JPS60229926A - Novel polymer and preparation and use thereof - Google Patents

Abstract

PURPOSE:To obtain a water-soluble poly(N-lower acylethyleneimine) polymer having improved surface activity, by carrying out cationic ring opening polymerization of a 2-oxazoline based compound in the presence of a 1:1 reaction product of the specific 2-oxazoline based compound and a cationic polymerization catalyst as a polymerization initiator. CONSTITUTION:The cationic ring opening polymerization of a 2-oxazoline based compound expressed by formula II (R3 is H or 1-3C alkyl) is carried out in the presence of a 1:1 reaction product of a compound expressed by formula I (R2 is 7-30C alkyl or aralkyl, etc.), e.g. 2-heptyl-2-oxazoline, and a cationic polymerization catalyst, e.g. sulfuric ester or sulfonic ester, as a polymerization initiator to give the aimed poly(N-lower acylethyleneimine) polymer, expressed by formula III (R1 and R3 are H or 1-3C alkyl; R2 is as described above, preferably 7- 18C alkyl; n is 2-300, preferably 3-50; X is terminal group), and having one N- higher acylethyleneimine bonded to the molecular ends.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new polymer, particularly a poly(lower acylethyleneimine) polymer, more specifically a water-soluble poly(N- (lower acyl ethyleneimine) polymer, its production method, and a novel surfactant made from it.

Conventionally, 2-
Methods for carrying out ring-opening cationic polymerization of substituted-2-oxazolines are described, for example, in J.

Macromol, Sci, Chem, 19
71, 5, 12'17.

J, Macromol, Sci, Chem,
1972,. 6, 1681゜Acta Poly
It is well known and is described in the literature such as J. M., 1980, 81142. Furthermore, surfactants having the structure (5), (6) or (7) below having a long-chain alkyl group at the end of the molecule are described in the document of )jPSP 4261925 and are well known.

R2-C=0 1 R8-〇 [In the formula, R1 represents a non-polymerizable hydrocarbyl group having 8 or more carbon atoms, R2 represents hydrogen or an alkyl group, and X
represents an inorganic or organic group at the terminal, and m represents 2 or more. imine) polymers are unknown.

As a result of extensive studies, the present inventors have discovered a one-to-one reaction product of a 2-substituted-2-oxazoline having a long-chain alkyl group, an aralkyl group, or an aryl group and a cationic polymerization catalyst such as methyl p-toluenesulfonate. The following general formula (1) is used as a polymerization initiator and is produced by ring-opening cationic polymerization of 2-substituted-2-oxazoline having an unsubstituted or short-chain alkyl group.
The inventors have discovered that a poly(N-lower acylethyleneimine) polymer in which one N-higher acylethyleneimine is bonded to the end of the molecule represented by the formula is water-soluble and exhibits excellent surface activity, leading to the present invention. .

That is, the present invention provides a water-soluble poly-13 (N-lower acyl ethyleneimine) polymer in which one N-higher acyl ethyleneimine is bonded to the terminal of the molecule represented by the following general formula (1). R1 represents hydrogen or an alkyl group having 1 to B carbon atoms; R2 represents an alkyl group, aralkyl group, or aryl group having 7 to 80 carbon atoms; R3 represents hydrogen or an alkyl group having 1 to 8 carbon atoms; X represents a terminal group, and n is 2 or more and 800 or less.

The present invention also provides a method for producing a polymer represented by the above general formula (1). That is, the present invention relates to a 2-oxazoline compound represented by the general formula (wherein R2 represents an alkyl group, an aralkyl group, or an aryl group having 7 to 80 carbon atoms) and a sulfuric acid ester, a sulfonic acid ester, an alkyl halide, a Lewis A 2-oxazoline represented by the general formula (wherein R8 represents hydrogen or an alkyl group having 1 to B carbon atoms) using a one-to-one reaction product with a cationic polymerization catalyst such as an acid or a protonic acid as a polymerization initiator. The present invention provides a method for producing a molecular terminal polymer by carrying out cationic ring-opening polymerization of a system compound.

Further, the present invention provides a surfactant comprising a polymer represented by the above general formula (1).

The present invention will be explained in detail below.

In the present invention, a compound capable of producing an N-higher acyl ethyleneimine bonded to the terminal of a molecule, that is, a component of the polymerization initiator used in the method of the present invention, is the general formula (2
) is a 2-oxazoline compound represented by 2
-hebutyl-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-titradecyl-2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2-heptadecyl-2
-oxazoline, 2-octadecyl-2-oxazoline, 2-butylbenzyl-2-oxazoline, 2-octylbenzyl-2-oxazoline, 2-dodecylbenzyl-2-oxazoline, and the like. These compounds can be made in a variety of ways, for example Liebigs An
n, Chem.

, P, 996-P, 1006 (1974/), the well water property of the end of Keyaki Kiurako is reduced, which is undesirable because the surface activity of the polymer is reduced.

The cationic polymerization catalyst, which is one component constituting the polymerization initiator used in the method of the present invention, has an ester group with a carbon number of 8.
The following sulfuric acid esters, sulfonic acid esters, alkyl halides in which the alkyl group has 8 or less carbon atoms, Lewis acids, protonic acids, etc. can be used. Specifically, methyl sulfate,
Methyl p-toluenesulfonate, ethyl p'-toluenesulfonate, propyl p-toluenesulfonate, methyl iodide, ethyl iodide, propyl iodide, methyl bromination, ethyl bromination, propyl bromination, methyl chloride,
Ethyl chloride, propyl chloride, boron trifluoride, titanium tetrachloride, antimony pentafluoride, trifluoromethanesulfonic acid, etc. can be used, but methyl p-toluenesulfonate is preferably used from the viewpoint of polymerization rate. When using a sulfuric acid ester or sulfonic acid ester whose ester group has 4 or more carbon atoms or a halogenated alkyl whose alkyl group has 4 or more carbon atoms, the cationic polymerization catalyst and the general formula (
2) The reaction rate of the 2-oxazoline compound represented by formula (2) becomes slower, and the reaction rate between the resulting one-to-one reaction product and the 2-oxazoline compound represented by general formula (2) becomes relatively faster. General formula (2) for cationic polymerization catalyst
A compound in which two or more 2-oxazoline compounds represented by the formula (2) are bonded is formed, making it difficult to obtain a one-to-one reaction product of the desired cationic polymerization catalyst and the 2-oxazoline compound represented by the general formula (2). Unfavorable to become.

The polymerization initiator used in the method of the present invention may be synthesized by reacting a cationic polymerization catalyst with a 2-oxazoline compound represented by general formula (2) without using a solvent, or by reacting with diethyl ether, acetonitrile, benzene, etc. The reaction may be carried out in an aprotic solvent such as nitrile. Reaction temperature is 80°
C~150'G! is preferred. After forming the 2-oxazoline compound represented by the general formula (2), the cationic polymerization catalyst is prepared by reprecipitating the reaction solution in diethyl ether to obtain a reaction product, then dissolving it in, for example, acetonitrile and re-precipitating it in diethyl ether. The reaction product is purified by repeating the precipitation operation to remove unreacted cationic polymerization catalyst and unreacted 2-oxoline compound added in excess.

In the present invention, monomers for producing poly(N-lower acylethyleneimine) represented by general formula (1), that is, monomers represented by general formula (3), include 2-oxazoline, 2-methyl-2-oxazoline, 2- Ethyl
Examples include 2-oxazoline, 2-n-propyl-2-oxazoline, and 2-ituprovir-2-oxazoline. These compounds can be made in a variety of ways, for example Liebigs Ann, Chem, P, 996-
P., 1006 (1974). When the number of carbon atoms in R8 in the above formula is 4 or more, the hydrophilicity of the side chain resulting from this decreases, so the surface activity of the polymer decreases, and the solubility of the polymer in water also decreases significantly, Undesirable.

Examples of the method for producing the polymer represented by the general formula (1) in the present invention include a bulk polymerization method and a solution polymerization method. In the case of the solution polymerization method, acetonitrile, benzonitrile, dimethylformamide, chloroform, etc. can be used as the solvent. The amount of solvent used is not particularly limited, but the amount of monomer charged is 100
It is preferable to use 20 to 2000 parts by weight.

In the present invention, the polymerization initiator for producing the polymer represented by the general formula (1), that is, the 2-oxazoline compound represented by the general formula (2), and the cationic polymerization catalyst in a ratio of 1:1.
The reaction product is used in an amount of 0.3 to 60 mol % based on the monomers charged.

The polymerization temperature and polymerization time are appropriately selected depending on the polymerization initiator, the type of monomer, or the type of solvent used.
Generally, at a polymerization temperature of 80°C or higher and 150″C or lower,
It is preferred to polymerize for 5 to 40 hours.

After completion of the polymerization, it is preferable to reprecipitate by injecting into a non-solvent such as the solvent in the reaction mixture or unreacted water, methanol, ethanol, hexane, diethyl ether, or a mixture thereof. 3 or more 50
If n is 2 or less, the balance between hydrophilicity and lipophilicity will be lost, resulting in a decrease in surface activity, and the solubility in water will also decrease, so it is preferable that n is 300.
If it exceeds the above range, the hydrophilicity becomes too strong, and the balance between hydrophilicity and lipophilicity is lost, resulting in a decrease in surface activity, making the mold undesirable.

In the present invention, Rr and X in general formula (1) are determined depending on the polymerization used and the type of cationic polymerization catalyst that is one of the components constituting the initiator.

Examples of R1 include hydrogen, methyl group, ethyl group, n-brobyl group, and isopropyl group.

can be mentioned. Here, A- is an anion derived from the negative atomic group of the polymerization initiator.

The polymer of the present invention is a white or slightly yellow waxy resin or solid resin, with one lipophilic higher acyl ethyleneimine bonded to the molecular end, and the remainder being hydrophilic poly-13 (N-lower acyl ethylene imine). It has the structure of

Since the block copolymer of the present invention has high surface activity and is easily soluble in water, it can be used as an O/W emulsifier, dispersant, and detergent.

The present invention will be explained in detail in Examples below.

Deuterated chloroform solvent was used to determine the composition of the polymerization initiator used in all Examples and Comparative Examples and the polymer in all Examples and Comparative Examples.
R20B Proton nmr equipment N (Newly manufactured by Hitachi 60MH
/:, ) was used to determine. The molecular weight of the polymer is C0R
RONA 117 Vapor Pressure Osmometer (manufactured by Corona)
It was determined by measuring at 40°C using chloroform as a solvent.

The molecular weight distribution of the polymer is determined by J A S COTRIROTO
R (manufactured by JEOL Co., Ltd.) was used as a 5ho column.
It was determined by gel permeation chromatography using dex Asog (manufactured by Showa Denko) and chloroform as a solvent at a solvent flow rate of 1 to 7 minutes.

Regarding the surface activity of the polymers in all Examples and Comparative Examples, each polymer was dissolved in distilled water to prepare a 1% by weight aqueous solution, and the surface tension of the aqueous solution was measured one day after the preparation using a denuis surface tension meter. Measured and judged. Measurement temperature is 20°
It is C.

In addition, regarding the solubility of the polymer in water in all Examples and Comparative Examples: Preparation 1 of the above 1% by weight aqueous solution
The solubility after 1 day was visually determined.

Example 1 After keeping a glass ampoule under a vacuum of 1 m+Hg for 30 minutes, the air was replaced with nitrogen gas, and diethyl ether 8.0-12-n-octyl-2-oxazoline 0.92 N ( 5.0 mmol). After cooling the glass ampoule in an ice-water bath, 1.871% of methyl p-toluenesulfonate was added under a nitrogen gas stream. (7'5 mm 1 lmol) was fully prepared. After melt-sealing the glass ampoule under a nitrogen gas flow, it was immersed in an oil bath adjusted to 80'C in advance, reacted for 2 hours, and then cooled to room temperature. Open the glass ampoule, drop the reaction solution into 4 o cc of diethyl ether under a nitrogen gas stream, and reconstitute the white powdery polymerization initiator N-methyl-2-n-octyl-2-oxazolinium tosylate. precipitated. After passing this offshore under a nitrogen gas stream,
Wash three times with 10 d each of diethyl ether, and then 1.
The solution was dissolved in 5-g of acetonitrile, reprecipitated again in 40-d of diethyl ether, and after filtration with 10-g of diethyl ether.
Washing was repeated three times to remove unreacted methyl p-toluenesulfonate and unreacted 2-n-octyl-2-oxazoline. Thereafter, diethyl ether was evaporated under reduced pressure and the mixture was thoroughly dried.

After keeping a separate glass ampoule at Jll [1 mHg] for 80 minutes, substitution was carried out with nitrogen gas, and under a nitrogen gas flow, 5.0 M of acetonitrile was used as the polymerization solvent, and 0.81 M of 2-methyl-2-oxazoline was used as the monomer. 10.0 mmol). After cooling the glass ampoule in an ice-water bath, 0.87 f (LO + 1 mol) of N-methyl-2-n-octyl-2-oxazolinium tosylate (A) produced by the above method was added as a polymerization initiator under a nitrogen gas stream. ) was prepared. Under a stream of nitrogen gas, the glass ampoule was melt-sealed and immersed in an oil bath previously adjusted to 80°C, polymerization was carried out for 20 hours, and the ampoule was cooled to room temperature.

After the polymerization was completed, the reaction solution was dropped into 80 W of diethyl ether to reprecipitate a white powdery polymer. After washing the 1o-diethyl ether polymer, the resulting polymer was
Vacuum drying (degree of vacuum: 5 mHg) was performed for 48 hours at 'C. The polymerization conditions shown in Table 1 G9 show the synthesis results of the polymerization initiator,
Table 2 shows the polymerization results, the determined polymer structure, the surface activity of the polymer, and the solubility of the polymer in water.

Table 2 shows that the polymer obtained by the method of Example 1 is soluble in water and exhibits excellent surface activity.

The polymerization initiator (B ) or (D), the same polymerization method as in Example 1, the polymer processing power method, was carried out.

Table 1 shows the synthesis results of the polymerization initiator, and Table 2 shows the polymerization results and physical property evaluation results. As shown in Table 2, it dissolves well, but its surface activity is poor. On the other hand, the polymer obtained by the method of Example 2 is soluble in water and exhibits excellent surface activity.

Example 8 A method for synthesizing a polymerization initiator was carried out in the same manner as in Example 1, except that the type of 2-oxazoline constituting one component of the polymerization initiator was changed as shown in Table 1. Using the obtained polymerization initiator (C), the same polymerization method and polymer treatment method as in Example 1 were carried out except that the type of monomer was changed as shown in Table 2. Table 1 shows the synthesis method of the polymerization initiator.
The polymerization results and physical property evaluation results are shown in Table 2. From the results shown in Table 2, the polymer obtained by the method of Example 8 is soluble in water and exhibits excellent surface activity.

Example 4 and Comparative Example 2 Using the polymerization initiator (D) obtained by the method of Example 2, the same polymerization method and polymer treatment method as in Example 1 are shown below, except that the type of monomer is changed. From the results shown in Table 2, the polymer obtained by the method of Example 4 is soluble in water and exhibits excellent surface activity. On the other hand, the polymer obtained by the method of Comparative Example 2 was insoluble in water, making it impossible to measure its surface activity.

Examples 5 to 7 Using the polymerization initiator (A) obtained by the method of Example 1, the same polymerization method and polymer treatment method as in Example 1 were performed except for changing the amount of polymerization initiator charged. Ta. The polymerization results and physical property evaluation results are shown in Table 2. The polymers obtained by the methods of Example 5, Example 6 and Example 7 were all dissolved in water,
Shows excellent surface activity.

Comparative Example B The same method for synthesizing a polymerization initiator as in Example 1 was carried out except that the type of cationic polymerization catalyst constituting one component of the polymerization initiator was changed. The obtained polymerization initiator E has protons n, m
, r, From the results of molecular weight measurements, it was found that it has the structure of the following formula. It is impossible to synthesize the polymer represented by general formula (1) from this polymerization initiator E.

As mentioned above, it is clear from Examples 1 to 7 and Comparative Examples 1 to a that it is suitable for use as a powder.

Claims (1)

[Scope of Claims] 1) In the following general formula C, R1 represents hydrogen or an alkyl group having 1 to B carbon atoms, and R2 represents an aralkyl group, an aralkyl group, or an aryl group having 7 to 30 carbon atoms. R8 represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is 2 or more and 3
00 or less, and X represents a terminal group. ] A water-soluble poly(N-lower acylethyleneimine) polymer in which one N-higher acylethyleneimine is bonded to the terminal of the molecule represented by: 2) The polymer according to claim 1, wherein R2 is an alkyl group having 7 to 18 carbon atoms. 8) The polymer according to claim 1, wherein R1 is a methyl group, R2 is an n-octyl group, and R8 is a methyl group. 4) The polymer according to claim 1, wherein R1 is a methyl group, R2 is an n-undecyl group, and R8 is an ethyl group. 5) The polymer according to claim 1, wherein R1 is a methyl group, R2 is an n-dodecyl group, and Ra is an n-propyl group. 6) The polymer according to claim 1, wherein n is 8 to 50. 7) A 2-oxazoline compound represented by the general formula (in the formula, R2 represents an alkyl group, an aralkyl group, or an aryl group having 7 to 80 carbon atoms) and a sulfuric acid ester, a sulfonic acid ester, an alkyl halide, a Lewis acid, or A one-to-one reaction product with a cationic polymerization catalyst such as protonic acid is used as a polymerization initiator, and the general formula (wherein R8 represents hydrogen or an alkyl group having 1 to 8 carbon atoms) [wherein R1 is hydrogen or carbon represents an alkyl group having 1 to 8 carbon atoms, R2 represents an alkyl group, aralkyl group, or aryl group having 7 to 80 carbon atoms, R8 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and n represents 2 to 800
In the following, X represents a terminal group. ] A method for producing a water-soluble polyCN-lower acylethyleneimine polymer in which one N-higher acylethyleneimine is bonded to the end of the molecule represented by 8) The polymerization initiator is N represented by the general formula (wherein R1 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R2 represents an aralkyl group or an aryl group having 7 to 80 carbon atoms) -Lower alkyl-2-higher alkylguoxazinonium tosylate A method for producing the polymer according to claim 7. 9) A method for producing a polymer according to claim far, wherein R2 is an alkyl group having 7 to 18 carbon atoms. 10) A method for producing a polymer according to JP-A No. 7, wherein the polymerization initiator is N-methyl-2-octyl-oxazinonium tosylate. 11) The polymerization initiator is N-methyl-2-n-undecyl-
A method for producing the polymer according to claim 7, which is xacillinium tresylate. 12) Process for producing a polymer according to claim 7, wherein the polymerization initiator is N-methyl-Qn-dodecyl-oxazolinium tosylate 71g) General formula [wherein R1 is hydrogen or a carbon number of 1 to 8] represents an alkyl group, R2 represents an alkyl group, aralkyl group, or aryl group having 7 or more carbon atoms under B0At, R8 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and n represents 2 or more and 8
00 or less, and X represents a terminal group] A surfactant consisting of a water-soluble poly(N-lower acylethyleneimine) polymer in which one N-higher acylethyleneimine is bonded to the end of the molecule represented by .