JPH0822917B2 - Poly (N-acylethyleneimine) -based random copolymer and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel random copolymer, specifically poly (N).
-Acylethyleneimine) random copolymer and a surfactant comprising the same.

[Conventional technology]

Conventionally, for example, 2-methyl-2-oxazoline, 2-
The method of performing ring-opening isomerization cationic homopolymerization of 2-substituted-2-oxazoline such as phenyl-2-oxazoline is described in, for example, Polymer Journal, 4 , 87 (1973), Journal of Polymer Science, B, 5 , 871 (196
7), Journal of Polymer Science, A-1,
4, are known and described in 2253 (1966) references the like.

In addition, a polymer having hydrophilicity in the main chain of the copolymer (N
-Formylethyleneimine) or poly (N-lower acylethyleneimine) block and lipophilic poly (N)
- acylethyleneimine) binary block copolymer having the combined block, 2-ethyl-2-oxazoline and 2-undecyl-2-oxazoline block copolymer in Adobansesu-in Chemistry Series, 142 , 320 in the literature (1975), further Saegusa et al Sho 59-230027 discloses and Macromolecules Cul's, 19, 535
(1986) and other publicly known documents.

[Problems to be Solved by the Invention]

Generally, as a high molecular compound having a surface-active property, as represented by a block polymer composed of a polyoxyethylene block and a polyoxypropylene block, unless the hydrophilic part and the lipophilic part are clearly divided into blocks, it is effective. It has been said that it has no surface activity. Regarding the oxazoline copolymer, it has only been found that the block copolymer has surface-active ability.

[Means for solving the problem]

Under the circumstances, the inventors of the present invention have conducted diligent research, and as a result, a random copolymer formed by combining a specific oxazoline monomer was found to have an interface even though the hydrophilic part and the hydrophobic part were not clearly divided into blocks. The present invention was completed by discovering that it has excellent activity.

That is, the present invention has the formula (I) (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) 2-oxazoline monomer represented by 5 to 95% by weight,
And formula (II) (In the formula, R ₂ represents an alkyl group having 6 to 22 carbon atoms, an aralkyl group or an aryl group.) A formula obtained by simultaneously ring-opening cationic polymerization of 5 to 95% by weight of a 2-oxazoline-based monomer represented by Repeating unit represented by III) and repeating unit represented by formula (IV) (Wherein R ₁ and R ₂ have the same meanings as described above), and a poly (N-acylethyleneimine) random copolymer having a molecular weight of 500 to 50,000 and a surfactant comprising the same. Is.

 The present invention will be described in detail below.

In the present invention, as the monomer capable of forming the repeating unit represented by the above formula (III), that is, the monomer represented by the formula (I), 2-oxazoline, 2-methyl-2-
Oxazoline, 2-ethyl-2-oxazoline, 2-n
-Propyl-2-oxazoline, 2-isopropyl-2
-Oxazoline and the like can be mentioned, and these can be used alone or in combination of two or more. These compounds are, for example, Liebigs Ann. Chem., P996 to p1009 (1974).
It can be made by the method described in. The above formula (II
When the number of carbon atoms of R _{1 in} the repeating unit represented by I) is 4 or more, the hydrophilicity of the side chain caused by this disappears, which is not preferable as a hydrophilic repeating unit. Among the above compounds, particularly preferred is 2-methyl-
2-oxazoline and 2-ethyl-2-oxazoline.

In the present invention, as the monomer capable of forming the repeating unit represented by the formula (IV), that is, the monomer represented by the formula (II), 2-hexyl-2-oxazoline, 2-
Heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-undecyl-2-oxazoline, 2-dodecyl-2-oxazoline, 2-tridecyl- 2-oxazoline, 2-tetradecyl-2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2-heptadecyl-2-
Oxazoline, 2-octadecyl-2-oxazoline,
2-nonadecyl-2-oxazoline, 2-eicosyl-
2-oxazoline, 2-heneicosyl-2-oxazoline, 2-docosyl-2-oxazoline, 2-benzyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-naphthyl-2-oxazoline, 2-anthryl-2- Examples include oxazoline, 2-pyrenyl-2-oxazoline, 2-perylenyl-2-oxazoline and the like. These may be used alone or in combination of two or more. Of these, R ₂ is preferably an alkyl group having 6 to 12 carbon atoms or a phenyl group. These compounds are described, for example, in Liebigs Ann. Chem., P996 to p1009 (197
It can be made by the method described in 4). The above formula (I
When R ₂ in the repeating unit represented by V) is an alkyl group, the number of carbon atoms is 5 or less and the lipophilicity of the resulting side chain is insufficient, and the characteristics of the random copolymer intended in the present invention are It is not preferable because it disappears.

The above-mentioned two groups of monomers, that is, the use ratio of the monomer represented by the formula (I) and the monomer represented by the formula (II) is in the range of 5 to 95% by weight, respectively, and is appropriately selected depending on the use. You can choose.

The random copolymer of the present invention has a hydrophilic monomer unit and a lipophilic monomer unit in the molecule and is useful as a surfactant, but the hydrophilic monomer unit has a relatively large content of 50 to 95% by weight. Are particularly suitable for use in aqueous media, while the lipophilic monomer units are relatively high in 50-
95% by weight is suitable for use in an oily medium or as a plastic additive.

Examples of the method for producing the random copolymer having the repeating unit represented by the above formula (III) and the repeating unit represented by the above formula (IV) in the present invention include a bulk polymerization method and a solution polymerization method. In the case of the solution polymerization method, examples of the solvent used include acetonitrile, dimethylformamide, chloroform, benzonitrile, methylene chloride, ethylene chloride and the like. Although the amount of the solvent used is not limited, it is preferably 20 parts by weight to 2000 parts by weight with respect to 100 parts by weight of all charged monomers.

As the polymerization initiator for forming the poly (N-acylethyleneimine) -based random copolymer of the present invention, a sulfuric acid ester, a sulfonic acid ester, an alkyl halide, a Lewis acid, a protic acid or the like can be used. , Dimethylsulfate, diethylsulfate, methyl p-toluenesulfonate (methyl tosylate), ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, methyl iodide, ethyl iodide, iodide Propyl, butyl iodide, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, methyl chloride, ethyl chloride, propyl chloride, butyl chloride, boron trifluoride, titanium tetrachloride, antimony pentafluoride, trifluoromethane Examples include sulfonic acid. The amount of the initiator used is determined by the molecular weight of the intended random copolymer, but it is generally used in the range of 0.1 to 25 mol% based on the monomer.

The poly (N-acylethyleneimine) -based random copolymer of the present invention is obtained by simultaneously polymerizing the monomer represented by the formula (I) and the monomer represented by the formula (II). For example, in the case of solution polymerization, a dehydrated and nitrogen-substituted polymerization vessel is charged with a dehydrated and purified solvent and an initiator and preferably maintained at 40 to 150 ° C., and the dehydrated and purified monomer represented by the formula (I) and A mixed solution of the monomer represented by the formula (II) is charged all at once or simultaneously while dropping, and the polymerization temperature is kept at 40 ° C or higher and 150 ° C or lower. The polymerization is usually carried out for 1 to 40 hours. The reaction time varies depending on the temperature, the amount of the polymerization initiator used, and the amount of the solvent used.

The production method as described above has an advantage that the polymerization reaction is carried out in one step, the operation is simple, and the polymerization rate is high, as compared with the production method of the block copolymer described in JP-A-59-230027. And is extremely preferable in terms of production efficiency.

After the polymerization, the copolymer can be isolated from the solution of the random copolymer thus obtained by a known method such as reprecipitation or solvent distillation. Unreacted monomers can be removed from the obtained copolymer by a known method such as re-precipitation, membrane separation, chromatographic method, or extraction method.

The molecular weight of the random copolymer thus obtained is 500 or more and 50,000 or less, and more preferably 1,000 or more and 10,000 or less for use as a surfactant.

The random copolymer of the present invention is also characterized in that it is easier to obtain a polymer having a higher molecular weight than the block copolymer described in JP-A-59-230027.

The random copolymer of the present invention is a white or pale yellow solid or a colorless or pale yellow viscous liquid, and has a repeating unit having a hydrophilic formamide structure or a lower acylamide structure in the polymer main chain and a lipophilic compound. And a repeating unit having an acylamide structure.

The novel random copolymer of the present invention is useful as a nonionic surfactant, and various detergents, emulsifiers, solubilizers, general-purpose polymer modifiers such as antistatic agents, antifogging agents,
There are applications such as compatibilizers.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 A 5-liter four-necked flask equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer was replaced with dry nitrogen, and then 1000 ml of acetonitrile and 93.10 g (0.500 mol) of methyl tosylate were charged. Stirring was started and the temperature of the system was raised in an oil bath. Under reflux, 876.5 g of 2-methyl-2-oxazoline (1
0.3 mol), and 2-heptyl-2-oxazoline 375 g
A mixture of (2.22 mol) was added dropwise over 3 hours and refluxed for 24 hours to carry out polymerization. After cooling, reprecipitation was performed with 20 liters of isopropyl ether, and after filtration, the polymer was vacuum dried at 80 ° C. for 48 hours. The composition ratio of the random copolymer was measured by a proton NMR device (solvent, deuterated chloroform), and the molecular weight was measured by a vapor pressure osmometer (solvent chloroform).

 Table 1 shows the results.

Example 2 119.2 g (0.64 mol) of methyl tosylate as an initiator for polymerization, 900 ml of acetonitrile as a solvent, and 960 g (11.3 mol) of 2-methyl-2-oxazoline as a monomer and 2
A mixture of 640 g (3.78 mol) of heptyl-2-oxazoline was used as a reaction reagent, polymerization was carried out under the same reaction apparatus and reaction conditions as in Example 1, and purification was carried out under the same conditions. Example 1
The composition ratio and molecular weight of the random copolymer were measured in the same manner as in.

 Table 1 shows the results.

Example 3 92.56 g (0.50 mol) of methyl tosylate as an initiator of polymerization, 600 ml of acetonitrile as a solvent, 870.0 g (8.78 mol) of 2-ethyl-2-oxazoline as a monomer and 373.2 g (1.66 of 2-undecyl-2-oxazoline). Mol)
As a reaction reagent, the same reaction apparatus as in Example 1,
Polymerization was performed under the reaction conditions, and purification was performed under the same conditions. The composition ratio and molecular weight of the random copolymer were measured in the same manner as in Example 1.

 Table 1 shows the results.

Example 4 186.2 g (1.00 mol) of methyl tosylate as an initiator for polymerization, 900 ml of acetonitrile as a solvent, 500.0 g (5.05 mol) of 2-ethyl-2-oxazoline as a monomer and 500.0 g (3.40) of 2-phenyl-2-oxazoline. Mol) was used as the reaction reagent, polymerization was carried out under the same reaction equipment and reaction conditions as in Example 1, and purification was carried out under the same conditions. The composition ratio and molecular weight of the random copolymer were measured in the same manner as in Example 1.

 Table 1 shows the results.

Comparative Example 1 186.2 g of methyl tosylate in the same reactor as in Example 1
(1.0 mol), 2-ethyl-2-oxazoline 2000.0 g
(20.18 mol) and 2000 ml of acetonitrile were used as reaction reagents to synthesize a homopolymer under the same reaction conditions as in Example 1. After that, reprecipitation was performed with 10 l of isopropyl ether, and the polymer was vacuum dried at 80 ° C. for 48 hours. The molecular weight of the homopolymer was measured by the same method as in Example 1.

 Table 1 shows the results.

Example 5, Comparative Example 2 The random copolymers obtained in Examples 1 to 4 were used as 1% aqueous solutions, and the 1% aqueous solution of the ethyloxazoline homopolymer obtained in Comparative Example 1, a 1% aqueous sodium laurate solution, and polyoxyethylene. Using a 1% (30 mol) lauryl ether aqueous solution as a control, water solubility (cloud point), surface tension, foaming property (fast foaming property, foam stability), and solubilizing ability were evaluated. The results are shown in Table 2.

Claims (2)

[Claims] 1. A formula (I) (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) 2-oxazoline monomer represented by 5 to 95% by weight,
And formula (II) (In the formula, R ₂ represents an alkyl group having 6 to 22 carbon atoms, an aralkyl group or an aryl group.) A formula obtained by simultaneously ring-opening cationic polymerization of 5 to 95% by weight of a 2-oxazoline-based monomer represented by Repeating unit represented by III) and repeating unit represented by formula (IV) (Wherein R ₁ and R ₂ have the same meaning as described above), and a poly (N-acylethyleneimine) -based random copolymer having a molecular weight of 500 to 50,000. 2. A surfactant comprising the poly (N-acylethyleneimine) random copolymer according to claim 1.