JP7237307B2 - Polymer having conjugated diene units and method for producing the same - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Law 1. May 8, 2018 Presented in the 67th (2018) Annual Meeting of the Society of Polymer Science, Vol. 67, No. 1, 2Pb024, published by the Society of Polymer Science May 24, 2018 67th SPSJ Annual Meeting Presented with a document (poster) at the Nagoya International Conference Center. June 6, 2018 Presented in the Proceedings of the Society of Fiber Science and Technology 2018 Vol.73 No.1 (Annual Conference) 2P205 published by the Society of Fiber Science and Technology. June 14, 2018 Presented a document (poster) at the Annual Meeting of the Society of Fiber Science and Technology, Tower Hall Funabori

The present invention relates to polymers having novel conjugated diene units, curable compositions containing said polymers, and methods of making said polymers and curable compositions.

BACKGROUND ART Vinyl group-containing polymers having vinyl groups as structural units (or repeating units) have long attracted attention 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), polymers obtained by group transfer polymerization of 4-vinylbenzyl methacrylate have the structure It is described that the unit has a styryl group and therefore exhibits thermosetting properties.

X. Thang, M. Hong, L. Falivene, L. Caporaso, L. Cavallo, E.-X. Chen, J. Am. Chem. -A polymer having an acrylic skeleton (or a unit containing a (meth)acryloyl group) in a structural unit obtained by ring-opening polymerization of methylene-γ-butyrolactone is cured with a radical initiator, and the acrylic skeleton is cured. It is described that chemical modification is possible by performing a radical type thiol-ene reaction. Tobias Robert, Stefan Friebel, Green Chemistry, 2016, 18, 2922 (Non-Patent Document 3) describes that a 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) describes bis(α-(halomethyl)acrylic acid ester), dithiol, dicarboxylic acid, and polycondensation based on a conjugate substitution reaction with bisphenol to obtain a polymer having an acrylic skeleton in the main chain, and that the obtained polymer exhibits degradability when treated with thiol under a basic catalyst. It is

"Encyclopedia of Plastics/Functional Polymer Materials" Editing Committee, "Encyclopedia of Plastics/Functional Polymer Materials", "Chapter 4 Thermoplastic Resin/2. Unsaturated Polyester Resin", p. 466-p. 481, Industrial Research Association Encyclopedia Publishing Center, 2004 (Non-Patent Document 5), as a polymer having a polymerization active group in the polymer main chain, unsaturated polyester is industrially produced, fiber It is used as a raw material for reinforced plastics. Since unsaturated polyesters are produced at high temperatures of 140 to 220° C., thermal polymerization of unsaturated bonds (or double bonds), which are polymerization active groups, poses a problem. For this reason, the monomer having a polymerization active group (unsaturated bond) is preferably an internal olefin monomer with low polymerization reactivity (or a monomer having no double bond at the end, a non-terminal olefin monomer), 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 for heat curing, and an initiator that generates radicals is added to facilitate polymerization. In addition, when internal olefin units are introduced into a polymer, the glass transition point of the polymer is lowered. Therefore, unsaturated polyesters generally distributed have low mechanical strength and cannot be used alone as a structural material.

A polymer having a conjugated diene (or 1,3-butadiene) as a structural unit has also been reported. R. M. Ottenbrite, G. R. Myers, Journal of Polymer Science: Polymer Chem. Ed., vol 11, 1973, 1443-1446 (Non-Patent Document 6) describes 2,3-bis(bromomethyl)-1,3-butadiene, Polymerization with N,N,N',N'-tetramethyl-1,12-dodecanediamine is described to give ionic oligomers with conjugated diene units.

N. Nishioka, S. Hayashi, T. Koizumi, Angewandte Chem. Int. Ed., 2012, 51, 3682-3685 (Non-Patent Document 7) describes propargyl methyl carbonate and 9,9-dioctylfluorene-2 , and 7-diboronic acid in the presence of a zero-valent palladium catalyst to obtain a cross-conjugated polymer, which was converted to a linear conjugated polymer by Diels-Alder reaction. what has been done is stated.

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 "Encyclopedia of Plastics/Functional Polymer Materials" Editing Committee, "Encyclopedia of Plastics/Functional Polymer Materials", "Chapter 4 Thermoplastic Resin/2. Unsaturated Polyester Resin", p. 466-p. 481, Sangyo Research Institute 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 made from itaconic acid of Non-Patent Document 3 spontaneously polymerizes and cures unless a polymerization inhibitor is coexisted. In addition, the polymer of Non-Patent Document 4 is prone to main chain scission due to hydrolysis of the ester bond and conjugate substitution reaction in the 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 polyesters with high stability and chemical resistance are used industrially, but due to their low polymerization reactivity, a polymerization initiator is required for heat curing. , Since it does not polymerize alone, it is necessary to coexist with a vinyl monomer such as styrene. Moreover, most of the unsaturated polyesters before curing are liquid and have low mechanical strength even after curing. Therefore, the unsaturated polyester is often used not by itself but by impregnating it into a structural material such as glass fiber. Therefore, it is desired to develop a polymer that can be used alone as a structural material, has excellent chemical resistance, and has high polymerizability.

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

However, since the 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 conjugated diene units is obtained, a high-molecular-weight polymer cannot be obtained. In addition, the cross-conjugated polymer of Non-Patent Document 7 requires the use of an expensive metal catalyst for polymerization, and the reaction must be carried out under reflux conditions for 24 hours, resulting in severe polymerization conditions and complicated operations.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide novel polymers having conjugated diene units, curable compositions containing said polymers, and processes for their preparation.

Another object of the present invention is to provide polymers having conjugated diene units which are highly reactive and useful as cross-linking agents, curable compositions containing said polymers, and processes for their preparation.

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 production method thereof.

As a result of intensive studies to achieve the above object, the present inventors have found that when a diene component represented by the following formula (1) is reacted with a diol and/or a dithiol, a conjugated diene unit is formed even under mild conditions. We have found that it can be introduced into the main chain of a polymer, and completed the present invention.

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.

(Wherein, X ¹ and X ² represent halogen atoms, and R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups)

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

[Wherein, Z ¹ and Z ² represent an arene ring, R ^a and R ^b represent substituents, p 1 and p 2 represent an integer of 0 or 1 or more, A ¹ and A ² represent an alkylene group, q1 and q2 represent an integer of 0 or 1 or more, Y is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, a divalent represented by the following formula (2a) or (2b) indicates the group of

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

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

(R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group, W represents a residue of a diol component and/or a dithiol component)
and W may preferably be a bisphenol residue in the above formula (3).

The present invention also includes a method for producing a polymer having the conjugated diene unit by polymerizing the component represented by the formula (1) and a diol component and/or a dithiol component in the presence of a base. It may be polymerized in a protic solvent.

The present invention also includes a curable composition containing at least the polymer having 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 crosslinker comprising a polymer having said conjugated diene units.

In the present specification and claims, the number of carbon atoms in a substituent may be indicated by C ₁ , C ₆ , C ₁₀ or the like. For example, a “C ₁ alkyl group” means an alkyl group with 1 carbon number, and a “C _6-10 aryl group” means an aryl group with 6 to 10 carbon atoms.

Further, in the present specification and claims, the residue of a diol component (or diol) and the residue of a dithiol component (or dithiol) are the portions of the two hydroxy groups of the diol excluding the hydrogen atoms. , and dithiol excluding the hydrogen atoms of the two thiol groups.

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 a diol and/or dithiol-derived ether and/or thioether, so it is resistant to acids and bases. It is stable and has high chemical resistance. Furthermore, 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 it has a conjugated diene unit in the polymer main chain, it can be used as a curable resin by itself, and has high reactivity compared to conventional vinyl group-containing polymers that do not contain conjugated diene units. and is useful as a cross-linking agent for resins. Furthermore, since it has a conjugated diene unit, chemical modification by reaction such as Diels-Alder reaction is also possible. Further, in the polymer having a conjugated diene unit of the present invention, since the component represented by the formula (1) has high reactivity with the diol component and/or the dithiol component, it can be easily produced without using an expensive metal catalyst. And it can be synthesized under mild conditions.

FIG. 1 is a ¹ H NMR spectrum of the compound (2,3-bis(iodomethyl)-1,3-butadiene) obtained in the synthesis of Monomer A in Example. 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. FIG. 9 shows the TG/DTA curve of the polymer obtained in Example 7, where the solid line is TG and the dotted line is DTA. 10 is the ¹ H NMR spectrum of the polymer obtained in Example 7. FIG. 11 is the 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 the ¹ H NMR spectrum of the polymer obtained in Example 8. FIG. 15 is the 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. FIG. 17 shows the TG/DTA curve of the polymer obtained in Example 9, where the solid line is TG and the dotted line is DTA. FIG. 18 shows the DSC curve of the polymer obtained in Example 9, where the solid line is the result of the first heating and the dotted line is the result of the second heating. 19 is the ¹ H NMR spectrum of the polymer obtained in Example 9. FIG. 20 is the 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. FIG. 22 is 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 shows the DSC curve of the polymer obtained in Example 10, where the solid line is the result of the first heating and the dotted line is the result of the second heating. 24 is the ¹ H NMR spectrum of the polymer obtained in Example 10. FIG. 25 is the 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. FIG. 27 shows the 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 the 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. 29 is the ¹ H NMR spectrum of the polymer obtained in Example 11. FIG. 30 is the 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 the ¹ H NMR spectrum of the polymer obtained in Example 12. FIG. 33 is the ¹³ C NMR spectrum of the polymer obtained in Example 12. FIG.

[Polymer having a conjugated diene unit]
The polymer having a conjugated diene unit of the present invention (hereinafter sometimes simply referred to as a conjugated diene-containing polymer) is a component represented by formula (1) (hereinafter sometimes simply referred to as a diene component (1)). , a polymer (or polymer, polycondensate) obtained by reacting (or polymerizing or condensing) a diol component and/or a dithiol component, and a conjugated diene unit that is a hydrocarbon group derived from the diene component (1) , a diol component and/or an ether and/or a thioether derived from a dithiol component, the polymer has high stability such as chemical resistance and excellent handleability. In the following description, "diene component (1)", "diol component" and "dithiol component" each represent a polymerization component (or monomer), and also units derived from each polymerization component (or polymer constituent unit).

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

(Wherein, X ¹ and X ² represent halogen atoms, and R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups)

The halogen atoms represented by ^X1 and ^X2 in formula (1) include fluorine, chlorine, bromine and iodine atoms. Preferred halogen atoms are bromine atoms, iodine atoms, more preferably iodine atoms. The halogen atoms represented by ^X1 and ^X2 may be the same or different, and are usually the same.

R ¹ to R ⁴ in the above formula (1) represent a hydrogen atom or an alkyl group, and the alkyl group includes a linear or branched C group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. _{A 1-6} alkyl group and the like are included. 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 or a methyl group, and usually undergo a nucleophilic substitution reaction (S _N 2 reaction). From the viewpoint of speed (or reactivity), it is a hydrogen atom with low 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) include 2,3-bis(fluoromethyl) ^{-1,3 -} butadiene, 2,3-bis(chloro 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, 2,3-bis(iodomethyl)-1,3-, wherein any one of R ¹ to R ⁴ is a methyl group or an ethyl group 2,3-bis(halomethyl)-1,3-penta to hexadiene such as hexadiene; 2,3-bis(iodomethyl)-4-methyl-1,3-pentadiene in which R ¹ and R ² are methyl groups; 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 etc. These components can be used individually or in combination of 2 or more types. Among these, 2,3-bis(halomethyl)-1,3-butadiene is preferred, 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 preferred from the viewpoint of being able to be prepared using only organic reagents without using heavy metal reagents.

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

(Diol component)
Diol components include aliphatic diols and aromatic diols.

Aliphatic diols include chain aliphatic diols and cyclic aliphatic diols. Chain aliphatic diols include alkanediols and polyalkanediols, and alicyclic diols include cycloalkanediols and di(hydroxyalkyl)cycloalkanes.

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

Cycloalkanediols include C _5-8 cycloalkanediols such as cyclohexanediol, and di(hydroxyalkyl)cycloalkanes include di(hydroxyC _1-4 alkyl) such as 1,4-cyclohexanedimethanol. and C _5-8 cycloalkanes.

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

[Wherein, Z ¹ and Z ² are arene rings, R ^a 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 and Y is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, or a divalent group represented by the following formula (2a) or (2b)

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

In the above formula (2), the arene ring (aromatic hydrocarbon ring) represented by ring Z ¹ and ring Z ² includes a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and a ring-assembled arene ring. etc.

Polycyclic arene rings include condensed bicyclic arene rings such as naphthalene ring, condensed polycyclic C _10-14 arene rings such as condensed tricyclic arene rings such as anthracene ring and phenanthrene ring, especially naphthalene. A ring is preferred.

The ring-aggregated arene ring includes biC _6-12 arene rings such as biphenyl ring, binaphthyl ring and phenylnaphthalene ring, with biphenyl ring being particularly preferred.

The types of ring Z ¹ and ring Z ² may be the same or different, and are usually the same in many cases.

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

Examples of substituents represented by R ^a and R ^b include halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups; alkoxy groups; acyl groups; nitro groups; etc.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like. The alkyl group includes linear or branched C _1-6 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Cycloalkyl groups include C _5-8 cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Aryl groups include C _6-10 aryl groups such as phenyl groups. Aralkyl groups include C _6-10 aryl-C _1-4 alkyl groups such as benzyl group. Alkoxy groups include linear or branched C _1-10 alkoxy groups such as methoxy groups. Acyl groups include C _1-6 acyl groups such as an acetyl group. Examples of substituted amino groups include dialkylamino groups and diacylamino groups. Examples of dialkylamino groups include di-C _1-4 alkylamino groups such as dimethylamino group, and examples of diacylamino groups include di-C alkylamino groups such as diacetylamino group. _{A 1-4} acylamino group and the like can be mentioned. The substituents represented by R ^a and R ^b may be the same or different.

Preferred R ^a 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, and linear or branched groups such as methoxy groups. It is 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, especially a methyl group. The types of R ^a and R ^b may be the same or different, and are usually the same in many cases.

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, especially 0. Note that the substitution numbers p1 and p2 may be the same or different. When the substitution numbers p1 and p2 are 2 or more, the types of the two or more R ^a and R ^b substituting on the same ring Z ¹ and ring Z ² may be the same or different. The substitution positions of R ^a and R ^b are not particularly limited.

Examples of the alkylene group represented by A ¹ and A ² include straight-chain or A branched C _2-6 alkylene group is included. The types of A ¹ and A ² may be the same or different, and are usually the same. Preferred A ¹ , A ² are linear or branched C _2-4 alkylene groups, more preferably linear or branched C _2-3 alkylene groups, especially ethylene groups.

The repeating numbers (addition mole numbers) 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, more preferably 0 or 1. be. In the present specification and claims, the "repeating number (number of moles added)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of moles added, and a preferred embodiment is Similar to the preferred integer range. Moreover, when q1 and q2 are two or more, two 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. It suffices if they are respectively substituted at appropriate substitution positions of ^Z2 . When the rings Z ¹ and Z 2 are benzene rings, the substitution positions of the group [--O--(A ¹ O) _q1 --H] and the group [--O--(A ² O) _q2 -- ^H ] are Y 2-, 3-, or 4-position, preferably 3- or 4-position, particularly 3-position, of the phenyl group that binds to . When the rings Z ¹ and Z ² are naphthalene rings, they are often substituted at any of the 5- to 8-positions of the naphthyl group bonded to Y at the 1- or 2-position. , the 1- or 2-position of the naphthalene ring is substituted (substituted in the relationship of 1-naphthyl or 2-naphthyl), and substituted in the relationship of 1,5-position, 2,6-position with respect to this substitution position is preferred, and substitution at the 2,6 positions is particularly preferred.

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

The cycloalkylene group includes C _5-10 cycloalkylene groups such as 1,1-cyclopentylene group, 1,2-cyclopentylene group, 1,1-cyclohexylene group and 1,2-cyclohexylene group. C _5-8 cycloalkylene groups are preferred, C _5-6 cycloalkylene groups are more preferred, and 1,1-cyclohexylene groups are particularly preferred.

In formulas (2a) and (2b), the arene rings represented by Ar ¹ , Ar ² and Ar ³ are the same as ring Z ¹ and ring Z ² including preferred embodiments.

The substituents represented by R ^c , R ^d and R ^e are the same as R ^a and R ^b including preferred embodiments. The substitution numbers r1, r2 and s of R ^c , R ^d and R ^e are the same as p1 and p2 including preferred embodiments.

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 preferred, bisphenols and bisnaphthols are more preferred, and bisphenols are particularly preferred.

Bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 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); 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 bisphenols; phthalide skeleton-containing bisphenols such as phenolphthalein, o-cresolphthalein and p-xylenolphthalein;

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, fluorene skeleton-containing bisnaphthols such as 9-bis(6-hydroxyethoxy-2-naphthyl)fluorene (BNEF); and phthalide skeleton-containing bisnaphthols such as α-naphtholphthalein.

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%, in the total diol components. This ratio may be the charged ratio of the monomers, but is preferably the ratio of the structural units introduced into the conjugated diene polymer.

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

Aliphatic dithiols include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1, Linear or branched C such as 6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol _2-20 alkanedithiols are included.

Aromatic dithiols include dimercapto _C6 such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,5-dimercaptonaphthalene, 2,6-dimercaptonaphthalene. _-10 arene; aromatic dithiols corresponding to diols represented by the formula (2), such as fluorene skeleton-containing dithiols and phthalide skeleton-containing dithiols.

Ether group-containing dithiols include bis(2-mercaptoethyl)ether, 1,2-bis(2-mercaptoethoxy)ethane, and the like.

Thioether group-containing dithiols include bis(2-mercaptoethyl)sulfide, 1,3-bis(2-mercaptoethylthio)propane, bis(4-mercaptophenyl)sulfide and the like.

These dithiols can be used alone or in combination of two or more. Among these dithiols, aromatic dithiols are preferred from the viewpoint of heat resistance, aliphatic dithiols are preferred from the viewpoint of stability and handling, and preferred aliphatic dithiols are linear or branched C _2-18 alkanes. A dithiol, more preferably a linear or branched C _5-16 alkanedithiol.

The ratio of the total amount of the diol component and the dithiol component can be selected from the range of about 0.1 to 2 mol per 1 mol of the component (1), and the ratio is gradually increased from 0.3 to 1.8. mol, 0.5 to 1.5 mol, or 0.8 to 1.2 mol. 9 to 1.1 mol, preferably 0.95 to 1.05 mol, more preferably 0.98 to 1.02 mol, especially 1 mol.

Further, 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, and is preferable. is stepwise 0.3 to 1.8 mol, 0.5 to 1.5 mol, 0.8 to 1.2 mol, or stepwise 0.1 to 1.5 mol, 0.8 to 1.2 mol, or 3 to 1 mol, 0.4 to 0.6 mol.

(Conjugated diene-containing polymer)
The conjugated diene-containing polymer of the present invention is a polymer obtained by polymerizing the diene component (1) and 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 represent a hydrogen atom or an alkyl group, W represents a residue of a diol component and/or a dithiol component)

In formula (3), R ¹ , R ² , R ³ and R ⁴ are the same as R ¹ , R ² , R ³ and R ⁴ in formula (1) above, including preferred embodiments.

W, which is a residue of the diol component and/or dithiol component, includes residues corresponding to the diol component and dithiol component, and preferable residue W is also a residue corresponding to the preferable diol component and/or dithiol component. is the base.

Regarding the molecular weight of the conjugated diene-containing polymer, the number average molecular weight Mn can be selected from the range of about 1,000 to 50,000, preferably 1,500 to 30,000, more preferably 2,000 to 20,000, particularly 2,500 to 10,000. Further, the molecular weight distribution D (Mw/Mn) can be selected from the range of about 1-5, preferably 1-3, more preferably 1-2. 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 -50 to 250°C, -10 to 230°C, 0 to 200°C, 10 to 180°C, 30 to 160°C, and 50 to 150°C.

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

The conjugated diene-containing polymers of the present invention exhibit 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 ) 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 250 to 350°C, particularly 280 to 330°C.

(Method for producing 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 dithiol component are reacted (or polymerized or condensed) in the presence of a base. It can be manufactured by

In the polymerization, the ratio of the total amount of the diol component and the dithiol component to 1 mol of the diene component (1) (feeding ratio) can be selected from the range of about 0.1 to 2 mol, and is gradually increased from 0.3 to 1.8 mol, 0.5-1.5 mol, 0.8-1.2 mol. Further, the diol component and the dithiol component may be used in an excess amount for polymerization with respect to the diene component (1). 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 organic bases include tertiary amines such as triethylamine, heterocyclic tertiary amines such as pyridine and morpholine, hexamethylenetetramine, diazabicycloundecene (DBU), diazabicyclononene (DBN), 1, 4-diazabicyclo[2.2.2]octane (DABCO) and the like. Inorganic bases include metal hydroxides, metal carbonates, metal alkoxides, and the like. Metal hydroxides include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide. Metal carbonates include alkali metal or alkaline earth metal carbonates such as sodium carbonate, sodium bicarbonate, and magnesium carbonate. Metal alkoxides include alkali metal linear or branched C _1-6 alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases can be used alone or in combination of two or more.

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

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

Polymerization may usually be carried out in the presence of a solvent, and either a protic solvent or an aprotic solvent may be used. From the viewpoint of reactivity, an aprotic solvent is usually used.

Aprotic solvents include ethers, ketones, nitriles, amides, pyrrolidones, sulfoxides and the like. Ethers include linear or cyclic ethers such as 1,4-dioxane and tetrahydrofuran. Ketones include acetone, methyl ethyl ketone, and the like. Acetonitrile etc. are mentioned as nitriles. Amides include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and the like. Pyrrolidones include 2-pyrrolidone, N-methyl-2-pyrrolidone and the like. These solvents can be used alone or in combination of two or more. Among these aprotic solvents, aprotic polar solvents are preferred from the viewpoint of the solubility of the resulting 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. 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 in the range of about 1 to 60 hours, preferably 6 to 48 hours, more preferably 12 to 36 hours.

The reaction may be carried out in air or under an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas. Moreover, although the reaction may be carried out under reduced pressure, it is usually carried out under increased pressure or normal pressure in many cases.

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

[Curable composition and its cured product]
The curable composition of the present invention should 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 radical polymerizable compound, the conjugated diene-containing polymer can function as a cross-linking agent (or curing agent).

Examples of the radically polymerizable compound include conjugated dienes, ethylenically unsaturated carboxylic acids, (meth)acrylic monomers, carboxylic acid vinyl esters, and aromatic vinyls.

Conjugated dienes include conjugated alkadienes such as 1,3-butadiene, isoprene and chloroprene.

Ethylenically unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, and itaconic acid.

(Meth)acrylic monomers include (meth)acrylic acid chains such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. linear or branched C _1-10 alkyl; C _6-10 aryl (meth)acrylate such as phenyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and the like ( hydroxy C _2-10 alkyl meth)acrylate; (meth)acrylamides such as (meth)acrylamide and N-methyl(meth)acrylamide; glycidyl (meth)acrylate; (meth)acrylonitrile and the like.

Carboxylic acid vinyl esters include C _1-10 alkanoic acid vinyl esters such as vinyl acetate and vinyl propionate.

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 and the conjugated diene-containing polymer can be selected from the range of former/latter (molar ratio) = about 99/1 to 50/50, preferably 98/2 to 65 /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.

Thermal radical polymerization initiators (or thermal polymerization initiators) include azo-based compounds such as azobisisobutyronitrile (AIBN), dimethylazoisobutyrate, and benzenediazonium chloride; benzoyl peroxide, di-t-butylperoxide. oxides, t-butyl perbenzoate, peroxides such as hydrogen peroxide, and the like.

Examples of photoradical polymerization initiators (or photopolymerization initiators) include benzoins such as benzoin and benzoin methyl ether; acetophenones such as acetophenone and 3-hydroxyphenylmethylketone; anthraquinones such as anthraquinone and anthraquinone-2-sulfonate. thioxanthones such as thioxanthone and 2-chlorothioxanthone; ketals such as benzyldimethylketal; and benzophenones such as benzophenone.

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, preferably 0.1 to 10 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. More preferably, it is 1 to 5 parts by mass. Further, 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 radical polymerizable compound, preferably 0.1 to 15 mol%, 0.5 to 10 mol %, 0.8 to 5 mol %, 1 to 2 mol %.

Moreover, the curable composition may contain various additives as necessary. Examples of the additives include fillers or reinforcing agents; coloring agents such as dyes and pigments; flame retardants; lubricants; stabilizers such as antioxidants, ultraviolet absorbers and heat stabilizers; ; dispersant; fluidity control agent 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 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. 1 to 10 parts by mass.

The curable composition of the present invention is easily cured by a curing treatment such as heating or irradiation with actinic 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.degree. C., preferably 50 to 100.degree. C., more preferably 60 to 80.degree. The heating time can be selected, for example, from the range of 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 curing agent) to obtain a crosslinked polymer corresponding to the radically polymerizable compound.

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

The cured product may be produced by molding the curable composition into a predetermined shape or by 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 substrate and the coating film may be cured. Moreover, the curable composition containing the radically polymerizable compound may generate crosslinked polymer particles according to a polymerization reaction such as emulsion polymerization or suspension polymerization.

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

[Evaluation method]
(IR spectrum)
Using an infrared spectrophotometer ("Cary 630 FTIR spectrophotometer" manufactured by Agilent Technologies), the measurement was performed by a single reflection type total reflection measurement method.

(NMR spectrum)
It was measured at 26° C. using a nuclear magnetic resonance (NMR) device ("AVANCE 400" and "AVANCE NEO" manufactured by Bruker). Deuterated DMSO or deuterated chloroform was used as a measurement solvent, and chemical shift values were calibrated with tetramethylsilane and solvent signals.

(molecular weight)
The molecular weight (number average molecular weight Mn) and the molecular weight dispersity D (Mw/Mn) of the polymer were measured using a size exclusion column "PL-gel, Mixed C (300 mm × 7.5 mm) heated to 40 ° C. on an EXTREMA chromatograph (JASCO) )” (Agilent Technologies Inc.) are loaded in series, and tetrahydrofuran (for high-performance liquid chromatography, no stabilizer, Wako Pure Chemical Industries) is flowed at 0.8 mL / min as an eluent, and ultraviolet absorption The chromatogram detected with a spectrometer "UV-4070" (detected at 254 nm, JASCO) and a differential refractometer (RI-4030, JASCO) was analyzed with 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 × 10 ² ) was calibrated and evaluated with a cubic curve.

(Thermophysical properties)
The melting point of the monomer was measured using a melting point measuring apparatus (manufactured by Stanford Research Systems, "MPA100 type melting point measuring apparatus Optimelt"). The curing temperature (T _cure ) and 10% weight decomposition temperature (T _d10 ) of the polymer were measured using a thermogravimetric differential thermal analyzer (TG/DTA, manufactured by Rigaku Co., Ltd., "Rigaku Thermo plus II TG8120") under a nitrogen stream. Below, the temperature was measured in the range from 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 determined by differential scanning calorimetry (DSC, manufactured by Rigaku Co., Ltd., "Rigaku Thermo plus II DSC8230") under nitrogen flow at a heating rate of 10. It was measured at °C/min in the range from room temperature to 20°C below the decomposition initiation 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) was added with a solution of bromine (25.2 g, 0.158 mol) in carbon tetrachloride (60 mL) for 4 hours. dripped over. After 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 mixture. (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 for the next reaction without purification (29.5 g, crude yield 47.3%). The resulting compound was placed in a brown bottle and stored in a freezer. The melting point, ¹ H NMR spectrum, and ¹³ C NMR spectrum data of the obtained compound (1,4-dibromo-2,3-bromomethyl-2-butene) are shown.

Melting point 151.3-156.1°C;
¹ H-NMR (400 MHz, 30° C., CDCl ₃ ) δ 6.51 (s, 8H, CH ₂ Br) ppm;
¹³ C-NMR (100 MHz, 30° C., CDCl ₃ ) δ 137.5, 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 stirred, and sodium thiosulfate (17.8 g, 113 mmol) and Potassium iodide (18.7 g, 113 mmol) was added and vigorously stirred at 45° C. for 2 hours. This suspension was poured into ice (85.2 g), and the aqueous layer was extracted with diethyl ether (120 mL) three times. After drying with magnesium, it was concentrated under reduced pressure to obtain an asbestos-like pale yellow compound (11.2 g, 89.7%). The resulting compound was dissolved in diethyl ether and stored in a freezer (0.122M). The obtained compound was confirmed to be the target 2,3-bis(iodomethyl)-1,3-butadiene (monomer A) by ¹ H NMR spectrum and IR spectrum. The melting point, ¹ H NMR spectrum and IR spectrum data of the obtained compound are shown below. Also, FIG. 1 shows the ¹ H NMR spectrum of the obtained compound.

melting point 86.6-87.5°C;
¹ H-NMR (400 MHz, 30° C., DMSO-d ₆ ) δ 4.20 (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 (C−I).

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

(dithiol component)
Monomer C: 1,10-decanedithiol, manufactured by Tokyo Chemical Industry Co., Ltd. (dicarboxylic acid component)
Monomer D1: adipic acid, manufactured by Fuji Film 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 a base and 1,4-dioxane (1.0 mL) as a solvent, monomer A (0.5 mmol) and monomer B1 (0.5 mmol) were mixed at room temperature. After stirring for 24 hours, polycondensation of Monomer A and Monomer B1 was attempted, and progress of polymerization was confirmed by ¹ H NMR spectrum. When the molecular weight of the obtained polymer was evaluated by size exclusion chromatography, three large and sharp peaks were observed in the extrapolation region of the calibration curve, and the number average molecular weight (Mn) of the peak on the highest molecular weight side was 1300, and the molecular weight dispersion The degree (D) was 1.05. Figure 2 shows the size exclusion chromatogram of the resulting 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 obtained polymer had a number average molecular weight (Mn) of 1,300 and a molecular weight distribution (D) of 1.03. Figure 3 shows the size exclusion chromatogram of the resulting polymer.

[Example 3]
Monomer A in the same manner as in Example 1 except that 1.1 mmol of potassium t-butoxide (t-BuOK) was used instead of DBU and 1.5 mL of dimethylsulfoxide (DMSO) was used instead of 1,4-dioxane. and monomer B1 were polymerized. The obtained polymer had a number average molecular weight (Mn) of 3900 and a molecular weight dispersity (D) of 2.08. FIG. 4 shows the size exclusion chromatogram of the resulting 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 obtained polymer had a number average molecular weight (Mn) of 7300 and a molecular weight dispersity (D) of 3.35. Figure 5 shows the size exclusion chromatogram of the resulting 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 obtained polymer had a number average molecular weight (Mn) of 2600 and a molecular weight distribution (D) of 1.38. FIG. 6 shows the size exclusion chromatogram of the resulting 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 obtained polymer had a number average molecular weight (Mn) of 5900 and a molecular weight dispersity (D) of 1.85. FIG. 7 shows the size exclusion chromatogram of the resulting 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 to obtain a polymer represented by the following formula (B1). got The obtained polymer had a number average molecular weight (Mn) of 10,500 and a molecular weight dispersity (D) of 2.14. FIG. 8 shows a size exclusion chromatogram of the polymer obtained in Example 7.

In addition, thermophysical properties of the obtained polymer were evaluated. The TG/DTA curve of the polymer obtained in Example 7 is shown in FIG.

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

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.): δ 156.9, 143.9, 140.8, 128.1, 115.8, 114.6, 69.7, 42.1, 31.7 ppm.

Table 1 shows the results of Examples 1-7.

As is clear from Table 1, when Monomer A and Monomer B1 were reacted in the presence of a base, the progress of the polycondensation reaction was confirmed, and a polycondensate of Monomer A and Monomer B1 was obtained (Example 1). Furthermore, an attempt was made to increase the molecular weight by changing the polymerization temperature from 25°C to 60°C to accelerate the reaction, but almost no change in molecular weight was observed due to the polymerization temperature (Example 2). This polycondensation reaction is thought _to proceed based on the _SN2 reaction, in which the concentration of both nucleophilic and electrophilic species defines the reaction rate, thus accelerating the reaction. requires increasing concentrations of nucleophiles. Therefore, in order to increase the production efficiency of the phenoxide anion, which is a nucleophilic species in this reaction, the reaction was performed using tBuOK, which quantitatively provides the phenoxide anion, as a base instead of DBU, and using DMSO as a solvent. A polymer with a high polymerization degree of 3900 and D=2.00 was obtained (Example 3). In Example 3, a precipitate was deposited as the reaction proceeded. In addition, in Examples 4 to 6 using a mixed solvent of DMSO and THF, DMF, and DMAc as the solvent, a precipitate was deposited during the reaction in the same manner as in Example 3, but in Example 7 using NMP as a solvent, No precipitate was deposited until after the reaction was completed, and the reaction proceeded in a homogeneous system. Furthermore, the polymer obtained in Example 7 has a higher degree of polymerization (Mn = 10500, D = 2.14) than Examples 3 to 6 in which precipitates were deposited during the reaction, and the solvent in which the resulting polymer dissolves It was found that a polymer with 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 obtained polymer was evaluated for molecular weight and thermophysical properties. 12 and 13 show the size exclusion chromatogram and TG/DTA curve of the polymer obtained in Example 8. FIG.

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

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.): δ 156.8, 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 obtained polymer was evaluated for molecular weight and thermophysical properties. 16 to 18 show the size exclusion chromatogram, TG/DTA curve and DSC curve of the polymer obtained in Example 9. FIG.

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

¹ H-NMR (400 MHz, CDCl ₃ , 26° C.): δ 7.92 (d, J=7.6 Hz, 1 H), 7.70-7.66 (m, 1 H), 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 obtained polymer was evaluated for molecular weight and thermophysical properties. 21 to 23 show the size exclusion chromatogram, TG/DTA curve and DSC curve of the polymer obtained in Example 10. FIG.

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

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.): δ 157.9, 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 obtained polymer was evaluated for molecular weight and thermophysical properties. 26 to 28 show the size exclusion chromatogram, TG/DTA curve and DSC curve of the polymer obtained in Example 11. FIG.

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

¹ H-NMR (400 MHz, CDCl ₃ , 26° C.): δ 7.72 (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 = 8.4 Hz, 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.): δ 156.0, 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]
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. Although part of the product was insoluble in organic solvents, it was soluble in chloroform. Formation of a polymer represented by the following formula (C) was confirmed from the part. The molecular weight of the polymer obtained from the THF soluble portion of the product was Mn=4200.

In this polymerization, a precipitate precipitated during the reaction, and when the precipitated solid was immersed in chloroform, it swelled without dissolving and changed to a transparent gel. Therefore, in Example 12, not only the polymerization reaction but also A cross-linking reaction between the conjugated diene and the thiol is thought to have occurred concurrently. Furthermore, the molecular weight distribution of the THF-soluble portion was as wide as D=3.57, and the peaks were 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 and 33 and below.

¹ H-NMR (400 MHz, CDCl ₃ , 26° C.): δ 5.30 (s, 2H), 5.14 (s, 2H), 3.36 (s, 4H), 2.45 (t, J=6 .9 Hz, 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.): δ 142.5, 116.4, 39.7, 36.2, 32.6, 30.1, 29.9, 29.6 ppm.

[Comparative Example 1]
Monomer A and monomer were used in the same manner as in Example 7, except that 1.0 mmol of monomer D1 was used instead of monomer B1, the charged amounts of monomer A and tBuOK were 1 mmol and 2.2 mmol, respectively, and the amount of NMP was 2.5 mL. An attempt was made to polymerize D1, but size exclusion chromatogram and ¹ H NMR spectrum did not confirm the formation of a polymer.

[Comparative Example 2]
Polymerization of Monomer A and Monomer D2 was attempted in the same manner as in Comparative Example 3, except that Monomer D2 was used instead of Monomer D1.

Table 2 shows the results of Examples 7-12 and Comparative Examples 1-2.

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

The Tg of the polymers obtained in Examples 9 to 11 were all observed to be around 130° C. The lower the Tg, the lower the T _cure , and the lower the Tg, the lower the heat curing temperature. In general, many polymers containing unsaturated bonds in their constituent units have a Tg lower than room temperature (25° C.) and exhibit elastomeric properties. In contrast, the Tg of the polymers obtained in Examples was higher than room temperature and did not exhibit properties as an elastomer. The reason for this is presumed to be that the proportion of the bisphenol skeleton in the structural units is large. In addition, as is clear from the DSC curves of FIGS. 18, 23 and 28, no exothermic peak was observed in the second heating indicated by the dashed line. It was found to be crosslinked (or cured).

When a dithiol was used instead of the diol, the polymerization proceeded and the corresponding polymer was obtained (Example 12), but it was suggested that the cross-linking reaction between the conjugated diene and the thiol occurred concurrently. Moreover, when a dicarboxylic acid was used instead of the diol, the polymerization did not proceed (Comparative Examples 1 and 2), probably because the carboxylate anion is less nucleophilic than the phenolate anion.

[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 were mixed at a weight ratio of styrene/butadiene skeleton in the polymer = 95/5. , AIBN 13 mg (2 mol% relative to the total amount of polymerizable groups contained in the polymer obtained in styrene monomer and the polymer obtained in Example 7) was added as an initiator and reacted at 65 ° C. for 24 hours without solvent. At this point, a pale yellow film-like solid was obtained.

Polystyrene is 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 functioned as a macrocrosslinking agent.

The novel conjugated diene-containing polymers of the present invention exhibit thermosetting properties and are useful as thermosetting resins and curable compositions. In addition, since the polymer of the present invention has a conjugated diene unit, it can be suitably used as a cross-linking agent, and can be chemically modified. is also possible. Since the polymer of the present invention has high chemical resistance, it is also useful as a coating agent 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.

(Wherein, X ¹ and X ² represent halogen atoms, and R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or linear or branched C _1-6 alkyl groups) A polymer having conjugated diene units in accordance with claim 1, wherein said diol component comprises 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).

[Wherein, Z ¹ and Z ² represent an arene ring, R ^a and R ^b represent substituents, p 1 and p 2 represent an integer of 0 or 1 or more, A ¹ and A ² represent an alkylene group, q1 and q2 represent an integer of 0 or 1 or more, Y is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, an alkylene group, a cycloalkylene group, a divalent represented by the following formula (2a) or (2b) indicates the group of

(In the formula, Ar ¹ , Ar ² and Ar ³ represent arene rings, R ^c , R ^d and ^Re represent substituents, r 1 , r 2 and s represent integers of 0 or more). ] The polymer having conjugated diene units 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 represent a hydrogen atom or a linear or branched C _1-6 alkyl group, W represents a residue of a diol component and/or a dithiol component) 6. The polymer having conjugated diene units according to claim 5, wherein W is a residue of bisphenols. A component represented by the following formula (1) and a diol component and/or a dithiol component are polymerized in the presence of a base to produce a polymer having a conjugated diene unit according to any one of claims 1 to 6. Method.

(Wherein, X ¹ and X ² represent halogen atoms, and R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or linear or branched C _1-6 alkyl groups) 8. The production method according to claim 7, wherein the polymerization is carried out in an aprotic solvent. A curable composition comprising at least a polymer having conjugated diene units according to any one of claims 1-6. 10. 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 comprising a polymer having a conjugated diene unit according to any one of claims 1-6.

Images