JP2024027102A - degradable polymer - Google Patents

Abstract

To provide a polymer that remains stable without decomposing in its application environment or in water, ensuring its long-term usability, yet capable of rapid decomposition at any time under specific conditions.SOLUTION: The present invention provides a polymer represented by the following formula (IIa).

Description

Application for exception to loss of novelty applied

The present invention relates to polytrimethylene carbonate-based polymers, methods for producing polytrimethylene carbonate-based polymers, and methods for decomposing the polymers.

The issue of raw materials and disposal of polymer materials, such as ocean plastic issues and the transition to a decarbonized society, is currently attracting attention as an issue that needs to be addressed on a global scale. Biodegradable polymers and polymers derived from renewable resources are expected to be part of the solution.

Known biodegradable polymers such as poly-L-lactic acid (PLLA) gradually decompose in an aqueous environment and show a continuous decline in physical properties over time. On the other hand, isosorbide polycarbonate derived from renewable resources has achieved high strength and high heat resistance, but is said to be not biodegradable.
In addition, it has recently been reported that polycaprolactone, which is known as a marine degradable polymer, decomposes relatively quickly, but during decomposition it produces oligomers with medium molecular weight, which are toxic to aquatic microorganisms and other ecosystems. (Non-patent Document 1).

In this way, controlling the timing and rate of polymer decomposition is important, and there is a need to achieve both long-term stable use and decomposition at any time using a rapid, low-energy process, and the realization of "on-demand decomposition" technology. .

Proceedings of the 71st Annual Conference of the Society of Polymer Science and Technology 2H05

An object of the present invention is to provide a polymer that does not decompose in the usage environment or in water and can be used stably for a long period of time, while being able to rapidly decompose at any time under specific conditions.

The present inventor focused on polytrimethylene carbonate (PTMC) when considering solving the above problems. Polytrimethylene carbonate is known as a polymer that exhibits enzymatic degradability and is used as a medical material, but it is stable in the environment of normal use, and on the other hand, there have been no reports of it degrading at the intended time. The present inventors realized the above-mentioned "on-demand decomposition" by including a mechanism for inducing decomposition in the side chain structure of the polytrimethylene carbonate skeleton, and further setting the decomposition initiation point at the end group of the polymer chain. We thought that it might be possible, and as a result of intensive study, we were able to complete the present invention.

（式（１）において、
Ｒは、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基、エステル基、アミド基、カルバメート基、ウレア基、水酸基、アミノ基、カルボキシ基、及びチオール基からなる群から選択され、
ここで、Ｒが、水酸基、アミノ基、カルボキシ基又はチオール基である場合は、保護基で保護されていてもよく、
Ｒが、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基である場合は、置換基を有してもよく；
Ｍは、水素原子、炭素数１～１０のアルキル基、アルケニル基、アルキニル基、ヒドロキシアルキル基、アミノアルキル基、ハロアルキル基、ホルミルアルキル基、シアノアルキル基、シアノ基、ホルミル基、及びアシル基からなる群から選択され；
Ｑ_１、Ｑ’_１、Ｑ_２およびＱ’_２は、水素原子、炭素数１～１０のアルキル基、ヒドロキシアルキル基、ホルミル基、及びビニレン基からなる群から選択される。）
［２］重合開始時の前記モノマーの濃度が０．１～１０ｍｏｌ／Ｌである、［１］に記載の方法。
［３］重合開始後に、反応混合物中のポリマー組成が最大となる時点付近において反応を停止する、［１］又は［２］に記載の方法。
［４］Ｒが、－（ＣＨ_２）_２ＯＣＨ_３、－（ＣＨ_２）_２ＣＨ_３、－ＣＨ_３、－Ｐｈ（フェ
ニル基）又はアダマンチル基から選択される、［１］又は［２］に記載の方法。
［５］前記ポリマーがポリトリメチレンカーボネート系のポリマーである、［１］に記載の方法。
［６］前記ポリマーが、以下の式（Ｉ）で表されるポリマーである、［１］に記載の方法。

（式（Ｉ）において、
Ｒ’は、水素原子、アセチル基、炭素数１～２０のアルキルカルボニル基、アリールカルボニル基、アルキルアミノカルボニル基、アリールアミノカルボニル基、アルキルオキシカルボニル基、又はアリールオキシカルボニル基であり；
Ｕは、重合に使用する開始剤の種類に応じて決まる様々なアルコール又はアミンに由来する基であり；
ｎは、１～１０００であり；
Ｒ、Ｍ、Ｑ_１、Ｑ’_１、Ｑ_２及びＱ’_２は、式（１）で定義した通りである。）
［７］（ｉ）以下の式（ＩＩ）で表されるポリマーを提供する工程、及び
（ｉｉ）前記ポリマーに、水酸基を活性化する触媒を添加する工程
を含む、前記ポリマーを分解する方法。

（式（ＩＩ）において、
Ｒは、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基、エステル基、アミド基、カルバメート基、ウレア基、水酸基、アミノ基、カルボキシ基、及びチオール基からなる群から選択され、
ここで、Ｒが、水酸基、アミノ基、カルボキシ基又はチオール基である場合は、保護基で保護されていてもよく、
Ｒが、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基である場合は、置換基を有してもよく；
Ｍは、水素原子、炭素数１～１０のアルキル基、アルケニル基、アルキニル基、ヒドロキシアルキル基、アミノアルキル基、ハロアルキル基、ホルミルアルキル基、シアノアルキル基、シアノ基、ホルミル基、及びアシル基からなる群から選択され；
Ｑ_１、Ｑ’_１、Ｑ_２およびＱ’_２は、水素原子、炭素数１～１０のアルキル基、ヒドロキシアルキル基、ホルミル基、及びビニレン基からなる群から選択され；
Ｕは、重合に使用する開始剤の種類に応じて決まる様々なアルコール又はアミンに由来する基であり；
ｎは、１～１０００である。）
［８］前記触媒が、有機系の触媒である、［７］に記載の方法。
［９］以下の式（Ｉａ）で表されるポリマー。

（式（Ｉａ）において、
Ｒ_１は、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基、エステル基、アミド基、カルバメート基、ウレア基、水酸基、アミノ基、カルボキシ基、及びチオール基からなる群から選択され、
Ｒ_１が、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基である場合は、置換基を有してもよく；
Ｒ’は、水素原子、アセチル基、炭素数１～２０のアルキルカルボニル基、アリールカルボニル基、アルキルアミノカルボニル基、アリールアミノカルボニル基、アルキルオキシカルボニル基、又はアリールオキシカルボニル基であり；
Ｍは、水素原子、炭素数１～１０のアルキル基、アルケニル基、アルキニル基、ヒドロキシアルキル基、アミノアルキル基、ハロアルキル基、ホルミルアルキル基、シアノアルキル基、シアノ基、ホルミル基、及びアシル基からなる群から選択され；
Ｑ_１、Ｑ’_１、Ｑ_２およびＱ’_２は、水素原子、炭素数１～１０のアルキル基、ヒドロキシアルキル基、ホルミル基、及びビニレン基からなる群から選択され；
Ｕは、重合に使用する開始剤の種類に応じて決まる様々なアルコール又はアミンに対応する基であり；
ｎは、１～１０００である。）
［１０］Ｒ_１が、－（ＣＨ_２）_２ＯＣＨ_３、－（ＣＨ_２）_２ＣＨ_３、－ＣＨ_３、－Ｐｈ（
フェニル基）又はアダマンチル基から選択される、［９］に記載のポリマー。
［１１］以下の式（ＩＩａ）で表されるポリマー。

（式（ＩＩａ）において、
Ｒ_１は、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基、エステル基、アミド基、カルバメート基、ウレア基、水酸基、アミノ基、カルボキシ基、及びチオール基からなる群から選択され、
Ｒ_１が、炭素数１～２０のアルキル基、アルコキシル基で置換されているアルキル基、アルケニル基、アルキニル基、シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基、アリール基である場合は、置換基を有してもよく；
Ｍは、水素原子、炭素数１～１０のアルキル基、アルケニル基、アルキニル基、ヒドロキシアルキル基、アミノアルキル基、ハロアルキル基、ホルミルアルキル基、シアノアルキル基、シアノ基、ホルミル基、及びアシル基からなる群から選択され；
Ｑ_１、Ｑ’_１、Ｑ_２およびＱ’_２は、水素原子、炭素数１～１０のアルキル基、ヒドロキシアルキル基、ホルミル基、及びビニレン基からなる群から選択され；
Ｕは、重合に使用する開始剤の種類に応じて決まる様々なアルコール又はアミンに由来する基であり；
ｎは、１～１０００である。）
［１２］Ｒ_１が、－（ＣＨ_２）_２ＯＣＨ_３、－（ＣＨ_２）_２ＣＨ_３、－ＣＨ_３、－Ｐｈ（フェニル基）又はアダマンチル基から選択される、［１１］に記載のポリマー。
を提供するものである。 That is, the present invention
[1] A method for preparing a polymer, including a step of polymerizing a monomer represented by the following formula (1).
[2]

(In formula (1),
R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group, selected from the group consisting of a carbamate group, a urea group, a hydroxyl group, an amino group, a carboxy group, and a thiol group,
Here, when R is a hydroxyl group, an amino group, a carboxy group or a thiol group, it may be protected with a protecting group,
When R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituent may have;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group. )
[2] The method according to [1], wherein the concentration of the monomer at the start of polymerization is 0.1 to 10 mol/L.
[3] The method according to [1] or [2], wherein after the start of polymerization, the reaction is stopped around the time when the polymer composition in the reaction mixture reaches its maximum.
[4] In [1] or [2], R is selected from -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph (phenyl group) or adamantyl group Method described.
[5] The method according to [1], wherein the polymer is a polytrimethylene carbonate-based polymer.
[6] The method according to [1], wherein the polymer is a polymer represented by the following formula (I).

(In formula (I),
R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000;
R, M, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are as defined in formula (1). )
[7] A method for decomposing the polymer, the method comprising: (i) providing a polymer represented by the following formula (II); and (ii) adding a catalyst that activates hydroxyl groups to the polymer.

(In formula (II),
R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group, selected from the group consisting of a carbamate group, a urea group, a hydroxyl group, an amino group, a carboxy group, and a thiol group,
Here, when R is a hydroxyl group, an amino group, a carboxy group or a thiol group, it may be protected with a protecting group,
When R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituent may have;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000. )
[8] The method according to [7], wherein the catalyst is an organic catalyst.
[9] A polymer represented by the following formula (Ia).

(In formula (Ia),
R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group , carbamate group, urea group, hydroxyl group, amino group, carboxy group, and thiol group,
When R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituted It may have a group;
R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group corresponding to various alcohols or amines depending on the type of initiator used for polymerization;
n is 1 to 1000. )
[10] R ₁ is -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph(
The polymer according to [9], which is selected from a phenyl group) or an adamantyl group.
[11] A polymer represented by the following formula (IIa).

(In formula (IIa),
R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group , carbamate group, urea group, hydroxyl group, amino group, carboxy group, and thiol group,
When R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituted It may have a group;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000. )
[12] The polymer according to [11], wherein R ₁ is selected from -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph (phenyl group), or adamantyl group .
It provides:

According to the present invention, it is possible to provide a polymer that does not decompose in the usage environment or in water and can be used stably for a long period of time, while being able to rapidly decompose at any time under specific conditions.
Furthermore, the present invention can provide a method for efficiently producing a polymer having such characteristics.

1 shows an outline of the decomposition mechanism of the polymer of the present invention and the method of decomposing the polymer of the present invention. 1 shows a ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of a reaction mixture of ring-opening polymerization of monomer 5a (monomer concentration 1 M) for 15 minutes. Fig. 3 shows changes over time in reaction mixture composition in ring-opening polymerization of monomer 5a with different monomer, initiator, and catalyst concentrations. ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6a-OH after 4 hours of homogeneous decomposition treatment is shown. 1 shows a ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6a-OH after 30 hours of homogeneous decomposition treatment. ¹ H NMR spectrum (4006 Hz, CDCl ₃ ) of polymer 6b-OH after 9 hours of homogeneous decomposition treatment is shown. The ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6b-OH after 30 hours of homogeneous decomposition treatment is shown. FIG. 8A shows changes over time in the amount of polymers in solution depolymerization treatment of polymers 6a-OH, 6a-Ac, 6b-OH, and 6b-Ac. FIG. 8B shows the degree of decomposition of each polymer subjected to in-solution depolymerization treatment for 30 hours. ¹ H NMR spectra (400 MHz, D ₂ O) in heavy water of each sample are shown. A) shows the results for the supernatant of DBU, b) for 6a-Ac, and c) for the supernatant 4 days after the heterogeneous decomposition treatment of 6b-Ac. The results of DSC measurement of polymer 6a-Ac immersed in ultrapure water for 24 hours are shown.

In this specification, "alkyl" may be any aliphatic hydrocarbon group that is linear, branched, cyclic, or a combination thereof. The number of carbon atoms in _the alkyl group is not particularly _{limited ;} ), and has 1 to 20 carbon atoms (C _{1 to 20} ). When the number of carbon atoms is specified, it means an "alkyl" having a carbon number within that range. For example, C _1-8 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, Includes n-heptyl, n-octyl, etc. In this specification, the alkyl group may have one or more arbitrary substituents. Examples of such substituents include, but are not limited to, an alkoxy group, a halogen atom, an amino group, a mono- or di-substituted amino group, a substituted silyl group, or an acyl group. When an alkyl group has two or more substituents, they may be the same or different. The same applies to the alkyl moieties of other substituents containing alkyl moieties (eg, alkoxy groups, arylalkyl groups, etc.).

In this specification, when a certain functional group is defined as "optionally substituted", the type of substituent, the substitution position, and the number of substituents are not particularly limited, and two or more substituents When it has groups, they may be the same or different. Examples of the substituent include, but are not limited to, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group, a halogen atom, a sulfo group, an amino group, an alkoxycarbonyl group, and an oxo group. Further substituents may be present in these substituents. Examples of such groups include, but are not limited to, halogenated alkyl groups and dialkylamino groups.

As used herein, the term "alkoxy group" refers to a structure in which the alkyl group is bonded to an oxygen atom, and includes, for example, a saturated alkoxy group that is linear, branched, cyclic, or a combination thereof. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, cyclopropylmethoxy group, n- Suitable examples include pentyloxy group, cyclopentyloxy group, cyclopropylethyloxy group, cyclobutylmethyloxy group, n-hexyloxy group, cyclohexyloxy group, cyclopropylpropyloxy group, cyclobutylethyloxy group, and cyclopentylmethyloxy group. Examples include:

1. Polymer One embodiment of the present invention is a polymer represented by the following formula (Ia) (hereinafter also referred to as "polymer 1 of the present invention").

The polymer represented by the above formula (Ia) is a polytrimethylene carbonate polymer having a specific ester structure introduced into the side chain. By having an ester structure in the side chain, as described below, it is possible to achieve both long-term stable use and rapid decomposition at any time using a low-energy process (on-demand decomposition technology).

In formula (I), R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group. , ester group, amide group, carbamate group, urea group, hydroxyl group, amino group, carboxy group, and thiol group.
R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group having a substituent. You may. Examples of the substituent include a halogen atom, an alkoxy group, a hydroxyl group, an amino group, a carboxy group, a thiol group, a sulfonyl group, a phosphoryl group, a guanidino group, and the like.
Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, adamantyl group (1-adamantyl group and 2-adamantyl group) ), exo-norbornyl group, endo-norbornyl group, and 2-bicyclo[2.2.2]octyl group.
R ₁ is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkyl group substituted with an alkoxy group having 1 to 3 carbon atoms which may have a substituent, or a substituted A phenyl group that may have a substituent, a cycloalkyl group that may have a substituent, a bicycloalkyl group that may have a substituent, or a tricycloalkyl group that may have a substituent. It is.
In addition, when R ₁ is an alkyl group substituted with an alkoxy group having 1 to 3 carbon atoms which may have a substituent, it is possible to exhibit biocompatibility in addition to degradability. Particularly preferred.

In one preferred aspect of the present invention, R ₁ is a methoxyethyl group (-(CH ₂ ) ₂ OCH ₃ ), an n-propyl group (-(CH ₂ ) ₂ CH ₃ ), a methyl group (-CH ₃ ), A phenyl group or an adamantyl group (1-adamantyl group and 2-adamantyl group).

In formula (I), R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. It is.
When R' is a hydrogen atom, both terminal groups become hydroxyl groups, which act as starting points for decomposition, ensuring long-term stable use and rapid, low-energy decomposition at any time. It becomes possible to achieve both (on-demand disassembly technology).

In formula (I), M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formylalkyl group, a cyanoalkyl group, a cyano group, or a formyl group. and acyl groups.

In one preferred aspect of the invention, M is a hydrogen atom.

In formula (1), Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group. selected.

In one preferred aspect of the invention, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are all hydrogen atoms.

In formula (Ia), U is a group derived from (corresponding to) various alcohols and amines, which is determined depending on the type of initiator used for polymerization.
For example, in [Synthesis Example 1] to [Synthesis Example 4], benzyl alcohol (BnOH) is used as an initiator, and U becomes Ph-CH ₂ -O-. In addition, in [Synthesis Example 1] to [Synthesis Example 8], water in the monomer opens the ring of the monomer, and as a result, 1,3-diol derived from the monomer (the carbon at the 2nd position is -OCOR) serves as an initiator, and the U portion is R'O-CH ₂ -CH(OCOR)-CH ₂ O- (R' represents R' in Scheme 3 of the example) becomes.

上記式で、ｍ、ｍ’は重合度であり、各々、１～５００の範囲である。
また、Ｒ’＝Ｈの場合は、以下の式で表される。

また、Ｕが、Ｙ（－Ｎ）ｘ－で表され、ｘが２の場合は、上記式で、Ｏ－Ｙ－Ｏの部分が、Ｎ－Ｙ－Ｎに置き代わった構造を有する。
また、ｘが３より大きい場合は、Ｙが更に－Ｏ－の結合を有する分岐状のポリマーとなることが理解できる。 Further, U is defined as Y(-O)x- or Y(-N)x-, and Y consists of an alkyl group having 1 to 20 carbon atoms including a substituent, and the substituent includes an alkenyl group, Examples include alkynyl group, cycloalkyl group, bicycloalkyl group, tricycloalkyl group, aryl group, halogen atom, alkoxy group, ester group, amide group, carbamate group, urea group, hydroxyl group, amino group, carboxy group, thiol group, etc. However, when the substituent is a hydroxyl group, amino group, carboxy group, or thiol group, benzyl group, tert-butyl group, tert-butoxycarbonyl group, pentafluorophenyl group, 2-nitrobenzyl group, 4-nitrobenzyl group , a tetrahydropyranyl group, a 2-pyridinyl sulfide group, or the like. Here, x is 1 to 100.
Here, if U is represented by Y(-O)x- and x is 2, the polymer represented by the formula (Ia) can also be represented by the following formula (Ia-1). .

In the above formula, m and m' represent the degree of polymerization, each ranging from 1 to 500.
Moreover, when R'=H, it is represented by the following formula.

Further, when U is represented by Y(-N)x- and x is 2, the structure has a structure in which the O-Y-O part is replaced with N-Y-N in the above formula.
Furthermore, it can be understood that when x is larger than 3, Y becomes a branched polymer having an -O- bond.

In formula (I), n is 1 to 1000.

The molecular weight (number average molecular weight) of the polymer of formula (I) is usually 100 to 1,000,000, preferably 1,000 to 500,000.
The above number average molecular weight is a value measured by gel permeation chromatography (GPC), and polystyrene, polymethyl methacrylate, or polyethylene oxide is used as a standard substance.

One preferable aspect of the polymer 1 of the present invention is a polymer represented by the following formula (IIa), in which R' in formula (I) is a hydrogen atom (hereinafter also referred to as "polymer 2 of the present invention"). ).

In formula (II), n is 1 to 1000.
Further, R ₁ , M, Q ₁ , Q' ₁ , Q ₂ , Q' ₂ and U are the same as described in detail for the polymer of formula (Ia).

Similar to the polymer of formula (Ia), the molecular weight (number average molecular weight) of the polymer of formula (IIa) is usually 100 to 1,000,000, preferably 1,000 to 500,000.

The polymer represented by formula (IIa) does not decompose in the usage environment or in water and can be used stably for a long period of time, while it can be rapidly decomposed at any time under specific conditions, i.e., it can be used for on-demand decomposition as described above. It is possible to realize this. The details will be described later.

2. Method for Preparing Polymer Another aspect of the present invention is a method for preparing a polymer, which includes a step of polymerizing a monomer represented by the following formula (1) (hereinafter also referred to as "preparation method of the present invention"). .

In formula (1), R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, It is selected from the group consisting of ester groups, amide groups, carbamate groups, urea groups, hydroxyl groups, amino groups, carboxy groups and thiol groups. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, adamantyl group (1-adamantyl group and 2-adamantyl group) ), exo-norbornyl group, endo-norbornyl group, and 2-bicyclo[2.2.2]octyl group.
Here, when R is a hydroxyl group, an amino group, a carboxy group or a thiol group, it may be protected with a protecting group. Examples of the protecting group include benzyl group, tert-butyl group, tert-butoxycarbonyl group, benzyloxycarbonyl group, pentafluorophenyl group, 2-nitrobenzyl group, 4-nitrobenzyl group, tetrahydropyranyl group, 2- Examples include pyridinyl sulfide group and 2,4-dinitrophenyl group.
In addition, an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, and an aryl group have a substituent. May have. Examples of the substituent include a halogen atom, an alkoxy group, a hydroxyl group, an amino group, a carboxy group, a thiol group, a sulfonyl group, a phosphoryl group, and a guanidino group. In the case of a sulfonyl group, phosphoryl group, and guanidino group, they may be protected with the above-mentioned protecting groups.
R is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkyl group substituted with an alkoxy group having 1 to 3 carbon atoms which may have a substituent, or a substituent. A phenyl group that may have a substituent, a cycloalkyl group that may have a substituent, a bicycloalkyl group that may have a substituent, or a tricycloalkyl group that may have a substituent. be.

In one preferred aspect of the present invention, R is a methoxyethyl group (-(CH ₂ ) ₂ OCH ₃ ), an n-propyl group (-(CH ₂ ) ₂ CH ₃ ), a methyl group (-CH ₃ ), or a phenyl group. group, adamantyl group (1-adamantyl group and 2-adamantyl group).

In formula (1), M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formylalkyl group, a cyanoalkyl group, a cyano group, or a formyl group. and acyl groups.

In one preferred aspect of the invention, M is a hydrogen atom.

In formula (1), Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group. selected.

In one preferred aspect of the invention, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are all hydrogen atoms.

In the preparation method of the present invention, it is preferred that the monomer concentration at the start of polymerization is high. Specifically, the concentration of the monomer in the reaction mixture at the start of polymerization is preferably 0.1 to 10 mol/L (0.1 to 10 M), and preferably 0.5 to 5 mol/L (0.5 to 5 M ), and even more preferably 1 to 5 mol/L (1 to 5 M).
Although not intending to be bound by theory, the monomer represented by formula (1), a 6-membered cyclic carbonate monomer, -7-ene, etc.), when the monomer concentration is low, intramolecular reactions occur preferentially to intermolecular reactions, producing a thermodynamically more stable five-membered cyclic carbonate compound, which leads to ring-opening polymerization. It was found that the disease tends to progress more slowly. Here, the solubility of the monomer changes depending on the structure of R, so depending on the type of monomer, it may be necessary to polymerize at a low concentration, but by increasing the concentration of the monomer within the above range, the molecule The ring-opening polymerization can proceed efficiently.

The preparation method of the present invention preferably includes a step of stopping the reaction around the time when the polymer composition in the reaction mixture reaches a maximum after the start of polymerization of the monomers.
Although not intended to be bound by theory, as the ring-opening polymerization reaction progresses, the monomer concentration decreases, and intramolecular reactions tend to occur preferentially, suppressing the progress of intermolecular reactions (polymerization reactions). It is in. Therefore, by stopping the reaction near the point at which the polymer composition in the reaction mixture reaches its maximum, the amount of impurity five-membered cyclic carbonate compounds produced can be kept low, making it possible to maximize the polymer yield. Therefore, it is preferable.

In order to stop the reaction near the point where the polymer composition in the reaction mixture reaches its maximum, it is preferable to monitor the progress of the reaction (reaction tracking). Specifically, after the start of the reaction, the composition in the reaction mixture is measured at predetermined time intervals, and the point at which the polymer composition in the reaction mixture reaches its maximum is calculated from the measured values, and the optimal reaction stop time is determined. can do.
The polymer composition in the reaction mixture is measured by measuring ¹ HNMR of the reaction mixture and calculating the composition (ratio) of the monomer, polymer, and five-membered cyclic carbonate compound in the reaction mixture, as detailed in the examples. This can be done by In addition, the composition of a similar reaction mixture can be calculated by real-time monitoring that combines infrared spectroscopy, high-performance liquid chromatography, and gas chromatography.
The time and conditions at which the polymer composition in the reaction mixture reaches its maximum differs depending on the monomer, but the optimal reaction termination time can be determined by tracking the reaction as described above, depending on the type of monomer and its initial concentration. can do.

To stop the reaction, it is preferable to add a reagent that inactivates the catalyst used in the polymerization. When an organic base such as 1,8-diazabicyclo[5.4.0]undec-7-ene is used as a polymerization catalyst, it is preferable to add an acid to the reaction mixture. As the acid, for example, benzoic acid, acetic anhydride, etc. can be used. Moreover, it is also possible to use an organic acid as a polymerization catalyst, and in that case, a base such as triethylamine can be used as a terminator.

The reaction is preferably stopped when the polymer composition in the reaction mixture is at a maximum. In this case, a system can be constructed and used that can track the reaction in real time and immediately stop the reaction.
Furthermore, the reaction can be stopped before or after the time when the polymer composition reaches its maximum.
Specifically, _T1 is within the time range in which the polymer composition reaches 80% of the maximum value at the time when the polymer composition reaches its maximum value, that is, the time period in which the polymer composition reaches 80% of the maximum value for the first time after the start of the reaction. , if the time when the polymer composition reaches its maximum value is T _max , and then the time when the polymer composition decreases to 80% of the maximum value again is T ₂ , then the time T to stop the reaction must be T _max . It is preferable that T ₁ ≦T≦T ₂ .
In addition, within the time range in which the polymer composition becomes 90% of the maximum value at the time when the polymer composition reaches its maximum value, that is, the time when the polymer composition first becomes 90% of the maximum value after the _start of the reaction, the polymer composition If the time when the polymer composition reaches its maximum is T _max , and the time when the polymer composition decreases and reaches 90% of the maximum value again is T ₄ , then the time T to stop the reaction is T ₃ ≦T≦T ₄ . It is more preferable to have the above-mentioned conditions, since it is possible to maximize the polymer yield and suppress impurities.
Therefore, in the preparation method of the present invention, the reaction is stopped around the time when the polymer composition in the reaction mixture reaches its maximum, that is, at the time when the polymer composition in the reaction mixture reaches its maximum, and before and after that time, i.e. , it is preferable that T ₁ ≦T≦T ₂ , and more preferably that T ₃ ≦T≦T ₄ .

In the preparation method of the present invention, it is possible to obtain a high molecular weight polymer in high yield when the concentration of the catalyst is low. The concentration of the catalyst is preferably 0.1 to 0.00001, more preferably 0.05 to 0.001 (catalyst/monomer ratio).

In the preparation method of the present invention, the monomer of formula (1) and a catalyst are added to a solvent to prepare a reaction mixture, and polymerization is performed.
As the solvent, any aprotic solvent can be used. Examples include, but are not limited to, deuterated chloroform (CDCl ₃ ), methylene chloride, chloroform, toluene, benzene, tetrahydrofuran, acetonitrile, acetone, hexane, diethyl ether, N,N-dimethylformamide, etc. do not have.

As the catalyst, any catalyst that can be used for polymerization of cyclic carbonates and lactones can be used. For example, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4. 4.0] Dec-5-ene, 4-dimethylaminopyridine, (-)-sparteine, trifluoromethanesulfonic acid, methanesulfonic acid, para-toluenesulfonic acid, diphenylphosphoric acid, N'-[3,5-bis (trifluoromethyl)phenyl]-N-cyclohexylthiourea, N'-[3,5-bis(trifluoromethyl)phenyl]-N-phenylurea, N-heterocyclic carbenes, mixtures thereof, etc. , but not limited to these.

As the initiator, either alcohol or amine can be used. For example, benzyl alcohol, 4-methylbenzyl alcohol, 1-pyrenebutanol, methanol, ethanol, 1-propanol, 1-butanol, isoamyl alcohol, lauryl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol , 1,12-dodecanediol, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, butylamine, hexylamine, ethylenediamine, hexamethylenediamine, benzylamine, 1,4- Examples include, but are not limited to, bis(aminomethyl)benzene, 1,3-bis(aminomethyl)benzene, and 1,2-bis(aminomethyl)benzene.

In the preparation method of the present invention, after the reaction mixture is prepared, it is usually allowed to stand at room temperature (for example, 10 to 30°C) for a predetermined period of time to react. As described above, after the reaction is stopped by adding an acid near the point where the polymer composition in the reaction mixture reaches its maximum, the reaction is terminated by stirring at room temperature (for example, 10 to 30° C.) for a predetermined period of time. Thereafter, the reaction solution is reprecipitated into cold 2-propanol or the like to recover the produced polymer.

By the preparation method of the present invention, polytrimethylene carbonate-based polymers can be obtained.
More specifically, by the preparation method of the present invention, a polymer represented by the following formula (I) can be obtained.

In formula (I), R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. It is.
n is 1 to 1000.
R, M, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are the same as described in detail for formula (1).

In formula (I), U is a (corresponding) group derived from various alcohols or amines depending on the type of initiator used in the polymerization.
For example, in [Synthesis Example 1] to [Synthesis Example 4], benzyl alcohol (BnOH) is used as an initiator, and U becomes Ph-CH ₂ -O-. In addition, in [Synthesis Example 1] to [Synthesis Example 8], water in the monomer opens the ring of the monomer, and as a result, 1,3-diol derived from the monomer (the carbon at the 2nd position is -OCOR) serves as an initiator, and the U portion is R'O-CH ₂ -CH(OCOR)-CH ₂ O- (R' represents R' in Scheme 3 of the example) becomes.

上記式で、ｍ、ｍ’は重合度であり、各々、１～５００の範囲である。
また、Ｒ’＝Ｈの場合は、以下の式で表される。

また、Ｕが、Ｙ（－Ｎ）ｘ－で表され、ｘが２の場合は、上記式で、Ｏ－Ｙ－Ｏの部分が、Ｎ－Ｙ－Ｎに置き代わった構造を有する。
また、ｘが３より大きい場合は、Ｙが更に－Ｏ－の結合を有する分岐状のポリマーとなることが理解できる。 Further, U is defined as Y(-O)x- or Y(-N)x-, and Y consists of an alkyl group having 1 to 20 carbon atoms including a substituent, and the substituent includes an alkenyl group, Examples include alkynyl group, cycloalkyl group, bicycloalkyl group, tricycloalkyl group, aryl group, halogen atom, alkoxy group, ester group, amide group, carbamate group, urea group, hydroxyl group, amino group, carboxy group, thiol group, etc. However, when the substituent is a hydroxyl group, amino group, carboxy group, or thiol group, benzyl group, tert-butyl group, tert-butoxycarbonyl group, pentafluorophenyl group, 2-nitrobenzyl group, 4-nitrobenzyl group , a tetrahydropyranyl group, a 2-pyridinyl sulfide group, or the like. Here, x is 1 to 100.
Here, if U is represented by Y(-O)x- and x is 2, the polymer represented by the formula (I) can also be represented by the following formula (I-1). .

In the above formula, m and m' represent the degree of polymerization, each ranging from 1 to 500.
Moreover, when R'=H, it is represented by the following formula.

Further, when U is represented by Y(-N)x- and x is 2, the structure has a structure in which the O-Y-O part is replaced with N-Y-N in the above formula.
Furthermore, it can be understood that when x is larger than 3, Y becomes a branched polymer having an -O- bond.

3. Another aspect of the present invention is a method for decomposing a polymer, (i) providing a polymer represented by the following formula (II), and (ii) adding a catalyst for activating hydroxyl groups to the polymer. (hereinafter also referred to as "the decomposition method of the present invention").

In formula (II), n is 1 to 1000.
Moreover, R, M, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are the same as those described in detail for the monomer of formula (1).
U is the same as described in detail for the polymer represented by formula (I).

In the present invention, a mechanism for inducing decomposition is included in the side chain structure of the polytrimethylene carbonate skeleton, which is potentially biodegradable but highly resistant to hydrolysis, as shown in formula (II), and further "On-demand decomposition" can be achieved by setting the decomposition starting point at the end group of the polymer chain.
More specifically, in a solution state, the polymer of formula (II) has an OH terminal group structure, and in the presence of a catalyst that activates the OH group, almost all molecular chains are converted within about one day. It is decomposed into one kind of low molecular weight substance (5-membered cyclic carbonate) (Polymer 1 (OH) and Polymer 2 (OH) in the graph of FIG. 1). On the other hand, even if known biodegradable polymers such as PLLA and PTMC are treated under similar conditions, no decomposition occurs. Even if the polymer of formula (II) has an OH terminal group structure, it does not decompose in the absence of a catalyst and stably maintains its polymer structure. In addition, when the terminal OH group is converted to another substituent (inactivated terminal), it exists almost stably even in the presence of a catalyst (Polymer 1 (Ac) and Polymer 2 (Ac) in the graph of Figure 1). . For this reason, the terminal structure of the OH group and the addition of a catalyst or the generation of a catalyst by some method serve as the starting switch for "on-demand decomposition."
While not intending to be bound by theory, decomposition occurs when (i) the activated terminal OH transesterifies with the side chain and (ii) the resulting secondary OH subsequently transesterifies with the adjacent main chain. A possible mechanism is to attack the carbonate bond of and generate a five-membered ring. The OH terminal newly generated by the formation of a five-membered ring repeats the same reaction in a chain manner. This type of depolymerization is called "end-initiated backbiting" type depolymerization. Because the thermodynamic stability of the 5-membered ring structure makes it difficult for the polymerization of the 5-membered ring carbonate structure to proceed, it is thought that the formation of this 5-membered ring serves as the driving force for rapid and chain-like decomposition. .

The polymer represented by formula (II) can also be provided by synthesizing the polymer represented by formula (II) by the preparation method of the present invention, and can also be provided by synthesizing the polymer represented by formula (II) using the preparation method of the present invention. By synthesizing a polymer represented by formula (I), and converting its terminal group into an OH group by hydrolysis, etc. or deprotection reaction in response to stimuli such as heat, light, pH, etc., the polymer represented by formula (II) is synthesized. It is possible to provide a polymer that

As the catalyst for activating the hydroxyl group, either an organic catalyst or a metal catalyst can be used, but it is preferable to use an organic catalyst from the viewpoint of reducing environmental burden.

Examples of the metal catalyst include tin octylate, aluminum isopropoxide, alkoxides of aluminum, zinc, iron, and cobalt.

As the organic catalyst, it is possible to use any catalyst that can be used for lactones and cyclic carbonates used as polymerization catalysts. For example, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4. 4.0] Dec-5-ene, 4-dimethylaminopyridine, (-)-sparteine, trifluoromethanesulfonic acid, methanesulfonic acid, para-toluenesulfonic acid, diphenylphosphoric acid, N'-[3,5-bis Examples include (trifluoromethyl)phenyl]-N-cyclohexylthiourea, N'-[3,5-bis(trifluoromethyl)phenyl]-N-phenylurea, N-heterocyclic carbenes, and mixtures thereof. There is no limitation to these.

In the decomposition method of the present invention, "adding a catalyst" includes not only intentional addition of a catalyst but also the generation of a catalyst by some method and the coexistence of the polymer of formula (II) and the catalyst. included. When a catalyst is generated by some method, for example, a photobase generator or a photoacid generator, such as 2-(9-oxoxanthene-2-yl)propionic acid 1,5,7-triazabicyclo[4.4 .0] deca-5-ene.

The above-described decomposition mechanism in the decomposition method of the present invention can occur regardless of the structure (R) of the side chain. Therefore, the physical properties (glass transition temperature, contact angle) and decomposition rate of the polymer can be controlled by the structure of the side chain R.
Although not intended to be bound by theory, for example, if the side chain is extremely bulky, it will affect the behavior of backbiting type depolymerization, so from the point of view of increasing the decomposition degree, R A group that is not extremely bulky, such as an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkyl substituted with an alkoxy group having 1 to 3 carbon atoms which may have a substituent. A phenyl group which may have a substituent, and a cycloalkyl group which may have a substituent are preferred. On the other hand, from the viewpoint of suppressing the degree of decomposition, an extremely bulky group such as an adamantyl group (1-adamantyl group and 2-adamantyl group) can be used as R.

The decomposition method of the present invention is preferably carried out in a solution (homogeneous solution). In this case, the polymer represented by formula (II) is dissolved in a solvent (eg, CDCl ₃ , tetrahydrofuran, methylene chloride, etc.) and a catalyst is added to perform decomposition.
Further, the decomposition method of the present invention can also be carried out in a heterogeneous system. In this case, the polymer represented by formula (II) is added to a solvent in which the polymer is insoluble, such as water or methanol, and a catalyst is added to perform decomposition.

By decomposing the polymer represented by formula (II) according to the decomposition method of the present invention, compounds represented by the following formulas (2) and/or (3), which are decomposition products, are obtained.

In formulas (2) and (3), R, M, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are the same as described in detail for the monomer of formula (1).

It is possible to further hydrolyze the compound of formula (2) and/or (3) to return it to glycerol and a carboxylic acid with R attached, and it is possible to synthesize the monomer of formula (1) from them. It is possible. Using the compound of formula (1) thus obtained, further polymers of formula (I) can be obtained. In this way it is possible to recycle the decomposition products of the polymer of formula (II).

The present invention will be explained below with reference to examples, but the present invention is not limited thereto.

1. Reagents and evaluation methods [Reagents]
Unless otherwise specified, each reagent was purchased from Fuji Film Wako Pure Chemicals, Tokyo Kasei Kogyo, Sigma-Aldrich Japan, or Kanto Kagaku and used as received. Benzyl alcohol (BnOH) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were purchased from Tokyo Kasei Kogyo and distilled under reduced pressure using calcium hydride. Deuterated chloroform (CDCl ₃ ) for reaction monitoring was purchased from Sigma-Aldrich Japan and distilled using calcium hydride.

[measuring equipment]
Nuclear magnetic resonance (NMR) was used to identify the structure of the synthesized molecule, and ¹ H and ¹³ C NMR measurements were performed using JEOL ECX-400 manufactured by JEOL Ltd. The measurement sample was dissolved in CDCl ₃ and the chemical shift was determined by setting tetramethylsilane (TMS) included as an internal standard to 0 ppm.
For elemental analysis, a PerkinElmer CHN elemental analyzer model 2400II was used.
The number average molecular weight (M _n ) and molecular weight distribution (D _M ) of the polymer were determined by gel permeation chromatography (GPC). A TSK-gel column SuperMultipore HZ-M was connected to a high-speed GPC device EcoSEC Elite HLC-8420GPC manufactured by Tosoh Corporation, and measurements were performed at a column temperature of 40° C. and a flow rate of 0.35 ml/min using tetrahydrofuran (THF) as an eluent.
Differential scanning calorimetry (DSC) was used to analyze the thermal properties of the polymer. Measurement was carried out using DSC3500 Sirius manufactured by NETZSCH under a nitrogen flow of 20 ml/min at a heating or cooling rate of 5° C./min.

2. Synthesis of Monomers (2-1) Monomers 5a to 5d (also referred to as "compounds 5a to 5d") for polymerizing the polymer of the present invention were synthesized according to Scheme 1 below.

(1) Synthesis of 3-methoxypropanoyl chloride (compound 2a) A 200 ml three-necked flask was purged with argon gas, and 3-methoxypropanoic acid (3.0 g, 29 mmol) and dehydrated dichloromethane (CH ₂ Cl ₂ ; 30 ml) were added. After the addition, the mixture was cooled in an ice bath, and a dehydrated CH ₂ Cl ₂ solution (20 ml) of oxalyl chloride (4.4 g, 35 mmol) was added dropwise. Then, a few drops of dimethylformamide were added and stirred overnight at room temperature. The solvent was distilled off to obtain Compound 2a as a yellow liquid (4.64 g). It was used in the next reaction without further purification.
¹ H NMR (400 MHz, CDCl ₃ ): δ 3.70 (t, J = 5.9 Hz, CH ₂ , 2H), 3.37 (s, CH ₃ , 3H), 3.12 (t, J = 5.9 Hz, CH ₂ , 2H )

(2) Synthesis of (2s,5s)-2-phenyl-1,3-dioxan-5-yl 3-methoxypropanoate (compound 3a) A 200 ml three-necked flask was replaced with argon gas, and cis-1,3 -O-benzylidene glycerol (compound 1; 4.3 g, 24 mmol), dehydrated pyridine (2.5 ml, 31 mmol), 4-dimethylaminopyridine (DMAP; 58 mg, 0.47 mmol), dehydrated CH ₂ Cl ₂ (20 ml). added. Next, a solution of compound 2a (3.5 g, 29 mmol) in dehydrated CH ₂ Cl ₂ (20 ml) was added dropwise and stirred at room temperature for 18 hours. After the reaction was completed, the reaction solution was suction filtered, and the resulting filtrate was washed twice with deionized water (50 ml) and once with a 5% aqueous sodium carbonate solution (50 ml). Thereafter, the organic layer was dried over magnesium sulfate, evaporated under reduced pressure, and purified by column chromatography (ethyl acetate:hexane = 3:7, R _f value = 3.6) to obtain compound 3a as a colorless and transparent liquid. (5.9 g, 92%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.46-7.56 (m, J = 7.7 Hz, Ar-H, 2H), 7.32-7.44 (m, J = 7.7 Hz, Ar-H, 3H), 5.55- 5.59 (s, 1H), 4.74-4.80 (m, CH, 1H), 4.27-4.36 (m, CH ₂ , 2H), 4.14-4.23 (m, CH ₂ , 2H), 3.71 (t, J = 6.3 Hz , CH ₂ , 2H), 3.37 (s, CH ₃ , 3H), 2.72 (t, J = 6.1 Hz, CH ₂ , 2H)

(3) Synthesis of (2s,5s)-2-phenyl-1,3-dioxan-5-yl butyrate (compound 3b) A 300 ml three-neck flask was replaced with argon gas, and compound 1 (5.0 g, 28 mmol) , triethylamine (4.6 _ml , 3.3 mmol), DMAP (76 mg, 0.62 mmol) and dry _CH2Cl2 (30 ml) were added. Next, a solution of commercially available butyryl chloride (compound 2b; 3.2 ml, 31 mmol) in dehydrated CH ₂ Cl ₂ (20 ml) was added dropwise and stirred overnight at room temperature. The reaction solution containing the precipitate was filtered, and the filtrate was washed twice with 50 ml of deionized water and once with 5% aqueous sodium carbonate solution (50 ml). Thereafter, the organic layer was dried over magnesium sulfate, evaporated under reduced pressure, and purified by column chromatography (ethyl acetate:hexane = 1:4, R _f value = 0.48) to obtain compound 3b as a colorless and transparent liquid. (6.6 g, 84%).
¹ H NMR (400 MHz, CDCl ₃ ): 7.48-7.55 (m, Ar-H, 2H), 7.34-7.42 (m, Ar-H, 3H), 5.56 (s, Ph-CH, 1H), 4.74- 4.72 (m, CH, 1H), 4.26-4.34 (m, CH ₂ , 2H), 4.15-4.22 (m, CH ₂ , 2H), 2.43 (t, J = 7.5 Hz, CH ₂ , 2H), 1.71 ( td, J = 15.0, 7.2 Hz, CH ₂ , 2H), 0.98 (t, J = 7.5 Hz, CH ₃ , 3H)

(4) Synthesis of (2s,5s)-2-phenyl-1,3-dioxan-5-yl acetate (compound 3c) A 200 ml three-necked flask was replaced with argon gas, and cis-1,3-O-benzylidene glycerol (Compound 1; 5.0 g, 28 mmol), dehydrated pyridine (3.0 ml, 37 mmol), 4-dimethylaminopyridine (DMAP; 73 mg, 0.60 mmol), and dehydrated CH ₂ Cl ₂ (30 ml) were added. Next, a solution of compound 2c (2.6 g, 33 mmol) in dehydrated CH ₂ Cl ₂ (20 ml) was added dropwise and stirred at room temperature for 23 hours. After the reaction, the reaction solution was suction filtered, and the resulting filtrate was diluted once with 5% aqueous sodium carbonate solution (100 ml), once with deionized water (100 ml), and once with saturated aqueous sodium chloride solution (100 ml). , washed. Thereafter, the organic layer was dried over magnesium sulfate, distilled off under reduced pressure, and purified by recrystallization in ethanol to obtain Compound 3c as a white solid (4.8 g, 78%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.48-7.56 (m, Ar-H, 2H), 7.32-7.42 (m, Ar-H, 3H), 5.57 (s, Ph-CH, 1H), 4.73 -4.72 (m, CH, 1H), 4.26-4.35 (m, CH ₂ , 2H), 4.14-4.24 (m, CH ₂ , 2H), 2.18 (s, CH ₃ , 3H)

(5) Synthesis of (2s,5s)-2-phenyl-1,3-dioxan-5-yl benzoate (compound 3d) A 200 ml three-necked flask was replaced with argon gas, and cis-1,3-O-benzylidene glycerol (Compound 1; 5.0 g, 28 mmol), triethylamine (4.6 ml, 3.3 mmol), 4-dimethylaminopyridine (DMAP; 7.2 mg, 0.059 mmol), and dehydrated CH ₂ Cl ₂ (31 ml) were added. . Next, a solution of compound 2d (4.3 g, 31 mmol) in dehydrated CH ₂ Cl ₂ (20 ml) was added dropwise and stirred at room temperature for 19 hours. After the reaction was completed, the reaction solution was suction filtered, and the resulting filtrate was washed twice with deionized water (50 ml). Thereafter, the organic layer was dried over magnesium sulfate, evaporated under reduced pressure, and purified by recrystallization in ethanol to obtain Compound 3d as a white solid (4.4 g, 56%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13-8.21 (m, Ar-H, 2H), 7.33-7.63 (m, Ar-H, 8H), 5.63 (s, Ph-CH, 1H), 4.94 -5.01 (s, CH, 1H), 4.39-4.49 (m, CH ₂ , 2H), 4.24-4.34 (m, CH ₂ , 2H)

(6) Synthesis of 1,3-dihydroxypropan-2-yl 3-methoxypropanoate (compound 4a) Add compound 3a (5.9 g, 22 mmol) and 80% acetic acid aqueous solution (178 ml) to a 300 ml eggplant flask. Stirred at room temperature for 48 hours. Thereafter, the solvent was distilled off under reduced pressure, and the remaining liquid was purified by column chromatography (dichloromethane:methanol=95:5). The product was obtained as a mixture of compound 4a and compound 4'a (3.1 g) and was used as such for the next synthesis.

(7) Synthesis of 1,3-dihydroxypropan-2-yl butyrate (compound 4b) Compound 3b (3.0 g, 11 mmol) and 80% acetic acid aqueous solution (30 ml) were added to a 300 ml eggplant flask and stirred at room temperature for 3 days. did. Thereafter, the solvent was distilled off under reduced pressure, and the remaining liquid was purified by column chromatography (dichloromethane:methanol=95:5). The product was obtained as a mixture of compound 4b and compound 4'b (1.4 g) and was used as such in the next synthesis.

(8) Synthesis of 1,3-dihydroxypropan-2-yl acetate (compound 4c) Compound 3c (2.7 g, 12 mmol) and 80% acetic acid aqueous solution (80 ml) were added to a 200 ml eggplant flask and stirred at room temperature for 3 days. did. Thereafter, the solvent was distilled off under reduced pressure, and the remaining liquid was purified by column chromatography (dichloromethane:methanol=95:5). The product was obtained as a mixture of compound 4c and compound 4'c (1.2 g) and was used as such in the next synthesis.

(9) Synthesis of 1,3-dihydroxypropan-2-yl benzoate (compound 4d) In a 300 ml eggplant flask, compound 3d (1.8 g, 6.4 mmol), tin(II) chloride (1.8 g, 9.6 mmol) ) and stirred at room temperature for 2 days. Next, it was washed once with a saturated aqueous sodium chloride solution (100 ml). Thereafter, the organic layer was dried over sodium sulfate, evaporated under reduced pressure, and purified by column chromatography (ethyl acetate:methanol=95:5). The product was obtained as a mixture of compound 4d and compound 4'd (0.48 g) and was used as such in the next synthesis.

(10) 2-oxo-1,3-dioxan-5-yl 3-methoxypropanoate (compound 5a)
After replacing the 30 ml Schlenk tube with argon gas, a mixture of compound 4a and compound 4'a (0.54 g), ethyl chloroformate (1.2 g, 11 mmol), and dehydrated tetrahydrofuran (THF: 10 ml) were added and placed in an ice bath. The mixture was cooled and stirred for 1 hour. A dehydrated THF solution (4 ml) of triethylamine (1.6 ml, 12 mmol) was added dropwise over 15 minutes. Thereafter, the mixture was further stirred at room temperature for about 1 hour, the resulting precipitate was filtered off, and the resulting filtrate was concentrated. The residue was dissolved in CH ₂ Cl ₂ (50 ml) and washed with saturated aqueous sodium chloride (50 ml). The organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography (ethyl acetate:hexane=7:3) to obtain 5a as a colorless and transparent oil (0.31 g, 50%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.22-5.28 (m, CH, 1H), 4.56-4.67 (m, CH ₂ , 2H), 4.45-4.54 (m, CH ₂ , 2H), 3.68 (t , J = 6.1 Hz, CH ₂ , 2H), 3.36 (s, CH ₃ , 3H), 2.68 (t, J = 6.1 Hz, CH ₂ , 2H)
^13C NMR (100 MHz, CDCl ₃ ): δ 170.9, 147.3, 69.8, 67.6, 62.6, 58.9, 35.0
Elemental analysis: Calculated value (%) C 47.06, H 5.92; Actual value (%) C 46.75, H 5.91

(11) 2-oxo-1,3-dioxan-5-yl butyrate (compound 5b)
After purging a 300 ml three-necked eggplant flask with argon gas, a mixture of compound 4b and compound 4'b (1.4 g), ethyl chloroformate (3.3 g, 31 mmol), and dehydrated THF (27 ml) were added and placed in an ice bath. The mixture was cooled and stirred for 15 minutes. A dehydrated THF solution (10 ml) of triethylamine (4.6 ml, 33 mmol) was added dropwise over 5 minutes. Thereafter, the mixture was stirred at room temperature for about 1 hour, the resulting precipitate was filtered off, and the resulting filtrate was concentrated. The residue was dissolved in CH ₂ Cl ₂ (50 ml) and washed with aqueous sodium chloride (50 ml). The organic layer was dried over magnesium sulfate, concentrated, and then purified by column chromatography (ethyl acetate:hexane=1:1) to obtain Compound 5b as a white solid (0.54 g, 33%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.17-5.24 (m, CH, 1H), 4.56-4.66 (m, CH ₂ , 2H), 4.43-4.52 (m, CH ₂ , 2H), 2.40 (t , J = 7.5 Hz, CH ₂ , 2H), 1.69 (td, J = 14.8, 7.4 Hz, CH ₂ , 2H), 0.98 (t, J = 7.5 Hz, CH ₃ , 3H)
^13C NMR (100 MHz, CDCl ₃ ) δ 172.9, 147.3, 69.9, 62.3, 35.9, 18.3, 13.6

(12) 2-oxo-1,3-dioxan-5-yl acetate (compound 5c)
After purging a 200 ml three-neck eggplant flask with argon gas, a mixture of compound 4c and compound 4'c (1.2 g), ethyl chloroformate (3.3 g, 31 mmol), and dehydrated THF (26 ml) were added and placed in an ice bath. The mixture was cooled and stirred for 30 minutes. A solution of triethylamine (4.6 ml, 33 mmol) in dehydrated THF (12 ml) was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for about 2 hours, the resulting precipitate was filtered off, and the resulting filtrate was concentrated. The residue was dissolved in CH ₂ Cl ₂ (50 ml) and washed with aqueous sodium chloride (50 ml). The organic layer was dried over sodium sulfate, concentrated, and then purified by column chromatography (ethyl acetate:hexane=1:1) to obtain 5c as a white solid (0.45 g, 33%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.17-5.23 (m, CH, 1H), 4.58-4.66 (m, CH ₂ , 2H), 4.45-4.53 (m, CH ₂ , 2H), 2.17 (s , CH ₃ , 3H)
^13C NMR (100 MHz, CDCl ₃ ) δ 170.2, 147.3, 69.9, 62.5, 20.9

(13) 2-oxo-1,3-dioxan-5-yl benzoate (compound 5d)
After purging a 200 ml three-neck eggplant flask with argon gas, a mixture of compound 4d and compound 4'd (0.48 g), ethyl chloroformate (0.95 g, 8.7 mmol), and dehydrated THF (8.1 ml) were added. The mixture was cooled in an ice bath and stirred for 30 minutes. A dehydrated THF solution (3.1 ml) of triethylamine (1.3 ml, 9.3 mmol) was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for about 2 hours, the resulting precipitate was filtered off, and the resulting filtrate was concentrated. The residue was dissolved in CH ₂ Cl ₂ (30 ml) and washed with aqueous sodium chloride (30 ml). The organic layer was dried over magnesium sulfate, concentrated, and then purified by column chromatography (ethyl acetate:hexane=6:4) to obtain Compound 5d as a white solid (0.15 g, 27%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.02-8.13 (m, Ar-H, 2H), 7.59-7.69 (m, Ar-H, 1H), 7.42-7.55 (m, Ar-H, 2H) , 5.44-5.50 (m, CH, 1H), 4.59-4.77 (m, CH ₂ , 4H)
^13C NMR (100 MHz, CDCl ₃ ) δ 165.7, 147.4, 134.1, 130.0, 128.8, 128.6, 70.0, 63.0

(2-2) Monomer 5e (also referred to as "compound 5e") for polymerizing the polymer of the present invention, in which R is an adamantyl group, was synthesized according to Scheme 1 above.

(1) Synthesis of (2s,5s)-2-phenyl-1,3-dioxan-5-yl adamantane-1-carboxylate (compound 3e) A 200 ml three-necked flask was replaced with argon gas, and cis-1,3 -O-benzylidene glycerol (Compound 1; 1.0 g, 5.6 mmol), triethylamine (1.2 ml, 8.3 mmol), 4-dimethylaminopyridine (DMAP; 68 mg, 0.56 mmol), dehydrated CH ₂ Cl ₂ ( 10 ml) was added. Next, a solution of compound 2e (6.4 g, 33 mmol) in dehydrated CH ₂ Cl ₂ (10 ml) was added dropwise under an ice bath, and the mixture was stirred at room temperature for 16 hours. After the reaction was completed, the reaction solution was suction filtered, and the resulting filtrate was washed twice with a 5% aqueous sodium carbonate solution (20 ml) and deionized water (50 ml). Thereafter, the organic layer was dried over magnesium sulfate, evaporated under reduced pressure, and purified by column chromatography (ethyl acetate:hexane = 1:9) to obtain compound 3e as a white solid (0.8 g, 42%). .
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.60-7.44 (m, Ar-H, 2H), 7.44-7.31 (m, Ar-H, 3H), 5.53 (s, Ph-CH, 1H), 4.68 -4.64 (m, OCH, 1H), 4.28-4.09 (m, CH ₂ , 4H), 1.94-2.08 (m, Ad, 9H), 1.78-1.67 (m, Ad, 6H).

(2) Synthesis of 1,3-dihydroxypropan-2-yl adamantane-1-carboxylate (compound 4e) Add compound 3e (4.8 g, 14 mmol) and 85% acetic acid aqueous solution (158 ml) to a 300 ml eggplant flask. Stirred at room temperature for 65 hours. Thereafter, the solvent was removed by vacuum drying, and the residue was dissolved in dichloromethane (50 ml) and washed once with a saturated aqueous sodium bicarbonate solution. Thereafter, the organic layer was dried over magnesium sulfate, evaporated under reduced pressure, and purified by column chromatography (dichloromethane:methanol=95:5). The product was obtained as a mixture of compound 4e and compound 4'e (3.2 g) and was used as such in the next synthesis.

(3) 2-oxo-1,3-dioxan-5-yl adamantane-1-carboxylate (compound 5e)
After purging a 300 ml three-necked eggplant flask with argon gas, a mixture of compound 4e and compound 4'e (2.5 g), ethyl chloroformate (3.8 g, 35 mmol), and dehydrated THF (38 ml) were added and placed in an ice bath. The mixture was cooled and stirred for 30 minutes. A dehydrated THF solution (8.1 ml) of triethylamine (4.2 ml, 30 mmol) was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for about 1 hour, the resulting precipitate was filtered off, and the resulting filtrate was concentrated. The residue was dissolved in CH ₂ Cl ₂ (50 ml) and washed with saturated aqueous sodium chloride (50 ml). The organic layer was dried over magnesium sulfate, concentrated, and then purified by column chromatography (ethyl acetate:hexane=4:6) to obtain Compound 5e as a white solid (0.88 g, 32%).
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.21-5.10 (m, OCH, 1H), 4.67-4.53 (m, CH ₂ , 2H), 4.52-4.37 (m, CH ₂ , 2H), 2.55-1.58 (m, Ad, 15H).
^13C NMR (100 MHz, CDCl ₃ ) δ 176.8, 147.4, 69.9, 62.1, 41.0, 38.6, 36.3, 27.8.

3. Synthesis of Polymers Polymers 6a to 6e of the present invention were synthesized according to Scheme 2 and Scheme 3 below. Here, in order to examine the polymerization conditions, a ring-opening polymerization test of monomer 5a was conducted under various conditions.

3-1. Study of polymerization conditions [Synthesis example 1]
(Condition 1) Ring-opening polymerization of monomer 5a (monomer concentration: 0.1M)
In a glove box under an argon gas atmosphere, monomer 5a (21 mg, 0.1 mmol) was placed in _a 2 ml vial, and BnOH (1.8 x 10 ^-2 M, 0 .1 ml), a DBU (1.9×10 ⁻² M, 0.14 ml) solution, and CDCl ₃ (0.76 ml) were added, and the mixture was allowed to stand at room temperature. Thereafter, a portion was taken out at a predetermined time, the reaction was stopped with a small amount of benzoic acid, and the resultant mixture was diluted with CDCl ₃ and measured by ¹ HNMR to confirm monomer conversion.

[Synthesis example 2]
(Condition 2) Ring-opening polymerization of monomer 5a (monomer concentration: 1M)
In a glove box under an argon gas atmosphere, monomer 5a (49 mg, 0.24 mmol), BnOH (0.1 M, 0.05 ml) prepared in distilled CDCl ₃ and DBU (9.9× 10 ⁻² M, 0.05 ml) solution and CDCl ₃ (0.16 ml) were added, and the mixture was allowed to stand at room temperature. Thereafter, a portion was taken out at a predetermined time, the reaction was stopped with a small amount of benzoic acid, and the resultant mixture was diluted with CDCl ₃ and measured by ¹ HNMR to confirm monomer conversion.

[Synthesis example 3]
(Condition 3) Ring-opening polymerization of monomer 5a (monomer concentration: 1M)
In a glove box under an argon gas atmosphere, monomer 5a (150 mg, 0.74 mmol), BnOH (7.3 × 10 ^-2 M, 0.05 ml) prepared in distilled CDCl ₃ and DBU ( 7.2×10 ⁻² M, 0.05 ml) solution and CDCl ₃ (0.65 ml) were added, and the mixture was allowed to stand at room temperature. Thereafter, a portion was taken out at a predetermined time, the reaction was stopped with a small amount of benzoic acid, and the resultant mixture was diluted with CDCl ₃ and measured by ¹ HNMR to confirm monomer conversion.

[Synthesis example 4]
(Condition 4) Ring-opening polymerization of monomer 5a (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5a (101 mg, 0.49 mmol), BnOH (7.2 × 10 ^-2 M, 0.035 ml) prepared in distilled CDCl ₃ and DBU ( 7.3×10 ⁻² M, 0.035 ml) solution and CDCl ₃ (0.093 ml) were added, and the mixture was allowed to stand at room temperature. Thereafter, a portion was taken out at a predetermined time, the reaction was stopped with a small amount of benzoic acid, and the resultant diluted with CDCl ₃ was measured by ¹ H NMR to confirm monomer conversion.

[Example 1]
Evaluation of time change in reaction mixture composition in ring-opening polymerization of 5a FIG. 2 shows a 1 H NMR spectrum (400 MHz, CDCl ₃ ) of the reaction mixture at 15 minutes of reaction in ring-opening polymerization of 5a (monomer concentration ¹ M).
As shown in FIG. 2, the reaction mixture of ring-opening polymerization of monomer 5a includes polymer 6a and by-product 5'a. Characteristic signals were observed between 4.8 and 5.4 ppm, and the composition of the reaction mixture at each time was calculated from these integral ratios and plotted as shown in FIG.

FIG. 3 shows the time course of the reaction mixture composition in the ring-opening polymerization of 5a with different monomer, initiator, and catalyst concentrations. Here, (a) to (d) in FIG. 3 are the results under the above conditions (condition 1) to (condition 4), and each condition is as follows.
Figure 3(a): [5a] ₀ = 0.1M, 5a/BnOH/DBU = 50/1/1 (condition 1)
Figure 3(b): [5a] ₀ = 1M, 5a/BnOH/DBU = 50/1/1 (condition 2)
Figure 3(c): [5a] ₀ = 1M, 5a/BnOH/DBU = 200/1/1 (condition 3)
Figure 3(d): [5a] ₀ = 3M, 5a/BnOH/DBU = 200/1/1 (condition 4)

As can be seen from FIG. 3, the monomer conversion rate and the reaction mixture composition, particularly the maximum production amount of polymer 6a, vary depending on the monomer, initiator, and catalyst concentrations. From this, regarding the polymerization of 5a, the monomer concentration was set to 3M, and the polymer yield was optimized by stopping the polymerization 35 minutes after the start of the polymerization. Since the time and conditions at which the polymer composition in the reaction mixture reaches its maximum differ depending on the monomer, similar reaction tracking was conducted for each of monomers 5b, 5c, and 5d to determine the optimal reaction termination time. For monomers 5b and 5c, the amount of polymer produced was about 80% under the high monomer concentration condition of 3M, similar to monomer 5a. Monomer 5d had low solubility in CH ₂ Cl ₂ , and even under 1M conditions, the reaction proceeded in a heterogeneous system and became a homogeneous solution as the polymerization progressed. Therefore, although the polymerization of 5d actually proceeded at a monomer concentration of 1M or less, the amount of by-product 5'd produced was kept low, and the maximum amount of polymer 6d produced was 80% or more. Thus, it has been suggested that the optimal monomer concentration range that maximizes polymer yield changes depending on the structure of the side chain.

3-2. Synthesis experiments for each polymer [Synthesis Example 1]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl 3-methoxypropanoate) (6a-OH) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5a (200 mg, 0.98 mmol), distilled CDCl ₃ (0.70 ml), and calcium hydride (a small amount) were added to a 2 ml vial, and the mixture was stirred for several hours. was pre-dried. After filtering the solution with a PTFE filter (0.2 μm) and concentrating once, a DBU (9.9×10 ^-2 M, 0.05 ml) solution prepared with distilled CDCl ₃ and CDCl ₃ (0.28 ml) were added. ) was added and left standing at room temperature for 35 minutes. Thereafter, a small amount of benzoic acid was added to the reaction solution and stirred for 3 hours to stop the reaction. This was reprecipitated twice into cold 2-propanol to give 6a-OH as a clear viscous material (89 mg, 45%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.26-5.34 (m, CH), 4.23-4.43 (m, CH ₂ ), 3.65 (t, J = 6.3 Hz, CH ₂ ), 3.34 (s, CH ₃ ), 2.62 (t, J = 6.3 Hz, CH ₂ )
GPC: M _n 11,900 g/mol, D _M = 1.17

[Synthesis Example 2]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl 3-methoxypropanoate) (6a-Ac) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5a (301 mg, 1.48 mmol), distilled CDCl ₃ (0.78 ml), and calcium hydride (a small amount) were added to a 2 ml vial and stirred for several hours to remove the monomer. Preliminary drying was performed. After filtering the solution with a PTFE filter (0.2 μm) and concentrating once, a DBU (0.14M, 0.05 ml) solution prepared with distilled CDCl ₃ and CDCl ₃ (0.42 ml) were added, and the mixture was heated to room temperature. It was left standing for 35 minutes. Thereafter, a small amount of acetic anhydride was added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated into cold 2-propanol to give 6a-Ac as a clear viscous material (217 mg, 72%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.23-5.40 (m, CH), 4.22-4.48 (m, CH ₂ ), 3.65 (t, J = 6.1 Hz, CH ₂ ), 3.34 (s, CH ₃ ), 2.62 (t, J = 6.1 Hz, CH ₂ )
GPC: M _n 12,000 g/mol, D _M = 1.16
DSC: T _g -13°C

[Synthesis Example 3]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl butyrate) (6b-OH) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5b (149 mg, 0.79 mmol), DBU (6.8 x 10 ^-2 M, 0.06 ml) solution prepared in distilled CDCl ₃ , and CDCl were placed in a 2 ml vial in a glove box under an argon gas atmosphere. ₃ (0.2 ml) was added, and the mixture was allowed to stand at room temperature for 80 minutes. Thereafter, a small amount of benzoic acid and CDCl ₃ (about 2 ml) were added to the reaction solution and stirred for 1 hour to stop the reaction. This was reprecipitated in methanol to obtain 6b-OH as a transparent viscous substance (131 mg, 88%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.23-5.36 (m, CH), 4.14-4.51 (m, CH ₂ ), 2.33 (t, J = 7.2 Hz, CH ₂ ), 1.66 (td, J = 14.7, 7.2 Hz, CH ₂ ), 0.95 (t, J = 7.5 Hz, CH ₃ )
GPC: M _n 29,300 g/mol, D _M = 1.34

[Synthesis Example 4]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl butyrate) (6b-Ac) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5b (149 mg, 0.79 mmol), DBU (6.6 x 10 ^-2 M, 0.06 ml) solution prepared in distilled CDCl ₃ , and CDCl were placed in a 2 ml vial in a glove box under an argon gas atmosphere. ₃ (0.2 ml) was added, and the mixture was allowed to stand at room temperature for 80 minutes. Thereafter, a small amount of acetic anhydride and CDCl ₃ (about 2 ml) were added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated in methanol to obtain 6b-Ac as a transparent viscous substance (141 mg, 95%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.24-5.34 (m, CH), 4.16-4.46 (m, CH ₂ ), 2.33 (t, J = 7.5 Hz, CH ₂ ), 1.66 (td, J = 14.8, 7.4 Hz, CH ₂ ), 0.95 (t, J = 7.2 Hz, CH ₃ )
GPC: M _n 34,900 g/mol, D _M = 1.33
DSC: T _g -5°C

[Synthesis Example 5]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl acetate) (6c-OH) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5c (130 mg, 0.81 mmol), DBU (0.1 M, 0.04 ml) solution prepared in distilled CDCl ₃ , and CDCl ₃ (0.04 ml) solution in a 2 ml vial were placed in a glove box under an argon gas atmosphere. 23 ml) was added thereto, and the mixture was allowed to stand at room temperature for 30 minutes. Thereafter, benzoic acid (7.48 mg) and CDCl ₃ (approximately 2 ml) were added to the reaction solution and stirred for 1 hour to stop the reaction. This was reprecipitated in methanol to give 6c-OH as a clear polymer (75 mg, 58%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.23-5.33 (m, CH), 4.19-4.49 (m, CH ₂ ), 2.11 (s, CH ₃ )
GPC: M _n 11,600 g/mol, D _M = 1.13

[Synthesis Example 5a]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl acetate) (6c-OH) 2 (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5c (200 mg, 1.25 mmol), DBU (0.1 M, 0.06 ml) solution prepared in distilled CDCl ₃ , and CDCl 3 (0.1 M) solution prepared in distilled CDCl ₃ were placed in a 2 ml vial in a glove box under an argon gas atmosphere. 36 ml) was added thereto and allowed to stand at room temperature for 2 hours. Thereafter, benzoic acid (4.37 mg) and CDCl ₃ (approximately 2 ml) were added to the reaction solution and stirred for 1 hour to stop the reaction. This was reprecipitated in methanol to give 6c-OH as a transparent polymer (156 mg, 78%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.23-5.33 (m, CH), 4.19-4.49 (m, CH ₂ ), 2.11 (s, CH ₃ )
GPC: M _n 42,100 g/mol, D _M = 1.64
A higher molecular weight product of polymer 6c-OH could be obtained than in Synthesis Example 5.

[Synthesis Example 6]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl acetate) (6c-Ac) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5c (130 mg, 0.81 mmol), DBU (0.1 M, 0.04 ml) solution prepared in distilled CDCl ₃ , and CDCl 3 (0.04 ml) solution prepared in distilled CDCl ₃ were placed in a 2 ml vial in a glove box under an argon gas atmosphere. 23 ml) was added thereto, and the mixture was allowed to stand at room temperature for 30 minutes. Thereafter, a small amount of acetic anhydride and CDCl ₃ (about 2 ml) were added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated in methanol to obtain 6c-Ac as a transparent polymer (141 mg, 94%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.22-5.33 (m, CH), 4.23-4.47 (m, CH ₂ ), 2.09-2.14 (s, CH ₃ )
GPC: M _n 11,500 g/mol, D _M = 1.14
DSC: T _g 23°C

[Synthesis Example 6a]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl acetate) (6c-Ac) 2 (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5c (150 mg, 0.94 mmol), DBU (0.12 M, 0.04 ml) solution prepared in distilled CDCl ₃ , and CDCl 3 (0.94 ml) solution prepared in distilled CDCl ₃ were placed in a 2 ml vial in a glove box under an argon gas atmosphere. 27 ml) was added thereto and allowed to stand at room temperature for 4 hours. Thereafter, a small amount of acetic anhydride and CDCl ₃ (about 2 ml) were added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated in methanol to give 6c-Ac as a transparent polymer (101 mg, 67%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 5.23-5.33 (m, CH), 4.19-4.49 (m, CH ₂ ), 2.11 (s, CH ₃ )
GPC: M _n 51,700 g/mol, D _M = 1.93
A higher molecular weight product of polymer 6c-Ac than in Synthesis Example 6 could be obtained.

[Synthesis Example 7]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl benzoate) (6d-OH) (monomer concentration: 1M)
In a glove box under an argon gas atmosphere, monomer 5d (200 mg, 0.90 mmol), DBU (0.09 M, 0.08 ml) solution prepared in distilled CDCl ₃ and CDCl ₃ (0.82 ml) were placed in a 2 ml vial. ) was added and left standing at room temperature for 240 minutes. Thereafter, benzoic acid (10 mg) and CDCl ₃ (about 2 ml) were added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated in methanol to give 6d-OH as a transparent polymer (105 mg, 52%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 7.93-8.01 (m, Ar-H), 7.48-7.56 (m, Ar-H), 7.33-7.43 (m, Ar-H), 5.43-5.52 ( m, CH), 4.31-4.51 (m, CH ₂ )
GPC: _Mn 27,100 g/mol, D _M = 1.53

[Synthesis Example 7a]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl benzoate) (6d-OH) 2 (monomer concentration: 1M)
In a glove box under an argon gas atmosphere, monomer 5d (150 mg, 0.68 mmol), DBU (0.08 M, 0.04 ml) solution prepared in distilled CDCl ₃ and CDCl ₃ (0.65 ml) were placed in a 2 ml vial. ) was added and left standing at room temperature for 220 minutes. Thereafter, several drops of acetic acid and CDCl ₃ (approximately 2 ml) were added to the reaction solution and stirred for 70 minutes to stop the reaction. This was reprecipitated in methanol to give 6d-OH as a transparent polymer (129 mg, 89%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 7.93-8.01 (m, Ar-H), 7.48-7.56 (m, Ar-H), 7.33-7.43 (m, Ar-H), 5.43-5.52 ( m, CH), 4.31-4.51 (m, CH ₂ )
GPC: M _n 40,000 g/mol, D _M = 1.29
A higher molecular weight product of polymer 6d-OH could be obtained than in Synthesis Example 7.

[Synthesis Example 8]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl benzoate) (6d-Ac) (monomer concentration: 1M)
In a glove box under an argon gas atmosphere, monomer 5d (150 mg, 0.68 mmol), DBU (0.09 M, 0.06 ml) solution prepared in distilled CDCl ₃ and CDCl ₃ (0.63 ml) were placed in a 2 ml vial. ) was added and left to stand at room temperature for 210 minutes. Thereafter, a small amount of acetic anhydride and CDCl ₃ (about 2 ml) were added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated twice in methanol to give 6d-Ac as a clear polymer (99 mg, 66%).
¹ H-NMR (396 MHz, CDCl ₃ ): δ 7.92-8.03 (m, Ar-H), 7.47-7.57 (m, Ar-H), 7.32-7.43 (m, Ar-H), 5.39-5.58 ( m, CH), 4.23-4.58 (m, _CH2 )
GPC: M _n 26,300 g/mol, D _M = 1.49
DSC: T _g 51°C
[Synthesis Example 9]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl adamantane-1-carboxylate) (6e-OH) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5e (149 mg, 0.53 mmol), DBU (0.07 M, 0.04 ml) solution prepared in distilled CDCl ₃ and CDCl ₃ (0.14 ml) were placed in a 2 ml vial. ) was added and left standing at room temperature for 80 minutes. Thereafter, benzoic acid (8.4 mg) and CDCl ₃ (approximately 2 ml) were added to the reaction solution and stirred for 60 minutes to stop the reaction. This was reprecipitated in methanol to give 6e-OH as a clear polymer (124 mg, 83%).
^1H -NMR (396 MHz, CDCl ₃ ): δ 5.32-5.18 (m, OCH), 4.47-4.41 (m, CH ₂ ), 2.11-1.61 (m, Ad).
GPC: _Mn 52,100 g/mol, D _M = 1.19

[Synthesis Example 10]
Synthesis of poly(2-oxo-1,3-dioxan-5-yl adamantane-1-carboxylate) (6e-Ac) (monomer concentration: 3M)
In a glove box under an argon gas atmosphere, monomer 5e (150 mg, 0.54 mmol), DBU (0.07 M, 0.04 ml) solution prepared in distilled CDCl ₃ and CDCl ₃ (0.14 ml) were placed in a 2 ml vial. ) was added and left to stand at room temperature for 80 minutes. Thereafter, a small amount of acetic anhydride and CDCl ₃ (about 2 ml) were added to the reaction solution and stirred for 1 hour to stop the reaction. This was reprecipitated in methanol three times to obtain 6e-Ac as a transparent polymer (149 mg).
^1H -NMR (396 MHz, CDCl ₃ ): δ 5.33-5.19 (m, OCH), 4.50-4.12 (m, CH ₂ ), 2.21-1.61 (m, Ad).
GPC: M _n 48,900 g/mol, D _M = 1.20
DSC: T _g 85°C

[Comparative example 1]
Synthesis of poly(trimethylene carbonate) (PTMC-OH) In a glove box under an argon gas atmosphere, trimethylene carbonate (TMC; 200 mg, 2.0 mmol), 1-(3,5-bis(trimethylene carbonate), Fluoromethyl)phenyl)-3-cyclohexyl-2-thiourea (TU: 36 mg, 0.097 mmol) and dry CH ₂ Cl ₂ (0.41 ml) were added. Further, a dehydrated CH ₂ Cl ₂ solution of BnOH (9.3 × 10 ^-2 M, 0.1 ml) was added, followed by a dehydrated CH ₂ Cl ₂ solution (0.2 M, 0.5 ml) of DBU, and 1 It was stirred overnight. Then, benzoic acid (63 mg) was added to the reaction solution and stirred for 5 hours to stop the reaction. This was reprecipitated in methanol to obtain PTMC-OH (160 mg, 80%).
GPC: M _n 17,200 g/mol, D _M = 1.16

[Comparative example 2]
Synthesis of poly(trimethylene carbonate) (PTMC-Ac) In a glove box under an argon gas atmosphere, TMC (300 mg, 2.9 mmol), TU (54 mg, 0.15 mmol), dehydrated CH ₂ Cl ₂ in a 2 ml vial. (1.3 ml) was added. Further, a dehydrated _CH2Cl2 solution _of BnOH (0.14M, 0.11 ml) was added, followed by a _{dehydrated CH2Cl2} solution of DBU (0.15M, 0.22ml), and the mixture was stirred for 4 days. Thereafter, a small amount of acetic anhydride was added to the reaction solution, and the reaction was stopped by stirring overnight. This was reprecipitated in methanol to obtain PTMC-Ac (255 mg, 85%).
GPC: _Mn 11,200 g/mol, D _M = 1.15

[Example 1]
Decomposition experiment in homogeneous solution
Decomposition experiments were conducted for each polymer according to the following scheme.

Dissolve 25-30 mg of each polymer (6a-OH, 6a-Ac, 6b-OH, 6b-Ac, PTMC-OH, PTMC-Ac) in CDCl ₃ , and add DBU corresponding to 0.5% of the monomer unit. and stirred at room temperature. At a predetermined time, 20-50 μl of each reaction solution was taken out, and after stopping the reaction with benzoic acid, it was diluted to about 2 ml of CDCl ₃ and ¹ HNMR measurement was performed. The degree of degradation was calculated from the integral ratio of the 5' signal and the polymer signal.

In addition, polymers 6c-OH, 6c-Ac, 6d-OH, 6d-Ac, 6e-OH, and 6e-Ac were treated with DBU in CDCl ₃ for 30 hours under similar conditions, and the degree of decomposition at that time was compared. .

FIG. 4 shows the ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6a-OH after 4 hours of homogeneous decomposition treatment.
FIG. 5 shows the ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6a-OH after 30 hours of homogeneous decomposition treatment.
FIG. 6 shows the ¹ H NMR spectrum (4006 Hz, CDCl ₃ ) of polymer 6b-OH after 9 hours of homogeneous decomposition treatment.
FIG. 7 shows the ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of polymer 6b-OH after 30 hours of homogeneous decomposition treatment.
FIG. 8A shows the time change in the amount of polymers in solution depolymerization treatment of polymers 6a-OH, 6a-Ac, 6b-OH, and 6b-Ac.
FIG. 8B shows the degree of decomposition of each polymer subjected to in-solution depolymerization treatment for 30 hours.

As shown in FIG. 8A, in the presence of a catalyst (DBU), almost all molecular chains of polymers 6a-OH and 6b-OH, which have an OH terminal structure, are reduced to one type of oligomer within about one day. It can be seen that it is decomposed into a molecular weight substance (5-membered cyclic carbonate). On the other hand, polymers 6a-Ac and 6b-Ac having an Ac group at the end exist almost stably even in the presence of a catalyst. This indicates that the terminal structure of the OH group and the addition of a catalyst serve as the initiation switch for "on-demand decomposition."
Also, from FIG. 8B, which shows the amount of 5' produced after a certain period of time as the degree of decomposition, more than 70% of 6c-OH and 6d-OH, which have an OH terminal group, are decomposed, and 6c-OH, which has an Ac terminal group, is decomposed. It has been shown that the decomposition of Ac and 6d-Ac is greatly suppressed. On the other hand, in 6e-OH, the decomposition is about 20%, indicating that if the side chain is extremely bulky, it also affects the behavior of backbiting type depolymerization. However, it has been shown that the degree of decomposition of polymers 6a-6d is strongly influenced by the structure of the end group.

[Example 2]
Decomposition experiments in heterogeneous systems
1 ml of heavy water was added to 10 mg of each polymer (6a-Ac, 6b-Ac, PTMC-Ac), DBU corresponding to 50% of the monomer units was added, and the mixture was stirred at 40°C. ¹ H NMR measurement of the supernatant of each reaction solution was performed at a predetermined time. The weight percent of the heavy water soluble portion was calculated based on the integral value of DBU.

FIG. 9 shows ¹ H NMR spectra (400 MHz, D ₂ O) in heavy water of each sample. Here, a) shows the results for the supernatant of DBU, b) for 6a-Ac, and c) for the supernatant 4 days after the heterogeneous decomposition treatment of 6b-Ac.

Table 1 shows the decomposition rates (%) of 6a-Ac, 6b-Ac, and PTMC-Ac at treatment times of 1, 4, and 7 days.

[Example 3]
Evaluation of water content properties of polymers
<Thermal property analysis of polymer 6a-Ac in a hydrated state>
It has recently been reported that biocompatible polymers contain special waters of hydration. DSC measurements were performed on polymer 6a-Ac that had been immersed in ultrapure water for 24 hours. As shown in FIG. 10, the presence of water that crystallized around −40° C. was observed during the cooling process. This shows similar results to aliphatic polycarbonate in the prior art (Biomacromolecules, 2017, 18, 3834-3843; ACS Biomater. Sci. Eng., 2021, 7, 472-481), which has been confirmed to have antithrombotic properties. ing. This suggests the possibility that 6a can be applied as an antithrombotic material.

Claims (12)

A method for preparing a polymer, comprising the step of polymerizing a monomer represented by the following formula (1).

(In formula (1),
R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group, selected from the group consisting of a carbamate group, a urea group, a hydroxyl group, an amino group, a carboxy group, and a thiol group,
Here, when R is a hydroxyl group, an amino group, a carboxy group or a thiol group, it may be protected with a protecting group,
When R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituent It may have;;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group. ) The method according to claim 1, wherein the concentration of the monomer at the start of polymerization is 0.1 to 10 mol/L. 3. The method according to claim 1, wherein after the initiation of polymerization, the reaction is stopped around the point at which the polymer composition in the reaction mixture reaches its maximum. The method according to claim 1 or 2, wherein R is selected from -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph (phenyl group) or adamantyl group. 2. The method of claim 1, wherein the polymer is a polytrimethylene carbonate-based polymer. The method according to claim 1, wherein the polymer is a polymer represented by the following formula (I).

(In formula (I),
R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group;
U is a group derived from various alcohols depending on the type of initiator used in the polymerization;
n is 1 to 1000;
R, M, Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are as defined in formula (1). ) A method for decomposing the polymer, the method comprising: (i) providing a polymer represented by the following formula (II); and (ii) adding a catalyst for activating hydroxyl groups to the polymer.

(In formula (II),
R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group, selected from the group consisting of a carbamate group, a urea group, a hydroxyl group, an amino group, a carboxy group, and a thiol group,
Here, when R is a hydroxyl group, an amino group, a carboxy group or a thiol group, it may be protected with a protecting group,
When R is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituent may have;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000. ) The method according to claim 7, wherein the catalyst is an organic catalyst. A polymer represented by the following formula (Ia).

(In formula (Ia),
R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group , carbamate group, urea group, hydroxyl group, amino group, carboxy group, and thiol group,
When R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituted It may have a group;
R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000. ) Polymer according to claim 9, wherein R ₁ is selected from -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph (phenyl group) or adamantyl group. A polymer represented by the following formula (IIa).

(In formula (IIa),
R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an aryl group, an ester group, an amide group , carbamate group, urea group, hydroxyl group, amino group, carboxy group, and thiol group,
When R ₁ is an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an alkoxyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or an aryl group, the substituted It may have a group;
R' is a hydrogen atom, an acetyl group, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group;
M is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl group, a haloalkyl group, a formyl alkyl group, a cyanoalkyl group, a cyano group, a formyl group, and an acyl group. selected from the group;
Q ₁ , Q' ₁ , Q ₂ and Q' ₂ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, a formyl group, and a vinylene group;
U is a group derived from various alcohols or amines depending on the type of initiator used in the polymerization;
n is 1 to 1000. ) Polymer according to claim 11, wherein R ₁ is selected from -(CH ₂ ) ₂ OCH ₃ , -(CH ₂ ) ₂ CH ₃ , -CH ₃ , -Ph (phenyl group) or adamantyl group.