JPH05125185A - Polyalkylene oxide-oxazoline block copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a polyalkylene oxide-oxazoline block copolymer hardly containing unreacted polyalkylene oxides, having controlled molecular weight of oxazoline block part. CONSTITUTION:A 2-oxazoline of formula I [R<6> is H, (substituted) alkyl or (substituted) aryl] is polymerized by using a compound of formula II [R<1> is (substituted) alkyl, etc.; R<2> and R<3> are H or methyl; R<4> and R<5> are H, (substituted) alkyl, etc.; Y is Cl, etc.; (a) is 5-10,000] as a cationic polymerization initiator or the 2-oxazoline of formula I is polymerized by using a compound of formula III as a cationic polymerization initiator to give a polyalkylene oxide-oxazoline block copolymer of formula IV or formula V [R<6> is H, (substituted) alkyl, etc.; X is Cl, Br, etc.; (b) is 3-10,000].

Description

Detailed Description of the Invention

[0001]

The present invention relates to a nonionic polymer surfactant, surface modifier, dispersant, compatibilizer, antistatic agent,
The present invention relates to a polyalkylene oxide-oxazoline block copolymer useful as an adhesive, a binder, a biocompatible material, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art It is known that poly (N-formylethyleneimine) or poly (N-acylethyleneimine) can be synthesized according to the following reaction formula (i) by cationic polymerization of 2-oxazoline-type monomers. [S. Kobayashi et al. , Encyc
lo. Poly. Sci. & Eng. Vol. 4,2n
dEd. , 525 (1986)].

[0003]

[Chemical 7] (In the formula, R'is a hydrogen atom or a lower alkyl group; R "
Is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group; Z is an electrophilic group such as Br, I or RSO ₃ ; R is a monovalent organic group; p is a positive integer. Represents; It is known that the living growth end of such a polymer can be deactivated by reacting it with a nucleophile such as water, ammonia, or a primary amine to terminate the polymerization [Kobayashi et al. , Proceedings of the 53rd Annual Meeting of the Chemical Society of Japan, p. 417 (1986)]. In this case, the termination reaction using the primary amine is as follows.
It is as shown in i).

[0004]

[Chemical 8] [In the formula, R ′, R ″, Z and p represent the same as those in the reaction formula (i), and R ₀ represents a monovalent organic group.] Such 2-oxazolines A block copolymer containing a poly (N-formylethyleneimine) or poly (N-acylethyleneimine) block (hereinafter, both are abbreviated as “oxazoline block”) and a polyethylene oxide block derived from , Useful as a surfactant.

As a method for producing such a block copolymer, for example, in place of RZ in the above reaction formula (i), halogenated polyethylene oxide represented by the following general formula (iii) is used as a polymerization initiator, and 2 -A method for polymerizing oxazolines has been proposed (JP-A-47-43000). _{- (OCH 2 CH 2) m} -X (iii) ( wherein, X represents Br or I.)

A method for polymerizing 2-oxazolines using a polyethylene oxide sulfonate represented by the general formula (iv) as a polymerization initiator has been proposed [JP-A-49-85199, T.S. Saegusa
et al. Eur. Polym. J. , Vol. 1
9, No. 10 / 11,955 (1983)]. _{- (OCH 2 CH 2) m} -OSO 2 R (iv)

However, in these conventional methods, since the initiation reaction rate is slower than the growth reaction rate of the polymerization, 2-
Even after the oxazoline monomer is completely consumed, a large amount of polyethylene oxide used as a polymerization initiator remains unreacted in the reaction system. Therefore, it was difficult to control the molecular weight of the oxazoline block portion of the synthesized block copolymer, and it was also difficult to remove unreacted polyethylene oxides.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a polyalkylene oxide having a controlled molecular weight of the oxazoline block portion, which contains almost no unreacted polyalkylene oxides. An object of the present invention is to provide a method capable of easily producing an oxazoline block copolymer. Another object of the present invention is to provide a novel polyalkylene oxide-oxazoline block copolymer.

As a result of earnest studies, the present inventors have used a compound having a structure in which a hydroxyl group at one end or both ends of polyalkylene oxide is converted to a haloacetic acid ester as a polymerization initiator to polymerize a 2-oxazoline monomer. And, it was found that the polymerization is rapidly initiated / progressed in a cationic / living manner, and a polyalkylene oxide-oxazoline block copolymer in which the molecular weight of the oxazoline block portion is regulated, which contains almost no unreacted polyalkylene oxides, can be obtained. The present invention has been completed based on the findings.

[0010]

Thus, according to the present invention, there is provided a polyalkylene oxide-oxazoline block copolymer characterized by being represented by the general formula (1).

[0011]

[Chemical 9]

Further, according to the present invention, there is provided a polyalkylene oxide-oxazoline block copolymer characterized by being represented by the general formula (2).

[0013]

[Chemical 10]

Further, according to the present invention, at least one 2-oxazoline represented by the general formula (3) is polymerized by using the compound represented by the general formula (4) as a cationic polymerization initiator. A method for producing a polyalkylene oxide-oxazoline block copolymer is provided.

[0015]

[Chemical 11]

[0016]

[Chemical 12]

Furthermore, according to the present invention, at least one 2-oxazoline represented by the general formula (3) is polymerized by using the compound represented by the general formula (5) as a cationic polymerization initiator. A method for producing a polyalkylene oxide-oxazoline block copolymer is provided.

[0018]

[Chemical 13]

The meaning of each symbol in these general formulas (1) to (5) is as follows. R ¹ is a (substituted) alkyl group or a (substituted) aryl group. Specific examples thereof include a methyl group, an ethyl group, a lauryl group, a stearyl group and a phenyl group. R ² and R ³ are both hydrogen atoms or one of them is a methyl group. R ⁴ and R ⁵ are each independently selected from a hydrogen atom, a (substituted) alkyl group and a (substituted) aryl group.

R ⁶ is a hydrogen atom, a (substituted) alkyl group or a (substituted) aryl group. Specifically, hydrogen,
Methyl group, ethyl group, iso-propyl group, n-propyl group, n-butyl group, n-amyl group, n-heptyl group,
Examples thereof include n-octyl group and phenyl group. X is C1, Br, I or a hydroxyl group. Y is C1, Br or I. a is an integer of 5 to 10,000, preferably 10
Is an integer of 5,000. b is an integer of 3 to 10,000, preferably 10
Is an integer of 5,000.

The present invention will be described in detail below. The polyalkylene oxide-oxazoline block copolymer represented by the general formula (1) in the present invention has the general formula (3)
Can be produced by subjecting at least one 2-oxazoline represented by the formula (4) to cationic ring-opening polymerization using the compound represented by the general formula (4) as a polymerization initiator. Among the polyalkylene oxide-oxazoline block copolymers represented by the general formula (1), those having a hydroxyl group at the terminal can be obtained by hydrolyzing the terminal halogen by the action of water.

The 2-oxazolines represented by the general formula (3) are 2-substituted or unsubstituted 2-oxazolines in which R ⁶ is a hydrogen atom, a (substituted) alkyl group or a (substituted) aryl group.

R ⁶ is a hydrogen atom; a saturated alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, C
Unsaturated alkyl groups such as H ₂ ═CHCH ₂ — or C ₂ F ₅
(Substituted) alkyl group such as halogen-substituted alkyl group such as — and CCl ₃ ; aryl group such as phenyl group; C ₆ H ₅ C
(Substituted) aryl groups such as aralkyl groups such as H ₂ — are included.

As such 2-oxazolines,
For example, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl 2
-Oxazoline, 2-isopropyl 2-oxazoline, etc. can be mentioned as a preferable example.

The 2-oxazolines are each alone,
Alternatively, two or more kinds can be used in combination. When two or more 2-oxazolines are used in combination, random copolymerization or block copolymerization may be used.

[0026] Thus, oxazoline block in the general formula (1) - [N (R 6 CO) CH 2 CH 2] b - is
Not only one type of 2-oxazoline homopolymer but also two or more types of 2- or more 2- (2) different substituents (R ⁶ ) at the 2-position.
It also means a random copolymer or a block copolymer using a combination of oxazolines.

The degree of polymerization b of the oxazoline block is 3 to.
It is 10,000, preferably 10 to 5,000. Here, the degree of polymerization b is 2 when the oxazoline block is two or more.
In the case of a random copolymer or a block copolymer in which -oxazolines are used in combination, the total amount of repeating units derived from each 2-oxazoline.
Polymers having a degree of polymerization b of more than 10,000 are difficult to synthesize, and those having a degree of polymerization b of less than 3 are unsuitable for use as a surfactant.

The compound represented by the general formula (4) is a polyalkylene oxide haloacetic acid ester (one terminal haloacetic acid ester), which acts as a cationic polymerization initiator of 2-oxazolines and has a polyalkylene oxide block. Form.

The polyalkylene oxide haloacetic acid ester can be easily synthesized by reacting polyalkylene oxide with haloacetic anhydride or haloacetic acid chloride in the presence of a base. As the halogen, chlorine (Cl), bromine (Br) or iodine (I) is used.

Here, as the polyalkylene oxide, polyethylene oxide, polypropylene oxide, or a copolymer of polyethylene oxide and polypropylene oxide is used. Copolymers include block copolymers and random copolymers.

[0031] Accordingly, the repeating units in Formula ^{(4) - (CR 2 HCR} 3 HO) a - is, - (CH ₂ CH ₂
O) _a - and _{- (CH 2 CH (CH 3} ) O) a - _{well, - (CH 2 CH 2 O} ) m (CH 2 CH (CH 3) O) n -
(However, m + n = a), - (CH 2 CH 2 O) m (CH 2
_{CH (CH 3) O) n} (CH 2 CH 2 O) m - ( where 2
It includes a random copolymer or a block copolymer represented by m + n = a) and the like. The polyalkylene oxide block in the general formula (1) is the same as the polyalkylene oxide block in the general formula (4).

The degree of polymerization a of the polyalkylene oxide used is 5 to 10,000, preferably 10 to 50.
00. When the polyalkylene oxide is a block copolymer or a random copolymer of polyethylene oxide and polypropylene oxide,
It is the total amount of each repeating unit. Polymerization degree a is 10,000
Polymers having a degree of polymerization of more than 5 are difficult to synthesize, and those having a degree of polymerization a of less than 5 are unsuitable for applications such as surfactants.

In the general formula (4), the other end (R ¹
O-) is an alkyl ether or an aryl ether, and R ¹ is a saturated alkyl group having usually 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, CH ₂ ═CHCH ₂ —
Such as unsaturated alkyl groups, or (substituted) alkyl groups such as halogen-substituted alkyl groups such as C ₂ F ₅ — and CCl ₃ ; aryl groups such as phenyl groups and aralkyl groups such as C ₆ H ₅ CH ₂ — (Substituted) aryl groups may be mentioned. R ¹ O— in the general formula (1) is the same as in the general formula (4).

In the general formula (4), R^Fourand
R^FiveIs a hydrogen atom; the number of carbon atoms is usually 1 to 18,
Preferably 1 to 12 saturated alkyl groups, CH₂= CHC
H₂Unsaturated alkyl group such as-, or C₂F_Five-, CCl₃
(Substituted) alkyl such as halogen-substituted alkyl groups such as
Group; aryl group such as phenyl group, C₆H_FiveCH₂− Etc.
Mention may be made of (substituted) aryl groups such as aralkyl groups. one
R in general formula (1)^Four And R^FiveIn the general formula (4)
It is the same as kicking.

By the way, the polyalkylene oxide chloroacetic acid ester contains chlorine (Cl) as another active halogen,
For example, when substituting with iodine (I) or bromine (Br), 2
-The reactivity with oxazoline compounds can be increased. Specifically, polyalkylene oxide chloroacetic acid ester is reacted with sodium iodide, potassium bromide, etc. in a solvent such as methyl ethyl ketone, and the product is purified by extraction and reprecipitation. Can be obtained. The reaction mixture may be directly used for the reaction with the 2-oxazoline compound without isolation of the iodine-substituted product or the bromine-substituted product. Furthermore, the reactivity of the 2-oxazoline compound can be enhanced by simultaneously adding polyalkylene oxide chloroacetic acid ester and sodium iodide or potassium bromide to the polymerization reaction system.

The reaction between the 2-oxazolines and the polyalkylene oxide haloacetic acid ester is carried out in an inert gas atmosphere such as argon in an inert organic solvent, preferably an aprotic organic solvent such as acetonitrile. The reaction temperature at this time is 0 to 120 ° C., preferably 20 to 100 ° C.
Is set to. The reaction time is set to a time sufficient for the 2-oxazolines to be polymerized substantially completely, but usually 1 to 1
It is 00 hours, preferably 5 to 50 hours. After completion of the reaction, the produced polymer is isolated by a method such as adding the reaction solution to a large amount of diethyl ether for precipitation or distilling off the solvent under reduced pressure.

The polyalkylene oxide-oxazoline block copolymer represented by the general formula (2) in the present invention is at least one of 2-type compounds represented by the general formula (3).
The oxazolines can be produced by subjecting the compound represented by the general formula (5) to a cationic ring-opening polymerization using a polymerization initiator. Among the polyalkylene oxide-oxazoline block copolymers represented by the general formula (2), those having a hydroxyl group at the terminal can be obtained by hydrolyzing the terminal halogen by the action of water.

The 2-oxazolines are each alone,
Alternatively, two or more kinds can be used in combination. When two or more 2-oxazolines are used in combination, random copolymerization or block copolymerization may be used.

The compound represented by the general formula (5) is a polyalkylene oxide haloacetic acid ester (both terminal haloacetic acid ester), which acts as a cationic polymerization initiator of 2-oxazolines and has a polyalkylene oxide block. Form.

This polyalkylene oxide haloacetic acid ester can be easily synthesized by reacting polyalkylene oxide with haloacetic anhydride or haloacetic acid chloride in the presence of a base. As the polyalkylene oxide, polyethylene oxide, polypropylene oxide, a block copolymer of polyethylene oxide and polypropylene oxide, or a random copolymer is used.

R ² , R ³ , R ⁴ and R ⁵ in the general formulas (2) and (5) are the same as those in the general formulas (1) and (4). The degree of polymerization a and b of each block in the general formula (2) are the same as in the general formula (1). Further, the polymerization reaction conditions of the block copolymer of the general formula (2) are the same as the above reaction conditions in the synthesis of the polymer of the general formula (1).

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition,% in the examples is based on weight unless otherwise specified.

[GPC Measurement Conditions] Mn and Mw of the alkylene oxide and the block copolymer were measured by gel permeation chromatography (GPC).

Measuring device: HLC8020 manufactured by Tosoh Solvent: LiBr (0.43 g / l) DMF solution Column: TSKgel 5000HxL + TSK manufactured by Tosoh
gel4000HxL + TSK gel3000HxL +
TSKgel2000HxL standard sample: Tosoh polyethylene oxide standard sample was used to prepare a calibration curve, and Mn and Mw were calculated.

Example 1 In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 1800, Mw / Mn = 1.05) 4.00 g
(2.22 mmol), sodium iodide 0.359 g
(2.88 mmol) and 2.00 g (20.1 mmol) of 2-ethyl-2-oxazoline were placed in a glass reaction vessel together with 4 ml of acetonitrile and stirred at room temperature for 2 hours, and then at a reaction temperature of 70 ° C. for 36 hours. It was heated and polymerized. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer.
The yield was 5.76 g (yield 93%).

When the molecular weight of the obtained block copolymer was measured by gel permeation chromatography (GPC), it showed only one peak, the number average molecular weight (Mn) was 2856, and the molecular weight distribution (Mw / Mn). ) Was 1.06. In addition, poly (2-
The ethyl-2-oxazoline) homopolymer was insoluble in benzene, but this block copolymer was soluble in benzene.

Example 2 In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 1800, Mw / Mn = 1.05) 4.00 g
(2.22 mmol), sodium iodide 0.359 g
(2.88 mmol) and 4.00 g (40.2 mmol) of 2-ethyl-2-oxazoline were placed in a glass reaction vessel together with 5 ml of acetonitrile and stirred at room temperature for 2 hours, and then at a reaction temperature of 70 ° C. for 36 hours. It was heated and polymerized. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer.
The yield was 6.00 g (100% yield).

With respect to the obtained block copolymer, G
When the molecular weight was measured by PC, only one peak was shown, Mn = 3436 and Mw / Mn = 1.06. Also, poly (2-ethyl-2-oxazoline)
The homopolymer was insoluble in benzene, but the block copolymer was soluble in benzene.

Example 3 In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 1800, Mw / Mn = 1.05) 4.00 g
(2.22 mmol), sodium iodide 0.359 g
(2.88 mmol) and 8.00 g (80.4 mmol) of 2-ethyl-2-oxazoline were placed in a glass reaction vessel together with 6 ml of acetonitrile and stirred at room temperature for 2 hours, and then at a reaction temperature of 70 ° C. for 36 hours. It was heated and polymerized. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer.
The yield was 11.52 g (96% yield).

Regarding the obtained block copolymer, G
When the molecular weight was measured by PC, only one peak was shown, Mn = 4906, and Mw / Mn = 1.10. Also, poly (2-ethyl-2-oxazoline)
The homopolymer was insoluble in benzene, but the block copolymer was soluble in benzene.

Example 4 In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 1800, Mw / Mn = 1.05) 2.00 g
(1.11 mmol), sodium iodide 0.179 g
(1.32 mmol), and 2-isopropyl-2-
2.00 g (17.7 mmol) of oxazoline was put into a glass reaction container together with 3.5 ml of acetonitrile, stirred at room temperature for 2 hours, and then heated at a reaction temperature of 70 ° C. for 48 hours to polymerize. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer. The yield was 4.00 g (100% yield).

Regarding the obtained block copolymer, G
When the molecular weight was measured by PC, only one peak was shown, Mn = 3235, and Mw / Mn = 1.14. The poly (2-isopropyl-2-oxazoline) homopolymer was insoluble in benzene, but this block copolymer was soluble in benzene.

[Example 5] In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 5400, Mw / Mn = 1.09) 2.00 g
(0.37 mmol), sodium iodide 0.090 g
(0.56 mmol) and 1.00 g (10.1 mmol) of 2-ethyl-2-oxazoline were placed in a glass reaction vessel together with 2 ml of acetonitrile and stirred at room temperature for 2 hours, and then at a reaction temperature of 70 ° C. for 48 hours. It was heated and polymerized. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer.
The yield was 2.79 g (yield 93%).

With respect to the obtained block copolymer, G
When the molecular weight was measured by PC, only one peak was shown, Mn = 7630, and Mw / Mn = 1.09. Also, poly (2-ethyl-2-oxazoline)
The homopolymer was insoluble in benzene, but the block copolymer was soluble in benzene.

Example 6 In an argon atmosphere,
Polyethylene glycol chloroacetic acid ester (ClCH ₂ COO (CH ₂ CH
₂ O) _a COCH ₂ Cl: Mn = 9000, Mw / Mn =
1.00 g (0.22 mmol), sodium iodide 0.10 g (0.66 mmol), and 2-
Ethyl-2-oxazoline 1.00 g (10.1 mmo
l) was placed in a glass reaction vessel together with 2 ml of acetonitrile and stirred at room temperature for 2 hours, and then the reaction temperature was 70 ° C.
Polymerization was carried out by heating for 48 hours. After this, cool to room temperature,
The reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer. The yield was 2.98 g (98% yield).

Regarding the obtained block copolymer, G
When the molecular weight was measured by PC, it showed only one peak, Mn = 12867, and Mw / Mn = 1.10.
Met. Further, the poly (2-ethyl-2-oxazoline) homopolymer was insoluble in benzene, but this block copolymer was soluble in benzene.

Example 7 In an argon atmosphere,
Monomethyl ether polyethylene glycol chloroacetic acid ester (CH ₃ O (CH ₂ CH ₂ O) _a COCH ₂ Cl:
Mn = 1800, Mw / Mn = 1.05) 2.00 g
(1.11 mmol), sodium iodide 0.179 g
(1.32 mmol), and 2-isopropyl-2-
2.00 g (17.7 mmol) of oxazoline was put into a glass reaction container together with 3.5 ml of acetonitrile, stirred at room temperature for 2 hours, and then heated at a reaction temperature of 70 ° C. for 48 hours to polymerize. Here, 2.00 g (20.2 mmol) of 2-ethyl-2-oxazoline and 1.0 ml of acetonitrile were further added, and the reaction temperature was changed to 70 ° C. at 48 ° C.
Polymerized for hours. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer. The yield was 5.58 g (yield 93%).

With respect to the obtained block copolymer, G
When the molecular weight was measured by PC, only one peak was shown, Mn = 4055 and Mw / Mn = 1.20. In addition, (2-ethyl-2-oxazoline / 2-
The isopropyl-2-oxazoline) block copolymer was insoluble in benzene, but this block copolymer was soluble in benzene.

Example 8 In an argon atmosphere,
Polyethylene oxide-polypropylene oxide block copolymer chloroacetic acid ester (ClCH ₂ CO
O (CH ₂ CH ₂ O) _m (CH ₂ CH (CH ₃ ) O) _n (CH
₂ CH ₂ O) _m COCH ₂ Cl: Mn = 8300, Mw / M
n = 1.05, m: n = 2: 1, 3.00 g (0.36)
mmol), sodium iodide 0.14 g (0.46 m
mol), and 2-ethyl-2-oxazoline 1.5
0 g (15.2 mmol) was placed in a glass reaction vessel together with 3 ml of acetonitrile, stirred at room temperature for 2 hours, and then heated at a reaction temperature of 70 ° C. for 48 hours to polymerize. Then, the mixture was cooled to room temperature and the reaction solution was poured into a large amount of diethyl ether to isolate a white powder polymer. Yield 4.4
It was 0 g (yield 98%).

For the block copolymer obtained, G
When the molecular weight was measured by PC, it showed only one peak, Mn = 12770, and Mw / Mn = 1.14.
Met. Further, the poly (2-ethyl-2-oxazoline) homopolymer was insoluble in benzene, but this block copolymer was soluble in benzene.

[0061]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a polyalkylene oxide-oxazoline block copolymer in which the molecular weight of the oxazoline moiety is controlled and which contains almost no unreacted polyalkylene oxides as compared with the prior art. .. INDUSTRIAL APPLICABILITY The polyalkylene oxide-oxazoline block copolymer of the present invention is a useful material that can be used for various purposes such as a nonionic polymer surfactant, a surface modifier, a dispersant, an antistatic agent, and an adhesive.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): Polyalkylene oxide-oxazoline block copolymer and method for producing the same [wherein the symbols have the following meanings. R
¹ is a (substituted) alkyl group or a (substituted) aryl group. R ² and R ³ are both hydrogen atoms,
Alternatively, either one is a methyl group. R ⁴ and R ⁵
Are each independently selected from a hydrogen atom, a (substituted) alkyl group and a (substituted) aryl group. R ⁶ is a hydrogen atom, a (substituted) alkyl group or a (substituted) aryl group. X is C1, Br, I or a hydroxyl group. a
Is an integer of 5 to 10000. b is 3 to 1000
It is an integer of 0. ] The polyalkylene oxide-oxazoline block copolymer characterized by being shown by these. 2. A general formula (2): [In the formula, the meaning of each symbol is as follows. R ² and R ³ are both hydrogen atoms or one of them is a methyl group. R ⁴ and R ⁵ are each independently selected from a hydrogen atom, a (substituted) alkyl group and a (substituted) aryl group. R ⁶ is a hydrogen atom,
It is a (substituted) alkyl group or a (substituted) aryl group.
X is C1, Br, I or a hydroxyl group. a is 5 to
It is an integer of 10,000. b is an integer of 3 to 10000. ] The polyalkylene oxide-oxazoline block copolymer characterized by being shown by these. 3. A compound represented by the general formula (3): [In the formula, R ⁶ is a hydrogen atom, a (substituted) alkyl group or a (substituted) aryl group. ] At least 1
Two types of 2-oxazolines are represented by the general formula (4): [In the formula, the meaning of each symbol is as follows. R
¹ is a (substituted) alkyl group or a (substituted) aryl group. R ² and R ³ are both hydrogen atoms,
Alternatively, either one is a methyl group. R ⁴ and R ⁵
Are each independently selected from a hydrogen atom, a (substituted) alkyl group and a (substituted) aryl group. Y is C1,
Br or I. a is an integer of 5 to 10000. ] The polyalkylene oxide characterized by polymerizing the compound shown by these as a cationic polymerization initiator-
Process for producing oxazoline block copolymer. 4. A compound represented by the general formula (3): [In the formula, R ⁶ is a hydrogen atom, a (substituted) alkyl group or a (substituted) aryl group. ] At least 1
The 2-oxazolines of the formula are represented by the general formula (5): [In the formula, the meaning of each symbol is as follows. R ² and R ³ are both hydrogen atoms or one of them is a methyl group. R ⁴ and R ⁵ are each independently selected from a hydrogen atom, a (substituted) alkyl group and a (substituted) aryl group. Y is C1, Br or I. a is an integer of 5 to 10000. ] The compound shown by these is superposed | polymerized as a cationic polymerization initiator, The manufacturing method of the polyalkylene oxide oxazoline block copolymer characterized by the above-mentioned.