JP2003238618A - Method for producing n-substituted (meth)acrylamide polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an N-substituted (meth)acrylamide polymer having a controlled molecular weight useful as a constituting component of a functional polymer. <P>SOLUTION: The N-substituted (meth)acrylamide polymer is produced by polymerizing an N,N-disubstituted (meth)acrylamide derivative shown by formula (1) (wherein R<SP>1</SP>is a hydrogen atom or a methyl group; R<SP>2</SP>is a hydrocarbon group; and X is a substituent convertible to a hydrogen atom) and then converting the substituent X in the resulting polymer into a hydrogen atom. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an N-substituted (meth)
Acrylamide polymer (in the present specification, “(meth)
“Acrylic” means “acryl” and / or “methacryl”. ) And an N-substituted (meth) acrylamide polymer obtained by the method.

[0002]

2. Description of the Related Art N-substituted (meth) acrylamide polymers, for example, N-alkyl (meth) acrylamide polymers have long been known as temperature-responsive polymers. For example, N-isopropylacrylamide polymer is 32
Lower critical solution temperature around ℃
al solution temperature: L
CST), which is characterized by hydration on the lower temperature side to show water solubility at the boundary of the temperature, and aggregation on the higher temperature side to show hydrophobicity. For this reason, homopolymers, copolymers and terpolymers of various molecular structures including N-alkyl (meth) acrylamide polymer structures have been actively studied, and not only temperature changes but also light, electric field, pH and the like.
Functional polymers that respond to various stimuli such as change and solvent exchange have been designed and widely applied.

As an application example of the above functional polymer, for example, a drug delivery system (DDS) (JP-A-9
JP-A-169850, JP-T-Hei 10-500148), heat-sensitive dimming material (see JP-A-5-96677), cell culture carrier (see JP-A-8-33486), pH sensitivity, Heat-sensitive microbeads (see Japanese Patent Application Laid-Open No. 9-136921), separation materials (Japanese Patent Application Laid-Open No.
No. 00-140632), absorbing material (Table 20)
No. 01-507955), and a biosensor (Preprints of the Society of Polymer Science, vol. 48, 2243-2244)
Pp. 1999).

[0004] By the way, N-substituted (meth) acrylamide polymers useful as constituents of the above-mentioned functional polymers have been mainly produced by a radical polymerization method. The union was conducted by combining N-isopropylacrylamide monomer with 2,2
-It is manufactured by radical polymerization in the presence of a radical polymerization initiator such as azobis (isobutylnitrile).

[0005] However, in such a conventional radical polymerization method, generally, only a polymer having a wide molecular weight distribution and lack of uniformity of molecular weight can be obtained. It has been difficult to precisely design a functional polymer containing a (meth) acrylamide polymer structure. Therefore, precise molecular design becomes possible,
There has been a demand for a novel method for producing an N-substituted (meth) acrylamide polymer that can provide a functional polymer material exhibiting higher stimulus responsiveness.

In response to this demand, RAFT (reversible), which has recently been developed as a living radical polymerization method, has been proposed.
e addition-fragmentation
A living polymerization of N-isopropylacrylamide by a chain transfer method has been reported,
According to this method, an N-isopropylacrylamide polymer having a narrow molecular weight distribution has been synthesized (Macromol).
ecules, 33, 6738-6745 (200
0)). In addition, a highly isotactic N-isopropylacrylamide polymer has also been synthesized by radical polymerization in the presence of a Lewis acid (J. Am. Che).
m. Soc. 123, 7180-7181 (200
1)).

[0007] Further, compared to the living radical polymerization method, it is possible to control molecular weight and stereoregularity at a higher level, and it is also known that living anion polymerization is generally known as a precision polymerization method capable of synthesizing a block copolymer. Legal,
Attempts have been made to apply the method to polymerization of N-substituted (meth) acrylamide monomers.

[0008]

However, when the N-isopropylacrylamide monomer is subjected to living radical polymerization by the RAFT method or when radical polymerization is carried out in the presence of a Lewis acid, the conventional radical polymerization method is used. Although it is possible to produce narrower molecular weight distributions and higher isotactic polymers, advanced molecular weight control and stereoregularity control comparable to living anion polymerization cannot be expected, and the synthesis of block copolymers There is a problem that can not be.

On the other hand, even when an N-substituted (meth) acrylamide monomer is subjected to living anion polymerization, an active proton on the nitrogen atom derived from the monomer and the amide structure in the formed polymer is not reacted at the polymer growth terminal. At present, living anionic polymerization of N-substituted (meth) acrylamide has not been achieved so far as it serves as a deactivator of anions.

An object of the present invention was obtained by a novel method for producing an N-substituted (meth) acrylamide polymer useful as a component of a stimuli-responsive polymer while controlling the molecular weight to a high degree, and a method for producing the same. It is to provide an N-substituted (meth) acrylamide polymer.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an active proton on a nitrogen atom of N-substituted (meth) acrylamide is converted into a hydrogen atom after polymerization. The molecular weight was controlled by polymerizing an N, N-disubstituted (meth) acrylamide derivative substituted with a convertible group, and then converting a group convertible into a hydrogen atom into a hydrogen atom in the obtained polymer. They have found that an N-substituted (meth) acrylamide polymer can be obtained, and have completed the present invention.

That is, the present invention provides a compound of the formula (I)

[0013]

Embedded image (I) (wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group, and X represents a substituent that can be converted to a hydrogen atom.) Provided is a method for producing an N-substituted (meth) acrylamide polymer, which comprises polymerizing a (meth) acrylamide derivative and then converting a substituent X in the obtained polymer to a hydrogen atom. In this production method, in particular, an N, N-disubstituted acrylamide derivative wherein R ¹ in the formula (I) is a hydrogen atom is
Anionically polymerize in the presence of a polymerization initiator and an organic compound containing at least one typical element selected from Group 12 and Group 13, and then substitute X in the obtained polymer
Is preferably converted to a hydrogen atom under acidic conditions.

[0014] The present invention also provides an N-substituted (meth) acrylamide polymer obtained by the above-mentioned production method.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The process for producing the N-substituted (meth) acrylamide polymer of the present invention is represented by the formula (I)

[0017]

Embedded image (I) (wherein R ¹ and R ² are as defined above;
Represents a substituent which can be converted to a hydrogen atom. )), An N-substituted (meth) acrylamide polymer is obtained by polymerizing an N, N-disubstituted (meth) acrylamide derivative, and then converting the substituent X in the obtained polymer to a hydrogen atom. More specifically, an N, N-disubstituted (meth) acrylamide derivative represented by the formula (I) is polymerized to form a compound represented by the formula (A)

[0018]

Embedded image (A) wherein R ¹ , R ² and X are as defined above, and m represents the degree of polymerization.
Obtaining an N-disubstituted (meth) acrylamide polymer,
And converting the substituent X in the resulting N, N-disubstituted (meth) acrylamide polymer of the formula (A) into a hydrogen atom to obtain a compound of the formula (B)

[0019]

Embedded image (B) (wherein R ¹ and R ² are as defined above, and m
Represents the degree of polymerization. )) To obtain an N-substituted (meth) acrylamide polymer having a repeating unit.

First, the substituents in the above formulas (I), (A) and (B) will be described.

The substituent R ¹ is a hydrogen atom or a methyl group, and is preferably a hydrogen atom, particularly from the viewpoint of improving anionic polymerizability.

Examples of the hydrocarbon group represented by the substituent ^{R 2,} for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec-
Butyl group, tert-butyl group, 2-methylbutyl group,
Examples include alkyl groups such as 3-methylbutyl group, n-octyl group, and 2-ethylhexyl group; cycloalkyl groups such as cyclopropyl group and cyclohexyl group; and aryl groups such as phenyl group. These groups may have another substituent, and examples of the other substituent include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxymethyl group, an isopropoxy group, and a tert-butoxy group; N,
Amino groups such as N-dimethylamino group and N, N-diethylamino group; and halogen atoms such as chlorine, bromine and fluorine. Of these, the hydrocarbon groups represented by substituent R ^2, an alkyl group is particularly preferred.

The substituent X is a group that can be converted into a hydrogen atom after polymerization, and is, for example, a group represented by the formula (II)

[0024]

Embedded image (II) (Where R³And R⁴Represents a hydrogen atom or a hydrocarbon group
Represent each, R⁵Represents a hydrocarbon group. Where replace
Group R³, R⁴And R⁵Is a substituent R ²Charcoal
Hydrocarbons having the same meaning as the hydride group but identical to each other
Or a different hydrocarbon group.
No. ), For example, methoxymethyl group, ethoxy
Xymethyl group, n-propoxymethyl group, isopropoxy
Cimethyl group, tert-butoxymethyl group, 1-methoxy
Siethyl group, 1-methoxy-1-methylethyl group, 1-
Ethoxyethyl group, 1-ethoxy-1-methylethyl group
1-alkoxyalkyl group such as tert-butyldim
1- (trialkylsiloxy) such as tylsiloxymethyl group
B) an alkyl group; 1- (N, N) such as a pyrrolidinomethyl group;
-Dialkylamino) alkyl group; methylthiomethyl
1- (alkylthio) alkyi group, ethylthiomethyl group and the like
Kill group; tert-butyl group, dicyclopropylmethyl
Group, dimethylcyclopropylmethyl group, dimethylphenyi group
Tertiary alkyl such as methyl group and methyldiphenylmethyl group
Group; triphenylmethyl group, p-methoxyphenyldi
Phenylmethyl group, bis (p-methoxyphenyl) phenyl
A group having a trityl structure such as a n-methyl group; p-methoxy
Phenyl group, p- (methoxymethoxy) phenyl group, 2
An aryl group such as -methoxy-1-naphthyl group; benzyl
Group, p-methoxybenzyl group, 2,4-dimethoxyben
Zyl group, 3,4-dimethoxybenzyl group, 2-acetoxy
A 4-methoxybenzyl group, an o-nitrobenzyl group, etc.
Aralkyl group; allyl group; vinyl group; cyanomethyl group;
Methyl carbamate group, ethyl carbamate group, ter
t-butyl carbamate group, benzyl carbamate group, etc.
Carbamate group; methoxy group; methylthio group, trif
To mention alkylthio groups such as phenylmethylthio groups
Can be.

Among these substituents which can be converted to a hydrogen atom, the group X which can be converted to a hydrogen atom under acidic conditions includes:
1-alkoxyalkyl group; 1- (trialkylsiloxy) alkyl group; 1- (N, N-dialkylamino) alkyl group; 1- (alkylthio) alkyl group; tertiary alkyl group; Can be.
Among them, the synthesis of the N-substituted (meth) acrylamide derivative of the formula (I) is easy, and it is stable under polymerization conditions, especially under anionic polymerization conditions. From the viewpoint that the group X can be easily converted to a hydrogen atom,
1- (alkoxyalkyl) groups; 1- (trialkylsiloxy) alkyl groups; 1- (N, N-dialkylamino) alkyl groups; 1- (alkylthio) alkyl groups are preferred. Among them, a 1-alkoxyalkyl group represented by the formula (II) is more preferable. Particularly, among the 1-alkoxyalkyl groups represented by the formula (II), a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, and a tert-butoxymethyl group are more preferably exemplified.

The number of degrees of polymerization m in the formulas (A) and (B) is not particularly limited, but is preferably from 10 to 50,000, more preferably from 10 to 50,000, from the viewpoint of handleability of the obtained polymer. 10,000.

Specific examples of the N, N-disubstituted (meth) acrylamide derivatives of the formula (I) having the substituents described above include N-methoxymethyl-N-methyl (meth) acrylamide, N-ethyl- N-methoxymethyl (meth) acrylamide, N-methoxymethyl-Nn-propyl (meth) acrylamide, N-isopropyl-N
-Methoxymethyl (meth) acrylamide, Nn-butyl-N-methoxymethyl (meth) acrylamide, N
-Sec-butyl-N-methoxymethyl (meth) acrylamide, N-tert-butyl-N-methoxymethyl (meth) acrylamide, N-methoxymethyl-N-2
-Methylbutyl (meth) acrylamide, N-methoxymethyl-N-3-methylbutyl (meth) acrylamide, N-methoxymethyl-Nn-octyl (meth) acrylamide, N-2-ethylhexyl-N-methoxymethyl (meth) Acrylamide, N-cyclopropyl-
N-methoxymethyl (meth) acrylamide, N-cyclohexyl-N-methoxymethyl (meth) acrylamide, N-methoxymethyl-N-phenyl (meth) acrylamide, N-ethoxymethyl-N-isopropyl (meth) acrylamide, N- Isopropyl-Nn-propoxymethyl (meth) acrylamide, N-isopropoxymethyl-N-isopropyl (meth) acrylamide, N-tert-butoxymethyl-N-isopropyl (meth) acrylamide, N-isopropyl-N- (trimethyl (Siloxymethyl) (meth) acrylamide, N
-Isopropyl-N-pyrrolidinomethyl (meth) acrylamide, N-isopropyl-N-methylthiomethyl (meth) acrylamide, N-tert-butyl-N-
Isopropyl (meth) acrylamide, N-isopropyl-N-triphenylmethyl (meth) acrylamide,
N-isopropyl-N-p-methoxyphenyl (meth)
Acrylamide, N-benzyl-N-isopropyl (meth) acrylamide, N-allyl-N-isopropyl (meth) acrylamide, N-isopropyl-N-vinyl (meth) acrylamide, N-cyanomethyl-N-isopropyl (meth) acrylamide, N-tert-butyltoxoxycarbonyl-N-isopropyl (meth) acrylamide, N-isopropyl-N-methoxy (meth)
Acrylamide, N-isopropyl-N-methylthio (meth) acrylamide, N-isopropyl-N-methylthio (meth) acrylamide and the like can be mentioned. Among them, N-methoxymethyl-N-methyl (meth) acrylamide, N-ethyl-N-methoxymethyl (meth) acrylamide, N-methoxymethyl-NN-propyl (meth) acrylamide, N-isopropyl-N
-Methoxymethyl (meth) acrylamide, Nn-butyl-N-methoxymethyl (meth) acrylamide, N
-Sec-butyl-N-methoxymethyl (meth) acrylamide, N-tert-butyl-N-methoxymethyl (meth) acrylamide, N-methoxymethyl-N-2
-Methylbutyl (meth) acrylamide, N-methoxymethyl-N-3-methylbutyl (meth) acrylamide, N-methoxymethyl-Nn-octyl (meth) acrylamide, N-2-ethylhexyl-N-methoxymethyl (meth) Acrylamide, N-cyclopropyl-
N-methoxymethyl (meth) acrylamide, N-cyclohexyl-N-methoxymethyl (meth) acrylamide, N-methoxymethyl-N-phenyl (meth) acrylamide and the like are preferable.

The N, N-disubstituted (meth) acrylamide derivative of the formula (I) can be synthesized by a known method. For example, a protecting group for an amide group is introduced into N-substituted (meth) acrylamide. It can be synthesized by applying the technique. More specifically, by reacting (meth) acrylamide such as isopropylacrylamide with an alkali metal alkoxide such as potassium tert-butoxide in an organic solvent such as tetrahydrofuran, and reacting with a halogenated alkyl ether such as chloromethyl methyl ether. And N, N-disubstituted (meth) acrylamide derivatives used in the present invention, such as N-isopropyl-N-methoxymethylacrylamide. Further, under a basic condition, a (meth) acrylic acid halide compound such as (meth) acrylic acid chloride and a compound of the formula (C)

[0029]

Embedded image (C) It can also be synthesized by reacting an amine compound represented by the formula (wherein R ² and X are as defined above).

Next, the step of polymerizing the N, N-disubstituted (meth) acrylamide derivative of the formula (I), which is the first step in the method for producing an N-substituted (meth) acrylamide polymer of the present invention, will be described. .

The polymerization method that can be employed in this step is not necessarily limited to a specific polymerization method. For example, a usual radical polymerization method, SFRP (sta
blefree radical polymeriz
) method, RAFT method, ATRP (atom t)
transfer radial polymeriz
ation) method, GTP (group transfer)
r polymerization) method, anionic polymerization method, and the like. Above all, anionic polymerization is preferred from the viewpoint that the molecular weight distribution of the obtained polymer is narrow and the polymerization conversion of the monomer is high.

In the present invention, the polymerization methods include ordinary radical polymerization, SFRP, RAFT, ATRP
When a radical polymerization method such as a polymerization method or a GTP method is employed, a known polymerization initiator system can be used in each polymerization method. For example, as the initiator used in the radical polymerization method, 2,2-azobis (Isobutyronitrile) (J. Am. Chem. Soc., 1).
23, 7180-7181 (2001)).

The polymerization initiator used in the above-mentioned anionic polymerization method is not necessarily limited to a specific one, and any known anionic polymerization initiator can be used. Examples thereof include an organic lithium compound and an organic sodium compound. And organic metal compounds such as organic potassium compounds and organic magnesium compounds.

Specific examples of the above-mentioned organic lithium compound include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium,
sec-butyllithium, isobutyllithium, ter
alkyl lithium and alkyl dilithium such as t-butyl lithium, n-pentyl lithium, n-hexyl lithium, tetramethylene dilithium, pentamethylene dilithium, hexamethylene dilithium; phenyl lithium, m-tolyl lithium, p-tolyl lithium , Xylyllithium, aryllithium and aryldilithium represented by lithium naphthalene; benzyllithium, diphenylmethyllithium, trityllithium,
1,1-diphenyl-3-methylpentyl lithium, α
Aralkyl lithium and aralkyl dilithium represented by dilithium and the like formed by the reaction of methylstyryllithium, diisopropenylbenzene and butyllithium; lithium amide represented by lithium dimethylamide, lithium diethylamide, lithium diisopropylamide and the like; methoxylithium , Ethoxylithium, n
-Lithium propoxy, lithium isopropoxy, n-
Butoxylithium, sec-butoxylithium, ter
Lithium alkoxides represented by t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, 4-methylbenzyloxylithium and the like. .

Specific examples of the organic sodium compound include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium, isobutyl sodium, tert-butyl sodium, n-pentyl sodium, alkyl sodium and alkyl disodium such as n-hexyl sodium, tetramethylene disodium, pentamethylene disodium, hexamethylene disodium; phenyl sodium, m-tolyl sodium, p-tolyl sodium, xylyl sodium;
Aryl sodium and aryl disodium represented by sodium naphthalene and the like; benzyl sodium,
Aralkyl sodium and aralkyl disodium represented by disodium and the like formed by the reaction with sodium diphenylmethyl, trityl sodium, diisopropenylbenzene and butyl sodium; sodium represented by sodium dimethylamide, sodium diethylamide, sodium diisopropylamide and the like Amide: methoxysodium, ethoxysodium, n-
Sodium propoxy, sodium isopropoxy, n
Sodium butoxy, sec-butoxy sodium,
Sodium alkoxide represented by sodium tert-butoxide, sodium pentyloxy, sodium hexyloxy, sodium heptyloxy, octyloxy, phenoxy, sodium 4-methylphenoxy, benzyloxy, sodium 4-methylbenzyloxy, and the like. .

Specific examples of the organic potassium compound include methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium,
sec-butyl potassium, isobutyl potassium, ter
alkyl potassium and alkyl dipotassium such as t-butyl potassium, n-pentyl potassium, n-hexyl potassium, tetramethylene dipotassium, pentamethylene dipotassium, hexamethylene dipotassium; phenyl potassium, m-tolyl potassium, p-tolyl potassium, xylyl potassium Aralkyl potassium and aralkyl dipotassium represented by dipotassium and the like formed by reaction with benzyl potassium, diphenylmethyl potassium, trityl potassium, diisopropenyl benzene and butyl potassium; potassium Potassium amide represented by dimethylamide, potassium diethylamide, potassium diisopropylamide, etc .; methoxy potassium, ethoxy Potassium, n- propoxy potassium,
Potassium isopropoxy, potassium n-butoxy, se
potassium c-butoxy, potassium tert-butoxide,
Examples include potassium alkoxides represented by pentyloxy potassium, hexyloxy potassium, heptyloxy potassium, octyloxy potassium, phenoxy potassium, 4-methylphenoxy potassium, benzyloxy potassium, 4-methylbenzyloxy potassium, and the like.

Specific examples of the above-mentioned organomagnesium compound include dimethyl magnesium, diethyl magnesium,
Examples include dibutylmagnesium, ethylbutylmagnesium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, tert-butylmagnesium chloride, and tert-butylmagnesiumbromide.

Among the above polymerization initiators, alkyl lithium, aryl lithium, aralkyl lithium, alkyl sodium, aryl sodium, aralkyl sodium, alkyl potassium are preferred in terms of high polymerization initiation efficiency and smooth progress of the polymerization reaction. , Aryl potassium and aralkyl potassium are preferred, and sec-butyllithium, tert-butyllithium, 1,1-diphenyl-3-methylpentyllithium, sodium naphthalene, potassium naphthalene and diphenylmethyl potassium are particularly preferred.

Some of the organometallic compounds which are polymerization initiators used in the above-mentioned anionic polymerization method include cyclic conjugated dienes, linear conjugated diene compounds, vinyl aromatic hydrocarbon compounds, α, β-unsaturated compounds. Although used as a living anionic polymerization initiator such as a carboxylic acid ester compound, a living polymer itself having an active terminal of these organometallic compounds may be used as a polymerization initiator in the polymerization step of the production method of the present invention. Alternatively, any polymer may be anionized with an anionic reagent (for example, tert-butyllithium) and used as a polymerization initiator in the polymerization step of the production method of the present invention.

In the present invention, one of the above-mentioned polymerization initiators may be used alone as the polymerization initiator.
Further, two or more kinds may be used in combination.

In the present invention, the amount of the polymerization initiator used in the polymerization reaction is not necessarily limited, but the polymerization initiator is used in an amount within the range of 0.01 to 20 mol per 100 mol of the total of the monomers used. It is preferable to use it in such a ratio that the target polymer can be produced smoothly.

In the present invention, when the anionic polymerization method is selected as the polymerization method for the N, N-disubstituted (meth) acrylamide derivative of the formula (I), the polymerization growth terminal is stabilized by stabilizing the polymerization growth terminal during the anion polymerization. In order to obtain “living anionic polymerization” capable of suppressing the side reaction of the above, a co-catalyst for living anionic polymerization may be used in addition to the above-mentioned polymerization initiator. According to living anionic polymerization,
A polymer or a block copolymer having a narrower molecular weight distribution can be obtained. In the case of an N-substituted (meth) acrylamide polymer having a narrow molecular weight distribution, the LCST of the aqueous polymer solution
Transfer is possible in a narrower range of conditions. Moreover, in the case of a block copolymer of an N-substituted (meth) acrylamide derivative, the copolymer can be developed for more various applications by utilizing the hydrophilicity or hydrophobicity of the copolymerized block.

As the co-catalyst described above, it acts on the terminal of polymerization growth to enable living polymerization.
An organic compound containing at least one typical element selected from Group 12 and Group 13 is exemplified. Preferred of such typical elements are zinc, boron and aluminum, and thus preferred as the organic compound are
Organic zinc compounds, organic borane compounds, organic aluminum compounds and the like. Among these, an organic zinc compound and an organic borane compound are more preferable in that the anionic polymerization reaction proceeds smoothly, and particularly, the compound represented by the formula (III)

[0044]

Embedded image wherein ZnR ⁶ R ⁷ (III) (wherein R ⁶ and R ⁷ each represent a hydrocarbon group).
Here, the hydrocarbon groups of the substituents R ⁶ and R ⁷ have the same meaning as the hydrocarbon group of the substituent R ² , but may be the same hydrocarbon group or different hydrocarbon groups. Is also good. ) Are preferred.

Specific examples of the organozinc compound represented by the formula (III) include dimethylzinc, diethylzinc, di-n-
Examples include propyl zinc, diisopropyl zinc, di-n-butyl zinc, di-sec-butyl zinc, diisobutyl zinc, diphenyl zinc and the like. Among them, diethyl zinc and diphenyl zinc are preferred in that the polymerization reaction proceeds smoothly.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, and ethylaluminum sesquichloride. , Diethylaluminum hydride, diisobutylaluminum hydride, tri (2-ethylhexyl) aluminum, (2-ethylhexyl)
Aluminum dichloride, methylaluminoxane, ethylaluminoxane, dimethylphenoxyaluminum,
Diethylphenoxyaluminum, diisobutylphenoxyaluminum, dimethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2 6-di-t-butyl-
4-methylphenoxy) aluminum, methyldiphenoxyaluminum, ethyldiphenoxyaluminum,
Isobutyldiphenoxyaluminum, methylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butyl-4)
-Methylphenoxy) aluminum, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum and the like.

Specific examples of the organic borane compound include trimethylborane, triethylborane, triisobutylborane, triphenylborane, tris (pentafluorophenyl) borane, trifluoroborane diethyl ether complex, dimethylphenoxyborane, diethylphenoxyborane, diisobutyl Phenoxyborane, dimethyl (2,
6-di-t-butyl-4-methylphenoxy) borane,
Diethyl (2,6-di-t-butyl-4-methylphenoxy) borane, diisobutyl (2,6-di-t-butyl-4-methylphenoxy) borane, methyl diphenoxy borane, ethyl diphenoxy borane, isobutyl di Phenoxyborane, methyl bis (2,6-di-t-butyl-
4-methylphenoxy) borane, ethylbis (2,6-
Di-t-butyl-4-methylphenoxy) borane, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) borane, and the like.

In the present invention, a solvent may not be used in the polymerization, but is preferably used in order to make the polymerization system uniform. Such solvents include pentane, n-
Aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene; diethyl ether; Ether compounds such as tetrahydrofuran, 1,4-dioxane, anisole and diphenyl ether are exemplified. Among them, the above-mentioned ether compounds are preferably used from the viewpoint of excellent solubility of the polymerization initiator, the (meth) acrylamide derivative, other monomers, organic compounds as co-catalysts, and polymers, Diethyl ether, tetrahydrofuran and 1,4-dioxane are particularly preferred. These organic solvents may be used alone or in combination of two or more.

In the polymerization of the present invention, a polar additive used in ordinary anionic polymerization may be added to the polymerization system for the purpose of promptly proceeding the polymerization while maintaining the living property. Examples of the polar additive include dimethyl ether, dimethoxyethane, diethoxyethane, 12-crown-4, 15-crown-5,
Ether compounds such as 8-crown-6; trimethylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, 1,1,4,7 Organic nitrogen compounds such as 1,10,10-hexamethyltriethylenetetramine, pyridine, 2,2'-dipyridyl; organic phosphorus compounds such as triethylphosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane; Inorganic salts such as lithium, sodium chloride and potassium chloride; alkoxide compounds such as lithium (2-methoxyethoxy) ethoxide and potassium t-butoxide; tetraethylammonium chloride, tetraethylammonium bromide;
Organic quaternary salts such as tetraethylphosphonium chloride and tetraethylphosphonium bromide are exemplified. Only one of these polar additives may be used.
More than one species may be used in combination.

In the present invention, the polymerization reaction is preferably carried out under a high vacuum or in an atmosphere of an inert gas such as nitrogen, argon or helium, regardless of the type of polymerization (radical polymerization, anionic polymerization, etc.). Further, it is preferable to carry out the polymerization under sufficient stirring conditions so that the polymerization reaction system becomes uniform. Further, regarding the temperature of the reaction system during the polymerization,
There is no particular limitation, and suitable temperature conditions can be selected according to the type of monomer used and the like. However, in many cases, a temperature in the range of −100 ° C. to + 100 ° C. is preferably adopted, and −80 ° C. Temperatures in the range of ° C to + 50 ° C are more preferably employed.

In the present invention, the desired polymer (for example, N, N-disubstituted (meth)
At the stage where the acrylamide polymer has been formed, the polymerization reaction can be stopped by adding a polymerization terminator to the reaction mixture. As such a polymerization terminator, for example, a protic compound such as a methanol solution of methanol, acetic acid, or hydrochloric acid can be used. Although the amount of the polymerization terminator is not particularly limited, it is generally preferable to use the polymerization terminator in a ratio of 1 to 100 mol per 1 mol of the polymerization initiator used.

In the present invention, the method for separating and obtaining the desired polymer (for example, the N, N-disubstituted (meth) acrylamide polymer of the formula (A)) from the reaction mixture after terminating the polymerization reaction includes, in particular, There is no limitation, and any method according to a known method can be adopted. For example, a method in which the reaction mixture is poured into a poor solvent for the polymer to precipitate and obtain the polymer, a method in which the solvent is distilled off from the reaction mixture to obtain the polymer, and the like can be adopted.

According to the polymerization reaction of the present invention described above, a polymer having an arbitrary molecular weight can be produced. The molecular weight of the polymer that can be produced is wide, but in general, the number average molecular weight is preferable from the viewpoint of the handleability of the polymer that can be used to produce a polymer in the range of 1,000 to 5,000,000, and is preferably 1,000 to 1,000,000. The range is more preferred. Here, the obtained polymer has a very narrow molecular weight distribution and a highly uniform molecular weight. In addition, a polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less, preferably 1.05 to 1.3 can be produced, but the rate of addition of monomer into the polymerization system, the rate of diffusion, etc. , A polymer having a wide molecular weight distribution can be obtained.

The polymerization in the present invention is not limited to homopolymerization of the N, N-disubstituted (meth) acrylamide derivative represented by the above formula (I), but may be random copolymerization with other monomers, block copolymerization with other monomers. Copolymerization such as copolymerization, graft copolymerization, alternating copolymerization, or gradient copolymerization can be performed.

When obtaining a block copolymer,
First, after polymerizing another monomer copolymerizable with the N, N-disubstituted (meth) acrylamide derivative of the formula (I), a growing terminal of the obtained polymer is added to the growing terminal of the formula (I) used in the present invention. The N, N-disubstituted (meth) acrylamide derivative may be polymerized sequentially, or after the N, N-disubstituted (meth) acrylamide derivative of the formula (I) is polymerized first, The other monomer described above may be sequentially polymerized at the growth end.

The monomer which can be copolymerized with the N, N-disubstituted (meth) acrylamide derivative of the formula (I) is not particularly restricted but includes, for example, styrene, o-methylstyrene, m-methylstyrene, p-methyl Aromatic vinyl compounds such as styrene, α-methylstyrene, vinylnaphthalene and vinylanthracene; 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, Conjugated diene compounds such as 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclohexadiene; methyl (meth) acrylate, (meth) Ethyl acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl (meth)
Lauryl acrylate, glycidyl (meth) acrylate,
2- (N, N-dimethylamino) ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate,
Α, such as 2-hydroxyethyl (meth) acrylate, 2- (2-hydroxyethyl) ethyl (meth) acrylate, methyl α-methoxyacrylate, methyl α-ethoxyacrylate, methyl crotonate, and ethyl crotonate; β-
Unsaturated carboxylic acid ester compound; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N, N
-Acrylamide compounds such as diisopropylacrylamide; α, β-unsaturated carboxylic compounds such as (meth) acrylic acid and crotonic acid; α, β such as methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone and ethyl isopropenyl ketone -Unsaturated ketone compounds;
Α, β-unsaturated nitrile compounds such as (meth) acrylonitrile; and lactone compounds such as ε-caprolactone.

Next, the second step in the method for producing an N-substituted (meth) acrylamide polymer of the present invention,
The polymer obtained as described above, specifically, N, N-disubstituted (meth) having a repeating unit of the formula (A)
The substituent X present in the molecule of the acrylamide polymer is converted into a hydrogen atom to form an N- having a repeating unit of the formula (B).
The step of obtaining a substituted (meth) acrylamide polymer will be described.

The reaction conditions for converting the substituent X in the polymer to a hydrogen atom are not necessarily limited, and may vary slightly depending on the structure of the substituent X, but the removal of the amide group protected by the protecting group is not limited. The conditions used for protection can be applied (Protective Groups in
Organic Synthesis, third
division, A Wiley-Intersie
nce Publication, JOHN WILE
Y & SONS, INC. , 632-653).
Preferably, the polymer obtained in the steps described above (eg, an N, N-disubstituted (meth) acrylamide polymer of formula (A)) is treated under acidic conditions (ie, in the presence of an acidic substance). By doing so, the substituent X can be converted to a hydrogen atom. Specifically, the polymer (for example, the N, N-disubstituted (meth) acrylamide polymer of the formula (A)) obtained in the step described above is converted into a water-miscible organic solvent capable of dissolving the polymer. (Dioxane, THF, etc.), and an acidic substance and water may be added thereto to perform acid hydrolysis.

Examples of such acidic substances include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as acetic acid, propionic acid and citric acid; and acidic ion exchange resins. The seed may be used as an acidic substance, or two or more kinds may be used in combination.

The amount of the acidic substance to be used may be determined based on the amount of the polymer (for example, N, N-
The molar number of the substituent X present in the di-substituted (meth) acrylamide polymer) is usually preferably 0.001 to 1000 times, more preferably 0.01 to 100 times, More preferably, it is 0.1 to 10 moles.

In the present invention, the substituent X in the polymer (for example, the N, N-disubstituted (meth) acrylamide polymer of the formula (A)) obtained in the step described above is converted to a hydrogen atom. The temperature at this time is not particularly limited, and suitable temperature conditions can be selected according to the type of the substituent X to be used and the like. However, a temperature in the range of −60 ° C. to + 100 ° C. is preferably employed. , A temperature in the range of 0 ° C to 80 ° C is more preferably employed.

In the present invention, the time for converting X in the polymer to a hydrogen atom is not particularly limited, and although it depends on the conditions employed, it can be usually completed within 24 hours. Depending on the type and conditions of X, the conversion can be completed within 30 minutes.

Although the method for producing the N-substituted (meth) acrylamide polymer of the present invention has been described above, the N-substituted (meth) acrylamide polymer obtained by the production method of the present invention has a highly controlled molecular weight. It is useful as a component of a stimuli-responsive polymer.

[0064]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

In the following Synthesis Examples and Examples, commercially available products (reagents) were used as they were, except that solvents and compounds purified and prepared as described below were used. The transfer and supply of the solvent and the like during the polymerization were performed under vacuum. * Tetrahydrofuran : A commercially available product was refluxed for one day in the presence of sodium, then refluxed for three hours in the presence of lithium aluminum hydride, and then distilled under a nitrogen stream. * N-isopropylacrylamide : A commercially available product recrystallized from n-hexane was used. * N, N-diethylacrylamide : A commercially available product was distilled under reduced pressure in the presence of calcium hydride, and diluted to a predetermined concentration with tetrahydrofuran before use. * Diphenylmethylpotassium : 2.9 diphenylmethane
After adding 0.5 M potassium naphthalene tetrahydrofuran solution (11.2 mmol) to 1 g (17.3 mmol) and reacting at room temperature for 48 hours, a solution diluted to a predetermined concentration with tetrahydrofuran was used. Note that diphenylmethane is commercially available in the presence of calcium hydride.
The mixture was stirred for a time and distilled under reduced pressure. * Diethyl zinc : A commercial product was used after being diluted to a predetermined concentration with tetrahydrofuran.

In the following Examples and Comparative Examples, polymerization was carried out under a vacuum by a break seal method. The measuring apparatus, measuring conditions, evaluation / test methods, etc. used for various measurements were as follows. . * GPC (gel permeation chromatography)
-) : ・ Equipment: Tosoh HLC-8020 ・ Column: Tosoh G5000H _XL , G4000
H _XL and G3000H _XL are connected in series. ・ Eluent: tetrahydrofuran ・ Eluent flow rate: 1.0 ml / min ・ Column temperature: 40 ° C. ・ Molecular weight calculation: Measured based on differential refractive index (RI)
It was determined in terms of polystyrene using monodisperse polystyrene as a standard. * ¹ H-NMR ( ¹ H-nuclear magnetic resonance) and ¹³ C-N
MR : ・ Apparatus: DPX300 (300MH) manufactured by Bruker
z) ・ Solvent: deuterated chloroform * IR (infrared absorption) spectrum : ・ Equipment: JIR-AQS20M FT- manufactured by JEOL
IR * Solubility test : Test method: At room temperature (25 ° C.), 10 mg of a polymer was mixed with 1 cc of a solvent in a sample bottle, shaken, and the degree of dissolution was visually evaluated.

Synthesis Example 1 (N-isopropyl-N-methoxymethylacrylamide (hereinafter referred to as N-MOM-NIPA)
M) (in some cases, abbreviated as M) 18.48 g of N-isopropylacrylamide (163.3 mm
ol), 20.08 g of potassium tert-butoxide (1
78.9 mmol) and weigh 4 tetrahydrofuran 4
Dissolved in 50 ml. There, 14.54 g of chloromethyl methyl ether (180.6
(mmol) and 35 ml of tetrahydrofuran were added dropwise over 20 minutes, the temperature was raised to room temperature, and the mixture was stirred overnight.

Next, 200 ml of dry hexane was introduced into the reaction system.
Was added to form a white precipitate of potassium chloride. The precipitate was removed by filtration, and the solvent was distilled off under reduced pressure. The residue was extracted with water (5% aqueous sodium hydroxide solution) and diethyl ether, anhydrous magnesium sulfate was added to the diethyl ether layer, and the mixture was allowed to dry overnight. Subsequently, the solvent was distilled off under reduced pressure to obtain 22.24 g of a colorless and transparent liquid. further,
The obtained liquid is dissolved in a developing solvent (hexane: ethyl acetate = 10).
(0: 5 to 10: 3), and purified by silica gel column chromatography, followed by distillation under reduced pressure in the presence of calcium hydride and methylene blue (boiling point 94 to 96).
C./7 to 9 mmHg) to obtain 3.82 g as a main fraction. The obtained compound was analyzed by ¹ H-NMR and ¹³ C-NMR.
The analysis confirmed that the product was N-MOM-NIPAM. ¹ H-NMR and ¹³ C-NMR spectra are shown in FIGS. 1 and 2, respectively.

Example 1 1.36 ml of diethylzinc was added to 2.44 ml of a tetrahydrofuran solution containing 0.122 mmol of diphenylmethylpotassium in a glass ampoule under vacuum at -78 ° C.
27.2 ml of a tetrahydrofuran solution containing mol. The reaction turned from red to yellow. After standing for 30 minutes, 8.86 ml of a tetrahydrofuran solution containing 4.43 mmol of N-MOM-NIPAM was added and stirred. The reaction solution immediately disappeared. After leaving at −78 ° C. for 24 hours, a small amount of methanol was added to terminate the polymerization. ¹ H
-NMR confirmed that no monomer remained in the reaction solution, and confirmed that the polymerization conversion was 100%.

The resulting reaction solution was poured into a large amount of hexane,
After removing the zinc compound by filtration, diethyl ether
With a mixed solution of n-hexane and benzene.
And freeze-dried to obtain a polymer 1A. Got
The GPC chart of the polymer is unimodal and has a number average molecular weight.
Was 4700 and the molecular weight distribution was 1.30. Also, ¹
The number average molecular weight calculated from 1 H-NMR was 5,100.
Was. GPC chart of polymer 1A,¹H-NMR spec
Torr,^ThirteenC-NMR spectrum and IR spectrum
3 to 6 are shown in FIGS.

Subsequently, 0.25 g of polymer 1A was added to 1,4-
Dissolve in 4 ml of dioxane and add 0.15
After stirring at room temperature for 24 hours, the mixture was freeze-dried to obtain polymer 1B. When a solubility test was performed on the polymers 1A and 1B, the polymer 1A was soluble in benzene and insoluble in water, whereas the polymer 1B was insoluble in benzene and soluble in water. GPC of polymer 1B
The chart was unimodal, the number average molecular weight was 3,200, and the molecular weight distribution was 1.21. Further, ¹ H-NMR,
By measurement of ¹³ C-NMR and IR spectra, polymer 1 was obtained.
B confirmed that the N-methoxymethyl group in polymer 1A was completely converted to a hydrogen atom. G of polymer 1B
PC chart, ¹ H-NMR spectrum, ¹³ C-NM
The R spectrum and the IR spectrum are shown in FIGS. 3, 7 to 9, respectively.

Example 2 Under the same conditions as in Example 1, 23.8 ml of a tetrahydrofuran solution containing 1.19 mmol of diethylzinc were added to 1.80 ml of a tetrahydrofuran solution containing 0.0901 mmol of diphenylmethyl potassium. The reaction turned from red to yellow. After leaving for 30 minutes, N-MO
11.76 ml of a tetrahydrofuran solution containing 5.88 mmol of M-NIPAM was added and stirred. The reaction solution immediately disappeared. After leaving at −78 ° C. for 24 hours, a small amount of methanol was added to terminate the polymerization. ¹ H-NMR confirmed that no monomer remained in the reaction solution, and that the polymerization conversion was 100%.

The obtained reaction solution was poured into a large amount of hexane,
After removing the zinc compound by filtration, the precipitate was reprecipitated with a mixed solution of diethyl ether and n-hexane, and further freeze-dried with benzene to obtain a polymer 2A. The GPC chart of the obtained polymer was unimodal, the number average molecular weight was 9,600, and the molecular weight distribution was 1.15.

Subsequently, 0.25 g of polymer 2A was added to 1,4-
Dissolve in 4 ml of dioxane and add 0.15
After stirring for 24 hours at room temperature, the mixture was freeze-dried to obtain polymer 2B. When a solubility test was performed on the polymers 2A and 2B, the polymer 2A was soluble in benzene and insoluble in water, whereas the polymer 2B was insoluble in benzene and soluble in water. GPC of polymer 2B
The chart was unimodal, the number average molecular weight was 4,800, and the molecular weight distribution was 1.25. Further, ¹ H-NMR,
^{According to 13} C-NMR and IR spectrum measurements, polymer 2 was obtained.
B confirmed that the N-methoxymethyl group in the polymer 2A was completely converted to a hydrogen atom.

Example 3 Under the same conditions as in Example 1, 14.6 ml of a tetrahydrofuran solution containing 0.731 mmol of diethyl zinc was added to 0.83 ml of a tetrahydrofuran solution containing 0.0416 mmol of diphenylmethyl potassium. The reaction turned from red to yellow. After leaving for 30 minutes, NM
12.2 ml of a tetrahydrofuran solution containing 6.09 mmol of OM-NIPAM was added and stirred. The reaction solution immediately disappeared. After leaving at −78 ° C. for 24 hours, a small amount of methanol was added to terminate the polymerization. ¹ H-NMR confirmed that no monomer remained in the reaction solution, and that the polymerization conversion was 100%.

The resulting reaction solution was allowed to stand for 48 hours to precipitate zinc, then poured into a large amount of hexane, and after removing the zinc compound by filtration, reprecipitated with a mixed solution of diethyl ether and n-hexane. And lyophilized with benzene to obtain a polymer 3A. G of the obtained polymer 3A
The PC chart is unimodal and the number average molecular weight is 1900
0, molecular weight distribution was 1.15.

Subsequently, 0.25 g of the polymer 3A was added to 1,4-
Dissolve in 4 ml of dioxane and add 0.15
After stirring at room temperature for 24 hours, the mixture was freeze-dried to obtain polymer 3B. When a solubility test was performed on the polymers 3A and 3B, the polymer 3A was soluble in benzene and insoluble in water, whereas the polymer 3B was insoluble in benzene and soluble in water. GPC of polymer 3B
The chart is unimodal, the number average molecular weight is 11,000,
The molecular weight distribution was 1.20. Further, ¹ H-NM
R, ¹³ C-NMR and IR spectrum measurements confirmed that in polymer 3B, the N-methoxymethyl group in polymer 3A was completely converted to a hydrogen atom.

Comparative Example 1 Under the same conditions as in Example 1, N-isopropylacrylamide 4.8 was added to 1.35 ml of tetrahydrofuran solution containing 0.0676 mmol of diphenylmethyl potassium.
9.7 ml of a tetrahydrofuran solution containing 5 mmol was added and stirred. After leaving at −78 ° C. for 24 hours, a small amount of methanol was added. No polymer was obtained from the reaction solution, and N-isopropylacrylamide was almost quantitatively recovered.

Comparative Example 2 In a glass ampoule at 0 ° C. under vacuum, 25.4 ml of a tetrahydrofuran solution containing 1.27 mmol of diethylzinc was added to 2.08 ml of a tetrahydrofuran solution containing 0.104 mmol of diphenylmethylpotassium. The reaction turned from red to yellow. After leaving for 30 minutes, N, N
8.38 ml of a tetrahydrofuran solution containing 4.19 mmol of diethylacrylamide was added and stirred. The reaction solution immediately disappeared. After 2 minutes at 0 ° C., a small amount of methanol was added to terminate the polymerization. ¹ H-NMR confirmed that no monomer remained in the reaction solution, and that the polymerization conversion was 100%.

The obtained reaction solution was poured into a large amount of hexane, the zinc compound was removed by filtration, reprecipitated with a mixed solution of diethyl ether and n-hexane, and further freeze-dried with benzene to obtain polymer 4A. Got. The GPC chart of the obtained polymer 4A was unimodal, the number average molecular weight was 4,500 and the molecular weight distribution was 1.06.

Subsequently, 0.25 g of polymer 4A was added to 1,4-
Dissolve in 4 ml of dioxane and add 0.15
Then, the mixture was stirred at room temperature for 24 hours.
The N-ethyl group therein could not be converted to a hydrogen atom.

[0082]

According to the method for producing an N-substituted (meth) acrylamide polymer of the present invention, one of the substituents substituted on the nitrogen atom is N, which can be converted into a hydrogen atom after polymerization. Since the N-disubstituted (meth) acrylamide derivative is polymerized, and then the substituent convertible to a hydrogen atom in the polymer is converted to hydrogen, the molecular weight distribution is narrow and the uniformity of the molecular weight can be increased. N with controlled molecular weight
-It is possible to produce substituted (meth) acrylamide polymers. Further, the N-substituted (meth) acrylamide polymer obtained by this production method is suitably used as a functional polymer exhibiting high stimulus responsiveness.

[Brief description of the drawings]

FIG. 1 shows N-MOM-NIP obtained in Synthesis Example 1.
It is a < ¹ > H-NMR spectrum of AM.

FIG. 2 shows N-MOM-NIP obtained in Synthesis Example 1.
It is a ¹³ C-NMR spectrum of AM.

FIG. 3 is a GPC chart of polymer 1A and polymer 1B obtained in Example 1.

Figure 4 is a polymer 1A obtained in Example 1 ¹ H-
It is an NMR spectrum.

FIG. 5 is a diagram showing ¹³ C of polymer 1A obtained in Example 1.
-It is an NMR spectrum.

FIG. 6 is an IR chart of polymer 1A obtained in Example 1.

Figure 7 is a polymer 1B obtained in Example 1 ¹ H-
It is an NMR spectrum.

FIG. 8 is a diagram showing ¹³ C of polymer 1B obtained in Example 1.
-It is an NMR spectrum.

FIG. 9 is an IR chart of polymer 1B obtained in Example 1.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 15, 2002 (2002.3.1)
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

[0018]

Embedded image (A) wherein R ¹ , R ² and X are as defined above, and m represents the degree of polymerization.
Obtaining an N-disubstituted (meth) acrylamide polymer,
And converting the substituent X in the resulting N, N-disubstituted (meth) acrylamide polymer of the formula (A) into a hydrogen atom to obtain a compound of the formula (B)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019]

Embedded image (B) (wherein R ¹ and R ² are as defined above, and m
Represents the degree of polymerization. )) To obtain an N-substituted (meth) acrylamide polymer having a repeating unit.

   ────────────────────────────────────────────────── ─── Continuation of front page    F-term (reference) 4J015 DA02 DA03 DA04 DA05                 4J100 AM15P AM21P BA05P BA06P                       BA10P BA20P BA38P BA40P                       BA41P BA53P BA77P BA94P                       BC02P BC04P BC43P BC65P                       CA01 CA31 DA36 FA03 HB25                       HB44 HB52 HC27

Claims (6)

[Claims] 1. A compound of the formula (I) (I) (wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group, and X represents a substituent that can be converted to a hydrogen atom.) A method for producing an N-substituted (meth) acrylamide polymer, comprising polymerizing a (meth) acrylamide derivative, and subsequently converting a substituent X in the obtained polymer to a hydrogen atom. 2. The method according to claim 1, wherein the substituent X in the formula (I) is represented by the formula (II): (II) The production method according to claim 1, wherein R ³ and R ⁴ each represent a hydrogen atom or a hydrocarbon group, and R ⁵ represents a hydrocarbon group. 3. A compound of the formula (I) wherein R ¹ is a hydrogen atom.
Is anionically polymerized in the presence of a polymerization initiator and an organic compound containing at least one typical element selected from Group 12 and Group 13; 3. The method according to claim 1, wherein the substituent X in the union is converted into a hydrogen atom under acidic conditions. 4. The method according to claim 3, wherein the typical element contained in the organic compound is at least one selected from zinc and boron. 5. The organic compound having the formula (III) ## STR3 ## ^ZnR 6 ^R 7 (III) (wherein, ^{R 6} and ^{R 7} each represents a hydrocarbon group.) In the organic zinc compound represented by the The production method according to claim 3 or 4, wherein 6. An N-substituted (meth) acrylamide polymer obtained by the production method according to claim 1.