JPH0790034A - Graft polymer having polyethyleneimine derivative chain as grafted chain and its production - Google Patents

Abstract

PURPOSE:To obtain the subject polymer improved in thermal properties, having special surface activity, useful as a high-molecular surfactant, surface modifier, adhesive, etc., obtained by copolymerization of a specific acrylic macromonomer and a radical or anionic polymerizable monomer. CONSTITUTION:This graft polymer having >=5000 number-average molecular weight and made up of (1) a recurring unit of formula I [R<1> is H or CH3; R<2> is H, a (substituted) alkyl or aryl; R<3> is a (substituted) alkyl; X is O or NR<4> (R<4> is H, an alkyl or an aryl); (n) is 5-100] and (2) a recurring unit of formula II [R<5> is H or a (substituted) alkyl; R<6> is a (substituted) aryl, an alkoxycarbonyl, a (substituted) carbamoyl or nitrile] at the molar ratio (1)/(2) or (1:100) to (1:10) is obtained by copolymerization of an acrylic macromonomer of formula III having polyethyleneimine derivative chain and a radical or anionic polymerizable monomer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a nonionic polymer surfactant, surface modifier, dispersant, compatibilizer, antistatic agent, polymer dielectric agent, adhesive, binder, biocompatible material, etc. The present invention relates to a graft polymer having a novel polyethyleneimine derivative chain as a graft chain 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 by cationic polymerization of 2-oxazoline type monomers (S. Kobayashi et.
al. , Encyclo. Poly. Sci. &
Eng. Vol. 4 2nd Ed. , 525
(1986)). It is known that the living growing terminal of such a polymer is reacted with a nucleophile such as water, ammonia, or a primary amine to terminate the polymerization (Kobayashi et al., The Chemical Society of Japan No. 1). 53 Proceedings of Autumn Meeting, p. 417 (1986)). Furthermore, a styryl-type macromonomer having such a poly (N-formylethyleneimine) or poly (N-acylethyleneimine) chain is a method for polymerizing 2-oxazolines using a styryl-type compound (initiation Agent method) is known (DA.
Tomalia, et. al. U.S. Pat. No. 4,26
1,925 (1981); Kobayashi,
Japan-US Polymer Symposos
m, 24 (1985)). There is also known a method (terminating agent method) of terminating the living growing cation end of a poly (N-acylethyleneimine) chain using a styryl type compound as a terminator (terminating agent method) (S. Kobayashi).
i, et. al. , Polym. Bull. 13 , 47
7 (1985)).

[0003]

The above-mentioned initiator method and termination method are effective for synthesizing styryl-type macromonomers, but they are of acrylic type or methacrylic type (these are collectively referred to simply as acrylic type). When a compound of (1) is used as a polymerization initiator, the growth reaction is slow with an acrylic type initiator, and the carbon-carbon double bond of the initiator gradually decreases during the reaction. However, an acrylic macromonomer having a polyethyleneimine derivative chain could not be synthesized. Therefore, the present inventor conducted research for the purpose of providing an acrylic macromonomer expected to have a polymerization activity different from that of a styryl type, and as a result, produced an acrylic macromonomer having a novel polyethyleneimine derivative chain. Succeeded in doing
Furthermore, it has come to be possible to provide a novel graft polymer having a unique functionality and capable of various applications by using such a novel macromonomer.

[0004]

Thus, according to the present invention, a repeating unit represented by the formula (4) and a repeating unit represented by the formula (5) are included, and (4) / (5) = 1/1
00 to 1/10 and a number average molecular weight of 5,000
There is provided a graft polymer having a polyethyleneimine derivative as a graft chain, which is characterized by the above.

[0005]

[Chemical 4](In the formula, R¹Is H or CH₃, R²Is H or (substituted) alk
Group or aryl group, R³ Is a (substituted) alkyl group, X is
O or NR_Four, R^FourIs H or an alkyl group or an aryl group,
n represents an integer of 5 to 100. )

[0006]

[Chemical 5] (In the formula, R ⁵ represents H or a (substituted) alkyl group, R ⁶ represents a (substituted) aryl group, an alkoxycarbonyl group, a (substituted) carbamoyl group or a nitrile group.)

Further, according to the present invention, there is provided a polyethyleneimine derivative chain characterized in that an acrylic macromonomer having a polyethyleneimine derivative chain represented by the formula (6) is copolymerized with a radically or anionically polymerizable monomer. A method for producing a graft polymer having a graft chain is provided.

[0008]

[Chemical 6] (In the formula, R ¹ is H or CH ₃ , R ² is H or a (substituted) alkyl group or a (substituted) aryl group, R ³ is a (substituted) alkyl group, X is O or NR ₄ , R ⁴ is H or (Alkyl group or aryl group, n represents an integer of 5 to 100.)

The acrylic macromonomer having a polyethyleneimine derivative chain used in the present invention is a novel compound and is represented by the above formula (6). Such an acrylic macromonomer having a polyethyleneimine derivative chain is produced by reacting the compound represented by the formula (7) with (meth) acrylic acid or its derivative in the presence of a base. The (meth) acrylic acid in the present invention means acrylic acid or methacrylic acid.

[0010]

[Chemical 7] (Wherein R ² is H or a (substituted) alkyl group or aryl group, R ³ is a (substituted) alkyl group, Y is OH or NHR ₄ ,
R ⁴ is H or an alkyl group or an aryl group, n is 5 to 10
Represents an integer of 0. )

Here, the alkyl group of R ² , R ³ and R ⁴ usually means a C _{1 to} C ₁₈ , preferably a C _{1 to} C ₁₂ alkyl group. Examples of the substituted alkyl group for R ² include a benzyl group, an alkoxyalkyl group, a halogenated alkyl group and a fluorine-containing alkyl group. Examples of the substituted alkyl group for R ³ include a benzyl group and a methoxymethyl group. Furthermore, examples of the alkyl group or aryl group of R ⁴ include a methyl group, a butyl group, a benzyl group, and a phenyl group.

The compound represented by the formula (7) is, for example, 2
-Oxazolines can be obtained by livingly polymerizing a compound using a cationic polymerization initiator and then reacting the living growing end with water, ammonia, or a nucleophile such as a primary amine. Examples of the cationic polymerization initiator include p-toluenesulfonic acid ester, benzenesulfonic acid ester, methanesulfonic acid ester, trifluoromethanesulfonic acid ester, alkyl iodide, alkyl bromide, alkyl chloride, benzyl bromide, benzyl chloride, dimethyl sulfate. Are used. At this time, n
The value of can be controlled by changing the molar ratio of the starting material 2-oxazoline compound and the initiator. In reacting the living growing end with water, for example, a method of heating in the presence of an alkaline reagent such as sodium carbonate to hydrolyze the growing end can be adopted.

The compound of formula (7) thus obtained is reacted with (meth) acrylic acid or its derivative in the presence of a base to give a polyethyleneimine derivative chain of formula (6). It is possible to obtain an acrylic macromonomer having As the base, for example, triethylamine, tributylamine, pyridine, etc. are used. Further, as the (meth) acrylic acid derivative,
Examples thereof include (meth) acrylic acid halides such as acryloyl chloride and methacryloyl chloride, (meth) acrylic acid esters, and (meth) acrylic acid anhydrides. The reaction temperature is generally -20 ° C to + 150 ° C, preferably 0 ° C to + 120 ° C.

The acrylic macromonomer having a polyethyleneimine derivative chain represented by the formula (6) is obtained by polymerizing a compound of the 2-oxazoline group represented by the formula (8) in a living manner by using a cationic polymerization initiator. It is also obtained by directly reacting a living growing terminal of a poly (N-formylethyleneimine) or poly (N-acylethyleneimine) polymer produced by the reaction with a salt of (meth) acrylic acid or a metal ester compound. You can do it. Examples of the salt or metal ester compound of (meth) acrylic acid include metal salts of sodium, potassium, silver, copper and calcium; and (meth) acrylic acid and a base such as butylamine, dipropylamine, trimethylamine, triethylamine and pyridine. A mixture; or an ammonium salt formed from the mixture; a sulfonium salt such as trisdimethylsulfonium (meth) acrylate; a metal ester compound of (meth) acrylic acid with silicon, tin, titanium, or the like is used. The reaction temperature is usually -20 ° C to +
It is in the range of 150 ° C, preferably 0 ° C to + 120 ° C.

[0015]

[Chemical 8] (In the formula, R ² represents H or a (substituted) alkyl group or an aryl group.)

The novel graft polymer having a polyethyleneimine derivative chain of the present invention as a graft chain is obtained by copolymerizing the thus obtained acrylic type macromonomer having a polyethyleneimine derivative chain with a radical or anionic polymerization reactive monomer. Can be obtained. Examples of the radical or anionic polymerization-reactive monomer copolymerized with an acrylic macromonomer having a polyethyleneimine derivative chain include styrene and
Styrene compounds such as vinyltoluene and α-methylstyrene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) (Meth) acrylic acid derivatives such as 2-ethylhexyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide; ethylene such as ethylene, propylene and butylene. Unsaturated monoolefins; diolefins such as butadiene, isoprene, piperylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ethers such as vinyl acetate and vinyl propionate Teru; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl ketones such as vinyl methyl ketone and methyl isopropenyl ketone; nitrogen-containing vinyl compounds such as nitroethylene, 2-vinylpyridine, 4-vinylpyridine and N-vinylpyrrolidone; methyl vinyl sulfone And sulfur-containing vinyl compounds such as vinylphosphonic acid, diethyl vinylphosphonate, and vinylphosphonamide such as vinylphosphonamide. These monomers can be used alone or in combination of two or more.

The graft polymer having a polyethyleneimine derivative chain as a graft chain is obtained by copolymerizing an acrylic macromonomer having a polyethyleneimine derivative chain with the above comonomer, or by polymerizing these comonomers with polyethyleneimine. It can be obtained by graft-polymerizing an acrylic macromonomer having a derivative chain. In copolymerizing the acrylic macromonomer having a polyethyleneimine derivative chain with the above-mentioned comonomer, a solvent is optionally used in a mixture of these monomers, and a radical polymerization initiator or an anionic polymerization initiator is added. Alternatively, a method of irradiating with light or radiation can be used. The solvent used at this time does not interfere with the copolymerization reaction and is appropriately selected depending on the kind of the monomer, and examples thereof include acetonitrile, benzonitrile, nitromethane, toluene, tetrahydrofuran, t-butanol, and water. Can be mentioned. The polymerization initiator used for copolymerization is, for example, a known radical generator such as benzoyl peroxide or azobisisobutyronitrile, or a redox radical generator such as hydrogen peroxide-iron. Examples of radical polymerization initiators, organic metal-based initiators such as butyllithium and methylmagnesium bromide, and other known anionic polymerization initiators. The polymerization temperature for carrying out such polymerization is not particularly limited, but it is usually +2 when carrying out radical polymerization.
0 ° C to + 150 ° C, usually -78 ° C to + 25 ° C when anionic polymerization is carried out, and usually -20 ° C to + 50 ° C when light or radiation polymerization is carried out.
℃ is suitable.

The graft polymer having the polyethyleneimine derivative thus obtained as a graft chain has the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5), 4) / (5)
= 1/100 to 1/10. Further, it is a novel graft polymer having a number average molecular weight of 5,000 or more, preferably 5,000 to 500,000 by GPC (gel permeation chromatography).

Since such a graft polymer has a polyethyleneimine derivative chain as a graft chain, the softening point and glass transition point of the polymer are increased and the thermal properties are improved. A graft polymer having such a polyethyleneimine derivative chain as a graft chain,
It is a polymer that has a special surface activity, and is a useful material that can be used for various purposes such as polymer surfactants, surface modifiers, and adhesives.

[0020]

As described above, according to the present invention, it is possible to obtain a novel graft polymer which is useful for various applications as described above.

[0021]

【Example】

Reference Example 1 (1) Production of Oxazoline Polymer Compound 6.85 g (80.5 mmol) of 2-methyl-2-oxazoline in a glass polymerization tube placed under an argon atmosphere.
Pour a solution of 8 ml of acetonitrile in 0 ℃
Maintained at 0.749 g of methyl p-toluenesulfonate
(4.02 mmol) dissolved in 4 ml of acetonitrile was added, mixed well, and then sealed at 80 ° C. for 2 hours.
The reaction was allowed for 0 hours. After cooling to room temperature and opening, the reaction mixture was transferred to Rausco and 4.66 g (44
(mmol) and 2 ml of water and shaken well, the aqueous layer was separated, and the water was distilled off under reduced pressure to dry. Chloroform (40 ml) was added to this residue, and the mixture was stirred for 12 hours, suction filtered to remove insolubles, chloroform was distilled off under reduced pressure and dried to quantitatively obtain a terminal hydroxy type 2-oxazoline polymer compound. It was GPC for this compound
When the molecular weight according to was measured, a value of 1800 was obtained. Therefore, in the above formula (7), it was found that R ² and R ³ are both CH ₃ , Y is OH, and n is 21. (2) Production of macromonomer 3.4 g of the above polymer compound under an argon atmosphere
Was dissolved in 8 ml of methylene chloride and kept at 0 ° C., and 0.48 g of triethylamine (2.4 equivalents based on the polymer compound) dissolved in 2 ml of methylene chloride was added. Then, a solution of 0.37 g of acryloyl chloride (2.0 equivalents based on the polymer compound) dissolved in 6 ml of methylene chloride was added, and the temperature of the reaction system was raised to room temperature, followed by stirring for 24 hours. To the reaction mixture was added saturated aqueous sodium hydrogencarbonate solution (20 ml), the mixture was stirred for 8 hours, the aqueous layer was separated, and the water was evaporated under reduced pressure to dry the residue. Chloroform (40 ml) was added to this residue and the mixture was stirred for 12 hours, suction filtered to separate insoluble matter, dried over anhydrous sodium sulfate, and chloroform was distilled off under reduced pressure to obtain 2.2 g of macromonomer (yield: 62%) was obtained. In this formula (6), R ¹ is H, R ² and R ³ are CH ₃ , and X is O in this macromonomer. When the molecular weight of this macromonomer was measured by GPC, it showed only one peak and the molecular weight (Mn) was 190.
It was asked to be 0. The degree of polymerization (n) calculated from this result was 21.3.

¹ H-NMR (CDCl ₃ , δ value) is as follows. _{2.1 (br, s, CH 3} C = 0,63H) 2.9 and _{3.0 (s, CH 3 N,} 3H) 3.4 (br, s, CH 2 N, 82H) 4.0~ _{4.4 (br, CH 2 OC =} 0,2H) 5.7~6.4 (br, m, CH 2 = CH, 3H) from this result, the degree of polymerization (n) was calculated as 21. The IR spectrum (cm ^-1 ) is as follows. 1630c, 1720

Reference Example 2 The procedure for producing the oxazoline-based polymer compound of Reference Example 1 was repeated in exactly the same manner to obtain a polymer compound. A macromonomer was obtained with a yield of 81% by the same procedure as in the latter stage of Reference Example 1 except that 2.0 equivalents of methacryloyl chloride were used instead of acryloyl chloride with respect to this polymer compound. This macromonomer has the same structure as R in the above formula (6).
¹ , R ² and R ³ are all CH ₃ and X is O. Further, when the molecular weight of this macromonomer was measured by GPC, only one peak was shown, and the molecular weight (Mn) was determined to be 2010. The degree of polymerization (n) calculated from this result was 22.4. ^! H-NMR
(CDCl ₃ , δ value) is as follows. _{1.9 (s, CH 3 C =} C, 3H) 2.1 (br, s, CH 3 C = O, 66H) 2.9 and _{3.0 (s, CH 3 N,} 3H) 3.4 ( br, s, CH ₂ N, 86H) 4.0-4.4 (br, CH ₂ OC = O, 2H) 5.6 and 6.1 (s, CH ₂ = C, 1H each) The degree of polymerization n was calculated to be 21. The IR spectrum (cm ^-1 ) is as follows. 1630, 1710

Reference Example 3 An oxazoline-based polymer compound was prepared according to the method of Reference Example 1,
A polymer compound was prepared using 2-ethyl-2-oxazoline and methyl p-toluenesulfonate. Then, using 2.0 equivalents of acryloyl chloride with respect to the polymer compound,
The reaction was performed according to the procedure of the first half of the production of the macromonomer in Reference Example 1 to obtain a dried product extracted with an aqueous sodium hydrogen carbonate solution. Then, instead of extracting this residue with 40 ml of chloroform, extraction with 20 ml of methylene chloride was repeated 3 times, and the same procedure as in the latter stage of Reference Example 1 was performed to perform macromonomer (yield 91% )
Got In this macromonomer, R ¹ is H, R ² is C ₂ H ₅ , R ³ is CH ₃ and X is O in the formula (6). Also, regarding this macromonomer, GPC
When the molecular weight was measured by, only one peak was shown, and the molecular weight (Mn) was determined to be 2110. The degree of polymerization (n) calculated from this result was 20.4.

Reference Example 4 (1) Production of Oxazoline Polymer Compound Reference Example 1 was prepared using 2-n-butyl-2-oxazoline.
Cationic polymerization was performed according to the method of the preceding paragraph. The reaction mixture was transferred to a flask and 4.66 g (44
(mmol) and 2 ml of water were added and reacted at 100 ° C. for 18 hours for hydrolysis. 10 ml of water was added thereto, extraction with 10 ml of methylene chloride was repeated 3 times, and the extracted solution of methylene chloride was dried over anhydrous sodium sulfate.
Methylene chloride was distilled off under reduced pressure and dried to obtain a terminal hydroxy type 2-oxazoline polymer almost quantitatively. When the molecular weight of this polymer compound was measured by GPC, a value of 3300 was obtained. Therefore, in this polymer compound, R ² is n-C ₄ H ₉ in the formula (7),
It was found that R ³ is CH ₃ , Y is OH and n is 26. (2) Production of Macromonomer Acryloyl chloride (2.0 equivalents relative to the compound) was used for the above-mentioned polymer compound, and the reaction and purification were carried out according to the procedure of Reference Example 3 to obtain the macromonomer (yield
2%) was obtained. The molecular weight measured by GPC is 3530,
The degree of polymerization (n) was calculated to be 27.1. In this macromonomer, R ¹ is H and n-C in the formula (6).
₄ H ₉ and R ³ are CH ₃ , and X is O.

Reference Example 5 The procedure of the first stage of Reference Example 4 was repeated in exactly the same manner to obtain a polymer compound. Next, the reaction and purification were carried out in the same manner as in the latter part of Reference Example 4 except that 2.0 equivalents of methacryloyl chloride was used instead of acryloyl chloride with respect to this polymer compound to obtain a macromonomer with a yield of 82%. It was The molecular weight measured by GPC was 3430, and the degree of polymerization (n) was calculated to be 26.2. In this macromonomer, R ¹ is CH ₃ , nC ₄ H ₉ , R ³ is CH ₃ and X is O in the formula (6).

Reference Example 6 (1) Production of Oxazoline-Based Polymer Compound 1.76 g (17.8 mmol) of 2-ethyl-2-oxazoline in a glass polymerization tube under an argon atmosphere.
Put in a solution of 5 ml of acetonitrile in 0 ℃
Kept at 0.63 g of methyl p-toluenesulfonate
A solution prepared by dissolving (3.4 mmol) in 1 ml of acetonitrile was added, mixed well, sealed, and reacted at 80 ° C. for 20 hours. After cooling to room temperature and opening the package, the temperature is set to 0 ° C.
-4 ml of a saturated acetonitrile solution of propylamine was added, and the mixture was reacted at 0 ° C for 4 hours. Thereafter, the solvent and the like were distilled off under reduced pressure, and the residue was dried to quantitatively obtain a terminal ammonium salt type 2-oxazoline-based polymer compound. A p-toluenesulfonate ion is bonded to the terminal of this polymer compound. (2) Production of macromonomer To 2.3 g of the above polymer compound dissolved in 13 ml of methylene chloride, 1.20 g of triethylamine (4.0 equivalents to the above polymer compound) at 0 ° C. in an argon atmosphere. ) Dissolved in 2 ml of methylene chloride was added. Next, 0.751 g of acryloyl chloride (3.0 equivalents to the above-mentioned polymer compound) was added to 3 ml of methylene chloride.
What was melt | dissolved in was added, the temperature of the reaction system was raised to room temperature, and it stirred for 24 hours. To the reaction mixture was added 20 ml of saturated aqueous sodium hydrogen carbonate solution, the mixture was stirred for 4 hours, and extraction with 10 ml of methylene chloride was repeated 3 times to collect an extraction solution. The extract was dried over anhydrous sodium sulfate, and methylene chloride was distilled off under reduced pressure to obtain a macromonomer with a yield of 75%. This macromonomer has the following formula (6) in which R ¹ is H, R ² is C ₂ H ₅ , and R ³ is C.
H ₃ and X were N (n-C ₃ H ₇ ), and the degree of polymerization (n) was 9.5.

Example 1 0.095 g of the acrylic macromonomer obtained in Reference Example 1
(0.05 mmol) and styrene 0.249 g (2.3
9 mmol) was charged into a polymerization tube under an argon atmosphere, and 1.0 ml of t-butanol and 0.017 g (0.10 mmol) of azobisisobutyronitrile (AIBN) were added.
The polymerization tube was sealed with a rubber balloon filled with argon and heated at 80 ° C. for 5 hours to cause reaction. After reaction, cool to room temperature, add a small amount of chloroform and add dropwise to diethyl ether to reprecipitate the product, then suction-filter using a glass filter to isolate the polymer, and dry under reduced pressure at room temperature to obtain white. Solid copolymer 0.217
g (yield 63% based on the total amount of charged monomers) was obtained. At this time, it was confirmed from the ¹ H-NMR data measured immediately after the completion of the reaction that all the vinyl groups in the macromonomer and styrene were consumed, so that although the polymerization reaction was 100% complete, It is considered that the yield loss occurred during the purification process of the polymer due to precipitation. About the obtained copolymer, chloroform was used as a solvent for G
As a result of analysis by PC, a molecular weight distribution curve having one broad peak was obtained, and it was found that a homopolymer consisting only of macromonomers did not exist. The molecular weight (Mn) was 14,000. ¹ H-N
MR (CDCl ₃ , δ value) is as follows. 0.7-2.5 (br, signals, CCH ₂ C +
CCHC + CH ₃ C = O + CH ₃ C, total 216
H) 2.9 and _{3.0 (s, CH 3 N,} 3H) 3.4 (br, s, CH 2 N, 88H) 6.0~7.2 (br, C 4 H 5, 225H) ( In addition to these signals, a singlet was found at a δ value of 1.1, which indicates the presence of a methyl group derived from the AIBN fragment, and this signal was excluded from consideration. The ratio of CH ₂ N and C ₄ H ₅ was obtained from this analysis value, and the copolymerization composition ratio of macromonomer and styrene was calculated to be 1:44 (however, the charging ratio was 1:48). there were. In addition, the IR spectrum (c
m- ¹ ) was 1630 and 1720.

The copolymer obtained in Example 1 was dissolved in C ₄ D ₆ and its ¹ H-NMR was measured to find a δ value:
Only a broad signal attributed to CH ₂ CH over 1.0 to 2.5 and a signal attributed to a phenyl group at a δ value of 6.3 to 7.2 are observed.
This is a signal derived from styrene, and no signal derived from a macromonomer is observed. On the other hand, when this copolymer is dissolved in D ₂ O, it becomes a milky white suspension solution, and in ¹ H-NMR, a broad signal attributed to CH ₃ C═O at δ value: 2.1, and δ value: 3 Only a broad signal attributed to CH ₂ N centered at 0.5 was observed. Therefore, the copolymer of the first embodiment is in C ₆ D ₄ to form micelles in which is positioned a styrenic moiety lipophilic outwardly, also the D ₂ O in the hydrophilic N- acetyl ethyleneimine chains It can be seen that it forms micelles located on the outside and can be used as a polymer surfactant.

Example 2 0.192 g of the acrylic macromonomer obtained in Reference Example 1
(0.10 mmol) and methyl methacrylate 0.411
g (4.1 mmol) was used, and a copolymerization reaction was carried out in the same manner as in Example 1 except that 1.0 ml of acetonitrile was added instead of t-butanol as a solvent. Reaction is 2
After a lapse of time, the same treatment as in Example 1 was carried out to obtain 0.410 g of a white solid copolymer (yield 68% based on the total amount of charged monomers). When the obtained copolymer was subjected to GPC analysis in the same manner, a molecular weight distribution curve having one broad peak was obtained. Molecular weight (Mn)
Was 13,000. ¹ H-NMR (CDCl ₃ , δ
Value) is as follows. _{0.7~2.6 (br, signals, CH 3} C + C
CH ₂ C + CCHC + CH ₃ C = O, total 269
H) 2.9 and 3.0 (s, CH ₃ N, 3H) 3.4 (br, s, CH ₂ N, 88H) 3.6 (s, CH ₃ O, 120H) From this analytical value, CH ₂ When the ratio of N and CH ₃ O was determined and the copolymerization composition ratio of the macromonomer and methyl methacrylate was calculated, it was 1:39 (however, the charging ratio was 1:41). IR spectrum (cm ^-1 ) is 163
It was 0,1720. 1.2 mg of the copolymer obtained in Example 2 and 100.9 mg of polymethylmethacrylate having a molecular weight of 14,000 were dissolved in 1.9 ml of chloroform, cast on a glass plate, and allowed to stand at room temperature for 36 hours. And gradually dried to obtain a cast film. The thus obtained N-acetylethyleneimine chain content of 0.31% by weight was used to drop water droplets on the glass side and the air side of the film, and the contact angle of water was measured using a contact angle measuring device manufactured by Kyowa Interface Science Measured. The average value of 30 measurements each has a contact angle of 7 on the air surface side.
The contact angle on the glass surface side was 51 ° while it was 4 °. From this, it is understood that the hydrophilic N-acetylethyleneimine graft chain is localized on the glass surface side having a large surface free energy during the film formation, and as a result, the wettability to water is increased.

Example 3 0.203 g of the acrylic macromonomer obtained in Reference Example 2
(0.10 mmol) and methyl methacrylate 0.482
g (4.81 mmol), 1.0 ml of acetonitrile was added instead of t-butanol as a solvent, and AI was added.
A copolymerization reaction was carried out in the same manner as in Example 1 except that the amount of BN was increased to 0.035 g (0.21 mmol). The reaction was completed in 2 hours, and the same treatment as in Example 1 was carried out to give 0.507 g of a white solid copolymer (yield 74% based on the charged amount).
%) Was obtained. The GPC analysis result of the obtained copolymer showed a molecular weight distribution curve having one peak, and the molecular weight (Mn) was 15,000. ¹ H-NMR (C
DCl ₃ , δ value) is as follows. _{0.7~2.6 (br, CH 3 C,} 147H, br, C
CH ₂ C, 98H, s, CH ₃ C = O, 66H, tota
1 311H) 3.0 (s, CH ₃ N, 3H) 3.4 (br, s, CH ₂ N, 88H) 3.6 (s, CH ₃ O, 144H) From this analytical value, CH ₂ N and CH _When the ratio of ₃ O was determined and the copolymerization compositional ratio of the macromonomer and methyl methacrylate was calculated, it was 1:49 (however, the charging ratio was 1:48). IR spectrum (cm ^-1 ) is 163
It was 0,1720. 0.4 mg of the copolymer obtained in Example 3 and 98.2 mg of polymethylmethacrylate having a molecular weight of 14,000 were dissolved in 1.9 ml of chloroform, and a cast film was prepared in the same manner as in Example 2. Obtained. The contact angle of water was measured in the same manner as in Example 2 for the thus obtained film having an N-acetylethyleneimine chain content of 0.10% by weight. The average value of 30 measurements each has a contact angle on the air surface side of 72 °, whereas the contact angle on the glass surface side is 45 °, and the copolymer of the present invention has excellent surface activity. It can be seen that it is.

Example 4 0.176 g of the acrylic macromonomer obtained in Reference Example 4
(0.05 mmol) and styrene 0.417 g (4.0
0 mmol) and no solvent was added, and a copolymerization reaction was carried out in the same manner as in Example 23. The reaction was completed in 1 hour, and 0.480 g of a white solid copolymer (yield with respect to the charged amount) was treated in the same manner as in Example 1 except that a chloroform solution was poured into n-hexane for reprecipitation purification. 99%). GP about the obtained copolymer
The C analysis result showed a molecular weight distribution curve having one peak, and the molecular weight (Mn) was 43,000. ¹ H-N
MR (CDCl ₃ , δ value) is as follows. _{0.8~2.7 (br, CH 2 C,} 212H, br, C
HC, 106H, br, CCH ₂ CH ₂ C, 108H, b
r, CH ₂ C = O, 54H, br, CH ₃ C, 81H, t
total 561H) 3.0 (s, CH ₃ N, 3H) 3.4 (br, s, CH ₂ N, 108H) 6.2-7.4 (br, C ₆ H ₅ , 525H) From this analytical value When the ratio of CH ₂ N and C ₄ H ₅ was calculated and the copolymerization composition ratio of the macromonomer and styrene was calculated, it was 1:80 (however, the charging ratio was 1:80). IR spectrum (cm ^-1 ) is 1630, 172
It was 0.

Example 5 0.354 g of the acrylic macromonomer obtained in Reference Example 4
(0.10 mmol) and methyl methacrylate 0.403
g (4.02 mmol) and AIBN 0.03
A copolymerization reaction was carried out in the same manner as in Example 1 except that the amount was increased to 4 g (0.21 mmol). The reaction was completed in 1 hour, and the same procedure as in Example 1 was carried out except that reprecipitation purification was carried out using n-hexane to give 0.54 of a white solid copolymer.
5 g (yield 72% based on the charged amount) was obtained. The GPC analysis result of the obtained copolymer showed a molecular weight distribution curve having one peak and a molecular weight (Mn) of 20,0.
It was 00. ¹ H-NMR (CDCl ₃ , δ value) is as follows. _{0.8~2.5 (br, CH 3 C,} 201H, br, C
CH ₂ C, 82H, br, CHC, 1H, br, CCH ₂
CH ₂ C, 108H, br, CH ₂ C = 0.54H, to
tal 446H) 3.0 (s, CH ₃ N, 3H) 3.4 (br, s, CH ₂ N, 104H) 3.6 (s, CH ₃ O, 120H) From these analytical values, CH ₂ N and CH _When the ratio of ₃ O was determined and the copolymerization composition ratio of the macromonomer and methyl methacrylate was calculated, it was 1:42 (however, the charging ratio was 1:40). IR spectrum (cm ^-1 ) is 163
It was 0,1720.

Example 6 0.170 g of the acrylic macromonomer obtained in Reference Example 5
(0.05 mmol) and styrene 0.273 g (2.6
2 mmol) and AIBN 0.024 without solvent.
A copolymerization reaction was conducted in the same manner as in Example 1 except that g (0.15 mmol) was used. The reaction is completed in 1 hour,
0.372 g of a white solid copolymer which was treated in the same manner as in Example 1 except that reprecipitation purification was performed using n-hexane.
(Yield 84% based on the charged amount) was obtained. The GPC analysis result of the obtained copolymer showed a molecular weight distribution curve having one peak, and the molecular weight (Mn) was 73,000.
Met. ¹ H-NMR (CDCl ₃ , δ value) is as follows. _{0.8~2.6 (br, CH 3 C,} 81H, br, CH 2
C, 92H, br, CCH ₂ CH ₂ C, 104H, br,
CH ₂ C = O, 52H, br, CHC, 1H, tota
l 330H) 3.0 (s, CH ₃ N, 3H) 3.4 (s, CH ₂ N, 104H) 6.2-7.2 (br, C ₆ H ₅ , 225H) From this analysis value, CH ₂ When the ratio of N and C ₆ H ₅ was obtained and the copolymerization composition ratio of the macromonomer and styrene was calculated, it was 1:45 (however, the charging ratio was 1:52). IR spectrum (cm ^-1 ) is 1630, 172
It was 0.

Example 7 0.377 g of the acrylic macromonomer obtained in Reference Example 5
(0.11 mmol) and methyl methacrylate 0.765
g (7.64 mmol) and AIBN0.039
A copolymerization reaction was performed in the same manner as in Example 1 except that g (0.24 mmol) was added. The reaction is completed in 1 hour,
The procedure of Example 1 was repeated, except that reprecipitation purification was carried out using n-hexane, and 1.027 g of a white solid copolymer was obtained.
(90% yield based on the charged amount) was obtained. The GPC analysis result of the obtained copolymer showed a molecular weight distribution curve having one peak and a molecular weight (Mn) of 15,000.
Met. ¹ H-NMR (CDCl ₃ , δ value) is as follows. 0.4 to 2.5 (br, CH ₃ C, 291H, br, C
H ₂ C, 142H, br, CCH ₂ CH ₂ C, 104H,
br, CH ₂ C = O, 52H, total 559H) 3.0 (s, CH ₃ N, 3H) 3.4 (s, CH ₂ N, 104H) 3.6 (s, CH ₃ O, 210H) The ratio of CH ₂ N and CH ₃ O was calculated from the analytical values, and the copolymerization composition ratio of the macromonomer and methyl methacrylate was calculated to be 1:70 (however, the charging ratio was 1:69). It was IR spectrum (cm ^-1 ) is 163
It was 0,1720.

Example 8 0.216 g of the acrylic macromonomer obtained in Reference Example 3
(0.10 mmol) and styrene 0.432 g (4.1
5 mmol) and without adding AIBN 0.034
A copolymerization reaction was carried out in the same manner as in Example 1 except that g (0.20 mmol) was used. The reaction is completed in 1 hour, n
0.529 g of a white solid copolymer which was treated in the same manner as in Example 1 except that re-precipitation purification was performed using hexane.
(Yield 82% based on the charged amount) was obtained. The GPC analysis result of the obtained copolymer showed a molecular weight distribution curve having one peak and a molecular weight (Mn) of 30,000.
Met. ¹ H-NMR (CDCl ₃ , δ value) is as follows. _{0.4~2.6 (br, CH 3 C,} 60H, br, CH 2
C, 82H, br, CHC, 41H, s, CH ₂ C =
O, 40H, total 223H) 3.0 (s, CH ₃ N, 3H) 3.4 (s, CH ₂ N, 80H) 6.1-7.2 (br, C ₆ H ₅ , 200H) This analysis When the ratio of CH ₂ N and C ₆ H ₅ was obtained from the value and the copolymerization composition ratio of the macromonomer and styrene was calculated, it was 1:41 (however, the charging ratio was 1:42). IR spectrum (cm ^-1 ) is 1630, 172
It was 0.

Example 9 0.349 g of the acrylic macromonomer obtained in Reference Example 5
(0.10 mmol) and 0.284 g of acrylamide
(3.99 mmol), 1.0 ml of acetonitrile was added instead of t-butanol as a solvent, and AIB was added.
A copolymerization reaction was performed in the same manner as in Example 1 except that 0.033 g (0.20 mmol) of N was used. The reaction was completed in 1 hour, and the product was washed with tetrahydrofuran and dried to obtain 0.438 g of a white powdery copolymer (yield 70% based on the charged amount). The obtained copolymer was not completely dissolved in dimethylformamide or chloroform, but dimethylsulfoxide (DMSO) made it a complete solution. For DMSO-d ₆ solution of the copolymer by measuring ¹ H-NMR, a copolymer of 1:40 methacrylic ester and acrylamide having poly -N-n-butylcarbonyl ethyleneimine chain,
It was confirmed that no unreacted monomer was contained.

Example 10 0.096 g of the acrylic macromonomer obtained in Reference Example 1
(0.05 mmol) and acrylonitrile 0.110 g
(2.08 mmol) was used and the copolymerization reaction was carried out in the same manner as in Example 1 except that the solvent was not added. The reaction was completed in 1 hour and dried to obtain 0.20 g (yield 97% based on the charged amount) of a solid copolymer having some elasticity. DMSO-d ₆ solution of the obtained copolymer ¹ H
-NMR was measured to confirm that it was a 1:40 copolymer of an acrylic ester having a poly-N-acetylethyleneimine chain and acrylonitrile, and contained no unreacted monomer.

Example 11 0.1% of acrylamide type macromonomer obtained in Reference Example 6
24 g (0.12 mmol) and methyl methacrylate 0.1.
146 g (1.46 mmol) and t as a solvent
-A copolymerization reaction was performed in the same manner as in Example 1 except that 1.0 ml of acetonitrile was used instead of butanol.
The reaction was completed in 1 hour, but the ¹ H-
From the NMR data, it was confirmed that all vinyl groups in the system had disappeared. This product was treated in the same manner as in Example 1 to obtain 0.220 g of a white solid copolymer (yield 81% based on the charged amount).

Claims (2)

[Claims] 1. A repeating unit represented by formula (1) and a formula:
A repeating unit represented by (2), (1) /
(2) = 1/100 to 1/10 and the number average molecule
Polyethylene characterized in that the amount is 5,000 or more
Grafted poly having a imine derivative as a graft chain
Mar. [Chemical 1](In the formula, R¹Is H or CH₃, R²Is H or (substituted) alk
Group or aryl group, R³ Is a (substituted) alkyl group, X is
O or NR_Four, R^FourIs H or an alkyl group or an aryl group,
n represents an integer of 5 to 100. ) [Chemical 2](In the formula, R^FiveIs H or a (substituted) alkyl group, R⁶Is (place
A) aryl group, alkoxycarbonyl group, (substituted)
Represents a luvamoyl group or a nitrile group. ) 2. The polyethyleneimine derivative chain according to claim 1, wherein an acrylic macromonomer having a polyethyleneimine derivative chain represented by the formula (3) is copolymerized with a radically or anionically polymerizable monomer. Graft polymer having a graft chain A method for producing a graft polymer. [Chemical 3] (In the formula, R ¹ is H or CH ₃ , R ² is H or a (substituted) alkyl group or a (substituted) aryl group, R ³ is a (substituted) alkyl group, X is O or NR ₄ , R ⁴ is H or (Alkyl group or aryl group, n represents an integer of 5 to 100.)