Recyclable polysilyl ether resin, method for manufacturing same, and method for manufacturing raw material compound by decomposition of said polysilyl ether resin

Abstract

A recyclable polysilyl ether resin has a structure represented by general formula (1). [In formula (1), Xi represents a specific polymer chain, m represents an integer of 2 or greater, bonds marked with *1 and *2 each represent a bond bonding to an adjacent structure, m bonds bonded to Xi each represent a bond bonded to an individual terminal of the polymer chain, R1 and R2 each represent a substituent such as a hydrogen atom, ni represents an integer of 2 or greater, and the plurality of Xi may be the same or different, the plurality of R1 may be the same or may be different, and the plurality of R2 may be the same or may be different.]

Description

Recyclable polysilyl ether resin, its manufacturing method, and method for manufacturing raw material compounds by decomposition of the polysilyl ether resin

[0001] The present invention relates to a polysilyl ether resin, a method for producing the same, and a method for producing a raw material compound by decomposing the polysilyl ether resin.

[0002] In recent years, from the viewpoint of resource conservation and environmental preservation, technologies for reusing and recycling various plastic products have attracted attention. For example, Japanese Patent Laid-Open Publication No. 2000-169624 (Patent Document 1) discloses a recyclable polyurethane resin, and a method for decomposing the polyurethane resin, in which the polyurethane resin is dissolved in a solubilizing agent containing a polyamine compound, a low-molecular-weight glycol, or an amino alcohol, and insoluble matter is removed as necessary, followed by hydrolysis with liquid water at 200 to 320°C, and the resulting polyamine compound and / or polyol compound is recovered. Furthermore, International Publication No. 2022 / 099210 (Patent Document 2) discloses the use of a monomer having a silyl ether bond to obtain a resin containing a silyl ether bond, and also discloses that such a resin can be hydrolyzed using a fluoride or the like.

[0003] JP 2000-169624 A International Publication No. 2022 / 099210

[0004] However, the polyurethane resin decomposition method described in Patent Document 1 requires treatment at relatively high temperatures, such as 200 to 320°C, and is not sufficient in terms of efficiently producing and recovering raw material compounds. Furthermore, when the technology described in Patent Document 2 is employed to decompose a resin by hydrolysis, the compound obtained by hydrolysis is different from the monomer used to produce the resin, and the original raw material compound cannot be obtained after decomposition. Patent Document 2 does not describe at all the structure of a resin in which polymer chains, such as polyolefin chains or polyether chains, are bonded (crosslinked) together via a silyl ether bond.

[0005] The present invention has been made in view of the problems associated with the prior art, and aims to provide: a recyclable polysilyl ether resin that enables efficient decomposition of the resin by a desilylation reaction, thereby enabling efficient production of the raw material compounds used in the production; a method for producing a recyclable polysilyl ether resin that enables efficient production of the polysilyl ether resin; and a method for producing a raw material compound by decomposition of a polysilyl ether resin that enables efficient production of the raw material compound by decomposition of the polysilyl ether resin.

[0006] As a result of extensive research conducted by the present inventors to achieve the above-mentioned object, they have found that by forming a polysilyl ether resin having a structure represented by the following general formula (1), it is possible to efficiently decompose the resin by a desilylation reaction, thereby making it possible to efficiently produce a polyol represented by the following general formula (2), which is a raw material compound used in the production, and to obtain a resin with high recyclability, which has led to the completion of the present invention.

[0007] That is, the present invention provides the following aspects.

[0008] [1] The following general formula (1):

[0009]

[0010] [In formula (1), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, bonds marked with *1 and *2 each represent a bond bonding to an adjacent structure, and bonds marked with *2 represent X ｉ There are (m-1) X ｉ Each of the m bonds bonded to R represents a bond bonded to a different end of the polymer chain (a different end of the polymer chain), １ and R ２Each of n is a substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; ｉ represents an integer of 2 or more, and n ｉ There are multiple Xs depending on the number of ｉ may be the same or different, and n ｉ There are multiple R １ may be the same or different, and n ｉ There are multiple R ２ may be the same or different.] A recyclable polysilyl ether resin having a structure represented by the following formula:

[0011] [2] X in formula (1) ｉ The recyclable polysilyl ether resin according to [1], wherein the polymer chain selected from the group consisting of linear or branched polybutadiene and its hydrogenated product (hydrogenated polybutadiene), and linear or branched polypropylene glycol.

[0012] [3] A polymer having a hydroxyl group at each end of the polymer chain, as shown in the following general formula (2):

[0013]

[0014] [In formula (2), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, and the m hydroxyl groups in the formula represent hydroxyl groups bonded separately to separate ends of the polymer chain, and at least one raw material compound selected from the group consisting of polyols represented by the following general formula (3):

[0015]

[0016] [In formula (3), R １ and R ２each represents one substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; １ and Z ２ and each represent one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom.] with

[0017] [4] The organosilicon compound is reacted with Z in the formula (3). １ and Z ２ and n is a hydrogen atom, and the raw material compound and the organosilicon compound are reacted using tris(pentafluorophenyl)borane as a polymerization catalyst.

[0018] [5] The polysilyl ether resin according to [1] or [2] is subjected to a desilylation reaction to cleave the silyl ether bond, thereby decomposing the polysilyl ether resin and obtaining a compound represented by the following general formula (2):

[0019]

[0020] [In formula (2), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or greater, and the m hydroxyl groups in the formula represent hydroxyl groups separately bonded to separate ends of the polymer chain.

[0021] Although the reason why the above object is achieved by the present invention is not entirely clear, the present inventors speculate as follows. Specifically, the recyclable polysilyl ether resin of the present invention has a structure represented by the general formula (1) above, in which the specific polymer chains are bonded via silyl ether bonds (i.e., the ends of the polymer chains are connected to each other via silyl ether bonds). As described in the method for producing a recyclable polysilyl ether resin of the present invention, a polysilyl ether resin having such a structure can be efficiently synthesized by reacting a raw material compound (polyol) represented by the general formula (2) above with an organosilicon compound (silylating agent) represented by the general formula (3) above, thereby connecting the polymer chains in the polyol raw material compound via silyl ether bonds, thereby extending the molecular chains or, if the polyol is branched, forming a three-dimensional crosslinked structure. Here, the reaction between the hydroxyl groups of the polyol raw material compound and the organosilicon compound is a reaction equivalent to the so-called alcohol protection reaction (a reaction in which the hydroxyl groups of an alcohol are protected by converting them to silyl ethers (i.e., the hydroxyl groups are derivatized with an organosilicon compound (silyl-etherifying the hydroxyl groups) to introduce a protecting group onto the hydroxyl groups), and by utilizing this reaction to connect the polyols together via a silyl ether bond, the structure represented by general formula (1) can be efficiently produced. The silyl ether bond in such a structure can be easily cleaved by utilizing a so-called desilylation reaction (deprotection reaction). Therefore, the polysilyl ether resin can be easily decomposed by a so-called desilylation reaction, and the polyol (raw material compound) used during production can be obtained by this decomposition (regenerated by returning it to the polyol (raw material compound)). In this desilylation reaction, for example, a known desilylation agent (e.g., a fluoride ion source used in a deprotection reaction from a silyl ether bond) can be used as appropriate (in particular, when a fluoride ion source is used, the reactivity with silicon is high and the reaction can proceed in a higher yield). In addition, the desilylation reaction can generally be carried out under mild conditions and is known as a method for obtaining decomposition products in a high yield.

[0022] Thus, the recyclable polysilyl ether resin of the present invention can be efficiently produced by reacting a raw material compound (polyol) represented by the general formula (2) with an organosilicon compound represented by the general formula (3) using a known alcohol protection reaction. Furthermore, after use, the polysilyl ether resin can be efficiently decomposed by a known deprotection reaction (desilylation reaction), thereby efficiently producing (regenerating) the raw material polyol (the raw material compound used during production). Thus, because the recyclable polysilyl ether resin of the present invention has a structure represented by the general formula (1), it is possible to achieve the effect of efficiently decomposing the resin by a desilylation reaction, thereby efficiently producing the raw material compound used during production.

[0023] The recyclable polysilyl ether resin of the present invention can be produced by linking polyols of various structures via silyl ether bonds by appropriately changing the structure (particularly the structure of the polymer chain portion) of the raw material compound (polyol) represented by the general formula (2) used in production. Therefore, it is possible to produce a polysilyl ether resin with desired physical properties depending on the type of polymer chain, the presence or absence of a branched structure, and even the valence of the hydroxyl groups in the polyol. For example, it is possible to simultaneously crosslink different types of polyols to form a block copolymer, or to adjust the physical properties of the polysilyl ether resin by changing the composition. In this way, the recyclable polysilyl ether resin of the present invention can be produced by linking polyols of various structures via silyl ether bonds. ｉ By changing the type of polymer chain, it is possible to appropriately adjust the physical properties to obtain desired physical properties depending on the application, etc. (For example, it is possible to obtain a polysilyl ether resin with desired improved mechanical properties, or to change the solubility depending on the application, etc.) As described above, the recyclable polysilyl ether resin of the present invention is easily decomposable and can be efficiently converted into raw materials, and can also be easily adjusted to have desired characteristics (physical properties) during production, for example, by appropriately selecting the types of raw material compounds during production to obtain resins with various excellent mechanical properties, and it is also possible to efficiently obtain resins with physical properties depending on the application.

[0024] According to the present invention, it is possible to provide: a recyclable polysilyl ether resin that enables efficient decomposition of the resin by a desilylation reaction, thereby enabling efficient production of the raw material compounds used in the production; a method for producing a recyclable polysilyl ether resin that enables efficient production of the polysilyl ether resin; and a method for producing a raw material compound by decomposition of a polysilyl ether resin that enables efficient production of the raw material compound by decomposition of the polysilyl ether resin.

[0025] 1 is a graph showing the IR spectra of the polysilyl ether resin obtained in Example 1 and the comparative resin obtained in Comparative Example 1.

[0026] The present invention will be described in detail below based on preferred embodiments thereof.

[0027] [Recyclable Polysilyl Ether Resin] The recyclable polysilyl ether resin of the present invention is a polysilyl ether resin represented by the following general formula (1):

[0028]

[0029] [In formula (1), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, bonds marked with *1 and *2 each represent a bond bonding to an adjacent structure, and bonds marked with *2 represent X ｉ There are (m-1) X ｉ The m bonds bonded to the polymer chain (X ｉ R represents bonds bonded separately to separate ends of the polymer chain (polymer chain selected as １ and R ２ Each of n is a substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; ｉ represents an integer of 2 or more, and ｉ There are multiple Xs depending on the number of ｉmay be the same or different, and n ｉ There are multiple R １ may be the same or different, and n ｉ There are multiple R ２ may be the same or different.]

[0030] Such X in formula (1) ｉ is one type of polymer chain (polymer chain having a linear or branched structure) selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000.

[0031] X in such a formula ｉ The polyolefin chain that can be selected as X has a number average molecular weight of 100 to 10,000 (more preferably 100 to 5,000, and even more preferably 300 to 2,000). ｉThe polyether chains that can be selected as the polysilyl ether resin have a number-average molecular weight of 100 to 10,000 (more preferably 100 to 5,000, and even more preferably 300 to 2,000). By setting the number-average molecular weights of the polyolefin chains and polyether chains at or above the respective lower limits, the ratio of polymer chains to silyl groups in the polysilyl ether resin increases, thereby making it possible to enhance the influence of the polymer chains on the properties of the polysilyl ether resin and more efficiently impart properties according to the type of polymer chain. Note that, when the number-average molecular weights of the polyolefin chains and polyether chains are below the respective lower limits, not only does the influence of the silyl moiety become greater, but recovery of the organosilicon compound during decomposition becomes difficult, tending to reduce the recycling effect. Furthermore, when the number-average molecular weights of the polyolefin chains and polyether chains are below the respective upper limits, the decrease in the hydroxyl group concentration of the raw material compound (polyol) can be more effectively suppressed compared to when the number-average molecular weights exceed the respective upper limits, making synthesis easier. As the number average molecular weight, a value determined by obtaining a molecular weight distribution by gel permeation chromatography may be used, or, if the number of hydroxyl groups in the polyol before crosslinking is known, a value obtained by calculation from the hydroxyl value may be used.

[0032] In addition, X in formula (1) ｉ The polyolefin chain and the polyether chain that can be selected as X may have a linear or branched structure. ｉ When the structure of X is a linear structure, the value of m in the formula is 2, and ｉ Two bonds will be bonded to X. ｉ When the structure of X is a branched structure, the value of m in the formula is 3 or more, ｉ Depending on the value of m, three or more bonds are bonded to

[0033] In addition, X in such formula (1) ｉThe polyolefin chain that can be selected as is not particularly limited, and for example, linear or branched polybutadiene and its hydrogenated product, linear or branched polyethylene, linear or branched polypropylene, etc. can be suitably used. Among these, from the viewpoint of ease of synthesis of a raw material compound having a terminal hydroxyl group structure, linear or branched polybutadiene and its hydrogenated product (hydrogenated product: hydrogenated polybutadiene) are more preferred, linear polybutadiene and linear hydrogenated polybutadiene (hydrogenated polybutadiene) are even more preferred, and linear hydrogenated polybutadiene is particularly preferred.

[0034] In addition, X in the formula (1) ｉ The polyether chain that can be selected as the hydroxyl group is not particularly limited, and for example, a polypropylene glycol having a linear or branched structure, a polyacetal having a linear or branched structure, a polyethylene glycol having a linear or branched structure, or the like can be suitably used. Among these, from the viewpoint of facilitating the synthesis of a raw material compound having a hydroxyl group structure at its terminal, a polypropylene glycol having a linear or branched structure is preferred, and a polypropylene glycol that is linear or branched in three directions is more preferred.

[0035] Furthermore, m in the formula (1) is an integer of 2 or more. In the structure represented by the formula (1), X ｉ The number of bonds marked with *2 attached to the group (1) changes. In such formula (1), m may be an integer of 2 or greater, but is more preferably an integer of 2 to 10, even more preferably an integer of 2 to 5, and particularly preferably an integer of 2 to 3. By setting the value (integer) of m in such formula to 2 or greater, it becomes possible to efficiently produce a polysilyl ether resin having a structure represented by formula (1). Furthermore, by setting the value of m in such formula to be equal to or less than the above-mentioned upper limit, the proportion of silyl ether moieties (silyl ether bond moieties) present in the polysilyl ether resin can be further reduced compared to when the value exceeds the above-mentioned upper limit, which not only makes it possible to suppress the influence of the silyl ether moieties and more efficiently exhibit the properties of the polymer chain, but also tends to more efficiently exhibit the recycling effect.

[0036] In addition, the value of m in such a formula is X ｉ For example, the structure of X ｉ When the structure of X is a linear structure, the polymer chain has two ends, so the value of m in the formula is 2, and X ｉ Two bonds are bonded to X ｉ When the structure is a branched structure, the polymer chain has three or more ends, so the value of m in the formula is 3 or more, and X ｉ In this way, three or more bonds are bonded to X in formula (1). ｉ Each bond bonded to X represents a bond bonded to a different end of a polymer chain having a linear or branched structure. ｉ It will vary depending on the structure of the

[0037] In this way, in formula (1), the bond marked with *2 is X ｉ Depending on the structure, there will be (m-1) bonds marked with *2. Depending on the value of m, there will be multiple bonds marked with *2. In that case, the structure represented by formula (1) will be repeated three-dimensionally. When m is 2, the structure represented by formula (1) will be represented by the following formula (1-1):

[0038]

[0039] (In formula (1-1), X in the formula ｉ is a polymer chain having a linear structure, ｉ , R １ , R ２ , n ｉ and the meaning of each bond (such as the meaning of *1 and *2) are the same as those in formula (1) (preferable ones are also the same)), and when m is 3, the structure represented by formula (1) can be represented by the following formula (1-2):

[0040]

[0041] (In formula (1-2), X in the formula ｉ is a polymer chain having a branched structure branched in three directions, except that X in the formula ｉ , R １ , R２ , n ｉ and the meaning of each bond (such as the meaning of *1 and *2) are the same as those in formula (1) (preferable ones also have the same meanings).

[0042] In addition, in formula (1), the bonds marked with *1 and *2 indicate bonds that bond to adjacent structures, respectively. That is, the bonds marked with *1 and *2 indicate that the positions of *1 and *2 are positions that bond to the adjacent structures, respectively. The adjacent structure here basically means the structure of the structural portion (structural portion surrounded by parentheses) between the bonds marked with *1 and *2 in formula (1) above, but may also be a terminal group of the resin. The terminal group will differ depending on the components used during production and their ratios. Since the bonds marked with *1 and *2 are bonds that bond to the adjacent structures, a resin having a structure represented by formula (1) basically has a structure in which X in the formula ｉ The resulting polymer has a structure in which polymer chain portions (linear or branched polyolefin chains and / or polyether chains having a specific average molecular weight) represented by the formula (I) and silyl ether bond portions are alternately repeated.

[0043] In addition, in the structure represented by the formula (1), X ｉ m pieces (X ｉ The bonds of X are bonded to different ends of the polymer chain. ｉ The total number of bonds bonded to X are bonds bonded to different ends (separate ends) of the polymer chain. ｉ For example, when the polymer chain is linear, the total number of bonds bonded to X represents one bond bonded to one of the two ends and another bond bonded to the other end. ｉ has a branched structure, it represents one bond bonded to one of the three or more ends and (m-1) bonds bonded separately to the other ends other than the end to which the bond bonded. In this way, the polysilyl ether resin having the structure represented by the formula (1) has a plurality (m: 2 or more) of polymer chains (Xｉ ) have a structure in which the ends of the ｉ Since is 2 or more, there are at least two X ｉ are connected by a silyl ether bond).

[0044] In addition, R in the formula (1) １ and R ２ Each of R is a substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group. １ and R ２ For convenience, the "hydrogen atom" selected as is considered to be one type of substituent.

[0045] Such R in formula (1) １ and R ２ The aryl group that can be selected as R preferably has a carbon number of 6 to 10 (more preferably 6 to 9, and even more preferably 6 to 8). By setting the carbon number of such an aryl group to the upper limit or less, the steric hindrance of the raw materials used during production is reduced compared to when the carbon number exceeds the upper limit, and the target resin tends to be synthesized more efficiently. １ and R ２ The aryl group that can be selected as R may have a substituent, and such a substituent includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. １ and R ２ As the aryl group that can be selected as , from the viewpoint of further reducing the influence of steric hindrance, a phenyl group, a dimethylphenyl group, and a methylphenyl group are more preferable, a phenyl group and a methylphenyl group are even more preferable, and a phenyl group is particularly preferable.

[0046] Furthermore, R in formula (1) １ and R ２The aliphatic hydrocarbon group that can be selected as R preferably has a carbon number of 1 or more and 10 or less (more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less). By making the carbon number of such an aliphatic hydrocarbon group equal to or less than the upper limit, the steric hindrance of the raw materials used in the production is reduced, and the target resin can be synthesized more efficiently. １ and R ２ The aliphatic hydrocarbon group that can be selected as may be linear, branched, or cyclic, and may have a substituent. Examples of the substituent that such an aliphatic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a cyclohexane group, and a vinyl group.

[0047] In addition, the R １ and R ２ From the viewpoint of improving chemical stability, the aliphatic hydrocarbon group that can be selected as is more preferably a linear, branched, or cyclic alkyl group, even more preferably a branched or linear alkyl group, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0048] In addition, R in such formula (1) １ and R ２ From the viewpoint of easier synthesis of the raw materials, each of R is more preferably one type of substituent (a group other than a hydrogen atom) selected from the group consisting of an aryl group (more preferably an aryl group having 6 to 10 carbon atoms) and an aliphatic hydrocarbon group (more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms). １ and R ２ is more preferably one selected from the group consisting of a phenyl group, an ethyl group, an n-propyl group, and an isopropyl group, from the viewpoint that the organosilicon compound as a raw material is less likely to volatilize and the raw material is easier to handle, and R １ and R ２ It is particularly preferred that both are phenyl groups.

[0049] In addition, n in the formula (1) ｉ is an integer of 2 or more (preferably 100 or more), and indicates the number of repetitions of the structure enclosed in parentheses in the formula. ｉ In this case, there are two or more structures enclosed in parentheses in the formula depending on the number of X ｉ may be the same or different, and multiple R １ may be the same or different, and multiple R ２ may be the same or different. ｉ When different types of polymer chains are selected as the polysilyl ether resin, the polysilyl ether resin is endowed with physical properties according to the type of polymer chain.

[0050] Furthermore, the structure represented by the formula (1) is preferably at least one of the structure represented by the formula (1-1) and the structure represented by the formula (1-2), since a polysilyl ether resin having such a structure can be more easily produced.

[0051] Hereinafter, a method for producing the recyclable polysilyl ether resin of the present invention, which can be suitably employed as a method for producing the recyclable polysilyl ether resin of the present invention, will be described.

[0052] [Method for Producing Recyclable Polysilyl Ether Resin] The method for producing a recyclable polysilyl ether resin of the present invention comprises:

[0053]

[0054] [In formula (2), X ｉrepresents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, and the m hydroxyl groups in the formula represent hydroxyl groups bonded separately to separate ends of the polymer chain, and at least one raw material compound selected from the group consisting of polyols represented by the following general formula (3):

[0055]

[0056] [In formula (3), R １ and R ２ each represents one substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; １ and Z ２ and each represent one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom.] with

[0057] The raw material compound is at least one selected from the group consisting of polyols represented by the general formula (2) above, each having a hydroxyl group at the end of the polymer chain. In such polyols represented by the formula (2), X in the formula (2) ｉ is one type of polymer chain (polymer chain having a straight chain or branched structure) selected from the group consisting of a linear or branched polyolefin chain having a number average molecular weight of 100 to 10,000 and a linear or branched polyether chain having a number average molecular weight of 100 to 10,000. ｉ is X in formula (1) ｉ (The same applies to preferred).

[0058] Furthermore, m in formula (2) is an integer of 2 or greater. Such m in formula (2) has the same meaning as m in formula (1) (the same applies to what is preferred). Therefore, m in formula (2) is more preferably an integer of 2 to 10, even more preferably an integer of 2 to 5, and particularly preferably an integer of 2 to 3. By setting the value of m (an integer) in such a formula to 2 or greater, it becomes possible to efficiently produce a polysilyl ether resin having a structure represented by formula (1). Setting the value of m in such a formula to not more than the upper limit makes it possible to further reduce the proportion of silyl ether moieties in the resulting polysilyl ether resin, compared to when the value exceeds the upper limit. This not only makes it possible to more efficiently develop the properties of the polymer chain, but also tends to make it possible to further enhance the recycling effect of the resulting polysilyl ether resin.

[0059] In the polyol represented by the formula (2), the m hydroxyl groups in the formula (groups represented by the formula: -OH in the formula (2)) are hydroxyl groups bonded to different ends of the polymer chain (different ends of the polymer chain). Therefore, the polyol represented by the formula (2) is ｉ In other words, the polyol represented by the above formula (2) having hydroxyl groups at the ends of the polymer chain is a polyol represented by the above formula (2) having m hydroxyl groups at the ends of the polymer chain, ｉ The term "a" has the same meaning as a compound having a hydroxyl group (a group represented by the formula: --OH in formula (2)) bonded to each end of a polymer chain represented by the formula:

[0060] The polyol represented by the formula (2) is ｉ The structure of the compound has a linear or branched structure (for example, X ｉ is a polypropylene glycol having a branched structure, the polyol represented by formula (2) has a branched structure, ｉ is a polypropylene glycol having a linear structure, the polyol represented by formula (2) will have a linear structure).

[0061] In the present invention, the raw material compound is at least one selected from the group consisting of polyols represented by the above formula (2). As such, the raw material compound may be one polyol represented by the above formula (2), or may be a mixture of two or more polyols represented by the above formula (2). When a mixture of two or more polyols represented by the above formula (2) is used as the raw material compound, X ｉ In this case, different polyols are used, and as a result, the structure represented by the formula (1) of the obtained polysilyl ether resin is ｉ This means that multiple structures with different types of X are included. ｉ It is possible to give characteristics according to the type of material.

[0062] The method for producing such a raw material compound (polyol) is not particularly limited, and it may be produced by a known method as appropriate so as to be the compound represented by the above formula (2). As such a raw material compound (polyol), commercially available products may be used as appropriate.

[0063] The organosilicon compound of the present invention is at least one selected from the group consisting of compounds represented by the above general formula (3). １ and R ２ Each of R in formula (3) is a substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group. １ and R ２ are R in formula (1), respectively. １ and R ２ (The same applies to preferred).

[0064] In addition, Z in the formula (3) １ and Z ２Each of Z represents one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom. From the viewpoint of ease of synthesis of an organosilicon compound having that functional group, such a functional group is more preferably a hydrogen atom or a chlorine atom, and further from the viewpoint of reaction yield, a hydrogen atom is particularly preferred. １ and Z ２ may be the same or different.

[0065] In addition, the organosilicon compound of the present invention is at least one selected from the group consisting of compounds represented by the above general formula (3).In this way, the organosilicon compound may be one compound represented by the above formula (3), or may be a mixture of two or more compounds represented by the above formula (3).In addition, when two or more compounds represented by the above formula (3) are contained, the reaction efficiency is higher, so it is preferable to select Z in each compound. １ Types and Z ２ It is preferable that the types of the respective compounds are the same.

[0066] Examples of such organosilicon compounds include diphenylsilane, dimethylsilane, diphenyldichlorosilane, dimethyldichlorosilane, diisopropylsilane, and dichlorodiisopropylsilane. Among these, from the viewpoint of improving chemical stability, diphenylsilane, dimethylsilane, and diisopropylsilane are more preferred, and diphenylsilane is particularly preferred.

[0067] The method for producing such an organosilicon compound is not particularly limited, and any known method can be used as appropriate. Furthermore, commercially available organosilicon compounds can also be used as appropriate.

[0068] In addition, in the present invention, the raw material compound is reacted with the organosilicon compound to obtain the recyclable polysilyl ether resin of the present invention having the structure represented by formula (1). This reaction can be said to be a reaction in which the raw material polyol (alcohol) is reacted with the organosilicon compound to form a silyl ether bond (silylation reaction) to obtain the polysilyl ether resin. In other words, it can be said to be a reaction in which the alcohol is protected with the organosilicon compound (alcohol protection reaction: a reaction in which a silyl group known as a protecting group is introduced to form a silyl ether bond), thereby sequentially bonding the polyol (alcohol) with a silyl ether bond. Therefore, the conditions for reacting the raw material compound with the organosilicon compound can be appropriately selected from reaction conditions used in known reactions that can be used to protect alcohols (known alcohol protection reaction: known silylation reaction), depending on the type of functional group in the organosilicon compound.

[0069] In addition, in order to improve the reaction yield, the reaction is carried out by converting the organosilicon compound into Z in the formula (3). １ and Z ２ In the reaction of the raw material compound with the organosilicon compound, it is preferable to use tris(pentafluorophenyl)borane as a polymerization catalyst. １ and Z ２In the case where all of the groups are hydrogen atoms, it is preferable to react the raw material compound with the organosilicon compound using tris(pentafluorophenyl)borane as a polymerization catalyst. Furthermore, the method for proceeding with the reaction between the raw material compound and the organosilicon compound using tris(pentafluorophenyl)borane as a polymerization catalyst (the method for silylation of the hydroxyl groups of a polyol) is not particularly limited, and the reaction may proceed under the conditions employed in known methods for silylation using tris(pentafluorophenyl)borane as a catalyst (the method for synthesizing silyl ethers), depending on the components used. For example, when reacting the raw material compound with the organosilicon compound, a method may be employed in which the raw material compound and the organosilicon compound are reacted in a solvent using the polymerization catalyst at 40 to 130°C (more preferably 80 to 120°C) for 0.1 to 1 hour. The solvent used in such a reaction is preferably a hydrocarbon solvent or a halogenated hydrocarbon solvent, since these solvents do not inhibit the reaction of forming a silyl ether bond and allow the reaction to proceed more smoothly. Among these, it is even more preferable to use xylene, toluene, dichloromethane, or dichlorobenzene.

[0070] Furthermore, the amounts of the raw material compound and the organosilicon compound used when reacting them are not particularly limited, but it is preferable to use the raw material compound and the organosilicon compound in amounts such that the molar amount of the organosilicon compound is 0.40 to 0.60 moles (more preferably 0.45 to 0.55 moles) per mole of hydroxyl groups in the raw material compound (polyol). By adjusting the amounts of the raw material compound and the organosilicon compound used so that they are within the above ranges, the reaction to form a silyl ether bond can proceed more smoothly. That is, by setting the molar amount of the organosilicon compound to be equal to or greater than the above lower limit, it is possible to efficiently prevent a situation in which the organosilicon compound is completely consumed by reaction with the hydroxyl groups, and the reaction does not proceed further despite the hydroxyl groups remaining, and this tends to allow the reaction to form silyl ether bonds to proceed more smoothly. On the other hand, by setting the molar amount to be equal to or less than the above upper limit, it is possible to efficiently prevent a situation in which the hydroxyl groups in the raw material compound are completely consumed by reaction with the organosilicon compound, and the reaction does not proceed further despite the organosilicon compound remaining, and this tends to allow the reaction to form silyl ether bonds to proceed more smoothly.

[0071] Furthermore, when tris(pentafluorophenyl)borane is used as a polymerization catalyst in the reaction between the raw material compound and the organosilicon compound, the amount of the polymerization catalyst used is preferably 0.001 to 0.10 mol (more preferably 0.002 to 0.05 mol) per mol of hydroxyl groups in the raw material compound (polyol). Setting the amount (molar amount) of the polymerization catalyst used to be equal to or greater than the lower limit tends to be more effective in improving the reaction rate, while setting it to be equal to or less than the upper limit tends to be more effective in reducing catalyst costs and reducing the effect of the catalyst on the physical properties of the polysilyl ether resin.

[0072] Furthermore, when the raw material compound and the organosilicon compound are reacted in a solvent, the content (total amount) of the raw material compound and the organosilicon compound in the solvent is preferably 5 to 50% by mass (more preferably 10 to 40% by mass). By setting the content (total amount) of the raw material compound and the organosilicon compound in such a solvent to be equal to or greater than the lower limit, a greater effect in terms of improving the reaction rate tends to be obtained, while by setting it to be equal to or less than the upper limit, the viscosity of the reaction solution can be maintained at a sufficiently low value, allowing the reaction to proceed more uniformly throughout the solution, and tending to further reduce variation in molecular weight.

[0073] Furthermore, when the raw material compound and the organosilicon compound are reacted in a solvent, it is preferable to use the raw material compound in an amount such that the concentration (molar concentration) of hydroxyl groups in the raw material compound (polyol) present in the solvent is 0.10 mol / L or more (more preferably 0.20 mol / L or more). By setting this concentration (molar concentration) of hydroxyl groups at or above the lower limit, a greater effect tends to be obtained in terms of improving the reaction rate.

[0074] In this way, the raw material compound (polyol) and the organosilicon compound are reacted to obtain the recyclable polysilyl ether resin of the present invention. The method for producing the recyclable polysilyl ether resin of the present invention has been described above. Below, the method for producing the raw material compound by decomposition of the polysilyl ether resin of the present invention will be described.

[0075] [Method for producing raw material compounds by decomposition of polysilyl ether resin] In the method for producing raw material compounds by decomposition of the polysilyl ether resin of the present invention, a desilylation reaction is carried out on the polysilyl ether resin of the present invention (recyclable polysilyl ether resin) to cleave the silyl ether bond, thereby decomposing the polysilyl ether resin and producing a compound represented by the following general formula (2):

[0076]

[0077] [In formula (2), X ｉrepresents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or greater, and the m hydroxyl groups in the formula represent hydroxyl groups bonded separately to separate ends of the polymer chain.

[0078] The polysilyl ether resin of the present invention has a structure represented by the above formula (1), in which a polyol is connected by a silyl ether bond. ｉIt can be said that the polysilyl ether resin of the present invention has a structure in which polymer chains represented by the formula (1) (linear or branched polyolefin chains and / or polyether chains having a specific average molecular weight) are connected by silyl ether bonds, with silyl ether bond portions and polymer chain portions being repeated alternately. From the structure represented by formula (1), such silyl ether bonds can be considered as linking groups connecting polymer chain portions in the polyol, and can also be recognized as protecting groups for the hydroxyl groups of the polyol (alcohol). Considering that such silyl groups are protecting groups for the hydroxyl groups of the polyol, it can be understood that the polysilyl ether resin of the present invention can be easily restored to the polyol originally used as a raw material by subjecting the polysilyl ether resin to a known reaction such as a desilylation reaction (deprotection reaction of the protecting group of the alcohol) to eliminate the silyl groups. Thus, according to the method for producing a raw material compound by decomposing a polysilyl ether resin of the present invention, it is clear that the polysilyl ether resin can be easily decomposed by desilylation, and that the variations in shape and molecular weight of the decomposed product obtained by cleaving the silyl ether bond can be made equivalent to those of the polyol raw material compound used in the production of the polysilyl ether resin. Therefore, the method for producing a raw material compound by decomposing a polysilyl ether resin of the present invention can be said to be a method that can efficiently produce the raw material compound used as the raw material for the polysilyl ether resin to be decomposed. Furthermore, since the obtained raw material compound can be reused to produce a polysilyl ether resin, it can be said that this method is effective for horizontal recycling. Below, the steps in the method for producing such a raw material compound will be explained.

[0079] In the present invention, the polysilyl ether resin of the present invention is decomposed by causing a desilylation reaction to proceed to cleave the silyl ether bond.

[0080] Such a desilylation reaction is a reaction in which a silyl protecting group (silyl compound) is removed from a silyl ether bond. The method for such desilylation is not particularly limited, and a method similar to a known desilylation reaction (a known deprotection reaction of a silyl protecting group carried out when an alcohol is protected with a silyl protecting group) can be employed. Examples of such a method include a method of desilylation (deprotection of a silyl protecting group) using a desilylation agent (deprotecting agent), a method of desilylation by hydrolysis in the presence of a catalyst, and other desilylation methods using an acid or a base.

[0081] When desilylation is performed using a desilylation agent, the desilylation agent is not particularly limited and known agents can be used as appropriate, but it is preferable to use a fluoride ion source. The fluoride ion source is not particularly limited, and known compounds that can be used for deprotection of silyl protecting groups using fluoride ions can be used as appropriate, such as potassium fluoride and tetrabutylammonium fluoride. The use of such a fluoride ion source enables desilylation using fluoride anions as a base. Furthermore, deprotection using the desilylation agent is preferably performed in a solvent. Examples of such solvents include water, methanol, ethanol, tetrahydrofuran, ethyl acetate, dimethylformamide, and mixtures thereof. The reaction temperature for deprotection using the desilylation agent varies depending on the solvent used and cannot be generally determined, but it is preferably about 20 to 100°C. The reaction time for the deprotection with fluoride ions varies depending on conditions such as the reaction temperature, and cannot be generally determined, but is preferably about 0.1 to 2.0 hours. The amounts of the polysilyl ether resin of the present invention used, the desilylation agent used, and the solvent used are not particularly limited, and may be appropriately adjusted so that the desilylation reaction proceeds.

[0082] Furthermore, when the desilylation reaction is carried out by hydrolysis in the presence of an acid catalyst, the reaction is preferably carried out using alcohol and / or water as a solvent, or in a solvent containing alcohol and / or water. The acid catalyst may be any known catalyst that can be used for desilylation, and is not particularly limited. Examples of such an acid catalyst include hydrochloric acid, acetic acid, acrylic acid, paranitrobenzoic acid, and fumaric acid. When the desilylation reaction is carried out by hydrolysis in the presence of such an acid catalyst, the reaction conditions are not particularly limited, and known reaction conditions may be appropriately employed. For example, reaction conditions may be employed in which the reaction temperature is 20 to 100°C and the reaction time is about 0.1 to 24 hours.

[0083] Furthermore, as a method for such a desilylation reaction, it is preferable to employ a method in which desilylation is carried out using a fluoride ion source and a fluoride anion as a base, from the viewpoints that the silyl protecting group can be selectively deprotected without affecting other functional groups, and that the reaction has high reactivity with silicon and can proceed in a higher yield.

[0084] In this way, the silyl ether bond in the polysilyl ether resin of the present invention is cleaved by the desilylation reaction, and the polysilyl ether resin of the present invention is decomposed to obtain at least one raw material compound selected from the group consisting of polyols (linear or branched polyols) represented by the general formula (2). Note that such polyols represented by formula (2) are the same as those described in the above-mentioned method for producing a recyclable polysilyl ether resin of the present invention (the same applies to preferred polyols).

[0085] As explained above, the recyclable polysilyl ether resin of the present invention can be synthesized by using polyols as raw material compounds and bonding (crosslinking) polyols together through a silyl protection reaction of alcohols. After use, the polysilyl ether resin can be easily decomposed by a simple method such as a deprotection reaction of the silyl protecting groups to return it to the original polyol as the raw material compound (return it to raw material), thereby enabling the raw material compound to be reused. Generally, a desilylation reaction (deprotection reaction) can be carried out under mild conditions and is known as a method for obtaining a decomposed product in high yield. Therefore, it is clear that the present invention makes it possible to efficiently decompose a polysilyl ether resin through a desilylation reaction, thereby efficiently producing the raw material compound used in the production.

[0086] Generally, a recyclable resin is required to have both recyclability and mechanical properties. The recyclable polysilyl ether resin of the present invention has a structure in which X in formula (1) ｉ The amount of polymer chain introduced is changed to stretch it, or X ｉ It is also possible to obtain desired physical properties (e.g., mechanical properties, solubility, etc.) by changing the structure of the polymer chain represented by the formula (I) to three-dimensionally crosslink it, or by appropriately changing the type of polymer chain to allow various types of polymer chains to coexist (for example, it is also possible to improve tensile properties by appropriately selecting the type of polymer chain). Thus, the recyclable polysilyl ether resin of the present invention is excellent in recyclability, and its mechanical properties can be easily adjusted to desired properties by changing the type of polymer chain or the amount of polymerized polymer chain, making it possible to achieve both recyclability and mechanical properties.

[0087] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0088] <Components Used in Examples and Comparative Examples> First, we will explain the components used in each of the Examples, etc. In the following Examples, etc., the polyols used may be abbreviated as polyols (A) to (D) below.

[0089] (1) Polyol (raw material compound) Polyol (A): hydrogenated polybutadiene having hydroxyl groups at both ends, manufactured by Mitsubishi Chemical Corporation, trade name: Polytail H, number average molecular weight (Mn): about 2000 Polyol (B): polypropylene glycol having hydroxyl groups at both ends, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 164-05895 (polypropylene glycol, diol type, 2000), number average molecular weight (Mn): about 2000 Polyol (C): polypropylene glycol having hydroxyl groups at each end of a three-way branched polymer chain, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 160-17605 (polypropylene glycol, triol type, 300), number average molecular weight (Mn): about 300 Polyol (D): Polypropylene glycol having a hydroxyl group at each end of a three-way branched polymer chain, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: 164-17625 (polypropylene glycol, triol type, 1500), number average molecular weight (Mn): about 1500 (2) Organosilicon compound Diphenylsilane: manufactured by Tokyo Chemical Industry Co., Ltd., product code: D2820 (3) Polymerization catalyst Tris(pentafluorophenyl)borane: manufactured by Tokyo Chemical Industry Co., Ltd., product code: T2313, B(C ６ H ５ ) ３ (4) Desilylation agent (fluoride ion source) Tetrabutylammonium fluoride (approximately 1 mol / L tetrahydrofuran solution): manufactured by Tokyo Chemical Industry Co., Ltd., product code: T1338 (5) Various solvents (solvents used in resin synthesis and property evaluation tests) Xylene: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product code: 240-00865 Tetrahydrofuran: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product code: 206-08744 Toluene-d8: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product code: 202-20542.

[0090] Example 1 Synthesis of Polysilyl Ether Resin In Example 1, the following reaction scheme (A):

[0091]

[0092] (In Example 1, X ｉ is the hydrogenated polybutadiene which is the main chain of the polyol (A), m is 2, and R １ and R ２ are both phenyl groups.) A polysilyl ether resin was synthesized according to the above. That is, the polyol (A) was used alone as a raw material compound (polyol), and first, the polyol (A) and tris(pentafluorophenyl)borane were dissolved in xylene to obtain a solution. Next, diphenylsilane was added to the solution, and the solution was allowed to stand for 60 minutes while heating so that the temperature of the solution was maintained between 80°C and 90°C, thereby reacting the polyol (A) with diphenylsilane to synthesize a polysilyl ether resin. After synthesizing the polysilyl ether resin in this way (after allowing to stand for 60 minutes), the synthesized polysilyl ether resin was recovered by volatilizing and removing the solvent, and then the solution was heated at a temperature of 120°C and a pressure of 100 kgf / cm. ２ The mixture was pressed under the conditions of 1.0 to 1.25 mm to form a film (thickness: 2 mm).

[0093] In the reaction for obtaining such a polysilyl ether resin, the amounts of tris(pentafluorophenyl)borane and diphenylsilane used are 0.02 mol (B(C)) per 1 mol of hydroxyl groups in the polyol (A), respectively. ６ H ５ ) ３ In the reaction for obtaining such a polysilyl ether resin, the amount of xylene used was adjusted so that the concentration of hydroxyl groups in the polyol (A) was 0.27 mol / L.

[0094] In Example 1, a polysilyl ether resin in a film form (thickness 1 mm) was also synthesized using the same method as above, except that the thickness during molding was changed to 1 mm for use in various tests described below (films of different thicknesses were also synthesized).

[0095] Example 2 A polysilyl ether resin was synthesized in the same manner as in Example 1, except for the following changes, to obtain a polysilyl ether resin in the form of a film.

[0096] <Changes to the method described in Example 1 (adopted in Example 2)> As the raw material compound (polyol), instead of using the polyol (A) alone, a mixture of the polyol (A) and the polyol (B) in a molar ratio ((A):(B)) of 1:1 was used. The amounts (molar ratios) of tris(pentafluorophenyl)borane and diphenylsilane used were each 0.015 mol (B(C)) per 1 mol of hydroxyl groups in the raw material compound (the mixture). ６ H ５ ) ３ The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the concentration of hydroxyl groups in the raw material compound (the mixture) was 0.20 mol / L. The thickness of the polysilyl ether resin during molding was changed from 2 mm to 1 mm.

[0097] Example 3 A polysilyl ether resin was synthesized in the same manner as in Example 1, except for the following changes, to obtain a polysilyl ether resin in the form of a film.

[0098] <Changes to the method described in Example 1 (adopted in Example 3)> As the raw material compound (polyol), instead of using the polyol (A) alone, a mixture of the polyol (A) and the polyol (C) in a molar ratio ((A):(C)) of 1.5:1 was used. The amounts (molar ratio) of tris(pentafluorophenyl)borane and diphenylsilane used were 0.002 mol (B(C)) per 1 mol of hydroxyl groups in the raw material compound (the mixture). ６ H ５ ) ３ The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the hydroxyl group concentration in the raw material compound (the mixture) was 0.40 mol / L. After the polysilyl ether resin was synthesized, the solvent was removed by volatilization during recovery, and a polysilyl ether resin in the form of a film having a thickness of 1 mm was obtained. ２ The polysilyl ether resin after solvent removal was used as it was in the form of a film without being pressed under the conditions of 1.

[0099] Example 4 A polysilyl ether resin was synthesized in the same manner as in Example 1, except for the following changes, to obtain a polysilyl ether resin in the form of a film.

[0100] <Changes to the method described in Example 1 (adopted in Example 4)> As the raw material compound (polyol), instead of using the polyol (A) alone, a mixture of the polyol (A) and the polyol (D) in a molar ratio ((A):(D)) of 1.5:1 was used. The amounts (molar ratio) of tris(pentafluorophenyl)borane and diphenylsilane used were 0.004 mol (B(C)) per 1 mol of hydroxyl groups in the raw material compound (the mixture). ６ H ５ ) ３The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the hydroxyl group concentration in the raw material compound (the mixture) was 0.40 mol / L. After the polysilyl ether resin was synthesized, the solvent was removed by volatilization during recovery, and a polysilyl ether resin in the form of a film having a thickness of 1 mm was obtained. ２ The polysilyl ether resin after solvent removal was used as it was in the form of a film without being pressed under the conditions of 1.

[0101] (Comparative Example 1) The polyol (A) was mixed at a temperature of 120°C and a pressure of 100 kgf / cm ２ The mixture was pressed under the conditions of (1) to obtain a film-like polyol (a product molded from Mitsubishi Chemical Corporation's trade name "Polytail H") (thickness: 2 mm), which was used as a comparative resin (hydrogenated polybutadiene having hydroxyl groups at both ends). In Comparative Example 1, in order to form test specimens for various tests, a 1 mm-thick film-like polytail (comparative resin) was also produced in the same manner as above, except that the thickness during molding was 1 mm.

[0102] <Evaluation of Properties of Polysilyl Ether Resins and Comparative Resins> Hereinafter, various measurement methods employed to evaluate the properties of the resins obtained in each example will be described, followed by a description of the measurement results.

[0103] [Regarding Measurement Method] <IR Measurement> The polysilyl ether resin obtained in Example 1 and the comparative resin obtained in Comparative Example 1 were each subjected to IR measurement using a Fourier transform infrared spectrometer (manufactured by Thermo Fisher Scientific K.K., trade name: Thermo Scientific, Nicolet iS20 FT-IR spectrophotometer) to analyze the structure of each resin. The obtained results are shown in FIG.

[0104] <Tensile Test> Measurement samples were prepared using the polysilyl ether resins obtained in Examples 1 to 4 and the comparative resin obtained in Comparative Example 1, and tensile tests were performed using a universal testing machine (Instron, 68TM-30) to determine the breaking strain (unit: %), breaking stress (unit: MPa), and elastic modulus (unit: MPa). Regarding the measurement sample, in Example 1, a test piece measuring 15 mm in length, 40 mm in width, and 2 mm in thickness was cut out. In Examples 2 to 4, a test piece measuring 5 mm in length, 40 mm in width, and 1 mm in thickness was cut out. In Comparative Example 1, a test piece measuring 10 mm in length, 40 mm in width, and 2 mm in thickness was cut out. The tensile test was performed at a tension speed of 10 mm / min and with a gauge length of 10 mm.

[0105] <Dissolution Test> Measurement samples were prepared using the polysilyl ether resins obtained in Examples 1 to 4 and the comparative resin obtained in Comparative Example 1, respectively. The measurement samples were placed in 11.0 mL of tetrahydrofuran and heated to 60°C. The temperature was maintained at 60°C, and the state of the measurement sample in tetrahydrofuran (whether it was dissolved or remained in tetrahydrofuran) was confirmed at specific intervals (5 minutes, 10 minutes, 30 minutes, and 120 minutes) after the temperature reached 60°C. The state of the measurement sample was confirmed as dissolved (completely dissolved), partially dissolved (partially dissolved), or remaining (not dissolved at all). The measurement samples were prepared by cutting test pieces measuring 5 mm in length, 10 mm in width, and 1 mm in thickness from each of the resins obtained in Examples 1 to 4 and Comparative Example 1.

[0106] Decomposition Test: Measurement samples were prepared using each of the polysilyl ether resins obtained in Examples 1 to 4, and a test for decomposing the resin with a desilylation agent was conducted as follows. Specifically, a measurement sample was first produced from each polysilyl ether resin obtained in each Example by cutting out a test piece measuring 5 mm in length, 10 mm in width, and 1 mm in thickness. Next, using each of the obtained measurement samples, the measurement sample and 0.3 mL of tetrabutylammonium fluoride (approximately 1 mol / L tetrahydrofuran solution) were added to 11.0 mL of tetrahydrofuran and heated to 60°C. The temperature was then maintained at 60°C and the solution was allowed to stand. The state of the measurement sample in tetrahydrofuran (whether it was dissolved in tetrahydrofuran or remained undissolved) was confirmed at specific intervals (5 minutes, 10 minutes, 30 minutes, and 120 minutes) after the temperature reached 60°C. The state of the measurement sample was confirmed to be dissolved (completely dissolved), partially dissolved (partially dissolved), or remaining (not dissolved at all).

[0107] In the decomposition test, the solvent was removed (dried) from the solution obtained after the decomposition test to obtain a precipitate (components present in the solvent), and the composition of the precipitate was then analyzed. The composition of the precipitate was analyzed by a nuclear magnetic resonance spectrometer (JEOL, JNMECX400P) using a solution obtained by dissolving the precipitate in toluene-d8. １ This was carried out by performing H NMR measurements.

[0108] [Measurement Results] <IR Measurement Results> As is clear from the results shown in FIG. 1 , in the infrared absorption spectrum of the polysilyl ether resin obtained in Example 1, a peak (peak within the dotted line in FIG. 1 ) not seen in the infrared absorption spectrum of the polyol (similar to the one used as the raw material compound in Example 1) serving as the comparative resin (Comparative Example 1) was observed in the range of 1100 to 1150 cm －１ It was found that such a 1100-1150 cm －１The peak around is thought to be a peak corresponding to a silyl ether bond, and these results demonstrate that a silyl ether bond is formed in the polysilyl ether resin obtained in Example 1. These measurement results confirm that a polysilyl ether resin was obtained by the method described in Example 1. It is clear from the methods (reaction conditions, etc.) employed in Examples 1 to 4 and the above measurement results that the resins obtained by the methods described in Examples 2 to 4 are also polysilyl ether resins.

[0109] <Results of Tensile Test> The measurement results of the tensile test are shown in Table 1 below. Table 1 also shows the types of resin raw materials used. In Table 1, polypropylene glycol is abbreviated as "PPG."

[0110]

[0111] As is clear from the results shown in Table 1, it was confirmed that all of the polysilyl ether resins obtained in Examples 1 to 4 exhibited larger breaking strains than the polyol (trade name "Polytail H", manufactured by Mitsubishi Chemical Corporation) used as the comparative resin in Comparative Example 1. The inventors speculate that such results are due to the fact that in each Example, the silyl ether bond (crosslink) causes molecular chain extension and crosslinking between molecular chains, making the resin less susceptible to breaking.

[0112] Furthermore, when comparing the polysilyl ether resins obtained in Examples 1 to 4 and taking into account the proportion of polymer chains made of polypropylene glycol based on the average molecular weight and the amount used of the polypropylene glycol used, it was found that the polysilyl ether resins obtained in Examples 1 and 3, in which the proportion of polymer chains made of polypropylene glycol contained in the molecule is considered to be zero or low, have a larger breaking strain.

[0113] Furthermore, when Examples 3 and 4, which used triol-type polypropylene glycol as the raw material compound (polyol), were compared, it was confirmed that even with triol-type polypropylene glycol, the breaking strain values ​​varied significantly depending on the average molecular weight, etc. Furthermore, when Examples 2 and 4, which used polypropylene glycol as the raw material compound (polyol), were compared, it was confirmed that the proportion and effect of the polymer chain portion consisting of polypropylene glycol in these resins were similar based on the average molecular weight and amount of polypropylene glycol used. However, it was also found that the resin obtained in Example 4, which used triol-type polypropylene glycol, had a larger breaking strain than Example 2, which used diol-type polypropylene glycol. Furthermore, it was confirmed that the polysilyl ether resins obtained in Examples 2 and 4, which are considered to have a larger proportion of polymer chains consisting of polypropylene glycol based on the average molecular weight of the polypropylene glycol used, had relatively low elastic moduli compared to Examples 1 and 3.

[0114] These results confirm that the mechanical properties of the resulting polysilyl ether resin can be easily adjusted by varying the structure and average molecular weight of the polyol used as the raw material compound, and that according to the present invention, it is possible to produce a resin having desired physical properties by appropriately changing the type of raw material compound (polyol) used, etc.

[0115] <Results of Dissolution Test> The measurement results of the dissolution test are shown in Table 2 below.

[0116]

[0117] As is clear from the results shown in Table 2, the polyol (manufactured by Mitsubishi Chemical Corporation, trade name "Polytail H") used as the comparative resin in Comparative Example 1 was confirmed to be dissolved in tetrahydrofuran after standing for 5 minutes at a temperature of 60°C. In contrast, the polysilyl ether resin obtained in Example 1 gradually dissolved over time, but was confirmed to remain even after 120 minutes had elapsed. Comparing the measurement results of Example 1 and Comparative Example 1, it is clear that the solubility of Example 1 was reduced. The inventors speculate that this is because the resin obtained in Example 1 is composed of resin molecules whose polymer chains are extended by silyl ether bonds (crosslinks), making it easier for the resin molecules to become entangled in the resin, resulting in a reduced solubility.

[0118] Next, focusing on the measurement results of the polysilyl ether resin obtained in Example 2, it was confirmed that the polysilyl ether resin in Example 2 dissolved in tetrahydrofuran after being left to stand for 5 minutes at a temperature of 60° C., as in Comparative Example 1. The inventors speculate that such results are due to the fact that the polysilyl ether resin obtained in Example 2 contains polymer chains made of polypropylene glycol as well as polymer chains made of hydrogenated butylene in the molecular structure of the resin molecule, and therefore has an increased affinity for tetrahydrofuran compared to the polysilyl ether resin obtained in Example 1, which contains only polymer chains made of hydrogenated butylene in its molecular structure.

[0119] Furthermore, when focusing on the measurement results of the polysilyl ether resins obtained in Examples 3 and 4 using triol-type polypropylene glycol as the raw material compound (polyol), it was confirmed that these resins remained in the solvent without dissolving even after standing for 120 minutes. The inventors speculate that such results are due to the fact that in Examples 3 and 4, the raw material compound is a triol-type, and therefore a three-dimensional crosslinked structure originating from the triol is formed, and the polymer chains are three-dimensionally connected to each other, making them unable to disperse in the solvent, resulting in a decrease in solubility.

[0120] As explained above, the results shown in Table 2 confirm that the solubility of the resulting polysilyl ether resin in a solvent varies depending on the structure of the raw material compound (polyol) (for example, due to differences in crosslinking structure or types of polymer chains), and that the solubility can be easily adjusted by changing the type and amount of raw material compound (polyol) used. These results confirm that, according to the present invention, it is possible to produce a resin having desired physical properties by appropriately changing the type, etc. of the raw material compound (polyol) used.

[0121] <Results of the Decomposition Test> The measurement results of the decomposition test are shown in Table 3 below.

[0122]

[0123] As is clear from the results shown in Table 3, all of the polysilyl ether resins obtained in Examples 1 to 4 to which fluoride ions had been added were confirmed to be soluble in tetrahydrofuran. Furthermore, by comparing the results of the decomposition test and the dissolution test for Example 1, it was confirmed that, since the solvent and temperature conditions used in each test were the same, the polysilyl ether resin became soluble in a shorter time when fluoride ions were added (in the decomposition test) than when fluoride ions were not added (in the dissolution test). Furthermore, in all of Examples 1 to 4, the results of the NMR analysis described above detected polyol, which is a raw material compound for the polysilyl ether resin, and confirmed that the raw material compound was produced in the solution after the decomposition test. Considering that polyol was confirmed as a raw material compound in all Examples, it is believed that in the decomposition test using the polysilyl ether resin, the silyl ether bond was cleaved by fluorine anions, decomposing the resin and producing the raw material compound (see Scheme (B) below). From these results, according to the present invention, for example, the following reaction scheme (B):

[0124]

[0125] It can be seen that it is also possible to efficiently produce and recover raw material compounds by utilizing a reaction (desilylation reaction) according to the following formula (1): In Example 1, the dissolution rate differs between the results of the decomposition test and the dissolution test. The inventors speculate that this is because, in the decomposition test, the silyl ether bond is cleaved by fluoride ions (fluoride anions), as shown in the above reaction scheme (B), thereby improving the solubility.

[0126] These results demonstrate that the silyl ether bond can be cleaved with a desilylation agent (fluoride ion source) to decompose the resin, thereby enabling the conversion of polysilyl ether resins into raw materials. In other words, it was found that the polysilyl ether resins obtained in each example can be decomposed into raw material compounds through a simple process such as a desilylation reaction. Furthermore, it is clear that horizontal recycling can be achieved by reusing the raw material compounds (polyols) obtained by decomposing the polysilyl ether resins in this manner.

[0127] As explained above, according to the present invention, it is possible to provide a recyclable polysilyl ether resin that enables efficient decomposition of the resin by a desilylation reaction to efficiently produce the raw material compounds used in the production; a method for producing a recyclable polysilyl ether resin that enables efficient production of the polysilyl ether resin; and a method for producing a raw material compound by decomposition of a polysilyl ether resin that enables efficient production of the raw material compound by decomposition of the polysilyl ether resin. Such a recyclable polysilyl ether resin of the present invention can be easily decomposed into the raw material compounds after use in various applications and can be reused to produce a resin, thereby enabling horizontal recycling and making it particularly useful from the viewpoints of resource conservation and environmental protection.

Claims

1. The following general formula (1): [In formula (1), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, bonds marked with *1 and *2 each represent a bond bonding to an adjacent structure, and bonds marked with *2 represent X ｉ There are (m-1) X ｉ Each of the m bonds bonded to R represents a bond bonded to a different end of the polymer chain, １ and R ２ Each of n is a substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; ｉ represents an integer of 2 or more, and n ｉ There are multiple Xs depending on the number of ｉ may be the same or different, and n ｉ There are multiple R １ may be the same or different, and n ｉ There are multiple R ２ may be the same or different.] A recyclable polysilyl ether resin having a structure represented by the following formula:

2. X in formula (1) ｉ 2. The recyclable polysilyl ether resin according to claim 1, wherein the polymer chain selected from the group consisting of linear or branched polybutadiene and its hydrogenated products, and linear or branched polypropylene glycol.

3. A polymer having a hydroxyl group at each end of the polymer chain, represented by the following general formula (2): [In formula (2), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or more, and the m hydroxyl groups in the formula represent hydroxyl groups bonded separately to separate ends of the polymer chain, and at least one raw material compound selected from the group consisting of polyols represented by the following general formula (3): [In formula (3), R １ and R ２ each represents one substituent selected from the group consisting of a hydrogen atom, an aryl group, and an aliphatic hydrocarbon group; １ and Z ２ and each represent one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom.] with 4. The organosilicon compound is reacted with Z in formula (3). １ and Z ２ and wherein each of the groups is a hydrogen atom, and the raw material compound and the organosilicon compound are reacted using tris(pentafluorophenyl)borane as a polymerization catalyst.

5. The polysilyl ether resin according to claim 1 is subjected to a desilylation reaction to cleave the silyl ether bond, thereby decomposing the polysilyl ether resin and producing a compound represented by the following general formula (2): [In formula (2), X ｉ represents one type of polymer chain selected from the group consisting of linear or branched polyolefin chains having a number average molecular weight of 100 to 10,000 and linear or branched polyether chains having a number average molecular weight of 100 to 10,000, m represents an integer of 2 or greater, and the m hydroxyl groups in the formula represent hydroxyl groups separately bonded to separate ends of the polymer chain.

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