight of the above polymer is in the range of 500 to 5, 0000, 0000,
  • a polymerization method comprising polymerizing in the presence of a catalyst comprising:
  • At least one kind of the first complexing agent and at least one Each of the second complexing agents of the species independently comprises at least one element selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S), and phosphorus (P).
  • O oxygen
  • N nitrogen
  • S sulfur
  • P phosphorus
  • Each of the at least one kind of the first complexing agent and the at least one kind of the second complexing agent is independently an ether compound, a metal alkoxide, an amine compound and a thioether compound. 19.
  • Each of the at least one kind of the first complexing agent and the at least one kind of the second complexing agent is independently an amide compound. The production method described in 1.
  • Each of the at least one kind of the first complexing agent and the at least one kind of the second complexing agent is independently a diamine compound. The production method described in 1.
  • Each of the at least one kind of the first complexing agent and the at least one kind of the second complexing agent is independently an aliphatic diamine compound. 19. The production method according to item 9.
  • At least one kind of the first complexing agent and at least one Item 19 The method according to Item 19, wherein each of the second complexing agents is independently a tertiary amine compound.
  • the diamine compound is selected from tetramethylethylene diamine (TMEDA) and diazabicyclo [2,2,2] octane (DABCO).
  • TMEDA tetramethylethylene diamine
  • DABCO diazabicyclo [2,2,2] octane
  • At least one kind of organometallic compound containing a metal belonging to Group IA of the periodic table is composed of normal butyllithium ( ⁇ —BuLi) and secondary butyllithium (s—BuLi). And an organic lithium compound selected from the group consisting of tert-butyllithium (t_BuLi) and at least one kind of the first complexing agent and at least one kind of the above-mentioned complexing agent.
  • each of the second complexing agents is independently selected from tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] octane (DABCO). 19.
  • TMEDA tetramethylethylenediamine
  • DABCO diazabicyclo [2,2,2] octane
  • the above-mentioned complex reacts with at least one kind of organometallic compound containing a metal of Group IA of the periodic table and at least one kind of the first complexing agent in a molar ratio represented by the following formula. 29.
  • A, / B, 2 0 0 1 ⁇ 1 1 1 0 0
  • A represents the molar amount of the group IA metal atom in at least one kind of organometallic compound used, and represents the molar amount of at least one kind of the first complexing agent used.
  • the above-mentioned complex is composed of at least one kind of organometallic compound containing a metal of Group IA of the periodic table and at least one kind of first complexing agent in a molar ratio represented by the following formula. 29.
  • a 2 / B 2 1/0. 25 to 1/1
  • a 2 represents the molar amount of the metal of the group IA in at least one kind of the organometallic compound in the complex
  • B 2 represents the molar amount of at least one kind of the first complexing agent in the complex.
  • At least one kind of the organometallic compound, at least one kind of the first complexing agent and at least one kind of the second complexing agent Is present in a molar ratio represented by the following formula:
  • a 3 / B 3 1 0 0 Z l ⁇ l / 2 0 0
  • each monomer unit constituting the polymer follows the nomenclature of the monomer from which the monomer unit is derived. Therefore, for example, the term “cyclic conjugated gen-based monomer unit” means a structural unit of a polymer resulting from polymerization of a monomeric cyclic conjugated gen-based monomer.
  • cyclic cyclic monomer unit means a structural unit of a polymer obtained by polymerizing a cyclic cyclic olefin which is a monomer, and its structure is represented by a cycloalkane. It is a molecular structure in which two carbons are the binding sites.
  • the cyclic conjugated polymer is a monomer unit in which some or all of a plurality of monomer units constituting a polymer chain are derived from a cyclic conjugated diene monomer. Z or a polymer comprising a derivative of the monomer unit.
  • a polymer having a polymer main chain containing a monomer unit derived only from a cyclic conjugated gen monomer, or a cyclic conjugated gen-based polymer examples thereof include a conjugated diene monomer and a polymer containing a monomer unit derived from at least one kind of monomer copolymerizable therewith.
  • homopolymers of cyclic conjugated gen monomers More specifically, homopolymers of cyclic conjugated gen monomers, copolymers of two or more cyclic conjugated gen monomers, cyclic conjugated gen monomers, and copolymers thereof. At least one other kind of polymerizable Examples thereof include a copolymer with a monomer.
  • a monomer unit derived from the cyclic conjugated monomer contained in the polymer chain is a monomer containing a cyclohexene ring.
  • An example is a polymer which is a unit.
  • the cyclic conjugated polymer of the present invention is selected from hydrogenation, halogenation, hydrogenation. Alkylation, arylation, ring opening and dehydrogenation.
  • a polymer obtained by performing at least one reaction is provided.
  • the cyclic conjugated diene monomer in the present invention is a cyclic conjugated diene having 5 or more membered rings constituted by carbon-carbon bonds.
  • a preferred cyclic conjugated diene monomer is a 5- to 8-membered cyclic conjugated diene formed by a carbon-carbon bond.
  • a particularly preferred cyclic conjugated diene monomer is a six-membered cyclic conjugated diene formed by a carbon-carbon bond.
  • 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclopentadiene and derivatives thereof can be exemplified.
  • Preferred examples of the cyclic conjugated monomer include 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives.
  • the most preferred cyclic conjugated monomer is 1,3-cyclohexadiene.
  • the other monomer which can be copolymerized with the cyclic conjugated diene monomer a conventionally known monomer which can be polymerized by anion polymerization can be exemplified.
  • chain conjugated diene such as 1,3-butadiene, isoprene, 2,3-dimethinole-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, or derivatives thereof.
  • Ene-based monomers styrene, ⁇ -methylinostyrene, ⁇ —methylstyrene, ⁇ —methylinostyrene, p—tert—butynolestyrene, 1,3—dimethylylstyrene, dibininolebenzene, Vinyl aromatic monomers such as vinylinolephthalene, vinylinoleanthracene, 1,1-diphenylenoethylene, m-diisoprenylbenzene, vinylpyridin, or derivatives thereof, and methacrylyl Sanme Chinore, ⁇ click Li Honoré Sanme chill, a click Li b d Application Benefits Le, main switch Honoré Biniruke tons, alpha - Xia Bruno a click Li Rusanme polar vinyl Le based single chill etc.
  • Polar monomers such as monomers or ethylene oxide, propylene oxide, cyclohexenoxide, cyclic lactone, cyclic lactam, cyclic siloxane, or ethylene Len and ⁇ -olefin monomers can be exemplified. These monomers at one depending on the need c or alternatively may be two or more, the mode of the copolymer obtained by Li in the production method of the present invention, if necessary Various selections are possible. For example, diblocks, triblocks, tetrablocks, multiblocks, radial blocks, asymmetric radial blocks, graph blocks, star blocks, comb blocks, etc.
  • monomer units derived from other copolymerizable monomers may be hydrogenated, halogenated, alkylated, arylated, etc. after completion of the polymerization reaction. It is not particularly limited that the monomer unit is derived by the above.
  • the content of the monomer unit derived from the cyclic conjugated monomer in the cyclic conjugated polymer of the present invention is not particularly limited because it is variously set depending on the intended use, but is generally not limited.
  • L is preferably in the range from 0 wt%. Or in the range of 1 to 100 wt%.
  • monomer units derived from the cyclic conjugated monomer may be used. Is preferably in the range of 5 to 100 wt%, more preferably in the range of 100 to 100 wt%, based on the total weight of the polymer chains. Most preferably, it is in the range of 15 to 100 wt%.
  • the cyclic conjugated Since it can be produced by Binganion polymerization, its molecular weight can be set arbitrarily, and its range is not particularly limited.
  • the number-average molecule i of the polymer chain is usually preferably in the range of 500 to 5, 000, 0000, depending on the application and purpose. Select and set as appropriate. For example, when it is used as a functional material, it is generally in the range of 500 to 2, 000, 0000, and 1, 0000 to: 1, 0000, 0000. It is preferably in the range of 0, particularly preferably in the range of 2,000 to 800,000, particularly in the range of 3,000 to 500,000. Something is most preferred.
  • the number-average molecular weight of the polymer chain is generally in the range of 20,000 to 5,500,000, It is preferable that it is in the range of 0 0 0 to 4, 0 0 0, 0 0 0, more preferably in the range of 4 0, 0 0 0 to 3, 0 0 0, 0 0 0, It is particularly preferable to be in the range of 40, 000 to 2, 0000, 0000, and most preferably in the range of 40, 000 to: L, 0000, 0000. I like it.
  • the cyclic conjugated polymer of the present invention has a polymer terminal with a conventionally known bifunctional or higher functional coupling agent (for example, dimethyl) for the purpose of adjusting the molecular weight or obtaining a star-shaped polymer if necessary.
  • a conventionally known bifunctional or higher functional coupling agent for example, dimethyl
  • a conventionally known bifunctional or higher functional coupling agent for example, dimethyl
  • the number average molecular weight (Mn) in the present invention is a number average molecular weight in terms of standard polystyrene measured by a G.P.C. (gel permeation chromatography) method.
  • MwZMn which is a standard of the molecular weight distribution of the cyclic gen-based polymer of the present invention, is in the range of 1.01 to 10 and preferably in the range of 1.03 to 7.0. , More preferably in the range of 1.03 to 5.0, particularly preferably in the range of 1.03 to 250, most preferably 1.0. It is in the range of 3 to 2.0.
  • the monomer unit A has a structure in which 1,2-bonds and 1,4-bonds are linked in a polymer main chain.
  • the ratio of 1,2-bonds measured by ' ⁇ -NMR is 40 mol% to 90 mo 1% based on the total of 1,2-bonds and 1,4 single bonds. It is necessary to exist in the range.
  • the ratio of 1,2-bond is preferably in the range of 40 to 85 mo 1%, and 40 to 80 mol%. Is more preferable, and the range of 40 to 70 mo 1% is most preferable.
  • a cyclic conjugated polymer having a glass transition temperature of 150 C or more, particularly a homoconjugated polymer having a 1,2-bond ratio in the range of 40 to 90 mol% is preferably used.
  • Polymers or block copolymers are most preferred for their thermal and mechanical properties.
  • the cyclic conjugated polymer obtained by the production method of the present invention is a cyclic conjugated block copolymer having a block unit in a polymer chain
  • the (polymer) block is used.
  • the unit is a block unit composed of a monomer unit derived from a cyclic conjugated gen-based monomer, a cyclic conjugated gen-based monomer, and other units copolymerizable therewith.
  • Block units composed of monomer units derived from the same monomer, and monomer units derived from other monomers copolymerizable with the cyclic conjugated gen-based monomer.
  • the block units that can be configured can be designed, and various block units can be designed as required.
  • cyclic conjugated gen-based blocks can be designed according to the purpose. Can be a copolymer it can.
  • the block unit of the present invention contains, in part or all, a monomer unit derived from a cyclic conjugated monomer, at least one molecule of the cyclic unit is contained in the block unit. It is necessary to contain a monomer unit derived from a conjugated gen-based monomer, and at least two monomer units derived from a cyclic conjugated gen-based monomer must be contained. It is preferable that they are continuously bonded, and it is more preferable that five or more monomer units are continuously bonded, and that ten or more monomer units are continuously bonded. This is particularly preferred for improving thermal and mechanical properties.
  • a block comprising a monomer unit derived from one or more cyclic conjugated gen-based monomers may be used.
  • Block consisting of units, one or more cyclic conjugated monomers and monomer units derived from one or more other monomers copolymerizable therewith.
  • Block units composed of monomer units derived from one or more other monomers copolymerizable with the cyclic conjugated gen-based monomer, and further polymerized according to the purpose.
  • the following method Can be enumerated.
  • a block unit containing a monomer unit derived from a cyclic conjugated diene monomer or a block unit composed of a monomer unit derived from a cyclic conjugated diene monomer is further included.
  • Polymerization is carried out in advance, and one or two or more other monomers copolymerizable therewith from one or both ends of the polymer are polymerized, and if necessary, further hydrogenated.
  • a method in which at least one reaction selected from halogenation, hydrogen halide, alkylation, arylation, ring opening, and dehydrogenation is performed.
  • One or two or more other monomers copolymerizable with the cyclic conjugated monomer are polymerized in advance, and the cyclic conjugated gen is polymerized at one or both ends of the polymer.
  • One or two or more other monomers copolymerizable with the monomer and, if necessary, the cyclic conjugated monomer are polymerized, and if necessary, further hydrogenated, halogenated, A method in which at least one kind of reaction selected from the group consisting of hydrogenation, hydrogenation, anoalkylation, arylation, ring opening and dehydrogenation is carried out.
  • a block unit containing a monomer unit derived from a cyclic conjugated diene monomer or a block unit composed of a monomer unit derived from a cyclic conjugated diene monomer is polymerized. Then, one or more other monomers copolymerizable therewith are polymerized, and a block unit or a cyclic conjugate containing a monomer unit derived from a cyclic conjugated diene monomer is further obtained.
  • One or two or more other monomers copolymerizable with the cyclic conjugated gen-based monomer are polymerized in advance, and a process containing a monomer unit derived from the cyclic conjugated gen-based monomer is performed.
  • Polymerize one or more other monomers sequentially, and select from hydrogenation, hydrogenation, hydrogenation, alkylation, arylation, ring opening, and dehydrogenation as needed.
  • a method of performing at least one type of reaction is performed in advance, and a process containing a monomer unit derived from the cyclic conjugated gen-based monomer is performed.
  • the cyclic conjugated gen-based monomer and one or more other copolymerizable monomers differing in polymerization rate from this are simultaneously polymerized to form a tapered block copolymer, which is necessary.
  • a method of performing at least one kind of reaction selected from hydrogenation, hydrogenation, hydrogen halide, anolequinolelation, arylation, ring opening, and dehydrogenation.
  • a block unit containing a monomer unit derived from a cyclic conjugated diene monomer or a block unit derived from a cyclic conjugated diene monomer can be polymerized and then copolymerized with this. Polymerize one or two or more other monomers, leaving the polymer end Known bifunctional or higher-functional coupling agents (for example, dimethyldichlorosilane, methinoletrichlorosilane, dimethinoresive mouth mosilane, methyltrile mouth mosilane, titanocene dichlorylate) , Methylene chloride, methylene bromide, black form, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.) And, if necessary, further hydrogenating. A method of performing at least one kind of reaction selected from halogenation, hydrogenation, hydrogenation, arylation, ring opening and
  • a cyclic conjugated monomer and one or more other monomers copolymerizable therewith are charged at different composition ratios and simultaneously polymerized, and further hydrogenated and halogenated as necessary.
  • a method for performing at least one kind of reaction selected from halogenation, hydrogenation, alkylation, arylation, ring opening and dehydrogenation.
  • the cyclic conjugated diene monomer is polymerized first, and one or two or more other re-copolymerizable monomers having a different polymerization rate at an arbitrary conversion are added and polymerized.
  • the remaining cyclic co-monomeric monomer is polymerized to form a live copolymer, and further hydrogenated, halogenated, and hydrogenated as necessary. Examples include a method of performing at least one kind of reaction selected from among alkylation, arylation, ring opening, and dehydrogenation, and various methods according to necessity.
  • a copolymer can be obtained.
  • block units containing monomer units derived from one or more cyclic conjugated gen-based monomers, or block units composed of cyclic conjugated gen-based monomer units can be copolymerized with this.
  • it is not particularly limited to contain a monomer unit derived from a kind or two or more kinds of other monomers.
  • the block unit consisting of a monomer unit derived from one or more other monomers copolymerizable with one or more cyclic conjugated monomers is one kind. It is not particularly limited to contain a monomer unit derived from two or more kinds of cyclic conjugated diene monomers.
  • the most preferred monomer unit or block unit derived from one or more cyclic conjugated dimeric monomers is a monomer containing a cyclohexene ring.
  • it is a block unit that contains or consists of it.
  • a preferred monomer derived from a cyclic conjugated monomer introduced into a part or all of the polymer main chain by a polymerization reaction The body unit is a monomer unit represented by the following formula (II), and the most preferred monomer unit is a monomer unit represented by the following formula (m). 6/16090
  • R 1 is each independently a hydrogen atom, a nitrogen atom, and ⁇ Alkyl group, C 2 ⁇ C 2. Unsaturated aliphatic hydrocarbon group, C 5 ⁇ C 2. Aryl groups, C 3 -C 2 . The cycloalkyl group is C 4 -C 2 .
  • Sik b Jefferies two Honoré group or 5- to 1 0-membered ring is a and least for the one nitrogen also oxygen or heterocyclic group der containing by sulfur and hetero B atom Ri, R 2 each, Independently a hydrogen atom, a halogen atom, a C i C alkyl group, a C 2 -C 20 unsaturated aliphatic hydrocarbon group, C 5 -C 2 .
  • a cycloalkynole group, a C 4 to C 2 Q cycle geninole group, or a 5- to 10-membered ring containing at least one nitrogen, oxygen or sulfur as a heteroatom each independently a is Ca or R 2 is a heterocyclic group, two R 2 s ⁇ fC R ⁇ r (continuous or! ⁇ and have the same meaning, n is an integer from 1 to 0) Indicates a linking group or group that forms.
  • the preferred carbon number of the alkyl group is 2-10.
  • the unsaturated aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms.
  • Preferred carbons in the aryl groups are 5-10.
  • the preferred carbon number of the cycloalkyl group is 5-10.
  • the preferred carbon number of the cyclogenenyl group is 5-10.
  • the preferred carbon number of the heterocyclic group is a 5- to 8-membered ring.
  • R 1 and R 2 include methyl, ethyl, ⁇ -propyl, iso-propyl, n-butyl, sec-butyl, tert- Butynole, pentynole, hexyl, cyclopentyl, cyclohexynole, vinyl, phenyl, tolyl, naphthyl, cyclopentagenyl, indenyl, pyridyl, And a piperidyl group.
  • the cyclic conjugated gen-based block copolymer of the present invention is required to have an elastomer property (rubber elasticity), at least two or more Tg (glass transition) higher than room temperature are required.
  • Tg glass transition
  • (Polymer) It is necessary to be composed of block units (rubber phase or soft segment).
  • Block copolymers having such a polymer chain structure are subject to restrictions.
  • the bundle phase When the bundle phase is less than its Tg, it acts as a physical bridge point, so that it can exhibit elastomer properties (rubber elasticity).
  • melt molding injection molding, blow molding, extrusion molding, etc.
  • solvent cast molding film molding, etc.
  • the cyclic conjugated gen-based block copolymer of the present invention can also exhibit re-elastomer properties (rubber-like properties) by crosslinking polymer chains.
  • At least a triblock cyclic conjugated gen-based block copolymer At least a triblock cyclic conjugated gen-based block copolymer.
  • At least one block unit consisting of at least two or more monomer units A, and at least one monomer unit selected from monomer units B to E At least one consisting of only At least a jib-opened cyclic conjugated gen-based block copolymer having at least one block unit.
  • At least one block unit X containing at least one monomer unit A and at least one kind selected from the monomer units B and E.
  • a triblock cyclic conjugated gen-based block having one block unit Y composed of monomer units and having a weight ratio of XZY in the range of 1/99 to 991.
  • a cyclic conjugated gen-based block copolymer which is at least a triblock, represented by
  • the cyclic conjugated gen-based block copolymer of the present invention is mainly composed of a cyclic conjugated gen-based (50 wt% or more of the block unit) in order to exhibit an elastomer property (rubber-like property).
  • At least a block unit (X block) composed of a monomer unit or a derivative thereof or a cyclic conjugated gen-based monomer unit and a vinyl aromatic monomer unit.
  • the number of block units (Y blocks) mainly composed of linear conjugated monomer units or their derivatives (more than 50 wt% of block units) or their derivatives is small. It is preferable that the polymer has a polymer main chain structure having one.
  • At least two block units (X blocks) composed of a cyclic conjugated gen-based monomer unit or a derivative thereof, and mainly a chain conjugated gen-based monomer unit Or a polymer main chain structure having at least one block unit (Y block) composed of a derivative thereof, and more preferably a cyclic conjugated diene monomer.
  • At least a block unit (X block) composed of a unit or a derivative thereof or a cyclic conjugated diene monomer unit and a vinyl aromatic monomer unit.
  • At least two block units (Y blocks) mainly composed of a chain conjugated diene monomer unit or a derivative thereof. It is particularly preferable that the polymer has a polymer main chain structure obtained by hydrogenating a single polymer.
  • At least two block units (X-blocks) composed of a cyclic conjugated monomer unit or a derivative thereof, and mainly a chain conjugated monomer unit or X-block.
  • X-blocks a polymer main chain structure obtained by hydrogenating a polymer having at least one block unit (Y block) composed of its derivative.
  • the resin is preferably a monomer unit derived from ⁇ - methylstyrene, and the monomer units constituting the block are derived from 1,3-butadiene and / or isoprene.
  • the preferred monomer units are preferred.
  • ⁇ When formed by polymerizing blocker 1,3-butadiene and rosin or isoprene, ⁇ the amount of vinyl bonds in the block can be set arbitrarily. Is not limited, but when low-temperature properties are required, the cis- and trans- 1,4—vinyl bonding strength is in the range of 10 to 90 m ⁇ 1% based on the total amount of bonding and vinyl bonding. Certain are preferred, most preferably in the range of 20 to 80 mo 1%.
  • the cyclic conjugated block polymer obtained by the production method of the present invention exhibits an elastomer property (rubber elasticity).
  • a linear block copolymer represented by the following formula (IV) and a radial block copolymer represented by the following formula (V) are preferred. Examples can be given.
  • [ ⁇ is an integer of 1 or more, and q is an integer of 2 or more.
  • Z is a residue of a polyfunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, or a polyfunctional organic group IA Indicates the residue of an initiator such as a metal compound.
  • X block is 10 to
  • Y block is 90 to 40 wt%. / 0 , preferably containing 85 to 50 wt% and having a number average molecular weight of 1,000 to 200,000, represented by X-Y-X A cyclic conjugated gen-based block copolymer of a triblock can be exemplified.
  • the cyclic conjugated gen-based polymer of the present invention has toughness.
  • the X block is 40 to 90 wt%, preferably 45 to 85 wt%
  • the Y block is 60 to: L0 wto / o , preferably containing 55 to 15 wt% and having a number average molecular weight of 1,000 to 2,000,
  • the cyclic conjugated diene-based block copolymer having the above-mentioned elastomer properties can be used for hydrogenation, halogenation, hydrogenation, alkylation, arylation, ring-opening and ring-opening. It can be a polymer obtained by performing at least one kind of reaction selected from dehydrogenation.
  • a mixture of at least one further complexing agent (second complexing agent) can be obtained by performing a polymerization reaction using a stabilized polymerization catalyst.
  • the catalyst used in the method of the present invention is thermally stable and does not cause a side reaction such as metallization.
  • a side reaction such as metallization.
  • at least one kind of cyclic conjugated monomer Alternatively, at least one kind of cyclic conjugated monomer and at least one other monomer copolymerizable therewith (chain conjugated monomer, vinyl aromatic monomer, (A polar monomer, an ethylene monomer, and an ⁇ -olefin monomer) can be used to form a cyclic conjugated system even under industrially advantageous high-temperature conditions.
  • the polymer of the present invention is a polymer obtained by subjecting a cyclic conjugated polymer to an addition reaction such as hydrogenation
  • the cyclic conjugated monomer unit in the cyclic conjugated polymer is
  • the saturation rate of the carbon-carbon double bond constituting the compound by the addition reaction is not particularly limited, it is generally from 0: to 100%, and from 1 to 100%. Is preferable, 5 to 100% is more preferable, 10 to: L is particularly preferable to be 0%, and 20 to 100% is most preferable. I like it.
  • examples of metals belonging to Group IA of the Periodic Table that can be employed in the polymerization catalyst include lithium, Mention may be made of sodium, potassium, norebidium, cesium, and fransium. It is preferably lithium, sodium or potassium, particularly preferably lithium or sodium, most preferably lithium.
  • the organometallic compound containing a Group IA metal of the present invention is an organometallic compound containing the above Group IA metals, such as lithium, sodium, potassium, norevidium, cesium, and francium.
  • organometallic compound containing a group IA metal an organometallic compound containing lithium, sodium, and potassium can be exemplified.
  • organometallic compound containing a group IA metal include lithium and sodium-containing organometallic compounds, and the most preferred organometallic compound containing a group IA metal and Thus, an organometallic compound containing lithium can be exemplified.
  • an organic lithium compound an organic sodium compound, and an organic potassium compound can be exemplified.
  • Particularly preferred are organic lithium compounds and organic sodium compounds, most preferred. Or an organic lithium compound.
  • an organic lithium compound most preferably used as a polymerization catalyst in a polymerization reaction is one or two or more organic molecules that bind to an organic molecule or an organic polymer containing at least one or more carbon atoms. It is an organic compound or an organic polymer compound containing at least one lithium atom (including lithium ion).
  • the organic molecules are C 1 and C 2 .
  • Alkyl group unsaturated aliphatic hydrocarbon radical of C 2 ⁇ C 20 of, C 5 ⁇ C 2.
  • a phenyl group is
  • organic polymer examples include polybutadiene, polyisoprene, polystyrene, polymethylstyrene, and polyethylene.
  • organic lithium compound used in the production method of the present invention include methyllithium, ethyllithium, n-propyllithium, and iso-propyllithium.
  • N butyllithium, sec — butynorium, tert — butynolidium, pentyllithium, hexyllithium, aryllithium, cyclohexane 9-Finole lithium, hexinole lithium, hexamethylen lithium, cyclopentageninole lithium, indenyl lithium, 9 — phenol olenin lithium , 91 Anthrinolemethyllithium, 1, 1-diphenyl-2-n-hexyllithium, 1.
  • the preferred organic lithium compound is not particularly limited as long as it forms a stable complex, but typical organic lithium compounds include methyllithium, ethyllithium, and ⁇ -propyl.
  • Lithium, iso — propyllithium, n — butynorellitium, sec — butynorellitium, tert — butynorrichium, cyclohexyllithium can be exemplified.
  • Preferred organolithium compounds that can be industrially employed are n-butyllithium (n-BuLi), sec-butyllithium (s-BuLi), tert-butyllithium (t-BuLi). L i), and the most preferred organolithium compound is n-platinolium (n-Bu L i).
  • the organometallic compound containing a Group IA metal employed in the production method of the present invention may be one kind or a mixture of two or more kinds as necessary.
  • the polymerization catalyst in the production method of the present invention is, as described above, A mixture of a complex obtained by reacting at least one kind of organometallic compound containing a Group IA metal with at least one kind of first complexing agent, and at least one kind of second complexing agent It is.
  • Type of the first complexing agent and the second complexing agent even the same, for different which may be c first complexing agent and the second complexing agent, in particular the kind limit
  • each of the at least one first complexing agent and the at least one second complexing agent (hereinafter often simply referred to simply as "complexing agent") is independent of each other.
  • the organic compound contains at least one element selected from the group consisting of, for example, oxygen (O), nitrogen (N), sulfur (S), and phosphorus (P). .
  • ether compounds Among these organic compounds, ether compounds, metal alkoxides, amide compounds and thioether compounds are preferred.
  • organic compounds include cyclic ether compounds (tetrahydrofuran, crown ether, etc.), metal alkoxide compounds, and amine compounds, and the most preferred are organic compounds. Is an amine compound.
  • R′R 2 N— group (R ′) is a polar group having an unshared electron pair, which can coordinate and form a complex with an organometallic compound containing a Group IA metal.
  • R 2 represents an alkyl group, a aryl group, or a hydrogen atom, which may be the same or different. You may. ) Or one or more organic amine compounds or organic high molecular amine compounds.
  • amide compounds particularly preferred amide compounds are tertiary (tertiary) amine compounds, and the most preferred tertiary amine compounds are
  • (Tertiary) amine compounds are tertiary (tertiary) diamine compounds.
  • the complexing agent according to the present invention include: getyl-ethanol, dibutyl ether, 1,2-dimethoxetane, tetrahydrofuran, and 2-methylthiohydran.
  • the tertiary (tertiary) amine compounds which are preferred complexing agents in the present invention include trimethylamine, triethylamine, tri-n-butylamine, quinucline and the like.
  • a particularly preferred complexing agent is an aliphatic amide compound, and the most preferred amide compound is an aliphatic diamine compound. Things.
  • the most preferred aliphatic diamine compounds include tetramethyl dimethylene diamine (TMMDA), tetraethyl methylenediamine (TEMDA), tetramethyl ethylenediamine, and the like.
  • TM EDA Tetraethyl Ethylene Diamine
  • TM PDA Tetramethyl Propylene Diamine
  • TEPDA Tetraethyl Propylene Diamine
  • TM BDA Tetramethyl Norrebutylene Diamine
  • TM BDA Tetraethylbutylenediamine
  • TABDA Tetramethylpentanediamine
  • THDA Tetraethylpentadiamine
  • TMHDA Tetramethylhexanediamine
  • TEHDA Tetraethylhexanediamine
  • DABCO 1, 4 diaza bicyclo [2, 2, 2] octane
  • the most preferred aliphatic diamine compound that can be industrially employed is an aliphatic diamine represented by the following formula (VI) that reacts with an organic lithium compound to form a stable complex.
  • VI aliphatic diamine represented by the following formula (VI) that reacts with an organic lithium compound to form a stable complex.
  • those having 1 to 6 carbon atoms between nitrogen and nitrogen atoms are preferable, those having 1 to 3 carbon atoms are particularly preferable, and aliphatic diamines having 2 carbon atoms are preferable. Most preferred.
  • TME DA tetramethylethylenediamine
  • DABCO 1,4 diazabicyclo [2,2,2] octane
  • the above-mentioned complexing agent preferably an amide compound, can be one kind or a mixture of two or more kinds as necessary.
  • an industrially preferred organometallic compound containing a Group IA metal and a complexing agent for preparing the polymerization catalyst used in the production method of the present invention includes methyllithium (MeLi), ethyllithium (E t L i), n—Propyrrolitium (n—Pr L i), iso—Propyrrolitium (i—Pr L i), n Butynorerium (n—Bu L i), sec—Butinole Organometallic compounds containing at least one Group IA metal selected from lithium (s-BuLi), tert-butylinoleritium (t-BuLi) and cyclohexyllithium ( Especially organic lithium compounds), tetramethylethylenediamine (TMDMA), tetramethylethylenediamine (TMEDA), tetramethylpropylenediamine (TMPDA), tetramethylethylenediamine.
  • TMDMA tetramethylethylenediamine
  • Hexandiamine ( TMHDA) and 1,4 diazabicyclo [2,2,2] octane (DABCO) are at least one complexing agent (especially an amine compound).
  • the most preferred combination is selected from n-butyllithium (n-BuLi), sec-butynolelithium (s-BuLi) and tert-butyllithium (t-BuLi).
  • n-BuLi n-butyllithium
  • s-BuLi sec-butynolelithium
  • t-BuLi tert-butyllithium
  • organolithium compound tetrametyrethylendiamine
  • TEDA tetrametyrethylendiamine
  • the method for synthesizing the complex by reacting the organometallic compound containing a Group IA metal with the first complexing agent is not particularly limited, and conventionally known techniques can be applied as necessary.
  • a method of dissolving an organometallic compound in an organic solvent in a dry inert gas atmosphere and adding a solution of a complexing agent thereto to synthesize a basic complex or a method of dissolving a complex in a dry inert gas atmosphere.
  • a method of dissolving the agent in an organic solvent, adding a solution of an organometallic compound to the solution, and synthesizing a basic complex can be exemplified. The method is appropriately selected as necessary.
  • the temperature condition at which the organometallic compound reacts with the first complexing agent can be appropriately selected generally in the range of ⁇ 100 to 100 ° C. Industrially, carry out at room temperature to 80 ° C. It is most preferable to carry out in the range of room temperature to 60 ° C.
  • Helium, nitrogen, and argon are preferred as the dry inert gas, and industrially, nitrogen or argon is preferably used.
  • the above-mentioned basic complex is a complex formed by reacting the following organometallic compound containing a Group IA metal with a first complexing agent, and is an organometallic compound containing a Group IA metal.
  • organometallic compound containing a Group IA metal is an organometallic compound containing a Group IA metal.
  • it is considered to have an associated state of 2 to 10 molecules, preferably 2 to 8 molecules or more, particularly preferably 2 to 6 molecules or more.
  • the above complex is prepared by reacting at least one organometallic compound containing a metal of Group IA of the periodic table with at least one first complexing agent in a molar ratio represented by the following formula. You.
  • A, / B, 2 0 0/1 ⁇ : 1/1 0 0,
  • A, / B, 50 c ⁇ 1/20
  • A, / B, 20 Z l ⁇ : 1/10, Most preferably
  • A represents the molar amount of the group IA metal atom in at least one kind of organometallic compound used
  • B represents the molar amount of at least one kind of the first complexing agent used
  • a polymerization reaction is carried out by coexisting a complex obtained by reacting an organometallic compound containing a Group IA metal with a first complexing agent and a second complexing agent in the form of a mixture.
  • a complex obtained by reacting an organometallic compound containing a Group IA metal with a first complexing agent and a second complexing agent in the form of a mixture.
  • the following method can be cited as a specific method.
  • the above methods can be appropriately selected as necessary. However, when the polymerization reaction is carried out at a high temperature, particularly at a temperature of 60 ° C or more, the above methods (1) to (3) can be used. As shown, a method of polymerizing via a two-step process of forming a complex and mixing the complex with a second complexing agent is preferred.
  • the amount of the second complexing agent to coexist with the above complex in the form of a mixture is not particularly limited, but the above-mentioned compound is added to the catalyst of the reaction system at the time when the cyclic conjugated monomer starts to be polymerized.
  • At least one organometallic compound, at least one kind of the first complexing agent, and at least one kind of the second complexing agent exist in a molar ratio represented by the following formula. Is preferred.
  • a 3 / B 3 1 00Z l ⁇ 1/200
  • a 3 / B 3 8 0 1 to 1 1 0 0,
  • a 3 / B 3 50Zl ⁇ l Z80
  • a 3 ZB 3 20Z 1 ⁇ : 150
  • a 3 is the molar amount of Group IA metal atom of the organometallic compound in least one well of the catalyst
  • B 3 is first of least one to as first complexing agent and less of the kind also in the catalyst Shows the total molar amount of diluent).
  • a 3 / B 3 1 .2 5 Z 1 ⁇ 1 no 5
  • Ranges correct most preferred as an industrial production conditions (through re A 3 and B 3 as defined above).
  • the most preferred polymerization method in the present invention is a method comprising the steps of: forming at least one organometallic compound containing a metal belonging to Group IA of the periodic table and at least one first complexing agent; In this method, a complex is formed, and a polymerization reaction is performed using a polymerization catalyst obtained by mixing the complex with a second complexing agent.
  • a 2 / B 2 1/0 .25 to 1 1
  • a 2 represents the molar amount of the metal of the group IA in at least one kind of the organometallic compound in the complex
  • B 2 represents the molar amount of at least one kind of the first complexing agent in the complex.
  • n-butyllithium n—BuLi
  • sec—butynolerichium s—BuLi
  • a 2 mo 1 organic lithium compound selected from tert-butyllithium (t_BuLi) and tetramethylethylethylene diamine, which is the first complexing agent.
  • TM EDA tert-butyllithium
  • DABCO 1,4-diazabicyclo [2,2,2] octane
  • An example is a method of forming a complex composed of the following, and further performing a polymerization reaction under the conditions set in the above range and coexisting with the second complexing agent.
  • a complex represented by the following formula (II) can be preferably exemplified as a complex structure.
  • G represents one or more kinds of organic metal compounds containing a Group IA metal.
  • J represents the first complexing agent.
  • g, j, and k are integers of 1 or more.
  • the complex synthesized by the above method is considered to be in a thermally unstable state and stabilized by the second complexing agent. Especially 60. Even under a temperature condition of C or higher, living anion polymerization of a cyclic conjugated diene monomer can be performed. In addition, it becomes possible to produce a cyclic conjugated polymer having a narrow molecular weight distribution even under a temperature condition of room temperature or higher.
  • the type of the second complexing agent coexisting with the basic complex is not particularly limited because it can be variously set according to the purpose, and the complexing agent used for the synthesis of the basic complex is not limited. Although they may be the same or different, it is economically advantageous that they are the same.
  • the type of polymerization in the production method of the present invention is not particularly limited, and gas phase polymerization, bulk polymerization (bulk polymerization), solution polymerization, or the like can be appropriately selected and employed.
  • a polymerization reaction process for example, a batch type, a semi-batch type, a continuous type, or the like can be appropriately selected and used.
  • the polymerization reactor can also be selected as needed in accordance with the purpose and requirements.
  • Examples include an autoclave, a coil reactor, a tube reactor, a ladder, and an extruder. You.
  • polymerization solvents include butane, n-pentane, n-hexane, n-heptane, and n-octane.
  • Iso-butane, n-nonane, n-aliphatic hydrocarbon solvents such as decane, cyclopentane, methinoresicyclopentane, cyclohexane, methinoresicyclohexane, Alicyclic hydrocarbon solvents such as ethynolecyclohexane, cyclohexane, cyclooctane, decalin, and nonolebonorenan, benzene, toluene, xylene, Examples include aromatic hydrocarbon solvents such as ethyl benzene and cumene, and ether solvents such as dimethyl ether, tetrahydrofuran and tetrahydropyran. Yes, you can make a timely selection according to your purpose.
  • polymerization solvents may be one kind or, if necessary, a mixture of two or more kinds.
  • Preferred examples of the polymerization solvent include an aliphatic hydrocarbon-based solvent, an alicyclic hydrocarbon-based solvent, and an aromatic hydrocarbon-based solvent.
  • the most preferred polymerization solvent is an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, or a mixed solvent thereof.
  • the most preferred polymerization solvent in the production method of the present invention is at least one polymerization solvent selected from n-hexane, cyclohexane and methylcyclohexane, or a mixture of two or more thereof. Solvent.
  • the amount of the polymerization catalyst used cannot be particularly limited because it varies depending on the purpose.
  • the polymerization temperature in the polymerization reaction of the present invention is set to various ones as required, but is generally from 100 to 150 ° C, preferably from 180 to 120 ° C. C, particularly preferably 30-30 It can be performed at 0 ° C, most preferably in the range of 0 to 100 ° C.
  • the polymerization reaction it is preferable to carry out the polymerization reaction at room temperature to 90 ° C, particularly preferably at 30 to 85 ° C, and more preferably at 40 to 80 ° C. Range is most preferred.
  • the time required for the polymerization reaction varies depending on the purpose and the polymerization conditions and cannot be particularly limited, but is usually 48 hours or less, particularly preferably 0.5 to 24 hours. In practice, it is most industrially preferable to carry out the treatment in the range of 1 to 10 hours.
  • the atmosphere of the reaction system in the polymerization reaction is preferably an inert gas such as helium, nitrogen, argon, etc., and is dried to + minutes and has a high purity with little impurities such as oxygen and carbon dioxide. It is particularly desirable that the inert gas be an inert gas.
  • the pressure of the polymerization reaction system may be controlled within the above-mentioned polymerization temperature range within a pressure range necessary for maintaining each monomer and polymerization solvent in a liquid phase, and may be appropriately set as necessary. Can be.
  • it is necessary to keep the polymerization system free from impurities that inactivate the polymerization catalyst and the growth (active) terminal, such as water, oxygen, and carbon dioxide. It is preferable to obtain a predetermined polymer.
  • the cyclic conjugated polymer is usually used when recovering a polymer from a polymer solution (reaction solution) of a known polymer.
  • reaction solution a polymer solution of a known polymer.
  • Conventionally known techniques can be employed.
  • a steam coagulation method in which the reaction solution is brought into direct contact with steam
  • a reprecipitation method in which a polymer poor solvent is added to the reaction solution to precipitate the polymer
  • a method in which the reaction solution is heated in a vessel to distill off the solvent A method in which the reaction solution is brought into contact with a heating roll to distill off the solvent, a method in which the solvent is distilled off with a vented extruder until pelletization, and a method in which the polymer solution is put into warm water and then extruded with a vent.
  • the most suitable method can be adopted depending on the properties of the cyclic conjugated gen-based polymer and the solvent used. .
  • a hydrogenation, a halogenation, a hydrogen halide, an alkylation, an arylation, a ring opening and a dehydrogenation may be further selected. It is also possible to carry out one kind of reaction.
  • the production method of the present invention comprises a step of performing a polymerization reaction and then performing a hydrogenation reaction
  • the polymerization reaction is carried out and the polymerization in which a cyclic conjugated monomer unit is contained in the polymer main chain.
  • a hydrogenation reaction is carried out in the presence of a hydrogenation catalyst to hydrogenate some or all of the carbon-carbon unsaturated bonds contained in the polymer, and the hydrogenated cyclic conjugated system You can get united.
  • the polymerization is carried out after a polymerization reaction of a force comprising a cyclic conjugated monomer unit or a polymer containing the same attains a predetermined (target) polymerization rate.
  • the reaction is stopped, a hydrogenation catalyst is added to the reactor ⁇ , hydrogen gas is introduced, and a hydrogenation reaction is subsequently carried out to produce a hydrogenated cyclic conjugated polymer.
  • the polymerization reaction can be stopped by a conventional method, a hydrogenation catalyst can be added to the same reactor where the polymerization reaction has been performed, and hydrogen can be introduced.
  • the polymerization reaction is stopped by a conventional method using a polymerization catalyst, the polymer solution is transferred to a different reactor from the polymerization reaction, a hydrogenation catalyst is added into the reactor, and hydrogen is introduced into the reactor.
  • a method of continuously producing a hydrogenated polymer by performing a polymerization reaction and a hydrogenation reaction continuously in a tube-type reactor can be exemplified.
  • the hydrogenation reaction is carried out in the presence of a polymer to be hydrogenated and a hydrogenation catalyst in a hydrogen atmosphere.
  • a polymer solution is maintained at a predetermined temperature in an atmosphere of hydrogen or an inert gas, and a hydrogenation catalyst is added with or without stirring. After the reaction temperature is maintained, hydrogen gas is introduced and pressurized to a predetermined pressure.
  • the hydrogenation reaction type a conventionally known technique can be adopted.
  • any of a batch system, a semi-batch system, a continuous system, or a combination thereof can be used as needed.
  • the hydrogenation catalyst that can be used in the hydrogenation reaction of the present invention is a catalyst that can obtain a required hydrogenation rate.
  • a substantially homogeneous hydrogenation catalyst organometallic compound, containing at least one metal selected from the group IVA to group IV metals or rare earth metals in the periodic table
  • organometallic complexes organometallic complexes
  • heterogeneous hydrogenation catalysts solid catalysts, supported catalysts
  • the most preferred hydrogenation catalyst in the present invention is a homogeneous hydrogenation catalyst, that is, an organometallic compound or an organometallic complex selected from IVA to Yin group metals or rare earth metals, or a vm group metal carrier. It is a supported catalyst (solid catalyst).
  • organometallic compounds and organometallic complexes which are preferred homogeneous hydrogenation catalysts are also particularly limited to being supported on inorganic compounds such as silica, zeolite, cross-linked polystyrene, or organic polymer compounds. It is not something that is done.
  • Examples of particularly preferred metals contained in the hydrogenation catalyst used in the present invention include titanium, konole, nickele, norethenium, orifice, and palladium.
  • ligands such as hydrogen, halogen, nitrogen compounds and organic compounds are coordinated or bonded.
  • ligands may be used alone or, if necessary, in combination of two or more types. Combinations are particularly preferred.
  • One or more hydrogenation catalysts may be used as needed.
  • the use in combination is not particularly limited.
  • the hydrogenation catalyst at least one kind of an organometallic compound or an organometallic complex selected from IVA to VI group metals or rare earth metals, and alkyllithium and alkylmagnesium are used. IA of alkyl aluminum, etc.!
  • the use of a combination of at least one organometallic compound selected from Group III and Group IV metals is the most industrially preferred method.
  • the hydrogenation catalyst is a solid catalyst
  • Preferred solid catalysts include rhenium, iron, cobalt, nickel, noretenium, rhodium, and no. It is possible to exemplify a supported catalyst containing at least one metal selected from radium and platinum, particularly preferably at least one metal selected from noletenium, rhodium and palladium. Examples of supported catalysts that can be included can be given.
  • the amount of the hydrogenation catalyst used in the hydrogenation reaction depends on the type of the polymer to be hydrogenated (polymer main chain structure). , Molecular weight, etc.) or hydrogenation conditions (solvent, temperature, concentration, solution Viscosity, etc.), but in general, the metal atom concentration is 0.:!
  • OOO ppm preferably 1 ppm for the polymer to be hydrogenated. Used in the range of ⁇ 50, OOO ppm, more preferably in the range of 5 ⁇ : 10, OOO ppm, particularly preferably in the range of 10 ⁇ , L0, OOO ppm. You.
  • the solvent be inert to the hydrogenation catalyst, highly soluble in the polymer to be hydrogenated.
  • aliphatic hydrocarbon-based solvents aliphatic hydrocarbon-based solvents, alicyclic hydrocarbon-based solvents, and aromatic hydrocarbon-based solvents are preferred, and aliphatic hydrocarbon-based solvents or alicyclic hydrocarbon-based solvents, or These mixed solvents are most preferred.
  • the hydrogenation reaction is carried out in the same solvent used for the polymerization reaction. It is most preferable to do it.
  • the concentration of the polymer solution during the hydrogenation reaction is particularly limited However, it is usually preferably 1 to 90 wt%, more preferably 2 to 60 wt%, and particularly preferably 3 to 40 wt%.
  • the concentration of the polymer solution is low, the operation efficiency for the hydrogenation reaction is low, which is economically disadvantageous. If the concentration is high, the viscosity of the polymer solution increases and the reaction rate decreases. The result is unfavorable.
  • the temperature of the hydrogenation reaction may be appropriately set as necessary, but is generally in the range of 170 to 500 ° C, preferably in the range of 110 to 300 ° C. There, particularly preferred properly is 2 0 ⁇ 2 5 0 ° no sufficient reaction rate can be obtained when c reaction temperature is C is too low, whereas, if the reaction temperature is too high hydrogenation catalyst loss Or undesired results such as degradation of the polymer.
  • the pressure of the hydrogenation reaction in the production method of the present invention is in the range of 0.1 to 500 kg / cm 2 G, preferably:! 4400 kg / cm 2 G, particularly preferably 2 3300 kg Z cm 2 G.
  • the time required for the hydrogenation reaction cannot be particularly limited because it is related to the amount and type of the hydrogenation catalyst, or the concentration of the polymer solution, and the temperature and pressure of the reaction system, but is usually 5 minutes. It can be carried out for up to 240 hours, preferably from 10 minutes to 100 hours, particularly preferably from 30 minutes to 48 hours.
  • the hydrogenation catalyst After completion of the hydrogenation reaction, the hydrogenation catalyst is used, if necessary, by adsorption separation using an adsorbent, sedimentation separation, separation by filtration, water or lower alcohol in the presence of an organic acid and / or an inorganic acid. It can be separated and recovered from the reaction solution by a conventionally known means such as a washing and removing method.
  • a steam coagulation method in which the reaction solution is brought into direct contact with steam
  • a reprecipitation method in which a poor solvent for the polymer is added to the reaction solution to precipitate the polymer
  • a method in which the reaction solution is heated in a vessel to distill off the solvent A method in which the reaction solution is brought into contact with a heating roll to distill off the solvent, a method in which the solvent is distilled off with a vented extruder, and a process is carried out up to pelleting.
  • An example is a method in which the solvent and water are distilled off using an extruder with a vent to perform pelletization, and the like.
  • the most appropriate method can be adopted accordingly.
  • Polymer obtained by hydrogenating monomer unit A of a cyclic conjugated polymer having a high content of 1,2-bonded monomer unit A obtained by the polymerization method of the present invention Is the most industrially preferred material with particularly high thermal and mechanical properties.
  • the above hydrogenation reaction and Z or other addition reaction, or the reaction selected from the elimination reaction and the ring opening reaction can be appropriately selected and carried out. However, it is preferable to carry out the optimal reaction according to the purpose.
  • a dehydrogenation reaction can be exemplified as a more specific and preferable example of the elimination reaction for a polymer, and this can be carried out by directly adopting a conventionally known technique. Can be done.
  • a cyclic conjugated polymer serving as a precursor is polymerized, and after continuous or cyclic conjugated polymer is separated and recovered, Continue This is a reaction for converting a part or all of the monomer units A contained in the polymer into an aromatic ring.
  • the dehydrogenation reaction of the present invention may be a conventionally known technique as it is, and is not particularly limited.
  • part or all of the monomer unit A in the polymer chain is an aromatic ring, preferably. It is desirable that it can be converted to a benzene ring.
  • the dehydrogenation reaction in the present invention may be a catalytic reaction or a stoichiometric reaction.
  • the cyclic conjugated diene-based polymer as a precursor is directly used as it is, After diluting with a solvent, preferably an organic solvent, a dehydration catalyst, a dehydrogenating reagent and the like are added as necessary, and the reaction is carried out under predetermined conditions.
  • the form of the dehydrogenation reaction of the present invention is a method of directly extracting a hydrogen atom or a molecule from a monomer unit in a polymer chain, or bonding with another compound such as hydrogen halide or hydrogen sulfonate.
  • Conventionally known reaction forms such as a method of pulling out in a state in which the reaction is performed or a method of pulling out by a disproportionation reaction, can be adopted as necessary.
  • a simple dehydrogenation reaction using a generally available reagent a method using quinones (quinones) as a dehydrogenation reagent can be exemplified.
  • Typical quinones include 1,4-benzoquinone (quinonone), tetrachlorone 1,2—benzoquinone (0-chloraninole), and tetraquinone.
  • Rolls 1 and 4 benzoquinone (p — kuroraninole), Tetrabromo-1,2—benzoquinone (0—bromanil), Tetrabromo-1,4,1 Benzoquinone (p—bromaninole), Tetrafluoro1,2—benzoquinone, Trafnoroleol 1,4 Benzoquinone, Tetraido 1,2 — Benzoquinone, Tetraido 1,4 —Benzoquinone, Tetrahydroxy 1,4 Benzoquinone, 2, 3 — dichloro-5, 6 — dicyano p — benzoquinone, 1, 2 — naphthoquinone, 1, 4-naphthoquinone, anthraquinone, one-cro
  • 1,4 benzoquinone (quinone), tetrachlorone 1, 2-benzoquinone ( o —Krorael), Tetraclo 1-, 4-benzobenzonin (p—Krolaninole), Tetrabromo 1,2—Benzoquinone (o—Bromaninore), Tetrabro It is preferable to use mo 1,4-benzoquinone (p-bromanyl), and it is most preferable to use tetraclo 1,4-benzoquinone (p-chloranil). New
  • the dehydrogenation reaction of the present invention is performed by dissolving the cyclic conjugated polymer in an organic solvent and performing the dehydrogenation reaction
  • the type and amount of the precursor are not particularly limited as long as they sufficiently dissolve the cyclic conjugated polymer as a precursor, and may be appropriately determined according to the solubility of the cyclic conjugated polymer. Just choose
  • organic solvents examples include butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane, and n-decane.
  • Aliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethinolecyclohexane, cycloheptane, cyclooctane, deca Alicyclic hydrocarbon solvents such as phosphorus and nonolebornane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and cumene, diethyl ether, tetra Ether solvents such as hydrofuran and tetrahydropyran, such as chloroform, methylene chloride, chlorobenzene, dichlorobenzene and trichlorobenzene.Halogenated hydrocarbon solvents and the like can be exemplified.
  • the reaction temperature in the dehydrogenation reaction is set to various values as necessary, but is generally 0 to 350 ° C, preferably 0 to 300 ° C, and particularly preferably. 0 to 250 ° C (: Most preferably, it can be carried out in the range of 0 to 200 ° C. From an industrial point of view, it is carried out in the range of room temperature to 200 ° C. It is advantageous to do so.
  • the time required for the dehydrogenation reaction depends on the purpose and reaction conditions. However, it is not particularly limited because it is variously different, but is usually within 48 hours, and is particularly preferably performed in the range of 1 to 24 hours.
  • the atmosphere in the dehydrogenation reaction system is preferably an inert gas such as nitrogen, argon, or helium, particularly an inert gas that is sufficiently dry and high in purity to suppress side reactions.
  • an inert gas such as nitrogen, argon, or helium, particularly an inert gas that is sufficiently dry and high in purity to suppress side reactions.
  • the pressure of the reaction system is not particularly limited, as long as it is within a range of pressure sufficient to maintain the catalyst, the reagent, the solvent, and the like in the liquid phase within the above reaction temperature range.
  • impurities which inactivate the dehydrogenation catalyst and the dehydrogenation reagent, or cause the cyclic conjugated gen-based polymer as a precursor to be decomposed or decomposed for example, water, oxygen, It is preferable to carry out the dehydrogenation reaction while taking care not to mix the carbon dioxide gas.
  • a conventionally known technique which is usually used when recovering a polymer from a polymer solution of a known polymer.
  • it can.
  • a steam coagulation method in which a reaction solution is brought into direct contact with steam
  • a reprecipitation method in which a polymer poor solvent is added to a reaction solution to precipitate a polymer
  • a method in which a reaction solution is heated in a vessel to distill off the solvent A method in which the reaction solution is brought into contact with a heating roll to distill off the solvent, a method in which the solvent is distilled off using a vented extruder, and a process is performed until pelletization. Examples of the method include pouring the polymer solution into warm water, and then distilling off the solvent and water with a vented extruder to perform pelletization, and the like. The most suitable method can be adopted depending on the nature of the solvent.
  • examples of the ring opening reaction in the production method of the present invention include an ozone oxidation reaction and a nitric acid oxidation reaction.
  • the cyclic conjugated polymer obtained by the production method of the present invention may be a stabilizer such as a heat stabilizer, an antioxidant, or an ultraviolet absorber, a lubricant, a nucleating agent, a plasticizer, or a dye, depending on its purpose and application.
  • a stabilizer such as a heat stabilizer, an antioxidant, or an ultraviolet absorber
  • a lubricant such as a lubricant, a nucleating agent, a plasticizer, or a dye
  • Pigments, bridging agents, foaming agents, antistatic agents, antislip agents, antiblocking agents, release agents, other polymeric materials, inorganic reinforcing materials (glass fillers, mineral fibers , Inorganic fillers, etc.) is not particularly limited to contain additives, reinforcing agents, etc. which are added to and blended with general polymer materials.
  • Known stabilizers such as heat stabilizers, antioxidants, and ultraviolet absorbers can be used as they are.
  • heat stabilizers such as phenolic, organic phosphate, organic phosphite, organic amide, organic thio, etc., antioxidants and ultraviolet absorbers are used. It is possible to do.
  • the amount of a stabilizer such as a heat stabilizer, an antioxidant, or an ultraviolet absorber is generally used in the range of 0.001 to 10 wt% with respect to the cyclic conjugated polymer.
  • Cyclic conjugated diene polymerization obtained by the production method of the present invention The body can be used as a single material or as a composite material with other polymer materials (including cyclic conjugated gen-based polymers), inorganic reinforcing materials, and organic reinforcing materials, depending on the purpose and application. It is also possible to use.
  • the other polymer material to be compounded may be a conventionally known organic polymer. It can be selected as needed, especially its type and quantity are not limited.
  • the cyclic conjugated polymer obtained by the production method of the present invention can be used as an excellent industrial material (such as a structural material or a functional material) as a high-performance plastic, a general-purpose plastic, a special elastomer, or a thermoplastic elastomer.
  • Thermosetting resins UV-curable resins, It can also be used as a curable resin such as an electron beam curable resin.
  • the chemicals used in the present invention were of the highest purity available. ⁇ General solvents were degassed according to conventional methods, refluxed and dehydrated over an active metal under an inert gas atmosphere, and then distilled and purified. Used.
  • the number average molecular weight (Mn) and molecular weight distribution (MwZn) of the polymer were measured using a liquid chromatograph (HLC-8082) manufactured by Tosoh Corporation of Japan. G.P.C. (gel permeation chromatography) using a column (Showex: K805 + K804 + K802) manufactured by K.K. The measured values in terms of standard polystyrene are shown.
  • Polymer chain structure analysis was performed using an NMR measuring device (JEOL 400, manufactured by JEOL, Japan). Measurement frequency, 4 0 0 MH z (1 H), is 1 0 0 MH z (13 C ).
  • the solvent at the time of measurement 0 - using Axis port opening benzene one d 4, sample concentration 1 0 wt%, was measured at 1 3 5 ° C.
  • the cyclohexane peak was referred to as 1.4 ppm.
  • the composition ratio of 1,2—bonds and 1,4—bonds can be determined.
  • H in 1.85 to 2.35 ppm was H (Ha) next to the olefin.
  • the ratio of 1, 2 — CHD is ⁇ , and 1.85 to 2.35 ⁇ ⁇ with respect to all the protons excluding the ones in the olefin part.
  • the ratio of the peak surface of H at m (Ha / Ha + Hb) is ⁇
  • the chemical shift of the polymerization catalyst (complex) was performed using an NMR measuring device (JEOL ⁇ -400) manufactured by JEOL, Japan. Measurement frequency, 4 0 0 MH z (1 H), 1 0 0 MH 2
  • the glass transition temperature (Tg) of the polymer was a value measured by the DSC method using DS200 manufactured by Seiko Electronic Industry Co., Ltd., Japan.
  • the conversion (mo 1%) of the monomer in the polymerization reaction system was measured using a gas chromatograph (GC14A) manufactured by Shimadzu Corporation, Japan, and remained in the reaction system. The value calculated by measuring the absolute amount of the used monomer (by the internal standard method) is shown. Ethylbenzene was used as the internal standard.
  • the mechanical and thermal practical properties of the polymer were measured by the following method.
  • the test was performed according to ASTM D790.
  • polycyclohexane-polyisoprene block copolymer is simply
  • CHD — Ip diblock copolymer Shown as "CHD — Ip diblock copolymer”. The same applies to other block copolymers.
  • N, N, N ', N'-tetramethylethylenediamine first complexing agent
  • TMEDA first complexing agent
  • n-BuLi n-butyllithium
  • TMEDA 4/2 (molar ratio).
  • reaction solution After heating and dissolving the reaction solution to 70 ° C, the reaction solution was gradually cooled to 178 ° C to precipitate a white (plate-like) crystal complex.
  • the obtained complex was taken out under a dry argon atmosphere, and washed repeatedly with cyclohexane to purify a white (plate-like) crystal complex.
  • 1,3-cyclohexadiene (1,3-CHD) is added to the cyclohexane solution of the mixture of the obtained complex and TMEDA.
  • the number-average molecular weight (Mn) of the obtained cyclohexadene (CHD) homopolymer was 9,700, and the molecular weight distribution (Mw
  • the 1,2-bond / 1,4-bond ratio of the cyclic conjugated gen-based monomer unit in the polymer was 56/44 (mo 1 ratio) and was measured by the DSC method.
  • the glass transition temperature (Tg) was 154 ° C.
  • 1,3-CHD (3.0 g) was added to a cyclohexane solution of a mixture of the obtained complex and MEDA, and a polymerization reaction was carried out at 70 ° C for 1 hour in a dry argon atmosphere. .
  • the reaction was stopped by adding a 10 wt% methanol solution of BHT [2, 6-bis (t-butyl) 14-methinoref enole], and a further large amount of methanol was added.
  • BHT 2, 6-bis (t-butyl) 14-methinoref enole
  • the polymer was separated with a mixed solvent of tanol / hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C to obtain a white polymer in a yield of 100 wt%.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 9
  • the molecular weight distribution (MwZMn) was 1.36.
  • the 1,2-bond Z1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 5149 (mo1 ratio), and the glass transition temperature measured by the DSC method. (T g) is 152. It was C.
  • 1,3-CHD3.Og was added, and a polymerization reaction was carried out at room temperature for 6 hours in a dry argon atmosphere. Immediately after the start of the reaction, the anion color disappeared.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 3
  • the molecular weight distribution (MwZMn) is 2.89. Was.
  • the 1,2-bond / 1,4-single bond ratio of the cyclic conjugated diene monomer unit in the polymer is 595 (mol ratio), and the glass transition temperature (T g) was only 88 ° C.
  • 1,3-CHD3.Og was added, and a polymerization reaction was carried out at 40 ° C for 6 hours under a dry argon atmosphere. Immediately after the start of the reaction, the anion color disappeared.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 2
  • the molecular weight distribution (MwZMn) was 2.92.
  • the 1,2—bond 1,4—bond ratio of the cyclic conjugated diene monomer unit in the polymer is 298 (mol ratio), and the DSC
  • Tg glass transition temperature measured by the method was only 87 ° C.
  • 1,3-CHD3.Og was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA, and a polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere. After the completion of the polymerization reaction, the reaction was stopped by adding 10 wt% of a methanol solution of BHT [2,6-bis (t-butyl) -141-methylphenol], and a further large amount was added. The polymer was separated with a mixed solvent of methanol Z hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C. All yields 100 wt%.
  • the i, 2—bond / 1,4 single bond ratio of the cyclic conjugated gen-based monomer unit in the polymer is 48/52, 51/49, 52/48, 54 /, respectively. It was 46 (mol ratio).
  • 1,3-CHD3.Og was added, and a polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere. After the completion of the polymerization reaction, the reaction was stopped by adding a 10 wt% methanol solution of BH-cho [2,6-bis (t-butyl) -141-methylphenol], and then a larger amount of methanol was added. The polymer was separated with a mixed solvent of ethanol and hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C.
  • N, N, N ', N', —tetramethyl propylenediamine (TMPDA) (first complexing agent) is dissolved in cyclohexane, and 1.0 M of TMPDA is dissolved.
  • TMPDA tetramethyl propylenediamine
  • 1,3-CHD (3.0 g) was added to a cyclohexane solution of the mixture of the obtained complex and TMPDA, and a polymerization reaction was carried out at 40 ° C for 4 hours in a dry argon atmosphere. Polymerization reaction completed After that, the reaction was stopped by adding a 10% by weight methanol solution of BH-cho [2,6-bis (t-butyl) -14-methylphenol] to stop the reaction. The polymer was separated with a mixed solvent of hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C. The yield was 100 wt%.
  • the 1,2 single bond Zl, 4 single bond ratio of the cyclic conjugated gen-based monomer unit in the obtained polymer was 47 Z53 (mo1 ratio).
  • TM EDA second complexing agent
  • hexane a 1.0 M solution of TM EDA (second complexing agent) in hexane was added after changing the amount of TM EDA (second complexing agent) added. And a mixture of TM EDA and hexane were obtained.
  • 1,3-CHD3.Og was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA, and a polymerization reaction was carried out at 60 ° C for 4 hours in a dry argon atmosphere. After the polymerization reaction is completed, BHT [2,6-bis (t-butyl)
  • the 1,2—bond / 1,4—bond ratio of the cyclic conjugated diene monomer unit in the obtained polymer is 4456, 522/48,
  • 1,3-CHD3.Og was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA, and a polymerization reaction was carried out at 40 ° C for 4 hours in a dry argon atmosphere.
  • the reaction was stopped by adding a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -41-methylphenol], and a larger amount of methanol Z was added.
  • BHT 2,6-bis (t-butyl) -41-methylphenol
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is the number average molecular weight (Mn) of the obtained CHD homopolymer.
  • the molecular weight distribution (MwZM n) was 1.09, which was 9,750.
  • the 1,2—bond 1,4 bond ratio of the cyclic conjugated diene monomer unit in the polymer is 550 (mo 1 ratio), and the glass transition temperature measured by the DSC method. (T g) was 156 ° C.
  • a polymerization reaction was carried out in the same manner as in Example 13 except that the reaction temperature between n-BuLi and TMEDA was 60 ° C.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 2
  • the molecular weight distribution (MwZMn) was 1.26.
  • 1, 2 —bond / of cyclic conjugated diene monomer unit in polymer The 1,4 bond ratio was 52Z48 (m01 ratio), and the glass transition temperature (Tg) measured by the DSC method was 1550C.
  • a polymerization reaction was carried out in the same manner as in Example 13 except that the reaction temperature of n-BuLi and TMEDA was set at 40 ° C.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 2
  • the molecular weight distribution (MwZMn) is 1.14
  • the 1 ⁇ 2 —bond Z 1,4 bond ratio of the cyclic conjugated diene monomer unit in the polymer is 54/46 (mol ratio), and the glass transition temperature measured by the DSC method. (T g) was 159 ° C.
  • 1,3-CHD3.Og was added, and the polymerization reaction was carried out at room temperature for 6 hours in a dry argon atmosphere. Immediately after the start of the reaction, the anion color disappeared. After the completion of the polymerization reaction, BHT [2, 6-bis (t_butyl)-4-methylphenol] was added to add a 10 wt% methanol solution to stop the reaction. The polymer was separated with a mixed solvent of ethanol and hydrochloric acid, washed with methanol, and dried at 80 ° C under vacuum. The yield was only 18 wt%.
  • the number average molecular weight (Mn) of the obtained CHD homopolymer was 2
  • the molecular weight distribution (Mw ZM n) was 3.19.
  • the 1,2-bond 1,4 single bond ratio of the cyclic conjugated gen-based monomer unit in the polymer is 2/98 (mol ratio), and the glass transition temperature measured by the DSC method. (T g) was only 87 ° C.
  • isoprene (Ip) 21.Og was added, and the polymerization reaction was carried out at 40 ° C for 1 hour in a dry argon atmosphere, thereby synthesizing a CHD-Ip diblock copolymer. .
  • the reaction was stopped by adding a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -14-methylphenol], and a further large amount of methanol Z was added.
  • BHT 2,6-bis (t-butyl) -14-methylphenol
  • methanol Z was added.
  • the polymer was separated with a mixed solvent of hydrochloric acid, washed with methanol, and dried in vacuum at 60 ° C. to obtain a viscous polymer in a yield of 100 wt%.
  • the number average molecular weight (Mn) of the obtained CHD-Ip-CHD triblock copolymer was 9,890, and the molecular weight distribution (Mw / Mn) was 1.04.
  • the 1,2-bond ⁇ 1,4 single bond ratio of the cyclic conjugated diene monomer unit in the polymer was 43 357 (mo1 ratio).
  • TM EDA first complexing agent
  • TM EDA second complexing agent
  • TME DA second complexing agent
  • m-DIPB m-diisopropenylbenzene
  • the reaction was stopped by adding a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -14-methylphenol], and furthermore, a large amount of methanol Z hydrochloric acid was added.
  • BHT 2,6-bis (t-butyl) -14-methylphenol
  • methanol Z hydrochloric acid was added.
  • the polymer was separated with a mixed solvent, washed with methanol, and dried in vacuum at 60 ° C to obtain a polymer exhibiting rubber elasticity with a yield of 100 wt%.
  • the number average molecular weight (Mn) of the obtained CHD—Ip—CHD triblock copolymer is 19,890, and the molecular weight distribution
  • TMEDA first complexing agent
  • 1,3-CHD (3.0 g) was added to a cyclohexane solution of a mixture of the obtained complex and TMEDA, and a polymerization reaction was carried out at 40 ° C for 6 hours in a dry argon atmosphere. After the completion of the polymerization reaction, the reaction was stopped by adding a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -41-methyl phenol], and a larger amount of methanol / The polymer was separated with a mixed solvent of hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C to obtain a white polymer in a yield of 10 O wt%.
  • BHT 2,6-bis (t-butyl) -41-methyl phenol
  • the number average molecular weight (Mn) of the obtained CHD homopolymer is 4
  • the molecular weight distribution (MwZMn) was 1.21.
  • the 1,2-linkage 1,4-linkage ratio of the cyclic conjugated diene monomer unit in the polymer was 51-49 (mol ratio), and the glass transition was measured by the DSC method.
  • the temperature (Tg) was 165 ° C.
  • TM tensile modulus
  • the UV spectroscopy confirmed that 72% of the cyclohexene unit was a cyclic conjugated polymer converted to a benzene ring.
  • TMEDA second complexing agent
  • the reaction solution is pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated to the same mo 1 as Li atoms.
  • the polymerization reaction was stopped by adding butanol, and the polymer solution was used as a stabilizer as a stabilizer manufactured by Ciba Geigy Co., Ltd., Switzerland [Inorega Knox B 215 (003 HX)] And remove the solvent according to a conventional method to obtain a CHD homopolymer. -Got it.
  • the number average molecular weight (Mn) of the obtained polymer was 20 and 100, and the molecular weight distribution was (MwZMn) 1.27.
  • the 1,4 single bond ratio was 48 to 52 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method was 151. It was C.
  • the autoclave was maintained at 60 ° C., and an additional force D of 1.1.25 mmol of TMEDA (second complexing agent) was applied.
  • the reaction solution is pumped to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated to the same degree as Li atoms.
  • Add butanol The polymerization reaction was stopped, and [Inoreganox B215 (003HX)] manufactured by Ciba Geigy Co., Ltd., Switzerland, was added as a stabilizer to the polymer solution, and the mixture was treated according to a conventional method. The solvent was removed to obtain a CHD homopolymer.
  • the obtained polymer had a number average molecular weight (Mn) of 20 and 500, and a molecular weight distribution (MwZMn) of 1.29.
  • the 1,2-bond Z1,4 bond ratio of the cyclic conjugated diene monomer unit in the polymer is 50 to 50 (mol ratio), and the glass transition temperature measured by the DSC method. (Tg) was 152 ° C.
  • TMEDA second complexing agent 11.25 mmo 1 was additionally added.
  • the number-average molecular weight (Mn) of the obtained assemblage was 20 and 200, and the molecular weight distribution (Mw / Mn) was 1.23.
  • the 1,4 single bond ratio is 6139 (mol ratio), and the glass transition temperature (g) measured by the DSC method is 158. It was C.
  • TC titanocene dichloride
  • DIBAL-H diisobutylanolenemium hydride
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was carried out at a hydrogen pressure of 35 kg Z cm 2 G for 6 hours.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated was 67 m 0 I%, which was calculated by ⁇ -NMR measurement.
  • the number average molecular weight (Mn) of the obtained polymer was 21 and 400, and the molecular weight distribution (MwZMn) was 1.22.
  • the glass transition temperature (Tg) measured by the DSC method was 201 ° C.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated which was calculated by 1 H-NMR measurement, was 100%.
  • the number average molecular weight (M n) of the obtained polymer was 20 and 800, and the molecular weight distribution (Mw / M n) was 1.24.
  • the glass transition temperature (Tg) measured by the DSC method was 23 ° C.
  • Cyclohexane (2400 g) was introduced into the autoclave and kept at room temperature under dry nitrogen.
  • TMEDA second complexing agent
  • 1,3-CHD 600 g was introduced into an autoclave and the polymerization reaction was carried out at 40 ° C for 4 hours.
  • the G, C. analysis showed that the 1,3--1 ⁇ 0 conversion after 4 hours was 97.4 mol%.
  • 700 g of cyclohexane was introduced to dilute the reaction solution, the temperature was raised to 80 ° C, and then another (fully dried according to a conventional method) with an electromagnetic induction stirrer 5 L
  • the reaction solution is pumped into a high pressure autoclave, and the polymerization reaction is stopped by adding dehydrated n-heptanol of the same mo1 as Li atoms, and the polymer solution is swirled as a stabilizer to the polymer solution.
  • [Inoreganox B215 (003HX)] manufactured by Ciba-GaiGi Co., Ltd. was added thereto, and the solvent was removed according to a conventional method to obtain a CHD homopolymer.
  • the number average molecular weight (Mn) of the obtained polymer was 43,800, and the molecular weight distribution (Mw / Mn) was 1.28.
  • the 1,2—bond / 1,4—bond ratio in the cyclic conjugated diene monomer unit in the polymer is 58 to 42 (mol ratio), and the glass measured by the DSC method.
  • the transition temperature (Tg) was 167 ° C.
  • TM tensile modulus
  • the heat distortion temperature (HDT: 1.82 Pa) was 1331 ° C.
  • TMEDA second complexing agent
  • 1,3-CHD600 g was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C for 6 hours.
  • the number average molecular weight (Mn) of the obtained polymer was 81,800, and the molecular weight distribution (MwZMn) was 1.32.
  • the 1,2—bond 1,4 bond ratio of the cyclic conjugated diene monomer unit in the polymer is 6337 (mo 1 ratio), and the glass was measured by the DSC method.
  • the transition temperature (Tg) was 171 ° C.
  • the heat distortion temperature (HDT: 1.82 MPa) was 135 ° C.
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was performed at a hydrogen pressure of 35 kg Z cm 2 G for 10 hours.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated was 87 m 0 1%.
  • the number average molecular weight (Mn) of the obtained polymer was 45,300, and the molecular weight distribution (MwZMn) was 1.27.
  • the glass transition temperature (Tg) measured by the DSC method was 228 ° C.
  • the heat distortion temperature (HDT: 1.82 MPa) is 188.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated was 79 mol 1%.
  • the number average molecular weight ( ⁇ ) of the obtained polymer was 83,600, and the molecular weight distribution (M w ZM n) was 1.41.
  • the glass transition temperature (T g) measured by the DSC method was 23 ° C.
  • the heat distortion temperature (HDT. 82 MPa) was 190 ° C.
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was carried out at a hydrogen pressure of 55 kg Z cm 2 G for 6 hours.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated which was calculated by '% -NMR measurement, was 10 Omo]%.
  • the number average molecular weight (Mn) of the obtained polymer was 44,100, and the molecular weight distribution (MwZMn) was 1.23.
  • the glass transition temperature (Tg) measured by the DSC method was 236 ° C.
  • the heat distortion temperature (HDT: 1.82 Pa) was 1992 ° C.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated was 100 mol%.
  • the number average molecular weight (Mn) of the obtained polymer was 82,700, and the molecular weight distribution (Mw / Mn) was 1.25.
  • the glass transition temperature (Tg) measured by the DSC method was 238 ° C.
  • the polymer flexural strength (FS) is 4 8 6 4 P a.
  • FS polymer flexural strength
  • FM flexural modulus
  • the heat distortion temperature (HDT: 1.82 MPa) was 198 ° C.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated was 100 mo 1%.
  • the number average molecular weight (Mn) of the obtained polymer was 81,900, and the molecular weight distribution (MwZMn) was 29.
  • D S The number average molecular weight (Mn) of the obtained polymer was 81,900, and the molecular weight distribution (MwZMn) was 29.
  • the glass transition temperature (Tg) measured by Method C was 238 ° C.
  • Example 3 2 Except that the carrier of the hydrogenation catalyst silica mosquito (S i ⁇ 2) and performed a hydrogenation reaction in the same manner as the actual ⁇ 2 9.
  • the hydrogenation rate of the double bond contained in the polymer to be hydrogenated which was calculated from the NMR spectrum, was 100%.
  • the number average molecular weight (Mn) of the obtained polymer was 82,100, and the molecular weight distribution (MwZMn) was 1.33.
  • the glass transition temperature (Tg) measured by the DSC method was 238 ° C.
  • Cyclohexane (2400 g) was introduced into the autoclave and kept at room temperature under dry nitrogen.
  • TMEDA second complexing agent 9.0 mmo
  • the 1,2-bonded 1,4 bond ratio of the cyclic conjugated diene monomer unit in the polymer is 640 (mol ratio), and the glass transition temperature (mol. T g) is 7 at 170 ° C.
  • Co (acac) 3 and TIBAL (triisobutylaluminum) were used as hydrogenation catalysts.
  • a catalyst solution prepared by adding (acac) 3 / TIBAL 1/6 (molar ratio) to cyclohexane was added to the polymer so as to have an addition force of 100 ppm with respect to the polymer.
  • the autoclave was replaced with hydrogen, the temperature was raised to 185 ° C, and the hydrogenation reaction was performed at a hydrogen pressure of 50 kg Z cm 2 G for 4 hours. After completion of the hydrogenation reaction, the autoclave was cooled to room temperature, and the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen.
  • TIBAL was treated by adding methanol according to a conventional method.
  • the hydrogenation rate of the cyclohexene ring of the obtained polymer was 100, as calculated by 'H-NMR. /.
  • the number average molecular weight (Mn) was 50,700 and the molecular weight distribution (Mw / Mn) was 1.21.
  • the glass transition temperature (Tg) measured by the DSC method was 235.
  • Flexural strength of the polymer is 4 6 8 4 MP a.
  • ( 1 MP a 1 0. 2 0 kg - f Bruno cm 2), flexural modulus (FM) at 6, 9 7 4 MP a there were.
  • the heat distortion temperature (HDT: 1.82 MPa) was 195 ° C.
  • TMEDA second complexing agent 22.5 mmo 1 was additionally added.
  • 1,3—45 g of CHD was introduced into an autoclave, and the polymerization reaction was carried out at 40 for 1 hour.
  • 210 g of isoprene (Ip) was introduced into the autoclave, and the polymerization reaction was carried out at 40 ° C for 1 hour and 30 minutes, and CHD-Ip diblock copolymer was obtained.
  • Ip isoprene
  • 1,3-CHD 45 was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 3 hours to obtain a CHD—Ip-CHD triblock copolymer.
  • the reaction solution is pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydration of n-heptano of mo 1 and the like of Li atoms is performed. Then, the polymerization reaction was stopped by the addition of a catalyst.
  • the number average molecular weight (Mn) of the obtained polymer was 9,700, and the molecular weight distribution (MwZMn) was 1.14.
  • the 1,2-bond Z1,4-bond ratio of the cyclic conjugated gen-based monomer unit in the polymer was 48 Z52 (moI ratio).
  • TMEDA second Complexing agent 28.1 mmo 1 was additionally added.
  • a polymerization reaction was carried out for 30 minutes to obtain an Ip—CHD diblock copolymer.
  • the polymerization reaction was carried out at 40 ° C. for 1 hour and 30 minutes to obtain an Ip—CHD—Ip triblock copolymer.
  • reaction solution was pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydration of n-butane was carried out with the same mo 1 as Li atoms.
  • the polymerization reaction was stopped by the addition of a reaction mixture.
  • the number average molecular weight (Mn) of the obtained polymer was 8,200, and the molecular weight distribution (Mw / Mn) was 1.08.
  • the 1,4 single bond ratio was 43 to 57 (mo 1 ratio).
  • Example 3 6 The inside of a 5 L high pressure autoclave with a magnetic induction stirrer that had been sufficiently dried was replaced with dry nitrogen according to a conventional method.
  • TMEDA second complexing agent 22.5 mmo 1 was additionally added.
  • reaction solution was pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method),
  • the polymerization reaction was stopped by adding dehydrated n-heptanol of the same mol as the Li atom.
  • the number average molecular weight (Mn) of the obtained polymer was 10,500, and the poly-molecular weight distribution (Mw / Mn) was 1.04.
  • the 1,2-bonded 1,4-bonded ratio of the cyclic conjugated gen-based monomer unit in the polymer was 4.555 (mo 1 ratio).
  • TC titanocene dichloride
  • DIBAL-H diisobutylaluminum hydride
  • the hydrogenation rate of the isoprene (Ip) portion was 100 mol 1%, as calculated by 1H-NMR measurement, and the CHD portion was not hydrogenated.
  • TMEDA second complexing agent
  • reaction solution was pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptano with the same mo 1 as Li atoms. And the polymerization reaction was stopped.
  • the number average molecular weight (Mn) of the obtained polymer was 41,500, and the molecular weight distribution (Mw / Mn) was 1.31.
  • the 1,2—bond 1,4—bond ratio of the cyclic conjugated gen-based monomer unit in the polymer was 49/51 (m 01 ratio), and was determined by the DSC method.
  • the glass transition temperature (Tg) of the CHD block measured was 152 ° C.
  • TS tensile strength
  • IMPa 10.20 kg ⁇ f / cm 2
  • TE tensile elongation
  • FM flexural modulus
  • the Izod climbing strength was N.B. (without breaking).
  • n-BuLi was added in an amount of 10.0 mmoI in terms of lithium atom, and TMEDA (first complexing agent) 5.0 mmo1 was added, followed by stirring at room temperature for 10 minutes. .
  • TMEDA second complexing agent
  • reaction solution was diluted by adding 1000 g of cyclohexane, heated to 70 ° C, and then equipped with another (fully dried according to a conventional method) electromagnetic induction stirrer.
  • the reaction solution was pumped to a 5 L high-pressure autoclave, and the polymerization reaction was stopped by adding dehydrated n-heptanol of the same mo 1 as Li atoms.
  • the number average molecular weight (M n) of the obtained polymer was 62,000, and the molecular weight distribution (Mw / M n) was 1.44.
  • the 1,2-bond Zl, 4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 48Z52 (molar ratio), which is the value of the CHD block measured by the DSC method.
  • the glass transition temperature (Tg) was 151 ° C.
  • TS tensile strength
  • TMEDA second complexing agent
  • 1,3-CHD 300 g and Ip300 g were mixed, introduced into an autoclave, and polymerized at 40 ° C. for 6 hours.
  • the number average molecular weight (Mn) of the obtained polymer was 40,100, and the molecular weight distribution (Mw / Mn) was 1.49.
  • the 1,2—bond 1,4—bond ratio of the cyclic conjugated diene monomer unit in the polymer is 51-49 (mo 1 ratio), and CHD is measured by the DSC method.
  • the glass transition temperature (Tg) of the block was 153 ° C.
  • the Izod (Izod) impact strength was NB (not broken).
  • the polymerization reaction was carried out in the same manner as in Example 38, except that the mixed monomer of 1,3-CHD480 g and Ipl20 g was used. 1, 3 after 6 hours by GC analysis. The 1 ⁇ 0 conversion was 96.6 m 0 1%.
  • the number average molecular weight (Mn) of the obtained polymer was 41 and 200, and the molecular weight distribution (MwZMn) was 1.41.
  • the 1,2-bond Zl, 4 single bond ratio of the cyclic conjugated gen-based monomer unit in the polymer is 52/488 (mo 1 ratio), which is measured by the DSC method.
  • the glass transition temperature (T g) of a CHD block is 1 It was 54 ° C.
  • the heat distortion temperature (HDT: 1.82 MPa) is 128. C.
  • the Izod (Izod) impact strength was 78.2 Jm.
  • TC titanocene dichloride
  • DIBAL-H diisobutylaluminum hydride
  • the hydrogenation rate of the isoprene (I ⁇ ) portion was 100%, and the hydrogenation rate of the CHD portion was 96%, as calculated from the NMR spectrum.
  • the obtained polymer had a number average molecular weight ( ⁇ ) of 42,400 and a molecular weight distribution (MwZM n) of 1.28.
  • the glass transition temperature (T g) of the hydrogenated CHD block measured by the DSC method was 23 ° C.
  • TS tensile strength
  • IMPa 10.20 kg-f / cm 2
  • TE tensile elongation
  • FM flexural modulus
  • the Izod (Izod) impact strength was NB (not broken).
  • the number average molecular weight (Mn) of the obtained polymer was 62,700, and the molecular weight distribution (MwMn) was 1.39.
  • the glass transition temperature (Tg) of the hydrogenated CHD block measured by the DSC method was 23 ° C.
  • the temperature was raised to 160 ° C. Further, the hydrogen pressure was set to 55 kg / cm 2 G and the hydrogenation reaction was performed for 6 hours.
  • the number average molecular weight (Mn) of the obtained polymer was 40,900, and the molecular weight distribution (MwZMn) was 33.
  • D S The number average molecular weight (Mn) of the obtained polymer was 40,900, and the molecular weight distribution (MwZMn) was 33.
  • the glass transition temperature (T g) of the hydrogenated CHD block measured by the C method is 232. C.
  • the Izod climbing strength was N.B. (without breaking).
  • the number average molecular weight ( ⁇ ) of the obtained polymer was 61,900, and the molecular weight distribution (MwZM n) was 1.46.
  • the glass transition temperature (Tg) of the hydrogenated CHD block measured by the DSC method was 230 ° C.
  • Cyclohexane (2400 g) was introduced into the autoclave and kept at room temperature under dry nitrogen.
  • n — Bu L i is converted to a lithium atom and is 15.0 m.
  • TM EDA first complexing agent
  • TMEDA second complexing agent 11.25 mm 01 was added with an additional force D.
  • reaction solution is pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydration of the molybdenum and the like is performed. Then, the polymerization reaction was stopped by the addition of a catalyst.
  • the number average molecular weight (Mn) of the obtained polymer was 40,600, and the molecular weight distribution (Mw / Mn) was 1.21.
  • the 1,2-bond 1,4 bond ratio of the cyclic conjugated gen-based monomer unit in the polymer is 5644 (mo 1 ratio).
  • the glass transition temperature (T g) of the product was 16 ° C.
  • the heat distortion temperature (HDT: 1.82 MPa) was 88 ° C.
  • n-BuLi was added in an amount of 10.0 mmo 1 in terms of lithium atom, and TMEDA (first complexing agent) 5.0 mmo 1 was added, followed by stirring at room temperature for 10 minutes. .
  • TMEDA second emulsifier
  • 1,3—CHDIOOg was introduced into an autoclave, and a polymerization reaction was performed at 40 ° C. for 2 hours to obtain a CHD homopolymer (polymer 1).
  • the number average molecular weights (M n) of the obtained polymers 1 to 3 were 100, 300, 49, 800, 60, and 700, respectively, and the molecular weight distribution (MwZM n ) Were 1.04, 1.10, and 1.25, respectively.
  • the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in Polymer 3 is 53 Z47 (mo 1 ratio), which is measured by DSC. Glass transition temperature of CHD block
  • Heat distortion temperature (HDT:. 1 8 2 MP a) is c
  • Example 4 8 was 7 8 ° C
  • TMEDA second complexing agent 11.25 mm 01 was additionally added.
  • 1,3-CHD300g and St300g were mixed, introduced into an autoclave, and polymerized at 40 ° C for 6 hours.
  • the resulting polymer was St—CHD diblock copolymer.
  • the temperature was raised to 70 ° C, and the reaction solution was pumped to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and Li atoms were removed.
  • the polymerization reaction was stopped by adding an equal mo 1 of dehydrated n-heptanol.
  • the number average molecular weight (Mn) of the obtained polymer was 40,080, and the molecular weight distribution (MwZMn) was 1.23.
  • the 1,2-bond Z 1, —bond ratio of the cyclic conjugated diene monomer unit in the polymer is 57/43 (mo 1 ratio), and is measured by the DSC method.
  • the glass transition temperature (T g) of the product was 161 ° C.
  • FS bending strength
  • IMP a 10.20 kg-f / cm 2
  • FM flexural modulus
  • the heat distortion temperature (HDT: 1.82 MPa) was 72 ° C.
  • Cyclohexane (2400 g) was introduced into an autoclave and kept at room temperature under dry nitrogen.
  • TMEDA second complexing agent 11.25 mm 01 was additionally added.
  • 1,3-CHD200g, Ip200g and St200g were mixed, introduced into an autoclave, and polymerized at 40 ° C for 6 hours.
  • the number average molecular weight (Mn) of the obtained polymer was 40,200, and the molecular weight distribution (MwZMn) was 1.21.
  • the 1,2—bond 1,4—bond ratio of the cyclic conjugated diene monomer unit in the polymer is 53 Z 47 (mo 1 ratio), which is measured by the DSC method.
  • the glass transition temperature (Tg) of the block was 156 ° C.
  • FS is 45.0 MPa, flexural modulus
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was performed at a hydrogen pressure of 35 kg / cm 2 G for 10 hours.
  • the hydrogenation rate of the CHD portion was 96%, as calculated by ' ⁇ -NMR measurement, and the St portion was not hydrogenated.
  • the number average molecular weight (Mn) of the obtained polymer was 40,400, and the molecular weight distribution (Mw / Mn) was 1.20.
  • the glass transition temperature (Tg) of the CHD block measured by the DSC method was 23 ° C.
  • the polymer flexural strength (FS) is 3 8 8 MP a.
  • IMP a 1 0. 2 0 kg - f / cm 2
  • flexural modulus (FM) was 4, 0 6 0 MP a .
  • the heat deformation temperature (HD: 1.82 MPa) was 90 ° C.
  • Example 51 The heat deformation temperature (HD: 1.82 MPa) was 90 ° C.
  • a hydrogenation reaction was carried out in the same manner as in Example 50 except that the polymer obtained in Example 48 was used.
  • the hydrogenation rate of the CHD portion was 96%, as calculated by NMR measurement, and the St portion was not hydrogenated.
  • the number average molecular weight (M n) of the obtained polymer was 40, 400, and the molecular weight distribution (M w ZM n) was 9. D S
  • the glass transition temperature (T g) of the CHD block measured by the C method was 234. C.
  • the heat distortion temperature (HDT: 1.82 MPa) was 82 ° C.
  • the temperature was raised to 160 ° C. Further, hydrogenation is performed for 6 hours at a hydrogen pressure of 55 kg Z cm 2 G. The reaction was performed.
  • the number average molecular weight ( ⁇ ) of the obtained polymer was 41,600, and the molecular weight distribution (Mw / Mn) was 1.29.
  • the glass transition temperature (Tg) measured by the DSC method was a hydrogenated CHD block force: 23 ° C, and a hydrogenated styrene block force: s147 ° C.
  • the heat distortion temperature (HDT: 1.82 MPa) was 129 ° C.
  • a hydrogenation reaction was carried out in the same manner as in Example 52 except that the polymer obtained in Example 48 was used.
  • the hydrogenation ratios of the St portion and the CHD portion both calculated by 1 H-NMR measurement were 100%.
  • the number average molecular weight (M n) of the obtained polymer was 41,000
  • the molecular weight distribution (MwZMn) was 1.26.
  • the glass transition temperature (T g) measured by the DSC method was a hydrogenated CHD blocker at 229 ° C and a hydrogenated styrene block force of s149.
  • the heat distortion temperature (HDT: 1.82 MPa) was 128 ° C.
  • TMEDA second complexing agent
  • 1,3-CHD 45 45 g of 1,3-CHD 45 was introduced into an autoclave and the polymerization reaction was carried out at 40 ° C for 1 hour.
  • the polymerization reaction was carried out at 40 ° C. for 3 hours to obtain a CHD—Bd—CHD triblock copolymer.
  • the reaction solution was pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and the molybdenum was dehydrated to the same level as Li atoms.
  • the polymerization reaction was stopped by adding Knol.
  • the number average molecular weight (M n) of the obtained polymer was 10,100, and the molecular weight distribution (Mw / M n) was 1.08.
  • the 1,2-bond Zl, 4 single bond ratio of the cyclic conjugated diene monomer unit in the polymer was 46/54 (mol ratio).
  • 10-Ommo1 was added as n-BuLi in terms of lithium atom, and then 5.0 Emo (first complexing agent) 5.0 mmo1 was added, followed by stirring at room temperature for 10 minutes. did.
  • TM EDA second (Complexing agent) 7.5 mmol was added.
  • 1,3-CHDIOOg was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C for 5 hours to obtain a CHD—Bd—CHD triblock copolymer.
  • reaction solution was pumped into another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method),
  • the polymerization reaction was stopped by adding dehydration n> butanol of the same mol as the Li atom.
  • the number average molecular weight (Mn) of the obtained polymer was 40,100, and the molecular weight distribution (MwZMn) was 1.15.
  • the 1,2-bond / 1,4-bond ratio of the cyclic conjugated gen-based monomer unit in the polymer is 51/49 (moI ratio), and the CHD measured by the DSC method.
  • the glass transition temperature (T g) of each block was 158 ° C.
  • the Izod climbing strength was N.B. (without breaking).
  • TMEDA second complexing agent
  • the number average molecular weight (Mn) of the obtained polymer was 61,200, and the molecular weight distribution (MwZMn) was 1.17.
  • the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer was 51-49 (mol ratio), and the CHD broth measured by the DSC method was used.
  • the glass transition temperature (Tg) of the product was 157 ° C.
  • TS tensile strength
  • Example 1 150 g of a 1 O w 1% cyclohexane solution of the polymer obtained in Example 7 was introduced into an autoclave, and then titanocene dichloride was used as a hydrogenation catalyst. (TC) and diisobutylaluminum hydride (DIBAL-H) were added to cyclohexane at TC / DIBAL-1/6 (molar ratio), and the catalyst solution was added to the polymer. On the other hand, T i It was added so as to be 29 O ppm in total.
  • TC titanocene dichloride
  • DIBAL-H diisobutylaluminum hydride
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was performed for 10 hours at a hydrogen pressure of 35 kg Zcn ⁇ G.
  • the hydrogenation rate of the CHD portion was 92%, and the hydrogenation ratio of the Bd portion was 98%, as calculated by ' ⁇ —NMR measurement.
  • the number average molecular weight (M n) of the obtained polymer was 41,200, and the molecular weight distribution (MwZM n) was 1.17.
  • the glass transition temperature (T g) of the CHD block measured by the DSC method was 23 ° C.
  • TS tensile strength
  • TE tensile elongation
  • FM flexural modulus
  • the Izod impact strength was about ⁇ (no break).
  • Example 59 A hydrogenation reaction was carried out in the same manner as in Example 59 except that the polymer obtained in Example 58 was used.
  • the hydrogenation rate of the CHD part was 98% and the hydrogenation rate of the Bd part was 100%, as calculated by NMR measurement.
  • the number average molecular weight (Mn) of the obtained polymer was 60,900, and the molecular weight distribution (Mw / Mn) was 1.11.
  • the glass transition temperature (Tg) of the CHD block measured by the DSC method was 227. C.
  • TS tensile strength
  • IMPa 10.20 kg-f / cm 2
  • TE tensile elongation
  • Example 5 100 g of a 10 wt% cyclohexane solution of the polymer obtained in 7 was introduced into an autoclave, and palladium was added.
  • the temperature was raised to 160 ° C. Further, the hydrogenation reaction was carried out at a hydrogen pressure of 55 kg Z cm 2 G for 6 hours.
  • the hydrogenation rates of the CHD portion and the Bd portion were both 100%, as calculated from the NMR spectrum.
  • the number-average molecular weight (Mn) of the obtained conjugate was 40,700, and the molecular weight distribution (MwZMn) was 1.16.
  • the glass transition temperature (g) of the hydrogenated ore-hexadiene mouth measured by the DSC method was 23 ° C.
  • TS tensile strength
  • IPa 10.20 kg ⁇ f / cm 2
  • TE tensile elongation
  • flexural strength a tensile strength of 14.7%
  • the (FS) was 19.2 MPa and the flexural modulus (FM) was 3,350 MPa.
  • the Izod impact strength was N.B. (not broken).
  • Example 61 A hydrogenation reaction was carried out in the same manner as in Example 61 except that the polymer obtained in Example 58 was used.
  • the number average molecular weight (Mn) of the obtained polymer was 62,300, and the molecular weight distribution (Mw / Mn) was 1.15.
  • the glass transition temperature (Tg) of the hydrogenated hexagonal hexagonal port measured by the DSC method was 229 ° C.
  • TS tensile strength
  • TE tensile elongation
  • the hydrogenation rate of the CHD part was 0% and the hydrogenation rate of the Bd part was 100%, as calculated by NMR analysis.
  • the number average molecular weight (Mn) of the obtained polymer was 10 and 200, and the molecular weight distribution (Mw / lvTn ”) was 1.09.
  • TMEDA second complexing agent
  • reaction solution is pumped to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and the dehydration of n-heptanol, which is equivalent to Li atoms, is performed.
  • the polymerization reaction was stopped by addition.
  • the catalyst solution prepared by adding to xane was added to the polymer so as to be 250 ppm as a metal atom (T i).
  • the autoclave was replaced with hydrogen, the temperature was raised to 75 ° C, and the hydrogenation reaction was performed at a hydrogen pressure of 10 kg / cm 2 G for 30 minutes.
  • n-BuLi was treated by adding metaphor.
  • the hydrogenation rate of the CHD portion of the obtained polymer calculated by 'H-NMR is 0%, and the 1, 2-vinyl portion, 1, 4-cis and trans portions of the Bd portion All had a hydrogenation rate of 100%.
  • the 1,2—linkage 1,4—linkage ratio of the cyclic conjugated diene monomer unit in the union was 48 Z52 (mo 1 ratio), and the CHD broth measured by the DSC method was used.
  • the glass transition temperature (g) of the product was 153.
  • the number average molecular weight (Mn) of the polymer was 79,600, and the molecular weight distribution (MwZMn) was 1.09.
  • This polymer had a tensile strength (TS) of 17.8 MPa and a tensile elongation (TE) of 85%.
  • Example 1 the polymerization catalyst (complex) synthesized in Example 1 was added with 0.10 mmol in terms of lithium atom.
  • TMEDA second complexing agent
  • 1,3-cyclohexadiene 120 g was charged into an autoclave, and a polymerization reaction was carried out at 30 ° C for 4 hours to obtain a CHD homopolymer.
  • SiCl 4 silicon tetrachloride
  • the mixture was added with [Inoreganox B215 (037HX)] and desolvation was performed according to a conventional method to obtain a CHD—Bd—CHD triblock copolymer exhibiting rubber elasticity. Obtained.
  • the 1,2—bond / ⁇ 1,4—bond ratio of the cyclic conjugated diene monomer unit in the polymer was 50/50 (mo 1 ratio), and was measured by the DSC method.
  • the glass transition temperature (Tg) of the CHD block was 155 ° C.
  • the number average molecular weight ( ⁇ ) of the obtained polymer was 112,000, and the molecular weight distribution (Mw / Mn) was 2.08.
  • Cyclohexane (2400 g) was introduced into the autoclave and kept at room temperature under dry nitrogen.
  • TMEDA second complexing agent 11.25 mm 01 was additionally added.
  • Ethylene (E t) is introduced into the auto click Loew, polymerization reaction was carried out for 1 hour at E t pressure 4 0 kg / cm 2 G, 4 0 e C.
  • the Et content in the obtained polymer calculated by 1 H-NMR measurement was 15 wt%.
  • the number average molecular weight (Mn) of the polymer was 23,400, and the molecular weight distribution (MwZMn) was 1.62.
  • the 1,2-bond / 1,4-bond ratio of the cyclic conjugated monomer unit in the polymer was 53/47 (m01 ratio), and the CHD broth measured by the DSC method.
  • the glass transition temperature (Tg) of the product was 157 ° C.
  • Example 1 The inside of a 10 Om1 Schlenk tube that had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane (18.0 g) and n-hexane (2.0 g) were injected into the Schlenk tube. The temperature of the solution was kept at room temperature, and the polymerization catalyst (complex) obtained in Example 1 was added in an amount of 0.07 mmol in terms of lithium atom.
  • the polymer solution was cooled to 110 ° C, 1.55 g of methyl methacrylate (MMA) was added, and the polymerization reaction was carried out at 10 ° C for 3 hours.
  • the reaction was stopped by adding a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -141-methylphenol], and a further large amount of methanol was added.
  • BHT 2,6-bis (t-butyl) -141-methylphenol
  • the polymer was separated with a mixed solvent of ethanol and hydrochloric acid, washed with methanol, and dried in vacuum at 80 ° C to obtain a white polymer in a yield of 8 lwt%.
  • the number average molecular weight (M n) of the obtained CHD—MMA jib mouth copolymer was 34,500, and the molecular weight distribution (MwZM T) was 1.72.
  • the 1,2—bond / ⁇ 1,4 single bond ratio of the cyclic conjugated genomer monomer unit in the polymer was 54 to 46 (mo 1 ratio), which was measured by the DSC method.
  • the glass transition temperature (Tg) of the CHD block was 154 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un polymère de diènes cycliques conjugués dont la chaîne principale comprend des unités d'au moins un monomère diène cyclique conjugué, seul ou en mélange avec des unités d'au moins un autre monomère capable de copolymériser avec le monomère diène. Les unités du monomère diène sont liées ensemble dans la chaîne principale par des liaisons 1,2 et 1,4, selon un rapport molaire comparativement élevé entre les liaisons 1, 2 et les liaisons 1,4. Ce polymère présente une répartition du poids moléculaire comparativement étroite ainsi que des caractéristiques thermiques et mécaniques améliorées. L'invention concerne également un procédé avantageux sur le plan industriel pour produire un diène polymère ayant d'excellentes caractéristiques, à l'aide d'un catalyseur spécifique.
PCT/JP1995/002362 1994-11-18 1995-11-17 Polymere ameliore de dienes cycliques conjugues et procede pour le fabriquer WO1996016090A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9705274A GB2307238B (en) 1994-11-18 1995-11-17 Improved cyclic conjugated diene polymer and process for producing the same
DE19581790T DE19581790T1 (de) 1994-11-18 1995-11-17 Verbessertes cyclisches, konjugiertes Dien-Polymeres und Verfahren zu seiner Herstellung
KR1019970702284A KR100208316B1 (ko) 1994-11-18 1995-11-17 개량 환상 공액 디엔 폴리머 및 그의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP30842994 1994-11-18
JP6/308429 1994-11-18

Publications (1)

Publication Number Publication Date
WO1996016090A1 true WO1996016090A1 (fr) 1996-05-30

Family

ID=17980950

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1995/002362 WO1996016090A1 (fr) 1994-11-18 1995-11-17 Polymere ameliore de dienes cycliques conjugues et procede pour le fabriquer

Country Status (6)

Country Link
KR (1) KR100208316B1 (fr)
CN (1) CN1166175A (fr)
DE (1) DE19581790T1 (fr)
GB (1) GB2307238B (fr)
MY (1) MY132118A (fr)
WO (1) WO1996016090A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10244213A1 (de) 2002-09-23 2004-04-01 Bayer Ag Verfahren zur Herstellung von Homo-, Copolymeren und/oder Blockcopolymeren mit Metallocenen mit einer Donor-Akzeptor-Wechselwirkung nach der lebenden Polymerisation
GB2464975A (en) 2008-11-01 2010-05-05 Dyson Technology Ltd Apparatus for foaming milk with temperature control
CN103140516B (zh) * 2010-07-30 2015-03-25 株式会社普利司通 共轭二烯化合物与非共轭烯烃的共聚物、橡胶组合物、交联橡胶组合物和轮胎
JP2020183526A (ja) 2019-05-03 2020-11-12 クレイトン・ポリマーズ・リサーチ・ベー・フェー ブロックコポリマー及びその使用
JP2020183525A (ja) 2019-05-03 2020-11-12 クレイトン・ポリマーズ・リサーチ・ベー・フェー ブロックコポリマー組成物、それから作製されたプリプレグ及び積層体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5871903A (ja) * 1981-10-06 1983-04-28 インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− １，２―ジ置換シクロヘキサ―３，５―ジエン系重合体及びその製造方法
JPS58216243A (ja) * 1982-06-10 1983-12-15 Japan Synthetic Rubber Co Ltd 電離放射線感応性材料
JPS63230707A (ja) * 1987-03-19 1988-09-27 Nippon Zeon Co Ltd 水素化炭化水素樹脂の製造方法
WO1994028038A1 (fr) * 1993-05-21 1994-12-08 Asahi Kasei Kogyo Kabushiki Kaisha Polymere diene conjugue cyclique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU216948A1 (en) * 1965-04-05 1982-11-07 B V Erofeev Process for producing polycyclohexadiene-1
JPH03230707A (ja) * 1990-02-05 1991-10-14 Fuji Electric Co Ltd 配電盤用箱体の通気口構造
CA2157897A1 (fr) * 1993-06-16 1994-12-22 Itaru Natori Nouveau polymere renfermant une unite moleculaire cyclique saturee
JP2784889B2 (ja) * 1994-09-01 1998-08-06 アミテック株式会社 踏圧パッド装置の被覆帯保持機構
JPH08216243A (ja) * 1995-02-16 1996-08-27 Japan Steel Works Ltd:The ノズル及びノズル制御弁回路並びにエア吹込方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5871903A (ja) * 1981-10-06 1983-04-28 インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− １，２―ジ置換シクロヘキサ―３，５―ジエン系重合体及びその製造方法
JPS58216243A (ja) * 1982-06-10 1983-12-15 Japan Synthetic Rubber Co Ltd 電離放射線感応性材料
JPS63230707A (ja) * 1987-03-19 1988-09-27 Nippon Zeon Co Ltd 水素化炭化水素樹脂の製造方法
WO1994028038A1 (fr) * 1993-05-21 1994-12-08 Asahi Kasei Kogyo Kabushiki Kaisha Polymere diene conjugue cyclique

Also Published As

Publication number Publication date
MY132118A (en) 2007-09-28
GB2307238B (en) 1999-02-24
KR100208316B1 (ko) 1999-07-15
DE19581790T1 (de) 1997-09-18
CN1166175A (zh) 1997-11-26
KR970706323A (ko) 1997-11-03
GB9705274D0 (en) 1997-04-30
GB2307238A (en) 1997-05-21

Similar Documents

Publication Publication Date Title
JP3102440B2 (ja) 新規な樹脂組成物
US5792824A (en) Cyclic conjugated diene polymer and method of producing same
US5795945A (en) Polymer containing a cyclic olefin monomer unit
WO1996016117A1 (fr) Materiau polymere composite
JPS59133203A (ja) 重合体の水添方法
JPH07258318A (ja) 重合触媒
WO1996016090A1 (fr) Polymere ameliore de dienes cycliques conjugues et procede pour le fabriquer
JPH08225614A (ja) 改良された環状共役ジエン系重合体及びその製造方法
TWI566835B (zh) 烯烴複分解觸媒及低分子量丁腈橡膠之製備方法
EP0738738B1 (fr) Polymere contenant des unites structurales moleculaires cycliques saturees
WO1994028038A1 (fr) Polymere diene conjugue cyclique
JP2794223B2 (ja) 新規な変性環状分子構造単位含有重合体
JP3441015B2 (ja) 飽和環状分子構造単位を含有する新規重合体
JP5037174B2 (ja) 共役ジエン系スターポリマー及びその製造方法
JPH08225616A (ja) 環状共役ジエン系ブロック共重合体
JP3101151B2 (ja) 環状共役ジエン系重合体及びその重合方法
JPWO2003016365A1 (ja) 環状共役ジエン系共重合体
CN111212860A (zh) 具有二烯单元和单烯烃单元的嵌段聚合物
JPH10152539A (ja) 環状共役ジエン系ブロック共重合体の製造方法
JPH0940723A (ja) 機能性重合体
JPH10152538A (ja) 環状共役ジエン系重合体の製造方法
JP3141190B2 (ja) 環状共役ジエン系共重合体
JPS60243110A (ja) リビング重合体用カツプリング剤及びリビングマクロアニオンの末端変性法
JPH08225603A (ja) 有機金属錯体を用いた重合方法
WO2022172925A1 (fr) Composition de polymère hydrogéné contenant un polymère modifié de diène conjugué hydrogéné ayant un groupe fonctionnel contenant du bore et son procédé de production

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 95195578.0

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CN DE GB KR SG US

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 9705274.0

Country of ref document: GB

ENP Entry into the national phase

Ref document number: 1997 793322

Country of ref document: US

Date of ref document: 19970314

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019970702284

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1019970702284

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1019970702284

Country of ref document: KR