JP2020158659A - Polymer having conjugated diene unit and method for producing the same - Google Patents

Abstract

To provide a novel polymer having a conjugated diene unit, a curable composition containing the polymer, and a method for producing them.SOLUTION: A component represented by the formula (1), and a diol component and/or dithiol component are polymerized to introduce a conjugated diene unit into a constitutional unit of a polymer (where X1 and X2 are a halogen atom, R1, R2, R3 and R4 are a hydrogen atom or an alkyl group). The diol may be an aromatic diol, preferably a bisphenol, particularly a bisphenol having a fluorene skeleton.SELECTED DRAWING: None

Description

The present invention relates to a polymer having a novel conjugated diene unit, a curable composition containing the polymer, and a method for producing the polymer and the curable composition.

Vinyl group-containing polymers having a vinyl group as a constituent unit (or repeating unit) have been attracting attention for a long time as polymer cross-linking agents, thermosetting resins, resist materials and the like.

For example, in Y. Mohan, V. Raghunadh, S. Sivaram, D. Baskaran, Macromolcules, 2012, 45, 3387 (Non-Patent Document 1), the polymer obtained by group transfer polymerization of 4-vinylbenzyl methacrylate is composed. It is described that it exhibits thermosetting property because it has a styryl group in the unit.

X. Thang, M. Hong, L. Falivene, L. Caporaso, L. Cavallo, E.-X. Chen, J. Am. Chem. Soc, 2016, 138, 14326 (Non-Patent Document 2) states 2 A polymer having an acrylic skeleton (or a unit containing a (meth) acryloyl group) as a constituent unit obtained by ring-opening polymerization of -methylene-γ-butyrolactone is cured by a radical initiator, and further, the acrylic skeleton is subjected to curing. It is described that chemical modification is possible by carrying out a radical-type thiol-ene reaction. Tobias Robert, Stefan Friebel, Green Chemistry, 2016, 18, 2922 (Non-Patent Document 3) describes that polyester having an acrylic skeleton can also be synthesized by polycondensation of itaconic acid.

In addition, Y. Kohsaka, T. Miyazaki, K. Hagiwara, Polym. Chem. 2018, 9, 1610 (Non-Patent Document 4) contains bis (α- (halomethyl) acrylic acid ester), dithiol, and dicarboxylic acid. It is described that a polymer having an acrylic skeleton in the main chain can be obtained by polycondensation based on a conjugated substitution reaction with bisphenol, and that the obtained polymer exhibits degradability when treated with thiol under a basic catalyst. Has been done.

"Plastic / Functional Polymer Material Encyclopedia" Editorial Committee, "Plastic / Functional Polymer Material Encyclopedia", "Chapter 4 Thermoplastic Resin / 2. Unsaturated Polyester Resin", p. 466-p. As described in 481, Encyclopedia Publishing Center of the Industrial Research Council, 2004 (Non-Patent Document 5), unsaturated polyester is industrially produced as a polymer having a polymerization active group in the polymer main chain, and fibers are produced. It is used as a raw material for reinforced plastics. Since unsaturated polyester is produced at a high temperature of 140 to 220 ° C., thermal polymerization of unsaturated bonds (or double bonds), which are polymerization active groups, becomes a problem. Therefore, as the monomer having a polymerization active group (unsaturated bond), an internal olefin monomer having low polymerization reactivity (or a monomer having no double bond at the terminal, a non-terminal olefin monomer) is preferable, and maleic anhydride. And fumaric acid are often used. However, since these internal olefin monomers do not polymerize by themselves, a comonomer such as styrene is required at the time of thermosetting, and in order to promote the polymerization smoothly, a measure is taken to add an initiator which is a radical generation source. Further, when the internal olefin unit is introduced into the polymer, the glass transition point of the polymer is lowered, so that the unsaturated polyester generally distributed has low mechanical strength and cannot be used alone as a structural material.

Polymers with conjugated diene (or 1,3-butadiene) as a constituent unit have also been reported. RM Ottenbrite, GR Myers, Journal of Polymer Science: Polymer Chem. Ed., Vol 11, 1973, 1443-1446 (Non-Patent Document 6) states that 2,3-bis (bromomethyl) -1,3-butadiene is described. It is described that N, N, N', N'-tetramethyl-1,12-dodecanediamine was polymerized to obtain an ionic oligomer having a conjugated diene unit.

N. Nishioka, S. Hayashi, T. Koizumi, Angewandte Chem. Int. Ed., 2012, 51, 3682-3685 (Non-Patent Document 7) describes propargyl methyl ester carbonate and 9,9-dioctylfluoren-2. , 7-Diboronic acid was cross-coupled polymerized in the presence of a zero-valent palladium catalyst to obtain a cross-conjugated polymer, and the obtained cross-conjugated polymer was converted into a linear conjugated polymer by the Diel's-Alder reaction. It is stated that it was done.

Y. Mohan, V. Raghunadh, S. Sivaram, D. Baskaran, Macromolcules, 2012, 45, 3387 X. Thang, M. Hong, L. Falivene, L. Caporaso, L. Cavallo, E.-X. Chen, J. Am. Chem. Soc, 2016, 138, 14326 Tobias Robert, Stefan Friebel, Green Chemistry, 2016, 18, 2922 Y. Kohsaka, T. Miyazaki, K. Hagiwara, Polym. Chem. 2018, 9, 1610 "Plastic / Functional Polymer Material Encyclopedia" Editorial Committee, "Plastic / Functional Polymer Material Encyclopedia", "Chapter 4 Thermoplastic Resin / 2. Unsaturated Polyester Resin", p. 466-p. 481, Industrial Research Council Encyclopedia Publishing Center, 2004 R. M. Ottenbrite, G. R. Myers, Journal of Polymer Science: Polymer Chemistry Edition, vol 11, 1973, 1443-1446, "Polyelectrolytes: Reaction of Ditertiary Amines with 2,3-Bis (bromomethyl) -1,3-butadiene" N. Nishioka, S. Hayashi, T. Koizumi, Angewandte Chemie International Edition, 2012, 51, 3682-3685, "Palladium (0) -Catalyzed Synthesis of Cross-Conjugated Polymers: Transformation into Linear-Conjugated Polymers through the Diels-Alder Reaction "

However, the polymers of Non-Patent Documents 1 to 4 have low stability, and in particular, the polymer of Non-Patent Document 3 using itaconic acid as a raw material spontaneously polymerizes and cures unless a polymerization inhibitor coexists. In addition, the polymer of Non-Patent Document 4 is easily cleaved in the main chain by hydrolysis of an ester bond or a conjugated substitution reaction in an acrylic skeleton (or (meth) acryloyl unit), and has stability against acids and bases, that is, chemical resistance. Remarkably low. As described in Non-Patent Document 5, unsaturated polyester having high stability and chemical resistance is industrially used, but since the polymerization reactivity is low, a polymerization initiator is required for thermosetting. Since it does not polymerize by itself, it is necessary to coexist with a vinyl monomer such as styrene. In addition, most unsaturated polyesters before curing are liquid and have low mechanical strength even after curing. Therefore, unsaturated polyester is often used by impregnating structural materials such as glass fibers instead of being used alone. Therefore, it is desired to develop a polymer that can be used alone as a structural material, has excellent chemical resistance, and is highly polymerizable.

On the other hand, a polymer having a conjugated diene unit having a conjugated diene as a constituent unit can be radically polymerized in the same manner as an acrylic skeleton-containing polymer (or a polymer having a (meth) acryloyl unit). In particular, if a conjugated diene unit can be introduced into the constituent unit as an external olefin (or terminal olefin or monomer having a double bond at the terminal) unit, it has higher reactivity than a polymer into which an internal olefin unit has been introduced. It can be polymerized, can be used as a cross-linking agent, and can be chemically modified by a reaction such as a Diels-Alder reaction. Moreover, since the conjugated diene unit is a hydrocarbon group, it is stable against acids and bases and is expected to have high chemical resistance.

However, since conjugated diene has low thermal stability and the introduction method has not been established, there are restrictions on the reaction conditions for introducing the conjugated diene unit into the polymer. Therefore, reports of polymers having conjugated diene units are limited. For example, in Non-Patent Document 6, although a low molecular weight oligomer having a conjugated diene unit can be obtained, a high molecular weight polymer cannot be obtained. Further, the cross-conjugated polymer of Non-Patent Document 7 needs to use an expensive metal catalyst and to be reacted under reflux conditions for 24 hours at the time of polymerization, and the polymerization conditions are harsh and the operation is complicated.

Therefore, an object of the present invention is to provide a novel polymer having a conjugated diene unit, a curable composition containing the polymer, and a method for producing these.

Another object of the present invention is to provide a polymer having a conjugated diene unit useful as a cross-linking agent, which has high reactivity, and a curable composition containing the polymer, and a method for producing these.

Still another object of the present invention is to provide a polymer having a conjugated diene unit that can be easily produced under mild conditions, a curable composition containing the polymer, and a method for producing the same.

As a result of diligent studies to achieve the above problems, the present inventors have reacted the diene component represented by the following formula (1) with a diol and / or dithiol to obtain a conjugated diene unit even under mild conditions. The present invention was completed by finding that it can be introduced into a polymer main chain.

That is, the polymer having a conjugated diene unit of the present invention is a polymer obtained by polymerizing a component represented by the following formula (1) with a diol component and / or a dithiol component.

(In the formula, X ¹ and X ² represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group).

The diol component may contain an aromatic diol, preferably a diol represented by the following formula (2), and more preferably bisphenols.

[In the formula, Z ¹ and Z ² represent an allene ring, ^Ra and R ^b represent substituents, p1 and p2 represent 0 or an integer greater than or equal to ^1, and A ¹ and A ² represent alkylene groups. q1 and q2 represent 0 or an integer of 1 or more, Y is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, and a divalent group represented by the following formula (2a) or (2b). Show the group of

(In the formula, Ar ¹ , Ar ² and Ar ³ represent arene rings, R ^c , R ^d and ^Re represent substituents, and r 1, r 2 and s represent integers greater than or equal to 0). ]

Further, the polymer having the conjugated diene unit of the present invention has the following formula (3).

(R ¹ , R ² , R ³ and R ⁴ indicate a hydrogen atom or an alkyl group, and W indicates a residue of a diol component and / or a dithiol component)
It may have a structural unit represented by, and preferably W may be a residue of bisphenols in the above formula (3).

The present invention also includes a method for producing a polymer having the conjugated diene unit in which the component represented by the formula (1) and the diol component and / or the dithiol component are polymerized in the presence of a base, and this method is not applicable. It may be polymerized in a protic solvent.

The present invention also includes a curable composition comprising a polymer having at least the conjugated diene unit, and the curable composition may further contain a radically polymerizable compound. The present invention also includes a cured product of the curable composition.

The present invention also includes a cross-linking agent containing a polymer having the conjugated diene unit.

In addition, in this specification and claims, the number of carbon atoms of a substituent may be indicated by C ₁ , C ₆ , C _{10, and the} like. For example, "C ₁ alkyl group" means an alkyl group having 1 carbon atom, and "C _6-10 aryl group" means an aryl group having 6 to 10 carbon atoms.

Further, in the present specification and the scope of patent claims, the residue of the diol component (or diol) and the residue of the dithiol component (or dithiol) are the portions of the diol excluding the hydrogen atoms of the two hydroxy groups, respectively. , And the portion of dithiol excluding the hydrogen atom of the two thiol groups.

Since the polymer having a novel conjugated diene unit of the present invention is composed of a conjugated diene unit which is a hydrocarbon group and an ether and / or a thioether derived from a diol and / or dithiol, it can also be used against acids and bases. It is stable and has high chemical resistance. Further, when the diol component contains an aromatic diol such as bisphenols, a polymer having excellent heat resistance can be obtained even if the constituent unit contains an unsaturated bond. Furthermore, since the polymer main chain has a conjugated diene unit, it can be used alone as a curable resin, and has high reactivity as compared with conventional vinyl group-containing polymers that do not contain a conjugated diene unit. It is useful as a cross-linking agent for resins. Further, since it has a conjugated diene unit, it can be chemically modified by a reaction such as Diels-Alder reaction. Further, since the polymer having the conjugated diene unit of the present invention has high reactivity between the component represented by the above formula (1) and the diol component and / or the dithiol component, it is convenient without using an expensive metal catalyst. And it can be synthesized under mild conditions.

FIG. 1 is a ¹ H NMR spectrum of a compound (2,3-bis (iodomethyl) -1,3-butadiene) obtained in the synthesis of monomer A of the example. FIG. 2 is a size exclusion chromatogram of the polymer obtained in Example 1. FIG. 3 is a size exclusion chromatogram of the polymer obtained in Example 2. FIG. 4 is a size exclusion chromatogram of the polymer obtained in Example 3. FIG. 5 is a size exclusion chromatogram of the polymer obtained in Example 4. FIG. 6 is a size exclusion chromatogram of the polymer obtained in Example 5. FIG. 7 is a size exclusion chromatogram of the polymer obtained in Example 6. FIG. 8 is a size exclusion chromatogram of the polymer obtained in Example 7. FIG. 9 is a TG / DTA curve of the polymer obtained in Example 7, where the solid line is TG and the dotted line is DTA. FIG. 10 is a ¹ H NMR spectrum of the polymer obtained in Example 7. FIG. 11 is a ¹³ C NMR spectrum of the polymer obtained in Example 7. FIG. 12 is a size exclusion chromatogram of the polymer obtained in Example 8. FIG. 13 is a TG / DTA curve of the polymer obtained in Example 8. FIG. 14 is a ¹ H NMR spectrum of the polymer obtained in Example 8. FIG. 15 is a ¹³ C NMR spectrum of the polymer obtained in Example 8. FIG. 16 is a size exclusion chromatogram of the polymer obtained in Example 9. FIG. 17 is a TG / DTA curve of the polymer obtained in Example 9, where the solid line is TG and the dotted line is DTA. FIG. 18 is a DSC curve of the polymer obtained in Example 9, and the solid line is the result of the first heating and the dotted line is the result of the second heating. FIG. 19 is a ¹ H NMR spectrum of the polymer obtained in Example 9. FIG. 20 is a ¹³ C NMR spectrum of the polymer obtained in Example 9. FIG. 21 is a size exclusion chromatogram of the polymer obtained in Example 10. FIG. 22 shows the TG / DTA curve of the polymer obtained in Example 10, where the solid line is TG and the dotted line is DTA. FIG. 23 is a DSC curve of the polymer obtained in Example 10, and the solid line is the result of the first heating and the dotted line is the result of the second heating. FIG. 24 is a ¹ H NMR spectrum of the polymer obtained in Example 10. FIG. 25 is a ¹³ C NMR spectrum of the polymer obtained in Example 10. FIG. 26 is a size exclusion chromatogram of the polymer obtained in Example 11. FIG. 27 is a TG / DTA curve of the polymer obtained in Example 11, where the solid line is TG and the dotted line is DTA. FIG. 28 is a DSC curve of the polymer obtained in Example 11, where the solid line is the result of the first heating and the dotted line is the result of the second heating. FIG. 29 is a ¹ H NMR spectrum of the polymer obtained in Example 11. FIG. 30 is a ¹³ C NMR spectrum of the polymer obtained in Example 11. FIG. 31 is a size exclusion chromatogram of the polymer obtained in Example 12. FIG. 32 is a ¹ H NMR spectrum of the polymer obtained in Example 12. FIG. 33 is a ¹³ C NMR spectrum of the polymer obtained in Example 12.

[Polymer with conjugated diene unit]
The polymer having a conjugated diene unit of the present invention (hereinafter, may be simply referred to as a conjugated diene-containing polymer) is a component represented by the formula (1) (hereinafter, may be simply referred to as a diene component (1)). , A polymer (or polymer, polycondensate) obtained by reacting (or polymerizing, condensing) a diol component and / or a dithiol component, and a conjugated diene unit which is a hydrocarbon group derived from the diene component (1). Since it is composed of ether and / or thioether derived from a diol component and / or a dithione component, it has high stability such as chemical resistance as a polymer and is excellent in handleability. In the following description, the "diene component (1)", "diol component" and "dithiol component" each represent a polymerization component (or monomer), and a unit (or polymer) derived from each polymerization component. It may represent a structural unit).

(Diene component (1))
In the present invention, since the component represented by the following formula (1) is a polymerization component (or monomer), a conjugated diene unit can be introduced as a constituent unit of the polymer under mild conditions without using a metal catalyst.

(In the formula, X ¹ and X ² represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group).

Examples of the halogen atom represented by X ¹ and X ² of the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred halogen atoms are bromine atoms, iodine atoms, and more preferably iodine atoms. The halogen atoms represented by X ¹ and X ² may be the same or different, and are usually the same.

R ^{1 to} R ⁴ of the above formula (1) represent a hydrogen atom or an alkyl group, and the alkyl group is a linear or branched C such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. _Examples include _1-6 alkyl groups. Preferred alkyl groups are linear or branched C _1-3 alkyl groups, more preferably methyl groups, ethyl groups, especially methyl groups. Preferred R ^{1 to} R ⁴ are a hydrogen atom, a linear or branched C _1-3 alkyl group, more preferably a hydrogen atom and a methyl group, and are usually reactions of a nucleophilic substitution reaction ( _SN 2 reaction). From the viewpoint of velocity (or reactivity), it is a hydrogen atom with small steric hindrance. The types of R ^{1 to} R ⁴ may be the same or different, and are usually the same.

Typical components represented by the above formula (1) are 2,3-bis (fluoromethyl) -1,3-butadiene and 2,3-bis (chloro) in which R ^{1 to} R ⁴ are all hydrogen atoms. 2,3-bis (halomethyl) -1, such as methyl) -1,3-butadiene, 2,3-bis (bromomethyl) -1,3-butadiene, 2,3-bis (iodomethyl) -1,3-butadiene , 3-butadiene; 2,3-bis (bromomethyl) -1,3-pentadiene, where any one of R ^{1 to} R ⁴ is a methyl group or an ethyl group, 2,3-bis (iodomethyl) -1,3- hexadiene such as 2,3-bis (halomethyl) -1,3-penta to hexadiene; ^{R 1} and ^{R 2} is a methyl group 2,3-bis (iodomethyl) -4-methyl-1,3-pentadiene etc. 2,3-bis (halomethyl) -4-methyl-1,3-pentadiene; 2,5-dimethyl-3,4-bis (halomethyl) -2,4-hexadiene in which R ^{1 to} R ⁴ are all methyl groups. And so on. These components can be used alone or in combination of two or more. Of these, 2,3-bis (halomethyl) -1,3-butadiene is preferable, and more preferably 2,3-bis (bromomethyl) -1,3-butadiene, 2,3-bis (iodomethyl) -1, 3-butadiene, particularly 2,3-bis (iodomethyl) -1,3-butadiene is preferable from the viewpoint that it can be prepared only with an organic reagent without using a heavy metal reagent.

The diene component (1) can be synthesized by a conventional method. For example, in the above formula (1), 2,3-bis (halomethyl) -1,3-butadiene in which R ^{1 to} R ⁴ are all hydrogen atoms , And the method described in the non-patent document "Yehiel Gaoni, and Shoshana Sadeh, J. Org. Chem., 1980, 45 (5), 870-881", and the method described in Examples. Further, the diene component (1) in which at least one of R ^{1 to} R ⁴ is an alkyl group can also be prepared by the same method as that of 2,3-bis (halomethyl) -1,3-butadiene.

(Diol component)
Examples of the diol component include aliphatic diols and aromatic diols.

Examples of the aliphatic diol include a chain aliphatic diol and a cyclic aliphatic diol. Examples of the chain aliphatic diol include alkane diols and polyalkane diols, and examples of the alicyclic diol include cycloalkane diols and di (hydroxyalkyl) cycloalkanes.

Examples of the alkanediol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-pentanediol. Examples thereof include C _2-10 alkanediols such as 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol and neopentyl glycol. Examples of the polyalkanediol include diethylene glycol, dipropylene glycol, triethylene glycol and the like, or tri-C _2-4 alkanediol and the like.

Examples of the cycloalkane diol include C _5-8 cycloalkane diol such as cyclohexane diol, and examples of the di (hydroxyalkyl) cycloalkane include di (hydroxy C _1-4 alkyl) such as 1,4-cyclohexanedimethanol. _Examples include C _5-8 cycloalkane.

Examples of the aromatic diol include dihydroxyarene such as hydroquinone and dihydroxynaphthalene; bis (hydroxyarene) represented by the following formula (2), bis [hydroxy (poly) alkoxyarene] and the like.

[In the formula, Z ¹ and Z ² are allene rings, ^Ra and R ^b are substituents, p1 and p2 are integers of 0 or 1 or more, A ¹ and A ² are alkylene groups, q1 and q2 are 0 or 1 or more. Indicates an integer of, and Y indicates a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, and a divalent group represented by the following formula (2a) or (2b).

(In the formula, Ar ¹ , Ar ² and Ar ³ are arene rings, R ^c , R ^d and ^Re are substituents, and r 1, r 2 and s are integers of 0 or more). ]

In the formula (2), as the arene ring for ring Z ¹ and ring Z ² (aromatic hydrocarbon ring), monocyclic arene ring such as a benzene ring, a polycyclic arene ring, ring assembly arene ring And so on.

Examples of the polycyclic arene ring include a fused dicyclic arene ring such as a naphthalene ring, a fused polycyclic C _10-14 arene ring such as a fused tricyclic arene ring such as an anthracene ring and a phenanthrene ring, and particularly naphthalene. Rings are preferred.

Examples of the ring-aggregated arene ring include a bi-C _6-12 arene ring such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring, and a biphenyl ring is particularly preferable.

The types of ring Z ¹ and ring Z ² may be the same or different from each other, and are usually the same.

Preferred rings Z ¹ and Z ² are C _6-10 arene rings such as a benzene ring and a naphthalene ring, and more preferably a benzene ring.

The substituents represented by R ^a and R ^b include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; a substituted amino group. And so on.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group. Examples of the cycloalkyl group include a C _5-8 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a C _6-10 aryl group such as a phenyl group. Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group. Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group. Examples of the acyl group include a C _1-6 acyl group such as an acetyl group. Examples of the substituted amino group include a dialkylamino group and a diacylamino group. The dialkylamino group is a diC _1-4 alkylamino group such as a dimethylamino group, and the diacylamino group is a diC such as a diacetylamino group. Examples thereof include _1-4 acylamino groups. The substituents represented by ^Ra and R ^b may be the same or different.

Preferred ^Ra and R ^b are linear or branched C _1-6 alkyl groups, C _5-8 cycloalkyl groups such as cyclohexyl groups, C _6-14 aryl groups, linear or branched such as methoxy groups. A chain C _1-4 alkoxy group, more preferably a linear or branched C _1-3 alkyl group such as a methyl group or an ethyl group, particularly a methyl group. The types of R ^a and R ^b may be the same or different from each other, and are usually the same.

The substitution numbers p1 and p2 of R ^a and R ^b are integers of 0 to 4, preferably integers of 0 to 2, more preferably 0 or 1, and particularly 0. The substitution numbers p1 and p2 may be the same or different from each other. When the number of substitutions p1 and p2 is 2 or more, the types of 2 or more R ^a and R ^b substituted into the same ring Z ¹ and ring Z ² , respectively, may be the same or different from each other. The replacement positions of R ^a and R ^b are not particularly limited.

Examples of the alkylene group represented by A ¹ and A ² include a linear group such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butandyl group, and a tetramethylene group. Examples thereof include a branched C _2-6 alkylene group. The types of A ¹ and A ² may be the same or different from each other, and are usually the same. Preferred A ¹ and A ² are a linear or branched C _2-3 alkylene group, more preferably a linear or branched C _2-3 alkylene group, particularly an ethylene group.

The number of repetitions (number of added moles) q1 and q2 of the oxyalkylene groups OA ¹ and OA ² may be 0 or an integer of 1 or more, for example, 0 to 10, preferably 0 to 6, and more preferably 0 or 1. is there. In the present specification and claims, the "repetition number (additional number of moles)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of additional moles. Similar to the preferred range of integers. When q1 and q2 are 2 or more, the 2 or more oxyalkylene groups OA ¹ and OA ² may be the same or different.

In the above formula (2), the substitution positions of the group [−O− (A ¹ O) _q1 −H] and the group [−O− (A ² O) _q2 −H] are not particularly limited, and the ring Z ¹ , It suffices to replace each of them at an appropriate replacement position of Z ² . The substitution positions of the group [−O− (A ¹ O) _q1 −H] and the group [−O− (A ² O) _q2 −H] are described later when the rings Z ¹ and Z ² are benzene rings. In many cases, the phenyl group bonded to is substituted at any of the 2-position, 3-position, and 4-position, preferably at the 3-position or 4-position, particularly at the 3-position. When rings Z ¹ and Z ² are naphthalene rings, they are often substituted at any of the 5th to 8th positions of the naphthyl group bonded at the 1st or 2nd position with respect to Y, and with respect to Y. , The 1-position or 2-position of the naphthalene ring is substituted (replaced in the relationship of 1-naphthyl or 2-naphthyl), and the substitution positions are substituted in the relationship of 1, 5-position, 2, 6-position. Is preferable, and it is particularly preferable to substitute at the 2nd and 6th positions.

In the formula (2), the alkylene group represented by Y is the same as the alkylene group represented by A ¹ and A ² , including the preferred embodiment.

Examples of the cycloalkylene group include C _5-10 cycloalkylene groups such as 1,1-cyclopentylene group, 1,2-cyclopentylene group, 1,1-cyclohexylene group and 1,2-cyclohexylene group. _These are preferably C _5-8 cycloalkylene groups, more preferably C _5-6 cycloalkylene groups, especially 1,1-cyclohexylene groups.

In the formulas (2a) and (2b), the arene ring represented by Ar ¹ , Ar ² and Ar ³ is the same as the ring Z ¹ and the ring Z ² including a preferable embodiment.

R ^c, substituents represented by ^{R d} and ^{R e,} including preferred ^embodiments, R a, is the same as ^{R b.} R ^{c, R d} and ^R number substitutions ^e r1, r2 and s, including preferred embodiments, it is the same as p1, p2.

These diols can be used alone or in combination of two or more. Among these diols, from the viewpoint of heat resistance, aromatic diols are preferable, and bisphenols and bisnaphthols, particularly bisphenols, are more preferable.

Examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane (bisphenol B), and 2,2-bis (3-methyl-4). -Hydroxyphenyl) Propane (bisphenol C), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (3-isopropyl-) Bisphenols such as 4-hydroxyphenyl) propane (bisphenol G), bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z); 9,9-bis ( 4-Hydroxyphenyl) fluorene (BPF), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) Fluorene skeleton-containing bisphenols such as, and phthalide skeleton-containing bisphenols such as phenol phthalein, o-cresol phthalein, and p-xylenol phthaleine.

Examples of bisnaphthols include bis (hydroxynaphthyl) C _1-10 alkanes such as bis (2-hydroxy-1-naphthyl) methane; 9,9-bis (6-hydroxy-2-naphthyl) fluorene (BNF), 9, Examples thereof include fluorene skeleton-containing bisnaphthols such as 9-bis (6-hydroxyethoxy-2-naphthyl) fluorene (BNEF); and phthalide skeleton-containing bisnaphthols such as α-naphtholphthaline.

The proportion of aromatic diols such as bisphenols is, for example, 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly 100 mol%, of the total diol components. Although this ratio may be the charging ratio of the monomer, it is preferably the ratio of the constituent units introduced into the conjugated diene polymer.

(Dithiol component)
Examples of the dithiol component include aliphatic dithiol, aromatic dithiol, ether group-containing dithiol, and thioether group-containing dithiol.

The aliphatic dithiols include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,5-pentanedithiol. Linear or branched C such as 6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonandithiol, 1,10-decandithiol, 1,12-dodecanedithiol. _2-20 alcandithiol can be mentioned.

Examples of the aromatic dithiol include dimercapto C ₆ such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,5-dimercaptonaphthalene, and 2,6-dimercaptonaphthalene. _-10 arene; aromatic dithiol corresponding to the diol represented by the above formula (2) such as fluorene skeleton-containing dithiol and phthalide skeleton-containing dithiol can be mentioned.

Examples of the ether group-containing dithiol include bis (2-mercaptoethyl) ether and 1,2-bis (2-mercaptoethoxy) ethane.

Examples of the thioether group-containing dithiol include bis (2-mercaptoethyl) sulfide, 1,3-bis (2-mercaptoethylthio) propane, and bis (4-mercaptophenyl) sulfide.

These dithiols can be used alone or in combination of two or more. Of these dithiols, aromatic dithiols are preferable from the viewpoint of heat resistance, aliphatic dithiols are preferable from the viewpoint of stability and handleability, and preferred aliphatic dithiols are linear or branched chain C _2-18 alkanes. Dithiol, more preferably linear or branched chain C _5-16 alkanedithiol.

The ratio of the total amount of the diol component to the dithiol component can be selected from the range of about 0.1 to 2 mol with respect to 1 mol of the component (1), and is stepwise from 0.3 to 1.8. It may be mol, 0.5 to 1.5 mol, 0.8 to 1.2 mol, but from the viewpoint of increasing the molecular weight (weight average molecular weight and number average molecular weight) of the obtained polymer, for example, 0. It is 9 to 1.1 mol, preferably 0.95 to 1.05 mol, more preferably 0.98 to 1.02 mol, and particularly 1 mol.

When the polymer of the present invention contains both the diol component and the dithiol component, the ratio of the dithiol component can be selected from the range of about 0.1 to 2 mol with respect to 1 mol of the diol component, which is preferable. Is stepwise from 0.3 to 1.8 mol, 0.5 to 1.5 mol, 0.8 to 1.2 mol, or stepwise from 0.1 to 1.5 mol, 0. It is 3 to 1 mol and 0.4 to 0.6 mol.

(Polymer containing conjugated diene)
The conjugated diene-containing polymer of the present invention is a polymer obtained by polymerizing the diene component (1) with a diol component and / or a dithiol component, and contains at least a structural unit represented by the following formula (3). There is.

(R ¹ , R ² , R ³ and R ⁴ indicate a hydrogen atom or an alkyl group, and W indicates a residue of a diol component and / or a dithiol component)

In the formula ^(3), R ^1, R 2, ^{R 3} and ^{R 4,} including the preferred embodiment, is the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1).

W, which is a residue of the diol component and / or the dithiol component, includes a residue corresponding to the diol component and the dithiol component, and the preferred residue W is also a residue corresponding to the preferred diol component and / or the dithiol component. Is the basis.

The molecular weight of the conjugated diene-containing polymer can be selected from the range of about 1000 to 50,000, and the number average molecular weight Mn is preferably 1500 to 30000, more preferably 2000 to 20000, and particularly 2500 to 10000. The molecular weight dispersion degree D (Mw / Mn) can be selected from the range of about 1 to 5, preferably 1 to 3, and more preferably 1 to 2. The number average molecular weight Mn and the weight average molecular weight Mw can be measured in terms of standard polystyrene using size exclusion chromatography (SEC).

The glass transition temperature (Tg) of the conjugated diene-containing polymer can be selected from the range of about -100 to 300 ° C., preferably, in the following steps, -50 to 250 ° C., -10 to 230 ° C., 0 to 200 ° C. The temperature is 10 to 180 ° C, 30 to 160 ° C, and 50 to 150 ° C.

When the diol component and / or the dithiol component contains an aromatic dithiol and / or an aromatic dithiol such as bisphenol, the glass transition temperature (Tg) of the conjugated diene-containing polymer can be selected from the range of about 80 to 300 ° C. Preferably, it is 80 to 250 ° C., 90 to 200 ° C., 100 to 180 ° C., 110 to 160 ° C., 120 to 150 ° C. in a stepwise manner. The glass transition temperature can be measured using a differential scanning calorimeter.

The conjugated diene-containing polymer of the present invention exhibits thermosetting properties. When the conjugated diene-containing polymer is measured using a thermogravimetric differential thermal analyzer (TG / DTA), an exothermic peak (curing temperature T _cure ) can be observed. The exothermic peak (curing temperature T _cure ) of the conjugated diene-containing polymer can be selected from the range of about 100 to 400 ° C., for example, 150 to 350 ° C., preferably 180 to 300 ° C., more preferably 200 to 280 ° C., particularly 220. ~ 260 ° C.

Since the conjugated diene-containing polymer of the present invention has high heat resistance and a 10% weight decomposition temperature (T _d10 ) is higher than the curing temperature T _cure , it can be thermally cured without decomposition of the polymer. The 10% weight decomposition temperature (T _d10 ) of the conjugated diene-containing polymer measured using a thermogravimetric differential thermal analyzer (TG / DTA) can be selected from the range of about 200 to 400 ° C., preferably 230 to 380 ° C. More preferably, it is 250 to 350 ° C, especially 280 to 330 ° C.

(Manufacturing method of conjugated diene-containing polymer)
The method for producing the conjugated diene-containing polymer of the present invention is not particularly limited, but for example, the diene component (1) and the diol component and / or the dithiol component are reacted (or polymerized or condensed) in the presence of a base. Can be manufactured by.

In the polymerization, the ratio (charge ratio) of the total amount of the diol component and the dithiol component to 1 mol of the diene component (1) can be selected from the range of about 0.1 to 2 mol, and the following steps are gradually performed from 0.3 to 2. It is 1.8 mol, 0.5-1.5 mol, 0.8-1.2 mol. Further, the diol component and the dithiol component may be polymerized by using an excess amount with respect to the diene component (1), and when the excess amount is used, the total amount of the diol component and the dithiol component with respect to 1 mol of the diene component (1). The ratio (preparation ratio) can be selected from the range of about 1 to 5 mol, preferably 1.1 to 4 mol, more preferably 1.2 to 3 mol, and particularly 1.3 to 2 mol.

The base may be either an organic base or an inorganic base. Examples of the organic base include tertiary amines such as triethylamine, heterocyclic tertiary amines such as pyridine and morpholin, hexamethylenetetramine, diazabicycloundecene (DBU), diazabicyclononen (DBN), 1, 4-diazabicyclo [2.2.2] octane (DABCO) and the like can be mentioned. Examples of the inorganic base include metal hydroxides, metal carbonates, and metal alkoxides. Examples of the metal hydroxide include alkali metals such as sodium hydroxide and calcium hydroxide, or alkaline earth metal hydroxides. Examples of the metal carbonate include alkali metals such as sodium carbonate, sodium hydrogencarbonate and magnesium carbonate, or alkaline earth metal carbonates. Examples of the metal alkoxide include alkali metal linear or branched C _1-6 alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide. These bases can be used alone or in combination of two or more.

Among these bases, strong bases such as DBU, DBN, metal hydroxide, and metal alkoxide are preferable, and sodium methoxide, potassium t-butoxide, and the like are particularly preferable from the viewpoint of improving the nucleophilicity of the diol component and / or the dithiol component. Alkali metal alkoxide is preferred.

The amount (or ratio) of the base used is not particularly limited and can be selected from the range of about 1.5 to 10 mol with respect to 1 mol of the diol component and / or the dithiol component. .8-8 mol, 2-6 mol, 2.1-4 mol.

The polymerization is usually carried out in the presence of a solvent and may be either a protic solvent or an aprotic solvent, but from the viewpoint of reactivity, an aprotic solvent is usually used.

Examples of aprotic solvents include ethers, ketones, nitriles, amides, pyrrolidones, sulfoxides and the like. Examples of ethers include chain or cyclic ethers such as 1,4-dioxane and tetrahydrofuran. Examples of ketones include acetone and methyl ethyl ketone. Examples of nitriles include acetonitrile and the like. Examples of the amides include N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc). Examples of pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone. These solvents can be used alone or in combination of two or more. Among these aprotic solvents, aprotic polar solvents are preferable from the viewpoint of solubility in the produced conjugated diene-containing polymer.

The polymerization temperature (or reaction temperature) is not particularly limited and can be selected from the range of about 0 to 200 ° C., preferably 5 to 100 ° C., more preferably 10 to 80 ° C., particularly 15 to 60 ° C., and usually Room temperature (or 20-30 ° C). If the polymerization temperature is too high, the conjugated diene may be decomposed or a cross-linking reaction may occur at the same time.

The reaction time is not particularly limited and can be selected from the range of about 1 to 60 hours, preferably 6 to 48 hours, and more preferably 12 to 36 hours.

The reaction may be carried out in air or in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas. The reaction may be carried out under reduced pressure, but is usually carried out under pressurized pressure or normal pressure.

After completion of the reaction, the conjugated diene-containing polymer, which is a product, is separated by a conventional separation method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. Can be separated and purified.

[Curable composition and its cured product]
The curable composition of the present invention may contain at least the conjugated diene-containing polymer as a curing component, and may further contain a radically polymerizable compound (or a radically polymerizable monomer). In the curable composition containing the radically polymerizable compound, the conjugated diene-containing polymer can function as a cross-linking agent (or a curing agent).

Examples of the radically polymerizable compound include conjugated diene, ethylene-based unsaturated carboxylic acid, (meth) acrylic-based monomer, carboxylic acid vinyl ester, and aromatic vinyl.

Examples of the conjugated diene include conjugated alkadiene such as 1,3-butadiene, isoprene, and chloroprene.

Examples of the ethylene-based unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, and itaconic acid.

Examples of the (meth) acrylic monomer include (meth) acrylic acid chains such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. C _1-10 alkyl (meth) acrylate; C _6-10 aryl (meth) acrylate such as phenyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like ( Hydroxy acrylate C _2-10 alkyl; (meth) acrylamide, (meth) acrylamides such as N-methyl (meth) acrylamide; glycidyl (meth) acrylate; (meth) acrylonitrile and the like.

Examples of carboxylic acid vinyl esters include C _1-10 alkanoic acid vinyl esters such as vinyl acetate and vinyl propionate.

Examples of aromatic vinyls include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene.

These radically polymerizable compounds can be used alone or in combination of two or more.

The ratio of the radically polymerizable compound to the conjugated diene-containing polymer can be selected from the range of the former / the latter (molar ratio) = about 99/1 to 50/50, and is preferably 98/2 to 65 in the following steps. / 35, 97.5 / 2.5 to 80/20, 97/3 to 90/10.

The curable composition may further contain a radical polymerization initiator, and the radical polymerization initiator may be either a thermal radical polymerization initiator or a photoradical polymerization initiator.

Examples of the thermal radical polymerization initiator (or thermal polymerization initiator) include azo compounds such as azobisisobutyronitrile (AIBN), dimethylazoisobutyrate, and benzenediazonium chloride; benzoyl peroxide and di-t-butylper. Examples thereof include oxides, t-butylperbenzoate, and peroxides such as hydrogen peroxide.

Examples of the photoradical polymerization initiator (or photopolymerization initiator) include benzoins such as benzoin and benzoin methyl ether; acetophenones such as acetophenone and 3-hydroxyphenylmethyl ketone; anthraquinone such as anthraquinone and anthraquinone-2-sulfonate. Classes; thioxanthones such as thioxanthone and 2-chlorothioxanthone; ketals such as benzyldimethyl ketal; benzophenones such as benzophenone and the like.

These radical polymerization initiators can be used alone or in combination of two or more.

The ratio of the radical polymerization initiator can be selected from the range of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the conjugated diene-containing polymer and the radically polymerizable compound, preferably 0.1 to 10 parts by mass. More preferably, it is 1 to 5 parts by mass. The ratio of the radical polymerization initiator can be selected from the range of about 0.01 to 20 mol% with respect to the total amount of the radically polymerizable compound, and is preferably 0.1 to 15 mol% in the following steps. It is 0.5 to 10 mol%, 0.8 to 5 mol%, and 1 to 2 mol%.

In addition, the curable composition may contain various additives, if necessary. The additives include fillers or reinforcing agents; colorants such as dye pigments; flame retardants; lubricants; stabilizers such as antioxidants, ultraviolet absorbers and heat stabilizers; mold release agents; antistatic agents; conductive agents. ; Dispersant; Flow conditioner and the like. These additives may be used alone or in combination of two or more. The ratio of the total amount of these additives is, for example, 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.1 part by mass, based on 100 parts by mass of the total amount of the conjugated diene-containing polymer and the radically polymerizable compound. 1 to 10 parts by mass.

The curable composition of the present invention is easily cured by heating or a curing treatment such as irradiation with active rays such as ultraviolet rays, X-rays, and electron beams.

The heating temperature for curing the curable composition can be selected from the range of about 40 to 150 ° C., preferably 50 to 100 ° C., and more preferably 60 to 80 ° C. The heating time can be selected from the range of, for example, about 10 minutes to 60 hours.

In the curable composition containing the radically polymerizable compound, the conjugated diene-containing polymer acts as a crosslinking agent (or a curing agent), and a crosslinked polymer corresponding to the radically polymerizable compound can be obtained.

The shape of the cured product obtained by curing the curable composition is not particularly limited, and the cured product has a two-dimensional structure such as a film, a sheet, or a plate; a cured product having a three-dimensional structure such as a lens. Things can be mentioned.

The cured product may be produced by molding the curable composition into a predetermined shape or injecting it into a predetermined mold and then performing a curing treatment according to the shape of the desired cured product. May be applied to a base material or a substrate and the coating film may be cured to produce the product. Further, the curable composition containing a radically polymerizable compound may generate crosslinked polymer particles by subjecting a polymerization reaction such as emulsion polymerization or suspension polymerization.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The evaluation methods and the monomers used in Examples and Comparative Examples are as follows.

[Evaluation method]
(IR spectrum)
It was measured by a single reflection type total reflection measurement method using an infrared spectrophotometer (“Cary 630 FTIR spectrophotometer” manufactured by Azilent Technology Co., Ltd.).

(NMR spectrum)
The measurement was carried out at 26 ° C. using a nuclear magnetic resonance (NMR) device (“AVANCE 400” and “AVANCE NEO” manufactured by Bruker Co., Ltd.). The measurement solvent was deuterated DMSO or deuterated chloroform, and the chemical shift value was calibrated with the signal of tetramethylsilane and the solvent.

(Molecular weight)
The molecular weight (number average molecular weight Mn) and molecular weight dispersion degree D (Mw / Mn) of the polymer were determined by the size exclusion column “PL-gel, Mixed C (300 mm × 7.5 mm) heated to 40 ° C. on the EXTREMA chromatograph (JASCO Corporation). ) ”(Agileant Technology Co., Ltd.) is loaded in series, and tetrahydrofuran (for high-speed liquid chromatograph, no stabilizer, Wako Pure Chemical Industries, Ltd.) is flowed as an eluent at 0.8 mL / min to absorb ultraviolet light. Chromatograms detected by the spectrometer "UV-4070" (detected at 254 nm, JASCO) and the differential refractometer (RI-4030, JASCO) were obtained from standard polystyrene (Tosoh, TSK gel oligomer kit, Mn: 1.03). × 10 ⁶ , 3.89 × 10 ⁵ , 1.82 × 10 ⁵ , 3.68 × 10 ⁴ , 1.63 × 10 ⁴ , 5.32 × 10 ³ , 3.03 × 10 ³ , 8.73 × It was evaluated by calibrating with a cubic curve according to 10 ² ).

(Thermal properties)
The melting point of the monomer was measured using a melting point measuring device (“MPA100 type melting point measuring device Optimelt” manufactured by StandResearch Systems). The curing temperature (T _cure ) and 10% weight decomposition temperature (T _d10 ) of the polymer were determined by using a thermogravimetric differential thermal analyzer (TG / DTA, manufactured by Rigaku Co., Ltd., “Rigaku Thermo plus II TG8120”). Below, the temperature was measured in the range of room temperature to 500 ° C. at a heating rate of 10 ° C./min. The curing temperature (T _cure ) and glass transition temperature (T _g ) of the polymer were measured by differential scanning calorimetry (DSC, manufactured by Rigaku Co., Ltd., "Rigaku Thermo plus II DSC 8230"), and the temperature rise rate was 10 under a nitrogen stream. The measurement was carried out at ° C./min from room temperature to 20 ° C. below the decomposition start temperature.

[Monomer (or polymerization component)]
(Diene component (1))
Synthesis of Monomer A (2,3-bis (iodomethyl) -1,3-butadiene).

A solution of 2,3-dimethyl-1,3-butadiene (12.9 g, 0.157 mol) in carbon tetrachloride (120 mL) and a solution of bromine (25.2 g, 0.158 mol) in carbon tetrachloride (60 mL) for 4 hours. Dropped over. After completion of the dropwise addition, N-bromosuccinimide (55.9 g, 0.314 mol), 2,2'-azobis (isobutyronitrile) (0.832 g, 5.07 mmol), and carbon tetrachloride were added to the mixed solution. (6.0 mL) was added and refluxed for 2 hours. After completion of the reaction, the reaction mixture was suction filtered and the filtrate was cooled to 0 ° C. The resulting yellow crystals were collected by filtration and used in the next reaction without purification (29.5 g, crude yield 47.3%). The obtained compound was placed in a brown bottle and stored in a freezer. The melting points, ¹ H NMR spectra, and ¹³ C NMR spectrum data of the obtained compound (1,4-dibromo-2,3-bromomethyl-2-butene) are shown.

Melting point 151.3 to 156.1 ° C;
^{1 1} H-NMR (400 MHz, 30 ° C., CDCl ₃ ) δ6.51 (s, 8H, CH ₂ Br) ppm;
¹³ C-NMR (100 MHz, 30 ° C., CDCl ₃ ) δ137.5,28.2 ppm.

Acetone (55 mL) was added to 1,4-dibromo-2,3-bromomethyl-2-butene (15.1 g) obtained in the above reaction, and the mixture was further stirred with sodium thiosulfate (17.8 g, 113 mmol). Potassium iodide (18.7 g, 113 mmol) was added and the mixture was vigorously stirred at 45 ° C. for 2 hours. This suspension is poured into ice (85.2 g), the aqueous layer is extracted 3 times with diethyl ether (120 mL), the mixed organic layer is washed 3 times with saturated brine (120 mL), and anhydrous magnesium sulfate is used. After drying over magnesium, the mixture was concentrated under reduced pressure to obtain an asbestos-like pale yellow compound (11.2 g, 89.7%). The obtained compound was dissolved in diethyl ether and stored in a freezer (0.122M). It was confirmed by ¹ H NMR spectrum and IR spectrum that the obtained compound was the target 2,3-bis (iodomethyl) -1,3-butadiene (monomer A). The melting point, ^{1 1} H NMR spectrum and IR spectrum data of the obtained compound are shown below. The ¹ H NMR spectrum of the obtained compound is shown in FIG.

Melting point 86.6-87.5 ° C;
^{1 1} H-NMR (400 MHz, 30 ° C., DMSO-d ₆ ) δ4.20 (s, 4H, CH ₂ I), 5.40 (s, 2H, = CH ₂ ), 5.63 (s, 2H, = CH ₂ ) ppm; IR (ATR) ν _max / cm ^-1 3093 (CH), 1584 (C = C), 904 (CI).

(Diol component)
Monomer B1: Bisphenol A, manufactured by Tokyo Kasei Kogyo Co., Ltd. Monomer B2: Bisphenol Z, manufactured by Tokyo Kasei Kogyo Co., Ltd. Monomer B3: Phenolphthaline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Monomer B4: 9,9- Bis (4-hydroxyphenyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd. Monomer B5: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd.

(Dithiol component)
Monomer C: 1,10-decandithiol, manufactured by Tokyo Chemical Industry Co., Ltd. (dicarboxylic acid component)
Monomer D1: Adipic acid, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Monomer D2: Isophthalic acid, manufactured by Tokyo Chemical Industry Co., Ltd.

[Example 1]
Using diazabicycloundecene (DBU) (1.1 mmol) as the base and 1,4-dioxane (1.0 mL) as the solvent, monomer A (0.5 mmol) and monomer B1 (0.5 mmol) were added at room temperature. was stirred for 24 hours, it was tried the polycondensation of monomers a and B1, the ^{1 H} NMR spectrum, the progress of the polymerization was confirmed. When the molecular weight of the obtained polymer was evaluated by size exclusion chromatography, three large and sharp peaks were observed in the extra region of the calibration curve, the number average molecular weight (Mn) of the peak on the highest molecular weight side was 1300, and the molecular weight was dispersed. The degree (D) was 1.05. FIG. 2 shows a size exclusion chromatogram of the obtained polymer.

[Example 2]
Monomer A and monomer B1 were polymerized in the same manner as in Example 1 except that the polymerization temperature was 60 ° C. The number average molecular weight (Mn) of the obtained polymer was 1300, and the molecular weight dispersion (D) was 1.03. FIG. 3 shows a size exclusion chromatogram of the obtained polymer.

[Example 3]
Monomer A as in Example 1 except that 1.1 mmol of potassium t-butoxide (t-BuOK) was used in place of DBU and 1.5 mL of dimethyl sulfoxide (DMSO) was used in place of 1,4-dioxane. And the monomer B1 were polymerized. The number average molecular weight (Mn) of the obtained polymer was 3900, and the molecular weight dispersion (D) was 2.08. FIG. 4 shows a size exclusion chromatogram of the obtained polymer.

[Example 4]
Monomer A and monomer B1 were polymerized in the same manner as in Example 3 except that 1.5 mL of a mixed solvent of DMSO and tetrahydrofuran (THF) was used instead of DMSO. The volume ratio of the mixed solvent was DMSO / THF = 2/1. The number average molecular weight (Mn) of the obtained polymer was 7300, and the molecular weight dispersion (D) was 3.35. FIG. 5 shows a size exclusion chromatogram of the obtained polymer.

[Example 5]
Monomer A and monomer B1 were polymerized in the same manner as in Example 3 except that 1.5 mL of N, N-dimethylformamide (DMF) was used instead of DMSO. The number average molecular weight (Mn) of the obtained polymer was 2600, and the molecular weight dispersion (D) was 1.38. FIG. 6 shows a size exclusion chromatogram of the obtained polymer.

[Example 6]
Monomer A and monomer B1 were polymerized in the same manner as in Example 3 except that 1.5 mL of N, N-dimethylacetamide (DMAc) was used instead of DMSO. The number average molecular weight (Mn) of the obtained polymer was 5900, and the molecular weight dispersion (D) was 1.85. FIG. 7 shows a size exclusion chromatogram of the obtained polymer.

[Example 7]
Monomer A and monomer B1 were polymerized in the same manner as in Example 3 except that 1.5 mL of N-methyl-2-pyrrolidone (NMP) was used instead of DMSO, and the polymer represented by the following formula (B1) was used. Got The number average molecular weight (Mn) of the obtained polymer was 10500, and the molecular weight dispersion (D) was 2.14. FIG. 8 shows a size exclusion chromatogram of the polymer obtained in Example 7.

Moreover, the thermophysical properties of the obtained polymer were evaluated. FIG. 9 shows the TG / DTA curve of the polymer obtained in Example 7.

¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 7 are shown in FIGS. 10, 11 and the following.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ7.12 (d, J = 8.4 Hz, 4H), 6.83 (d, J = 8.4 Hz, 4H), 5.43 (s, 2H), 5.39 (s, 2H), 4.69 (s, 4H), 1.62 (s, 6H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ156.9, 143.9, 140.8, 128.1, 115.8, 114.6, 69.7, 42.1, 31.7 ppm.

The results of Examples 1 to 7 are shown in Table 1.

As is clear from Table 1, when the monomer A and the monomer B1 were reacted in the presence of a base, the progress of the polycondensation reaction was confirmed, and a polycondensate product of the monomer A and the monomer B1 was obtained (Example). 1). Further, an attempt was made to change the polymerization temperature from 25 ° C. to 60 ° C. to accelerate the reaction and increase the molecular weight, but almost no change in the molecular weight was observed depending on the polymerization temperature (Example 2). This polycondensation reaction is considered to proceed based on the _SN 2 reaction, and in the _SN 2 reaction, the concentration of both the nucleophile and the electrophile regulates the reaction rate, thus accelerating the reaction. It is necessary to increase the concentration of nucleophiles. Therefore, in order to increase the production efficiency of phenoxide anion, which is a nucleophile in this reaction, tBuOK, which quantitatively gives phenoxide anion, was used as a base instead of DBU, and DMSO was used as a solvent to carry out the reaction. A polymer having a high degree of polymerization of 3900 and D = 2.00 was obtained (Example 3). In Example 3, a precipitate was precipitated as the reaction proceeded. Further, in Examples 4 to 6 in which a mixed solvent of DMSO and THF, DMF, and DMAc were used as the solvent, a precipitate was precipitated during the reaction as in Example 3, but in Example 7 in which NMP was used as the solvent, the precipitate was precipitated. The precipitate did not precipitate until after the reaction was completed, and the reaction proceeded in a uniform system. Further, the polymer obtained in Example 7 has a higher degree of polymerization (Mn = 10500, D = 2.14) as compared with Examples 3 to 6 in which a precipitate is precipitated during the reaction, and a solvent in which the produced polymer is dissolved. It was found that a polymer having a high degree of polymerization can be obtained by selecting.

[Example 8]
Monomer A and monomer B2 were polymerized in the same manner as in Example 7 except that 0.5 mmol of monomer B2 was used instead of monomer B1 to obtain a polymer represented by the following formula (B2).

The molecular weight and thermophysical properties of the obtained polymer were evaluated. 12 and 13 show the size exclusion chromatogram and TG / DTA curve of the polymer obtained in Example 8.

The ¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 8 are shown in FIGS. 14, 15 and the following.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ7.15 (d, J = 8.6 Hz, 4H), 6.82 (d, J = 8.6 Hz, 4H), 5.41 (s, 2H), 5.37 (s, 2H), 4.67 (s, 4H), 2.21 (br, 4H), 1.53 (br, 4H), 1.48 (br, 4H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ156.8, 141.9, 140.9, 128.7, 116.0, 115.0, 69.8, 45.6, 37.9, 27.0, 23.5 ppm.

[Example 9]
Monomer A and monomer B3 were polymerized in the same manner as in Example 7 except that 0.5 mmol of monomer B3 was used instead of monomer B1 to obtain a polymer represented by the following formula (B3).

The molecular weight and thermophysical properties of the obtained polymer were evaluated. 16-18 show the size exclusion chromatogram, TG / DTA curve, and DSC curve of the polymer obtained in Example 9.

¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 9 are shown in FIGS. 19, 20 and the following.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ7.92 (d, J = 7.6 Hz, 1H), 7.70-7.66 (m, 1H), 7.55-7.49 ( m, 1H), 7.21 (d, J = 8.6Hz, 4H), 6.84 (d, J = 8.6Hz, 4H), 5.40 (s, 2H), 5.36 (s, 2H), 4.69 (s, 4H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ170.4, 159.1, 153.0, 140.5, 134.7, 133.9, 129.7, 129.0, 126.5 126.0, 124.5, 116.3, 115.1, 92.1, 69.8 ppm.

[Example 10]
Monomer A and monomer B4 were polymerized in the same manner as in Example 7 except that 0.5 mmol of monomer B4 was used instead of monomer B1 to obtain a polymer represented by the following formula (B4).

The molecular weight and thermophysical properties of the obtained polymer were evaluated. 21 to 23 show the size exclusion chromatogram, TG / DTA curve, and DSC curve of the polymer obtained in Example 10.

¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 10 are shown in FIGS. 24 and 25 and below.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ7.72 (d, J = 7.2 Hz, 2H), 7.35-7.22 (m, 6H), 7.10-7.06 ( m, 4H), 6.75-6.69 (m, 4H), 5.36 (s, 2H), 5.31 (s, 2H), 4.62 (s, 4H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ157.9, 152.3, 140.8, 140.5, 139.0, 129.7, 128.2, 127.9, 126.6 120.7, 116.1, 114.9, 69.9, 64.7 ppm.

[Example 11]
Monomer A and monomer B5 were polymerized in the same manner as in Example 7 except that 0.5 mmol of monomer B5 was used instead of monomer B1 to obtain a polymer represented by the following formula (B5).

The molecular weight and thermophysical properties of the obtained polymer were evaluated. 26-28 show the size exclusion chromatogram, TG / DTA curve, and DSC curve of the polymer obtained in Example 11.

¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 11 are shown in FIGS. 29, 30 and the following.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ7.72 (d, J = 7.2 Hz, 2H), 7.36 (d, J = 7.2 Hz, 2H) 7.28 (t, J) = 7.2Hz, 2H), 7.23 (t, J = 7.2Hz, 2H), 6.94 (s, 4H), 6.91 (d, J = 8.4Hz, 2H), 6.62 (D, J = 8.4Hz, 2H), 5.38 (s, 2H), 5.29 (s, 2H), 4.62 (s, 4H), 2.84 (s, 6H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ156.0, 152.5, 141.1, 140.5, 138.5, 131.0, 128.2, 127.8, 127.1, 126.9, 126.7, 120.6, 114.9, 111.3, 69.5, 64.8, 17.1 ppm.

[Example 12]
When monomer A and monomer C were polymerized in the same manner as in Example 7 except that 0.5 mmol of monomer C was used instead of monomer B1, a part of the product was insolubilized in an organic solvent, but chloroform was soluble. From the part, the formation of the polymer represented by the following formula (C) was confirmed. The molecular weight of the polymer obtained from the THF-soluble portion of the product was Mn = 4200.

In this polymerization, a precipitate was precipitated during the reaction, and when the precipitated solid was immersed in chloroform, it swelled without being dissolved and changed to a transparent gel. Therefore, in Example 12, not only the polymerization reaction but also the polymerization reaction was carried out. It is considered that the cross-linking reaction between the conjugated diene and thiol also occurred. Furthermore, the molecular weight distribution of the THF-soluble portion was as wide as D = 3.57, and the peak was multimodal, suggesting branching and cross-linking of the obtained polymer. FIG. 31 shows a size exclusion chromatogram of the polymer obtained in Example 12.

¹ H NMR and ¹³ C NMR spectral data of the polymer obtained in Example 12 are shown in FIGS. 32, 33 and below.

^{1 1} H-NMR (400 MHz, CDCl ₃ , 26 ° C.): δ5.30 (s, 2H), 5.14 (s, 2H), 3.36 (s, 4H), 2.45 (t, J = 6) .9Hz, 4H), 1.60-1.54 (m, 4H), 1.36 (br, 4H), 1.27 (br, 8H) ppm;
¹³ C-NMR (100 MHz, CDCl ₃ , 26 ° C.): δ142.5, 116.4, 39.7, 36.2, 32.6, 30.1, 29.9, 29.6 ppm.

[Comparative Example 1]
Monomer A and monomer are the same as in Example 7, except that 1.0 mmol of monomer D1 is used instead of monomer B1, the amounts of monomer A and tBuOK charged are 1 mmol and 2.2 mmol, respectively, and the amount of NMP is 2.5 mL. An attempt was made to polymerize with D1, but no polymer formation was confirmed from the results of the size exclusion chromatogram and ¹ H NMR spectrum.

[Comparative Example 2]
An attempt was made to polymerize the monomer A and the monomer D2 in the same manner as in Comparative Example 3 except that the monomer D2 was used instead of the monomer D1, but no polymer formation was confirmed as in Comparative Example 1.

The results of Examples 7 to 12 and Comparative Examples 1 and 2 are shown in Table 2.

As is clear from Table 2, in any of the diols of the monomers B1 to B5, the polymerization proceeded with the monomer A to obtain the corresponding polymer (Examples 7 to 11). In each of the polymers obtained in Examples 7 to 11, an exothermic peak (curing temperature T _cure ) was observed near 250 ° C. on the DTA curve. This exothermic peak means the progress of cross-linking and curing associated with thermal polymerization of conjugated diene units. In particular, the polymers obtained in Examples 8 to 11 have a curing temperature (T _cure ) of 40 ° C. or more lower than the 10% weight decomposition temperature (T _d10 ), and can be thermally cured without polymer decomposition. It turned out that there was.

The Tg of the polymers obtained in Examples 9 to 11 was observed at around 130 ° C., the lower the Tg, the lower the T _cure, and the lower the Tg, the lower the thermosetting. In general, many polymers having an unsaturated bond as a structural unit have a Tg lower than room temperature (25 ° C.) and exhibit properties as an elastomer. On the other hand, the Tg of the polymer obtained in the examples was higher than room temperature and did not show the characteristics as an elastomer. It is presumed that the reason for this is that the bisphenol skeleton occupies a large proportion of the constituent units. Further, as is clear from the DSC curves of FIGS. 18, 23 and 28, the exothermic peak was not confirmed in the second heating shown by the broken line, so that the first heating represented by the solid line completely completed the heating. It was found to be crosslinked (or cured).

When dithiol was used instead of diol, the polymerization proceeded to obtain the corresponding polymer (Example 12), but it was suggested that the cross-linking reaction between the conjugated diene and the thiol occurred together. Further, when a dicarboxylic acid was used instead of the diol, the polymerization did not proceed probably because the carboxylate anion had lower nucleophilicity than the phenolate anion (Comparative Examples 1 and 2).

[Example 13]
400 mg of styrene monomer (manufactured by Yoneyama Yakuhin Kogyo Co., Ltd.) and 64 mg of the polymer (Mn = 10500, D = 2.14) obtained in Example 7 are weight-ratio of butadiene skeleton in styrene / polymer = 95/5. As an initiator, 13 mg of AIBN (2 mol% based on the total amount of styrene monomer and the polymerizable group contained in the polymer obtained in Example 7) was added, and the mixture was reacted at 65 ° C. for 24 hours without solvent. However, a pale yellow film-like solid was obtained.

Polystyrene was soluble in hexane and chloroform, but the solid obtained in Example 12 was insoluble in hexane and chloroform. From this result, it was found that the obtained film-like solid was a crosslinked polymer in which styrene was crosslinked, and the polymer obtained in Example 7 functions as a macrocrosslinking agent.

Since the novel conjugated diene-containing polymer of the present invention exhibits thermosetting property, it is useful as a thermosetting resin and a curable composition. Further, since the polymer of the present invention has a conjugated diene unit, it can be suitably used as a cross-linking agent, and further, it can be chemically modified. Therefore, new functionality is imparted depending on the use of the polymer. It is also possible. Since the polymer of the present invention has high chemical resistance, it is also useful as a coating agent or the like that requires high chemical resistance.

Claims (12)

A polymer having a conjugated diene unit obtained by polymerizing a component represented by the following formula (1) with a diol component and / or a dithiol component.

(In the formula, X ¹ and X ² represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group). The polymer having a conjugated diene unit according to claim 1, wherein the diol component contains an aromatic diol. The polymer having a conjugated diene unit according to claim 1 or 2, wherein the diol component contains a diol represented by the following formula (2).

[In the formula, Z ¹ and Z ² represent an allene ring, ^Ra and R ^b represent substituents, p1 and p2 represent 0 or an integer greater than or equal to ^1, and A ¹ and A ² represent alkylene groups. q1 and q2 represent 0 or an integer of 1 or more, Y is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, and a divalent group represented by the following formula (2a) or (2b). Show the group of

(In the formula, Ar ¹ , Ar ² and Ar ³ represent arene rings, R ^c , R ^d and ^Re represent substituents, and r 1, r 2 and s represent integers greater than or equal to 0). ] The polymer having the conjugated diene unit according to any one of claims 1 to 3, wherein the diol component contains bisphenols. The polymer having a conjugated diene unit according to any one of claims 1 to 4, which has a structural unit represented by the following formula (3).

(R ¹ , R ² , R ³ and R ⁴ indicate a hydrogen atom or an alkyl group, and W indicates a residue of a diol component and / or a dithiol component) The polymer having a conjugated diene unit according to claim 5, wherein W is a residue of bisphenols. The component represented by the following formula (1) and the diol component and / or the dithiol component are polymerized in the presence of a base to produce a polymer having the conjugated diene unit according to any one of claims 1 to 6. Method.

(In the formula, X ¹ and X ² represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group). The production method according to claim 7, wherein the polymerization is carried out in an aprotic solvent. A curable composition comprising a polymer having at least the conjugated diene unit according to any one of claims 1 to 6. The curable composition according to claim 9, further comprising a radically polymerizable compound. A cured product of the curable composition according to claim 9 or 10. A cross-linking agent containing a polymer having a conjugated diene unit according to any one of claims 1 to 6.

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