Recyclable polysilyl ether resin, method for producing the same, and method for producing raw material compound by decomposition of polysilyl ether resin

Abstract

To provide a recyclable polysilyl ether resin which efficiently decomposes a resin by a desilylation reaction, can efficiently produce a raw material compound used in production, and is recyclable.SOLUTION: A recyclable polysilyl ether resin has a structure represented by the following general formula (1), in the formula (1), Xi represents a specific polymer chain, m represents an integer of 2 or more, *1 and *2 represent a bond, m pieces of bonds bonded to Xi each represents a bond bonded to separate terminals, R1 and R2 are each a substituent, ni represents an integer of 2 or more, and the plurality of Xi, the plurality of R1 and the plurality of R2 may be the same or different.SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[0002] In recent years, technologies for reusing and recycling various plastic products have been attracting attention from the perspectives of resource conservation and environmental preservation. 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. The method then hydrolyzes the polyurethane resin with liquid water at 200 to 320°C, and recovers the resulting polyamine compound and / or polyol compound. 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. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-169624 [Patent Document 2] International Publication No. 2022 / 099210 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the method for decomposing polyurethane resins 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 decomposing a resin by hydrolysis using the technology described in Patent Document 2, 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. [Means for solving the problem]

[0006] As a result of extensive research to achieve the above object, the present inventors 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] [ka]

[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 is an integer of 2 or more, The bonds marked with *1 and *2 indicate bonds bonded to adjacent structures, respectively. *2 indicates X i There are (m-1) of them depending on the structure of X i each of the m bonds bonded to a different end of the polymer chain (each different end of the polymer chain), 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, n 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's depending on the number of 1 may be the same or different, and n i There are multiple R's depending on the number of 2 may be the same or different.] A recyclable polysilyl ether resin having a structure represented by the formula:

[0011] [2] X in formula (1) iThe 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] [ka]

[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 greater, and the m hydroxyl groups in the formula represent hydroxyl groups bonded separately to separate ends of the polymer chain. At least one raw material compound selected from the group consisting of polyols represented by the formula: The following general formula (3):

[0015] [ka]

[0016] [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, Z 1 and Z 2 each represents one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom. and at least one organosilicon compound selected from the group consisting of compounds represented by

[0023] A method for producing a recyclable polysilyl ether resin, comprising reacting the above polysilyl ether resin with a base of 1 to 2, to obtain the polysilyl ether resin according to [1] or [2].

[0017] [4] The organosilicon compound is reacted with Z in the formula (3). 1 and Z 2 and (iii) a compound (dihydrosilane) in which each of the groups represented by the formula (I) and (II) 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 producing a compound represented by the following general formula (2):

[0019] [ka]

[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 bonded separately to separate ends of the polymer chain. The present invention relates to a method for producing a raw material compound by decomposing a polysilyl ether resin, which produces at least one raw material compound selected from the group consisting of polyols represented by the following formula:

[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 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 etherification of the hydroxyl groups) to introduce a protecting group to the hydroxyl groups). By utilizing this reaction to connect the polyols together via silyl ether bonds, the structure represented by general formula (1) can be efficiently produced. Furthermore, the silyl ether bonds in such structures can be easily cleaved by a so-called desilylation reaction (deprotection reaction). Therefore, the polysilyl ether resin can be easily decomposed by a so-called desilylation reaction (deprotection reaction), and the polyol (raw material compound) used in the 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 (deprotection reaction) can generally be carried out under mild conditions and is known as a method for obtaining a decomposition product 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 efficiently decompose 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 polysilyl ether resins 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. iBy 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. [Effects of the Invention]

[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. [Brief explanation of the drawings]

[0025] [Figure 1] 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. DETAILED DESCRIPTION OF THE INVENTION

[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 The following general formula (1):

[0028] [ka]

[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 is an integer of 2 or more, The bonds marked with *1 and *2 indicate bonds bonded to adjacent structures, respectively. *2 indicates X i There are (m-1) of them depending on the structure of X i The m bonds bonded to the polymer chain (X i represents bonds bonded separately to separate ends of a polymer chain selected as 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, n 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's depending on the number of 1 may be the same or different, and n i There are multiple R's depending on the number of 2 may be the same or different.] The compound is characterized by having a structure represented by the following formula:

[0030] In this formula (1), X iis one type of polymer chain (straight-chain or branched 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.

[0031] X in such an equation 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). i The 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 is the influence of the silyl moiety greater, but recovery of the organosilicon compound during decomposition is difficult, which tends 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. iWhen the structure of is a linear structure, the value of m in the formula is 2, and X i Two bonds will be bonded to X. i When the structure is a branched structure, the value of m in the formula is 3 or more, and X i will have three or more bonds bonded to it depending on the value of m.

[0033] In addition, X in such formula (1) i The polyolefin chain that can be selected as the polyolefin chain 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 iThe number of bonds marked with *2 attached to m 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 (integer) of m in such formula to be equal to or less than the above upper limit, the proportion of silyl ether moieties (silyl ether bond moieties) in the polysilyl ether resin can be further reduced compared to when the value exceeds the above upper limit. This not only makes it possible to suppress the effects 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] Also, the value of m (an integer) in such an equation is X i For example, X i When the structure is a straight chain, 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, X in formula (1) has three or more bonds bonded to it depending on the number of m. i Each bond bonded to X represents a bond bonded to a different end of a polymer chain having a linear or branched structure, so the value of m (an integer) is 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 number 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] [ka]

[0039] (In formula (1-1), X in the formula i is a polymer chain with a linear structure, except that X in the formula 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). When m is 3, the structure represented by formula (1) can be expressed by the following formula (1-2):

[0040] [ka]

[0041] (In formula (1-2), X in the formula i is a polymer chain with a branched structure branched in three directions, except that X in the formula 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).

[0042] In addition, in formula (1), the bonds marked with *1 and *2 indicate bonds that bond to adjacent structures. 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. The adjacent structure here basically means the structure of the structural portion (the structural portion enclosed in parentheses) between the bonds marked with *1 and *2 in formula (1) above, but it 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 where X in the formula iThe 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 (X i The bonds of X (the total number of bonds bonded to X is m) are bonds bonded separately to different ends of the polymer chain. i The total m bonds bonded to X are bonds bonded separately 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 When X 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 (X i ) have a structure in which the ends of the groups are connected by a silyl ether bond (in formula (1), n i Since is greater than or equal to 2, 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] R in such equation (1) 1 and R 2The 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 upper limit is exceeded, 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 the aryl group, 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 2 The 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, such as 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, or a vinyl group.

[0047] In addition, the R 1 and R 2From the viewpoint of improving chemical stability, the aliphatic hydrocarbon group that can be selected as the alkyl group 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 aryl groups (more preferably aryl groups having 6 to 10 carbon atoms) and aliphatic hydrocarbon groups (more preferably aliphatic hydrocarbon groups 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 Depending on the number of X's, there may be multiple (2 or more) structures enclosed in parentheses in the formula. 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. In addition, X in each structure (structure enclosed in parentheses) 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 of manufacturing recyclable polysilyl ether resin] The method for producing a recyclable polysilyl ether resin of the present invention comprises: The polymer chain has a hydroxyl group at each end thereof, and the polymer chain has the following general formula (2):

[0053] [ka]

[0054] [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 bonded separately to separate ends of the polymer chain. At least one raw material compound selected from the group consisting of polyols represented by the formula: The following general formula (3):

[0055] [ka]

[0056] [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, Z 1 and Z 2 each represents one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom. and at least one organosilicon compound selected from the group consisting of compounds represented by The recyclable polysilyl ether resin of the present invention is obtained by reacting the above.

[0057] The raw material compound is at least one selected from the group consisting of polyols represented by the above general formula (2) having hydroxyl groups at the ends of the polymer chain. In such polyols represented by formula (2), X in formula (2) i is one type of polymer chain (straight-chain or branched 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. i is X in Equation (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 meaning 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 (integer) of m 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 (integer) of m in such a formula to not more than the upper limit can 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 further enhance the recycling efficiency of the resulting polysilyl ether resin.

[0059] In addition, in the polyol represented by the above formula (2), the m hydroxyl groups in the formula (groups represented by the formula: -OH in formula (2)) represent hydroxyl groups separately bonded to separate ends of the polymer chain (different ends of the polymer chain). Therefore, the polyol represented by the above 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 in which a hydroxyl group (a group represented by the formula: -OH in formula (2)) is bonded to each end of a polymer chain represented by the formula:

[0060] The polyol represented by the above formula (2) is i The structure of the compound may be linear or branched (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) has 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). Thus, the raw material compound may be one of the polyols represented by the above formula (2), or may be a mixture of two or more of the 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 of the obtained polysilyl ether resin represented by the formula (1) 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 Eq. (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 from the viewpoint of reaction yield, a hydrogen atom is particularly preferred. 1 and Z 2 may be the same or different.

[0065] 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). Thus, 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] Furthermore, 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 considered 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 considered 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 for protecting 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 starting compound with the organosilicon compound using tris(pentafluorophenyl)borane as a polymerization catalyst. The method for promoting the reaction between the starting 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. Depending on the components used, the reaction can be carried out under the conditions appropriately adapted from known methods for silylation using tris(pentafluorophenyl)borane as a catalyst (the method for synthesizing silyl ethers). For example, the reaction between the starting compound and the organosilicon compound can be carried out using the polymerization catalyst in a solvent 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 it does not inhibit the reaction to form a silyl ether bond and allows 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 fall 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). By using an amount (molar amount) of the polymerization catalyst that is equal to or greater than the lower limit, a greater effect in terms of improving the reaction rate tends to be obtained. On the other hand, by using an amount (molar amount) that is equal to or less than the upper limit, a greater effect in terms of reducing the catalyst cost and reducing the influence of the catalyst on the physical properties of the polysilyl ether resin tends to be obtained.

[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. On the other hand, by setting the content (total amount) 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 to be equal to or higher than the lower limit, a higher 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] The method for producing a raw material compound by decomposing a polysilyl ether resin of the present invention comprises the steps of: The polysilyl ether resin of the present invention (recyclable polysilyl ether resin) 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):

[0076] [ka]

[0077] [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 bonded separately to separate ends of the polymer chain. The method is characterized by producing at least one raw material compound selected from the group consisting of polyols represented by the following formula:

[0078] The polysilyl ether resin of the present invention has a structure represented by the above formula (1), which is a structure 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 (alcohol), 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 of the present invention to a known reaction such as a desilylation reaction (deprotection reaction of the protecting groups 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] Here, when the desilylation reaction is carried out using a desilylation agent (deprotection agent) to desilylate (deprotection of a silyl protecting group), 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 to deprotect a silyl protecting group 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 (deprotection of a silyl protecting group) using fluoride anions as a base. Furthermore, deprotection using the desilylation agent (preferably a fluoride ion source) is preferably carried out 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 other factors, and cannot be generally determined, but is preferably about 20 to 100°C. The reaction time for deprotection using 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 as to allow the desilylation reaction to proceed.

[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 catalysts 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 ones).

[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 can be 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). As such, 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 appropriately changing the type of polymer chain or the amount of polymerized polymer chain, making it possible to achieve both recyclability and mechanical properties. [Example]

[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] <Ingredients used in the examples and comparative examples> First, we will explain the components used in each example, 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 with hydroxyl groups at both ends, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: 164-05895 (polypropylene glycol, diol type, 2000), number average molecular weight (Mn): approximately 2000 Polyol (C): Polypropylene glycol with a hydroxyl group at each end of a three-way branched polymer chain, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: 160-17605 (polypropylene glycol, triol type, 300), number average molecular weight (Mn): approximately 300 Polyol (D): Polypropylene glycol with 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): approximately 1500 (2) Organosilicon compounds Diphenylsilane: Tokyo Chemical Industry Co., Ltd., product code: D2820 (3) Polymerization catalyst Tris(pentafluorophenyl)borane: Tokyo Chemical Industry Co., Ltd., product code: T2313, B(C6H5)3 (4) Desilylation agent (fluoride ion source) Tetrabutylammonium fluoride (approximately 1 mol / L tetrahydrofuran solution): Tokyo Chemical Industry Co., Ltd., product code: T1338 (5) Various solvents (solvents used in resin synthesis and property evaluation tests) Xylene: Fujifilm Wako Pure Chemical Industries, Ltd., product code: 240-00865 Tetrahydrofuran: 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] [ka]

[0092] (In Example 1, X i is the hydrogenated polybutadiene that is the main chain of the polyol (A), m is 2, and R 1 and R 2 are all phenyl groups.) A polysilyl ether resin was synthesized according to the following procedure. Specifically, the polyol (A) was used alone as the raw material compound (polyol), and first, the polyol (A) and tris(pentafluorophenyl)borane were dissolved in xylene to obtain a solution. Diphenylsilane was then added to the solution, and the solution was allowed to stand for 60 minutes while being heated 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 the polysilyl ether resin was synthesized in this manner (after being allowed to stand for 60 minutes), the synthesized polysilyl ether resin was recovered by volatilizing and removing the solvent, and then heated at a temperature of 120°C and a pressure of 100 kgf / cm. 2 The mixture was pressed under the conditions of (a) to (c) to form a film (thickness: 2 mm).

[0093] In the reaction to obtain such a polysilyl ether resin, the amounts of tris(pentafluorophenyl)borane and diphenylsilane used were 0.02 mol (B(CH)) and 0.5 mol (diphenylsilane), respectively, per mol of hydroxyl groups in the polyol (A). In addition, in the reaction to obtain 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 addition, 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 in order to utilize it 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] <Modifications to the method described in Example 1 (adopted in Example 2)> Instead of using the polyol (A) alone as the raw material compound (polyol), a mixture of the polyol (A) and the polyol (B) in a molar ratio ((A):(B)) of 1:1 was used. The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the amounts (molar ratio) of tris(pentafluorophenyl)borane and diphenylsilane used were 0.015 mol (B(C6H5)3) and 0.5 mol (diphenylsilane) per 1 mol of hydroxyl groups in the raw material compound (the mixture), respectively. The amount of xylene used was 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 has been changed from 2mm to 1mm.

[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] <Modifications to the method described in Example 1 (adopted in Example 3)> Instead of using the polyol (A) alone as the raw material compound (polyol), a mixture of the polyol (A) and the polyol (C) in a molar ratio ((A):(C)) of 1.5:1 was used. The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the molar ratio of tris(pentafluorophenyl)borane and diphenylsilane was 0.002 moles (B(C6H5)3) and 0.55 moles (diphenylsilane) per mole of hydroxyl groups in the raw material compound (the mixture). The amount of xylene used was changed so that the concentration of hydroxyl groups in the raw material compound (the mixture) was 0.40 mol / L. After synthesizing the polysilyl ether resin, the solvent was removed by evaporation during recovery, resulting in a 1 mm thick film of polysilyl ether resin. 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] <Modifications to the method described in Example 1 (adopted in Example 4)> Instead of using the polyol (A) alone as the raw material compound (polyol), a mixture of the polyol (A) and the polyol (D) in a molar ratio ((A):(D)) of 1.5:1 was used. The amounts of tris(pentafluorophenyl)borane and diphenylsilane used were changed so that the molar ratio of tris(pentafluorophenyl)borane and diphenylsilane was 0.004 mol (B(C6H5)3) and 0.55 mol (diphenylsilane) per 1 mol of hydroxyl groups in the raw material compound (the mixture). The amount of xylene used was changed so that the concentration of hydroxyl groups in the raw material compound (the mixture) was 0.40 mol / L. After synthesizing the polysilyl ether resin, the solvent was removed by evaporation during recovery, resulting in a 1 mm thick film of polysilyl ether resin. 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 (a) 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, 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, in order to form test specimens for various tests.

[0102] <Evaluation of the properties of polysilyl ether resin and comparative resin> The various measurement methods employed to evaluate the properties of the resins obtained in each example will be explained below, followed by a description of the measurement results.

[0103] [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 Figure 1.

[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). For Example 1, the measurement sample was prepared by cutting out a test piece measuring 15 mm in length, 40 mm in width, and 2 mm in thickness. For Examples 2 to 4, the measurement sample was prepared by cutting out a test piece measuring 5 mm in length, 40 mm in width, and 1 mm in thickness. For Comparative Example 1, the measurement sample was prepared by cutting out a test piece measuring 10 mm in length, 40 mm in width, and 2 mm in thickness. The tensile test conditions were a pulling speed of 10 mm / min and 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. At specific intervals (5 minutes, 10 minutes, 30 minutes, and 120 minutes) after the temperature reached 60°C, the state of the measurement samples in tetrahydrofuran (whether they were dissolved or remained in tetrahydrofuran) was confirmed. The state of the measurement samples was confirmed as dissolved (completely dissolved), partially dissolved (partially dissolved), or remaining (not dissolved at all). Measurement samples were prepared by cutting test pieces measuring 5 mm long, 10 mm wide, and 1 mm thick 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 test piece measuring 5 mm in length, 10 mm in width, and 1 mm in thickness was first cut out from each polysilyl ether resin obtained in each Example to produce a measurement sample. 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 1 H NMR measurements.

[0108] [About the 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, there is a peak (peak within the dotted line in FIG. 1) in the range of 1100 to 1150 cm , which is not observed in the infrared absorption spectrum of the polyol (similar to the one used as the raw material compound in Example 1) used as the comparative resin (Comparative Example 1). -1 It was found that such a phenomenon occurred in the vicinity of 1100-1150cm. -1 The peak around this point is thought to be a peak corresponding to a silyl ether bond, and these results indicate 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 is 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 the following Table 1. Table 1 also shows the types of resin raw materials used. In Table 1, polypropylene glycol is abbreviated as "PPG."

[0110] [Table 1]

[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 (manufactured by Mitsubishi Chemical Corporation, trade name "Polytail H") used as a 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 the polymer chain portion consisting of polypropylene glycol from 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 the polymer chain consisting 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 differences in 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. It was also confirmed that the polysilyl ether resins obtained in Examples 2 and 4, which are thought 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 confirmed 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.

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

[0116] [Table 2]

[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 have 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 passed. 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 within 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, 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 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 changes 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 of raw material compound (polyol) used.

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

[0122] [Table 3]

[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 resins could be dissolved 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 NMR analysis results detected polyol, which is a raw material compound for the polysilyl ether resin, confirming 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, resulting in decomposition of the resin and the production of the raw material compound (see Scheme (B) below). From these results, according to the present invention, for example, the following reaction scheme (B):

[0124] [ka]

[0125] It can be seen that it is possible to efficiently produce and recover raw material compounds by utilizing a reaction (desilylation reaction) according to the following formula: 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 the solubility is improved in the decomposition test by cleaving the silyl ether bond with fluoride ions (fluoride anions), as shown in the above reaction scheme (B).

[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, the polysilyl ether resins obtained in each example were found to be capable of being 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. [Industrial Applicability]

[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 resins, 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): 【Chemical 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; The bonds marked with *1 and *2 indicate bonds bonded to adjacent structures, respectively. *2 indicates X ｉ There are (m-1) of them depending on the structure of X ｉ each of the m bonds bonded to a different end of the polymer chain; 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, n 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 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. The polymer chain has a hydroxyl group at each end thereof, and the polymer chain has the following general formula (2): 【Chemistry 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 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 formula: The following general formula (3): 【Chemistry 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, Z １ and Z ２ each represents one functional group selected from the group consisting of a hydrogen atom, a trifluoromethanesulfonic acid group, a cyano group, and a halogen atom. and at least one organosilicon compound selected from the group consisting of compounds represented by 2. A method for producing a recyclable polysilyl ether resin, comprising reacting the above-mentioned polysilyl ether resin with a carboxylic acid to obtain the polysilyl ether resin of claim 1.

4. The organosilicon compound is reacted with Z in the 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): 【Chemistry 4】 [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 bonded separately to separate ends of the polymer chain.

1. A method for producing a raw material compound by decomposition of a polysilyl ether resin, comprising producing at least one raw material compound selected from the group consisting of polyols represented by the following formula:

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