JP6047791B2 - Polymer and production method thereof - Google Patents

Description

  The present invention relates to a polymer and a method for producing the same. More specifically, the present invention relates to a polymer (polyalkoxyoxirane) obtained by polymerizing alkoxyoxirane and a method for producing the same.

  Hitherto, polymer compounds that are easily decomposed by applying various stimuli are known, and representative examples thereof include acid-decomposable polymers that are decomposed by the action of an acid. As said acid-decomposable polymer, the peroxide polymer which has an oxygen-oxygen bond (OO bond) in a structure is mentioned, for example (refer nonpatent literature 1). However, although the above peroxide polymer is easily decomposed by reacting with an acid, on the other hand, even in the absence of acid, it is easily decomposed by stimuli other than acid such as light, heat, reducing agent, etc. Therefore, there was a problem that handling was not easy.

Polymer Journal, Vol. 35, no. 8, pp640-651, 2003

Therefore, an object of the present invention is to provide a polymer (acid-decomposable polymer) that is stable in the absence of an acid but can be easily decomposed by an acid, and a polymer that can produce the polymer with high efficiency. It is to provide a manufacturing method.
Another object of the present invention is stable in the absence of an acid, but can be easily decomposed by an acid, and the molecular weight is highly controlled (ie, high molecular weight and / or narrow molecular weight). It is an object of the present invention to provide a polymer having a distribution and a method for producing a polymer capable of producing the polymer with high efficiency.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer having a specific repeating structural unit can be easily decomposed by an acid, and further, the polymer has a specific monomer ( The present inventors have found that alkoxy oxirane) can be produced with high efficiency by polymerizing (cationic polymerization) with a cationic polymerization catalyst, and the present invention has been completed.

［式（１）中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ、水素原子、有機基、酸素原子含有基、窒素原子含有基、ハロゲン原子含有基、又は硫黄原子含有基を示し、Ｒ¹、Ｒ²、Ｒ³の２以上が互いに結合して環を形成していてもよい。Ｒ⁴は、有機基、酸素原子含有基、窒素原子含有基、ハロゲン原子含有基、又は硫黄原子含有基を示す。］
で表される繰り返し構造単位を有する重合体を提供する。 That is, the present invention provides the following formula (1):

In Expression ^{(1), R 1, R} 2, R 3 are each indicated a hydrogen atom, an organic group, an oxygen atom-containing group, the nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group, R ¹ , R ² and R ³ may be bonded to each other to form a ring. R ⁴ represents an organic group, an oxygen atom-containing group, a nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group. ]
The polymer which has a repeating structural unit represented by these is provided.

  Furthermore, the polymer having a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.30 or less is provided.

  Furthermore, the polymer having a number average molecular weight (Mn) of 2000 or more is provided.

Furthermore, the polymer in which R ¹ , R ² and R ⁴ in formula (1) are all alkyl groups having 1 to 6 carbon atoms and R ³ is a hydrogen atom is provided.

［式（ｉ）中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ、水素原子、有機基、酸素原子含有基、窒素原子含有基、ハロゲン原子含有基、又は硫黄原子含有基を示し、Ｒ¹、Ｒ²、Ｒ³の２以上が互いに結合して環を形成していてもよい。Ｒ⁴は、有機基、酸素原子含有基、窒素原子含有基、ハロゲン原子含有基、又は硫黄原子含有基を示す。］
で表されるオキシラン化合物を少なくとも含む単量体を、カチオン重合触媒の存在下で重合させ、下記式（１）

［式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、前記に同じ。］
で表される繰り返し構造単位を有する重合体を生成させる重合工程を含むことを特徴とする重合体の製造方法を提供する。 Further, the present invention provides the following formula (i)

Wherein ^{(i), R 1, R} 2, R 3 are each indicated a hydrogen atom, an organic group, an oxygen atom-containing group, the nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group, R ¹ , R ² and R ³ may be bonded to each other to form a ring. R ⁴ represents an organic group, an oxygen atom-containing group, a nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group. ]
A monomer containing at least the oxirane compound represented by the formula is polymerized in the presence of a cationic polymerization catalyst, and the following formula (1):

[In Formula (1), R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is the same as the above. ]
A method for producing a polymer comprising a polymerization step for producing a polymer having a repeating structural unit represented by the formula:

  Furthermore, the manufacturing method of the said polymer whose said cationic polymerization catalyst is a Lewis' acid is provided.

  Furthermore, the present invention provides a method for producing the above polymer in which a Lewis base coexists in the polymerization reaction.

  Furthermore, the polymer has a number average molecular weight (Mn) of 2000 or more and a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.30 or less. provide.

Furthermore, a R ^1, R ^2, an alkyl group of R ⁴ are both 1 to 6 carbon atoms in the formula (1), R ³ to provide a method for producing a polymer of a hydrogen atom.

  Furthermore, in the said superposition | polymerization process, the manufacturing method of the said polymer which polymerizes 2 or more types of the oxirane compound represented by Formula (i) is provided.

  Since the polymer of the present invention has the above structure, it is stable in the absence of an acid, but can be easily decomposed by an acid. For this reason, it can be particularly preferably used as a material used in applications requiring such characteristics. Furthermore, when the molecular weight of the polymer of the present invention is high or when the molecular weight distribution of the polymer is narrow, it can be expected to further exhibit excellent heat resistance and mechanical strength. Furthermore, since the method for producing a polymer of the present invention has the above-described configuration, the polymer can be produced with high efficiency (productivity).

FIG. 1 is a chart of ¹ H-NMR spectrum of the polymer obtained in Example 1. FIG. 2 is a chart of ¹ H-NMR spectrum of the polymer obtained in Example 2.

The polymer of the present invention is a polymer having at least a repeating structural unit represented by the following formula (1).

R ¹ , R ² and R ³ in the above formula (1) each represent a hydrogen atom, an organic group, an oxygen atom-containing group, a nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group.

  The organic group is not particularly limited as long as it contains a carbon atom, and examples thereof include a substituted or unsubstituted hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, Alkylthio group, alkenylthio group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, etc. Can be mentioned.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include (C _1-20 ) having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group and dodecyl group. Examples thereof include an alkyl group (preferably a C _1-10 alkyl group, more preferably a C _1-4 alkyl group). Examples of the alkenyl group include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 3-pentenyl group, 4-pentenyl group, 5-hexenyl group and the like can be mentioned. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C _2-10 alkynyl group, more preferably C _2-4 alkynyl group). Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a _cyclododecyl group; a C _3-12 cyclo group such as a cyclohexenyl group. An alkenyl group; a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptanyl group and a bicycloheptenyl group. As said aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example. Furthermore, examples of the hydrocarbon group include a group in which an aliphatic hydrocarbon group such as a cyclohexylmethyl group and a methylcyclohexyl group and an alicyclic hydrocarbon group are bonded; C _7-18 such as a benzyl group and a phenethyl group. aralkyl group (particularly, C _7-10 aralkyl group), C _6-10 aryl -C _2-6 alkenyl group such as a cinnamyl group, C _1-4 alkyl-substituted aryl groups such as tolyl group, a styryl group C _{2- And a} group in which an aliphatic hydrocarbon group such as a _4- alkenyl-substituted aryl group and an aromatic hydrocarbon group are bonded.

The substituent that the hydrocarbon group may have (substituent in the above-described substituted hydrocarbon group) is, for example, preferably a substituent having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms. Is a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) The aromatic ring may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, such as a phenoxy group, a tolyloxy group, or a naphthyloxy group; Aryloxy groups (preferably C _6-14 aryloxy groups); aralkyloxy groups such as benzyloxy groups and phenethyloxy groups (preferably C _{7-1 8} aralkyloxy groups); acyloxy groups such as acetyloxy groups, propionyloxy groups, (meth) acryloyloxy groups, and benzoyloxy groups (preferably C _1-12 acyloxy groups); mercapto groups; alkylthio groups such as methylthio groups and ethylthio groups Group (preferably C _1-6 alkylthio group, more preferably C _1-4 alkylthio group); alkenylthio group such as allylthio group (preferably C _2-6 alkenylthio group, more preferably C _2-4 alkenylthio group) ); Aromatic ring such as phenylthio group, tolylthio group, naphthylthio group and the like may have a substituent such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. Arylthio groups (preferably C _6-14 arylthio groups); aralkylthio groups such as benzylthio groups and phenethylthio groups (preferably C _{7-1 8} aralkylthio group); carboxy group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group (preferably C _1-6 alkoxy-carbonyl group); phenoxycarbonyl group, tolyloxycarbonyl group An aryloxycarbonyl group such as a naphthyloxycarbonyl group (preferably a C _6-14 aryloxy-carbonyl group); an aralkyloxycarbonyl group such as a benzyloxycarbonyl group (preferably a C _7-18 aralkyloxy-carbonyl group); Groups: mono- or dialkylamino groups (preferably mono- or di-C _1-6 alkylamino groups) such as methylamino group, ethylamino group, dimethylamino group, diethylamino group; acetylamino group, propionylamino group, benzoylamino An acylamino group such as a cyano group (preferably a C _1-11 acylamino group); an epoxy group-containing group such as a glycidyloxy group; an oxetanyl group-containing group such as an ethyloxetanyloxy group; an acyl group such as an acetyl group, a propionyl group, or a benzoyl group An oxo group; a group in which two or more of these are bonded via a C _1-6 alkylene group as necessary.

  Examples of the oxygen atom-containing group include a hydroxy group, a hydroperoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an isocyanate group, a sulfo group, and a carbamoyl group. Examples of the nitrogen atom-containing group include an amino group or a substituted amino group (mono or dialkylamino group, acylamino group, etc.), a cyano group, an isocyanate group, an isothiocyanate group, and a carbamoyl group. As said halogen atom containing group, a halogen atom, a halogenated hydrocarbon group, etc. are mentioned, for example. Examples of the sulfur atom-containing group include a mercapto group (thiol group), a sulfo group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and an isothiocyanate group. The organic group, oxygen atom-containing group, nitrogen atom-containing group, halogen atom-containing group, and sulfur atom-containing group described above can overlap each other.

R ¹ , R ² and R ³ in the above (1) are usually monovalent groups in many cases. However, in R ¹ , R ² and R ³ in the above formula (1), two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring.

Among them, as the R ^1, R ^2, respectively, an alkyl group having 1 to 6 carbon atoms (linear or branched C _1-6 alkyl group), more preferably a methyl group. Further, the above-mentioned R ^3, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (linear or branched C _1-6 alkyl group) and is more preferably a hydrogen atom.

R ⁴ in the above formula (1) represents an organic group, an oxygen atom-containing group, a nitrogen atom-containing group, a halogen atom-containing group, or a sulfur atom-containing group. The organic group as the above R ^4, an oxygen atom-containing group, the nitrogen atom-containing group, a halogen atom-containing group, the sulfur atom-containing group, said R ^1, R ^2, same groups as the groups exemplified as R ³ (1 valence Group). Among them, as the R ^4, an alkyl group having 1 to 6 carbon atoms (linear or branched C _1-6 alkyl group) and is more preferably a methyl group.

  In addition, the polymer of this invention may have only 1 type as a repeating structural unit represented by the said Formula (1), and may have 2 or more types. In addition, when it has 2 or more types of the repeating structural unit represented by the said Formula (1), the addition form (polymerization form) of these repeating structural units is not specifically limited, A random type (random polymerization) Form) or a block type (block polymerization form). That is, the polymer of the present invention may be a random copolymer or a block copolymer. Moreover, the structure of the polymer of this invention is not specifically limited, You may have any structures, such as a linear type, a branched type, and a star shape.

  The polymer of the present invention may have a repeating structural unit other than the repeating structural unit represented by the above formula (1) (sometimes referred to as “other repeating structural unit”). As the monomer constituting the other repeating structural unit (sometimes referred to as “other monomer”), the monomer constituting the repeating structural unit represented by the above formula (1) (that is, The monomer is not particularly limited as long as it is a monomer copolymerizable with the oxirane compound represented by formula (i), and examples thereof include a monomer having cationic polymerizability.

  Examples of the cationic polymerizable monomer include vinyl ether compounds [for example, 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, 3-chloropropyl vinyl ether, 3-bromopropyl vinyl ether, 2-cyanoethyl vinyl ether, (2 -Methoxycarbonylethyl) vinyl ether, (2-ethoxycarbonylethyl) vinyl ether, (2-phenoxycarbonylethyl) vinyl ether, (2-benzyloxycarbonylethyl) vinyl ether, (3-oxobutyl) vinyl ether, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether Etc.]; a cyclic ether compound other than the oxirane compound represented by the formula (i) [for example, ethylene oxide, propylene oxide, Limethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin, etc.]; benzaldehyde compounds [eg, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-ethylbenzaldehyde, 3-ethylbenzaldehyde] Ethylbenzaldehyde, 4-ethylbenzaldehyde, 2-isopropylbenzaldehyde, 3-isopropylbenzaldehyde, 4-isopropylbenzaldehyde, 2-t-butylbenzaldehyde, 3-t-butylbenzaldehyde, 4-t-butylbenzaldehyde, 2,3-dimethylbenzaldehyde 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzal Hydride, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde and the like]; α-olefin compounds [eg, ethylene, propylene, isobutene (isobutylene), 2-methyl-1-butene, 3-methyl-1-butene] 2-methyl-1-pentene, 4-methyl-1-pentene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene, etc.]; chain conjugated diene compounds [eg, butadiene, isoprene , 1,3-pentadiene, etc.]; olefinic hydrocarbon having a five-membered ring [example For example, vinylcyclopentane, isopropenylcyclopentane, 4-vinylcyclopentene, 2-methyl-4-isopropenylcyclopentene, etc.]; olefinic hydrocarbons having a six-membered ring [for example, vinylcyclohexane, 4-methylvinylcyclohexane, 3 -Methylvinylcyclohexane, 2-methylvinylcyclohexane, 1-methylvinylcyclohexane, 3-methylisopropenylcyclohexane, isopropenylcyclohexane, isopropenyl-3-methylcyclohexane, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl -4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohex Monoterpenes (β-pinene, d-limonene, etc.), diterpenes, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 4-phenylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, etc.]; Olefinic hydrocarbons having a ring structure of a member or more [for example, vinylcycloheptane, isopropenylcycloheptane, 4-vinylcycloheptene, 4-isopropenylcycloheptene, etc.]; cyclopentadiene compounds [for example, cyclopentadiene, 1 -Methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-cyclopentadiene, 5,5-dimethylcyclopentadiene, etc.]; cyclic olefin compounds [for example, cyclobutene, cyclopentene, cyclohexane Cene, dicyclopentadiene, indene, etc.]; cyclic conjugated diene compounds [eg, furan, thiophene, 1,3-cyclohexene, etc.]; heterocycle-containing vinyl compounds [eg, N-vinylcarbazole, N-vinyl-2-pyrrolidone, etc. ]; Vinylsilane compounds [e.g., vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, etc.]; allylsilane compounds [for example, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane , Allyldimethylmethoxysilane, allyltrimethylsilane, allyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, etc.]; acryloyloxysilane compounds [eg, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, etc.]; methacryloyloxysilane compounds [for example, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc.]; lactone compounds [β -Propiolactone, ε-caprolactone, δ-valerolactone, α, α-dimethyl-β-propiolactone, β-methyl beta-propiolactone, beta, beta-dimethyl -β--propiolactone], and others. The above cationic polymerizable monomers can be used singly or in combination of two or more. That is, the polymer of the present invention may have one or more other repeating structural units, or may have two or more.

  When the polymer of the present invention has other repeating structural units, the content (ratio) of the repeating structural units represented by the above formula (1) can be appropriately adjusted depending on the use of the polymer and the like. However, it is preferably 50% by weight or more and less than 100% by weight, more preferably 70% by weight or more, and still more preferably, based on the total amount of the polymer (total amount of repeating structural units constituting the polymer: 100% by weight). 80% by weight or more. When the content of the repeating structural unit represented by the above formula (1) is less than 50% by weight, the treatment of the residue after decomposing the polymer with an acid may be complicated. In addition, the polymer of this invention does not need to have another repeating structural unit.

  The terminal structure of the polymer of the present invention is not particularly limited. For example, the terminal structure is composed of an atomic group derived from a starting species of a cationic polymerization reaction (for example, a hydrogen halide adduct of vinyl ether), derived from a polymerization terminator And a terminal structure composed of an atomic group. In addition, examples of the terminal structure of the polymer of the present invention include an impurity in the system, a hydroxy group formed when the polymerization reaction starts from a proton due to a transfer reaction, and the like.

  Since the repeating structural unit represented by the above formula (1) of the polymer of the present invention contains an acetal structure as a skeleton constituting the main chain of the polymer, as a result, the polymer of the present invention is reacted with an acid. Can be easily decomposed. Since such an acetal structure is stable to stimuli other than acids such as heat, light, and a reducing agent, the polymer of the present invention has high stability in the absence of an acid.

  Although the number average molecular weight (Mn) of the polymer of this invention is not specifically limited, 2000 or more (for example, 2000-1 million) are preferable, More preferably, it is 2500-50000, More preferably, it is 3000-15000. If the number average molecular weight is less than 2,000, the heat resistance and mechanical strength of the polymer before decomposition may be insufficient. On the other hand, if the number average molecular weight exceeds 1,000,000, the productivity of the polymer may be lowered, or the solubility may be insufficient and handling may be difficult. In addition, the number average molecular weight of a polymer is computable as a value of standard polystyrene conversion by GPC method (gel permeation chromatography method), for example.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer of the present invention is not particularly limited, but is preferably 1.30 or less (for example, 1.00 to 1.30), more preferably. Is 1.25 or less (for example, 1.02 to 1.25), more preferably 1.20 or less (for example, 1.05 to 1.20). If the molecular weight distribution exceeds 1.30, the heat resistance and mechanical strength of the polymer before decomposition may be insufficient. The molecular weight distribution of the polymer can be calculated as a value in terms of standard polystyrene by, for example, the GPC method (gel permeation chromatography method).

The polymer of the present invention (a polymer having at least a repeating structural unit represented by the above formula (1)) is a monomer containing at least an oxirane compound (alkoxyoxirane) represented by the following formula (i): It can be produced by a method (manufacturing method) comprising at least a step of polymerizing in the presence of a polymerization catalyst to form the polymer of the present invention (sometimes referred to as “polymerization step”).

The oxirane compound represented by the above formula (i) is an essential monomer (monomer component) of the polymer of the present invention. ^{R 1, R 2, R 3} , R 4 in the formula (i) represents the same as ^{R 1, R 2, R 3} , R 4 in the repeating structural unit represented by the above formula (1). In producing the polymer of the present invention, the oxirane compound represented by the above formula (i) can be used singly or in combination of two or more. That is, in the above polymerization step, only one oxirane compound represented by formula (i) can be polymerized, or two or more of the oxirane compounds can be polymerized.

  As the monomer component of the polymer of the present invention, a monomer other than the oxirane compound represented by the above formula (i) (that is, the above-mentioned other monomers) can also be used. One of these other monomers can be used alone, or two or more of them can be used in combination.

  The content of the oxirane compound represented by the above formula (i) in the total amount (100% by weight) of the monomer components constituting the polymer of the present invention is not particularly limited, but is preferably 50 to 100% by weight, More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more. When the content of the oxirane compound represented by the above formula (i) is less than 50% by weight, the treatment of the residue after decomposing the polymer with an acid may be complicated.

As the cationic polymerization catalyst used in the polymerization reaction, a known or conventional cationic polymerization catalyst can be used, and is not particularly limited. For example, a periodic table group 4 element (titanium, zirconium, hafnium, etc.), a group 8 element (Iron, etc.), group 12 elements (zinc, etc.), group 13 elements (aluminum, gallium, indium, etc.), group 14 elements (silicon, germanium, tin, etc.), group 15 elements (bismuth, etc.) halides (halogenated) Metal), Lewis acids such as sulfates; and hydrogen acids (protonic acids) such as HCl, HF, H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , CF ₃ COOH, and CCl ₃ COOH. Examples of the metal halide include aluminum chloride (AlCl ₃ ), aluminum bromide (AlBr ₃ ), boron fluoride (BF ₃ ), boron chloride (BCl ₃ ), boron fluoride-diethyl ether complex (BF _3. OEt ₂ ), titanium tetrachloride (TiCl ₄ ), titanium bromide (TiBr ₄ ), iron chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ), stannous chloride (SnCl ₂ ), stannic chloride ( SnCl ₄ ), TiCl ₄ / Cl ₃ CCOOH, SnCl ₄ / Cl ₃ CCOOH, tungsten hexachloride (WCl ₆ ), molybdenum chloride (MoCl ₅ ), gallium chloride (GaCl ₃ ), niobium chloride (NbCl ₅ ), ethyldichloroaluminum (ethylaluminum dichloride, EtAlCl _2), ethylaluminum sesquichloride _{(C 6 H 15 Al 2 Cl} 3 , Diethylaluminum chloride (Et ₂ AlCl), zirconium chloride (ZrCl _4), hafnium tetrachloride (HfCl _4), indium chloride (InCl _3), and the like of zinc chloride (ZnCl _2). Among these, Lewis acid is preferable as the cationic polymerization catalyst, and metal halides (particularly, gallium chloride (GaCl ₃ ), zirconium chloride (IV) (ZrCl ₄ )) are more preferable. In addition, the said cationic polymerization catalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although the usage-amount (addition amount) of the said cationic polymerization catalyst is not specifically limited, 0.01-20 mol is preferable with respect to 100 mol of the total amount of the monomer component which comprises a polymer, More preferably, 0.1 -10 mol. If the amount of the cationic polymerization catalyst used is less than 0.01 mol, the yield of the polymer may be lowered. On the other hand, when the usage-amount of a cationic polymerization catalyst exceeds 20 mol, it may become a problem from a viewpoint of cost or catalyst removal.

  In the polymerization reaction, a cocatalyst may be used in combination with the cationic polymerization catalyst. In particular, when a Lewis acid is used as the cationic polymerization catalyst, the cocatalyst plays a role of initiating a cationic polymerization reaction by becoming an initial species or generating an initial species. As the cocatalyst, known or commonly used cocatalysts can be used, and are not particularly limited. Specifically, water, alcohol [for example, t-butanol, 2-phenylpropanol, etc.], protonic acid [for example, Mineral acids such as hydrogen chloride; carboxylic acids such as acetic acid and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc.] Ether compounds [eg, 1,4-bis (2-methoxy-2-phenylpropane), 1,4-bis (2-methoxy-2-propyl) benzene, etc.], alkyl halides [eg, t-butyl chloride Etc.], a hydrohalide adduct of vinyl ether [for example, a hydrogen chloride adduct of isobutyl vinyl ether ( BVE-HCl; iso-butoxyethyl chloride), etc.], iodine, include compounds such as halogenated trimethylsilyl. Among these, from the viewpoint of quantitativeness of the initiation reaction, a hydrogen halide adduct of vinyl ether is preferable. In addition, the said cocatalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although the usage-amount (addition amount) of the said cocatalyst is not specifically limited, For example, it can select suitably from the range of 0.1-10 mol with respect to 1 mol of said cation polymerization catalysts.

  In the polymerization reaction, it is preferable that a Lewis base coexists in addition to the cationic polymerization catalyst and the cocatalyst. By using the Lewis base together, side reactions are suppressed. Furthermore, the molecular weight distribution of the obtained polymer tends to be narrow (specifically, 1.30 or less). As the Lewis base, known or commonly used Lewis bases can be used, and are not particularly limited, and examples thereof include ether compounds and ester compounds. Examples of the ether compound include chain ethers such as diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, and dibenzyl ether; and cyclic ethers such as tetrahydrofuran and 1,4-dioxane. Examples of the ester compound include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, methyl benzoate, ethyl benzoate, and chloroformate. Examples include methyl, ethyl chloroformate, methyl chloroacetate, ethyl chloroacetate, ethyl dichloroacetate, ethyl trichloroacetate, and ethyl trifluoroacetate. Among them, the Lewis base is preferably a cyclic ether, an aliphatic carboxylic acid ester, or a halogenated aliphatic carboxylic acid ester. In addition, the said Lewis base can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The use amount (addition amount) of the Lewis base is not particularly limited, but is preferably 0.1 to 10,000 mol, more preferably 1 to 1000 mol with respect to 100 mol of the total amount of monomer components constituting the polymer. It is. If the amount of Lewis base used is less than 0.1 mol, side reactions may not be suppressed. On the other hand, when the amount of the Lewis base used exceeds 10,000 mol, the activity of the catalyst becomes low, and the rate of the polymerization reaction may decrease.

  In the above polymerization reaction, in particular, when a Lewis acid is used as a cationic polymerization catalyst and a Lewis base is used, the growth species in the cationic polymerization is stabilized, a long-life growth species is generated, and the polymerization is performed in a living manner. There is a tendency to progress easily. This tends to narrow the molecular weight distribution of the resulting polymer. Furthermore, the speed of cationic polymerization (living cationic polymerization) can be improved by finely adjusting the interaction between Lewis acid and Lewis base by selecting the combination of Lewis acid and Lewis base, polymerization conditions, and the like.

  In the said polymerization reaction, a solvent can also be used as needed. That is, a polymerization reaction can be performed in a solvent to produce the polymer of the present invention. Although it does not specifically limit as said solvent, For example, benzene, toluene, xylene, mesitylene (1,3,5-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), tetramethylbenzene, hexamethylbenzene, Aromatic hydrocarbons such as ethylbenzene, ethyltoluene, propylbenzene, ethylxylene, diethylxylene, propyltoluene, monochlorobenzene (chlorobenzene), dichlorobenzene, monofluorobenzene, difluorobenzene, monobromobenzene, dibromobenzene; pentane, hexane, Aliphatic hydrocarbons such as heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, decalin; methyl chloride, methylene chloride (dichloromethane), 1,2-dichloroethane, 1 1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichlorethylene, 1-chlorobutane, and halogenated hydrocarbons such as chloroform and the like. A solvent can also be used individually by 1 type, and can also be used in combination of 2 or more types (namely, as a mixed solvent). Of these, aromatic hydrocarbons and aliphatic hydrocarbons are preferable from the viewpoint of cationic polymerization catalyst and polymer solubility.

  The amount of the solvent used is not particularly limited, but is preferably 10 to 2000 parts by weight with respect to 100 parts by weight of the total amount of monomer components constituting the polymer, from the viewpoint of the cationic polymerization catalyst and the solubility of the polymer. More preferably, it is 100-1500 weight part.

  The polymerization temperature (reaction temperature) of the above polymerization reaction may be a reaction temperature at which cationic polymerization is usually carried out, and is not particularly limited. For example, −100 to 50 ° C. is preferable, and more preferably −80 to 10 ° C. If the polymerization temperature is less than -100 ° C, it may be disadvantageous in terms of cost because it requires equipment to maintain a low temperature. On the other hand, when the polymerization temperature exceeds 50 ° C., the molecular weight distribution of the produced polymer may become too wide. Further, during the polymerization reaction, it is not always necessary to keep the polymerization temperature constant. For example, the polymerization temperature may be appropriately changed (for example, changed continuously or stepwise) within the above temperature range.

  The polymerization time (reaction time) of the polymerization reaction is not particularly limited, but is preferably 15 seconds to 64 hours, and more preferably 5 minutes to 56 hours, for example.

  The polymerization reaction is not particularly limited, and can be carried out in any atmosphere such as air or an inert gas atmosphere. Especially, it is preferable to implement in inert gas atmosphere from a reactive viewpoint.

  The polymerization reaction can be stopped (terminated) by a known or common method such as addition of a polymerization terminator to the polymerization system. As the polymerization terminator, those capable of deactivating the cation growth terminal can be used, and are not particularly limited. Examples thereof include water; alcohols such as methanol; phenols such as 2,6-tert-butyl-hydroxytoluene. A carboxylic acid such as acetic acid. The polymer of the present invention is generated by the polymerization reaction.

  The method for producing a polymer of the present invention may further include a step of purifying the obtained polymer after the polymerization step. The purification means of the polymer is not particularly limited, for example, separation means such as water washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Any known or conventional purification means can be used. The method for producing a polymer of the present invention may include other steps such as a step of recovering unreacted raw materials and a cationic polymerization catalyst.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Under a dry nitrogen atmosphere, 3.1 mL of purified toluene, 0.25 mL of purified heptane, 0.4 mL of tetrahydrofuran (THF), and 0.28 mL of 2-methoxy-1-methylpropylene oxide are added to the container 1 so as to be uniform. Was stirred.
Next, 4.1 mL of purified toluene and 0.2 mL of a 1.06 M isobutoxyethyl chloride (IBVE-HCl) hexane solution were added to another container 2 and stirred uniformly. 0.5 mL of this was added to the container 1.
Next, 3 mL of purified toluene and 1 mL of hexane solution of gallium chloride (GaCl ₃ ) prepared to 200 mM were added to another container 3, stirred uniformly, and cooled to 0 ° C. 0.5 mL of this was added to the solution in the container 1 cooled to 0 ° C., and stirred uniformly to initiate polymerization, and stirring was continued for 4 hours (the polymerization temperature was kept at 0 ° C.).
In addition, all containers (container 1, container 2, container 3) are glass containers equipped with three-way stopcocks, and heated for 10 minutes using an industrial blaster that emits hot air at about 400 ° C. in a dry nitrogen atmosphere. What removed adsorbed water as much as possible was used.

The concentration of each component at the start of polymerization is shown below.
[2-Methoxy-1-methylpropylene oxide] = 0.5M
[IBVE-HCl] = 5 mM
[GaCl ₃ ] = 5 mM
[THF] = 1M
Thereafter (after stirring for 4 hours), 3 mL of methanol containing about 1% ammonia water was added to terminate the polymerization. About the mixture (solution) which stopped superposition | polymerization, after diluting with about 20 mL of dichloromethane, it wash | cleaned with water, the catalyst residue was removed, and the product (polymer) was collect | recovered by evaporating a solvent etc. after that.

The conversion ratio of the monomer (2-methoxy-1-methylpropylene oxide) in the polymerization was 89% (polymerization time: 4 hours). Moreover, the polymer obtained above had a weight average molecular weight (Mn) of 5300 and a molecular weight distribution (Mw / Mn) of 1.30.
The molecular weight of the polymer was chloroform as a mobile phase, 40 ° C., a flow rate of 1.0 mL / min, three columns “TSKgel Multipore H _XL- M” manufactured by Tosoh Corporation, and an RI-8020 detector. It calculated | required by the gel permeation column chromatography (GPC; polystyrene conversion). Also in Examples 2 and 3 below, the molecular weight and molecular weight distribution of the polymer were measured by the same method.

When ¹ H-NMR spectrum measurement of the polymer obtained above (measuring solvent: deuterated chloroform, apparatus: ECA500 (manufactured by JOEL)) was performed, a polymer having an acetal structure in the main chain (ring-opening polymer) ) Was confirmed to be generated. FIG. 1 shows a chart of ¹ H-NMR spectrum of the polymer. FIG. 1 shows to which proton of the polymer the ¹ H-NMR spectrum peak belongs. Integral ratio [g: (b, c, h, k) :( g, proton peak of b, c, h, and k, proton peak of a, f, and i shown in FIG. a, f, i)] was 1: 3: 6.
¹ H-NMR (CDCl ₃ ): δ [ppm] 4.4 to 4.2 (m), 4.1 to 3.9 (m), 3.7 to 3.3 (m), 1.9 to 1.7 (m), 1.4 to 1.1 (m), 1.0 to 0.8 (m)

Example 2
The amount of toluene (purified toluene) blended in container 1 was changed to 3 mL, 0.5 mL of ethyl acetate (EtOAc) was used instead of THF, and toluene 3 instead of GaCl ₃ solution (hexane and toluene solution). The same procedure as in Example 1 except that 0.4 mL of a mixture of 6 mL and 0.5 M of zirconium chloride (ZrCl ₄ ) prepared in ethyl acetate was used, and the polymerization time was changed to 48 hours. A polymerization reaction was carried out.

The concentration of each component at the start of polymerization is shown below.
[2-Methoxy-1-methylpropylene oxide] = 0.5M
[IBVE-HCl] = 5 mM
[ZrCl ₄ ] = 5 mM
[EtOAc] = 1M

  The conversion rate of the monomer (2-methoxy-1-methylpropylene oxide) in the polymerization was 85% (polymerization time: 48 hours). Moreover, the polymer obtained above had a weight average molecular weight (Mn) of 2000 and a molecular weight distribution (Mw / Mn) of 1.15.

FIG. 2 shows a chart of ¹ H-NMR spectrum of the polymer obtained above. FIG. 2 shows to which proton of the polymer the ¹ H-NMR spectrum peak belongs. Integral ratio [g: (b, c, h, k) :( g, proton peak of b, c, h, and k, proton peak of a, f, and i shown in FIG. a, f, i)] was 1: 3: 6.
¹ H-NMR (CDCl ₃ ): δ [ppm] 4.4 to 4.2 (m), 4.1 to 3.9 (m), 3.7 to 3.3 (m), 1.9 to 1.7 (m), 1.4 to 1.1 (m), 1.0 to 0.8 (m)

Example 3
Change the amount of toluene (purified toluene) blended in Vessel 1 to 3.0 mL, use 0.5 mL of ethyl acetate (EtOAc) instead of THF, and replace GaCl ₃ solution (hexane and toluene solution). The same as Example 1 except that 0.2 mL of a solution obtained by mixing 3.8 mL of toluene and a diethyl ether solution of zinc chloride (ZnCl ₂ ) prepared to 1.0 M was used, and the polymerization time was changed to 1 minute. The polymerization reaction was carried out.

The concentration of each component at the start of polymerization is shown below.
[2-Methoxy-1-methylpropylene oxide] = 0.5M
[IBVE-HCl] = 5 mM
[ZnCl ₂ ] = 5 mM
[EtOAc] = 1M

  The conversion in the above polymerization was 95% (polymerization time: 1 minute). Moreover, the polymer obtained above had a weight average molecular weight (Mn) of 570 and a molecular weight distribution (Mw / Mn) of 1.39.

(Evaluation of acid decomposability)
10 mg of the polymer obtained in Example 1 was dissolved in 4 g of tetrahydrofuran, 1 g of 1N hydrochloric acid was further added thereto, and the mixture was heated at 50 ° C. for 10 minutes. Thereafter, GPC measurement of the solution (measuring condition: same as the molecular weight measurement of the polymer) was performed, and the polymer peak disappeared.
On the other hand, 10 mg of the polymer obtained in Example 1 was dissolved in 5 g of tetrahydrofuran and heated at 50 ° C. for 10 minutes. Thereafter, GPC measurement of the solution (measurement condition: same as measurement of the molecular weight of the polymer) was performed, and there was no change in the peak of the polymer.
As described above, it was confirmed that the polymer of the present invention was easily decomposed by an acid. The polymer of the present invention was stable against heating at 50 ° C.

Claims (10)

Following formula (1)

Wherein (1), R ^1, R ² are each an alkyl group having 1 to 10 carbon atoms, nitrogen atom-containing group, or a sulfur atom-containing group, R ³ is a hydrogen atom, C 1 -C 10 to 10 alkyl groups, nitrogen atom-containing groups, or sulfur atom-containing groups, and two or more of R ¹ , R ² , and R ³ may be bonded to each other to form a ring. R ⁴ is an alkyl group having 1 to 10 carbon atoms, nitrogen atom-containing group, or represents a sulfur atom-containing group. ]
The polymer which has a repeating structural unit represented by these.   The polymer according to claim 1, wherein the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.30 or less.   The polymer according to claim 1 or 2, wherein the number average molecular weight (Mn) is 2000 or more. R ^1, R ² in the formula (1), even R ⁴ is either an alkyl group having 1 to 6 carbon atoms, the polymer according to any one of claims 1 to 3 R ³ is a hydrogen atom . Formula (i) below

Wherein ^{(i), R 1, R} 2 are each an alkyl group having 1 to 10 carbon atoms, nitrogen atom-containing group, or a sulfur atom-containing group, R ³ is a hydrogen atom, C 1 -C 10 to 10 alkyl groups, nitrogen atom-containing groups, or sulfur atom-containing groups, and two or more of R ¹ , R ² , and R ³ may be bonded to each other to form a ring. R ⁴ is an alkyl group having 1 to 10 carbon atoms, nitrogen atom-containing group, or represents a sulfur atom-containing group. ]
A monomer containing at least the oxirane compound represented by the formula is polymerized in the presence of a cationic polymerization catalyst, and the following formula (1):

[In Formula (1), R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is the same as the above. ]
A method for producing a polymer, comprising a polymerization step of producing a polymer having a repeating structural unit represented by the formula:   The method for producing a polymer according to claim 5, wherein the cationic polymerization catalyst is a Lewis acid.   The method for producing a polymer according to claim 5 or 6, wherein a Lewis base coexists in the polymerization reaction.   The number average molecular weight (Mn) of the polymer is 2000 or more, and the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.30 or less. A method for producing the polymer described in 1. The polymer according to any one of claims 5 to 8, wherein R ¹ , R ² and R ⁴ in the formula (1) are all alkyl groups having 1 to 6 carbon atoms, and R ³ is a hydrogen atom. Manufacturing method.   The method for producing a polymer according to any one of claims 5 to 9, wherein in the polymerization step, two or more oxirane compounds represented by formula (i) are polymerized.

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