JPH01236240A - Novel polymer compound - Google Patents

Abstract

PURPOSE:To obtain a polymer compound having both an oleophilic group and a hydrophilic group, by introducing a beta-hydroxylalkyl group and a carboxyalkyl group into a polyethyleneimine molecule and treating it with an acid or an alkali. CONSTITUTION:The hydrogen atoms. bonded to the nitrogen atoms. of polyethyleneimine of formula I (wherein p is 5-2350) are replaced by beta- hydroxyalkyl groups and carboxyalkyl groups to obtain a compound having these two kinds of groups, and this compound is treated with an acid or an alkali to obtain a polymer compound having repeating units each represented by formula II (wherein X is a group selected from among those of formulas III, IV, V, VI and VII, M is any one of H, Na, K, Li, Ca and Mg (the last two are present in an amount corresponding to their valences), R1 is a 10-16C alkyl, l is 1-2330, m is 0 or 1-1400, n is 1-1880, and l+m+n=5-2350). By virtue of the amphoteric surface activity of this compound, it is useful as an agent in various fields, for example, as a paper strengthening agent or a paper quality improver in the paper industry, as a dyeability improver and shrink-proofing agent in the fiber industry or for cosmetic compositions, detergent compositions, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel polymer compound.

More specifically, the polymer compound of the present invention is a novel compound having amphoteric surface activity obtained by introducing a β-hydroxyalkyl group and a carboxyalkyl group into the nitrogen atom of polyethyleneimine and treating it with acid or alkali. It is a high-molecular compound that utilizes its amphoteric surface activity to be used in various industries, such as filter paper strengtheners and paper quality improvers in the paper industry, adhesion promoters in the adhesive industry, and dyeability of various fibers in the textile industry. A useful polymer compound that exhibits extremely excellent performance as a conditioner, anti-shrink agent, flame retardant, antistatic agent, etc., as well as in cosmetic compositions, cleaning compositions, lubricating oil additives, rust preventive agents, anti-fogging agents, etc. It is.

[Conventional technology and problems]

As an amphoteric polymer using polyethyleneimine as a starting material, poly-(
N-propionic acid)-ethyleneimine, poly-(N-methylenesuccinic acid)-ethyleneimine, poly-(N-succinic acid)-ethyleneimine, poly-(N-methyleneglutaric acid)-ethyleneimine, poly-( N-tricarballylic acid)-ethyleneimine, etc., Journal of the American Chemist Society Vol. 77, No. 47
43 pages (1955) and Special Publication No. 48-20203,
Furthermore, regarding polymers having dithiocarbamate groups obtained by reacting polyethyleneimine, sodium hydroxide, and carbon disulfide, etc., Wangka Journal Vol. 69, p. 716 (19
There was a report in 1966).

Applications of these amphoteric polymer compounds include applications in cleaning agents, bleaching agents, etc. according to Japanese Patent Publication No. 48-20203;
Application to adhesion promoters by Japanese Patent Publication No. 48-3644, cosmetic compositions by Japanese Patent Publication No. 54-23135, etc. The structural formulas of these compounds are characterized by a high content ratio of tin and carboxylic acid. Therefore, it has high hydrophilicity and is highly stable as an aqueous solution, but since it does not contain a lipophilic group, it can only be used within a limited range in terms of performance or application.

[Means for solving problems]

The present inventors focused on these problems and conducted intensive research, and as a result, by introducing a β-hydroxyalkyl group and a carboxyalkyl group into the polyethyleneimine molecule, it imparts lipophilicity and carboxyl groups. or its salt (
It has been discovered that by changing the balance between hydrophilicity and lipophilicity, the properties can be broadened and applied to a wide range of applications.

That is, the polymer compound of the present invention is a novel polymer compound having a repeating unit represented by the following general formula.

In the above formula, X is -CH2CHIC00M%CL
CH.

CHz CHCooM, -CHC) 12cOO month,
CHzCHC00MC00M -C) One type selected from the group consisting of ICOO group ClhCOOM, where M is hydrogen atom, sodium atom, potassium atom, lithium atom, calcium atom distributed according to valence, calcium atom distributed according to valence. Indicates any magnesium atom. Furthermore, R represents an alkyl group having 10 to 16 carbon atoms. , m, n
are respectively 1-2330.0 or 1-1400.1-188
Indicates an integer of 0, and the sum of β, m, and n is 5 to 2350
It is.

The polymer compound of the present invention is a polyethyleneimine represented by the following formula (II) (where p
indicates 5 to 2350. ) is used as a starting material, the hydrogen bonded to the nitrogen of this polyethyleneimine is substituted with a β-hydroxyalkyl group and a carboxyalkyl group, and these two types of substituents are simultaneously present in the same molecule. It is obtained by treatment with an alkali, and the β-hydroxyalkyl group is an epoxyalkane CH3+CH, ±9GHz GHz (II[
)\. / (where q is an integer of 9 to 15) is introduced by addition reaction to the chlorine atom of polyethyleneimine, and the carboxyalkyl group is an ethylenically unsaturated monomer having a carboxylic acid ester bond or a nitrile group in the molecule. The polymer is introduced by subjecting it to a Michael addition reaction on the tin atom of polyethyleneimine, followed by treatment with acid or alkali.

To describe the method for producing the polymer compound of the present invention, first, polyethyleneimine and epoxy alkane are mixed at 50 to 1
The reaction is carried out at 50° C. for 1 to 30 hours to carry out an addition reaction, and this reaction is carried out either by mixing the above raw materials as they are or in an organic solvent. The molecular weight of polyethyleneimine is 200 to 20.
000, the reaction can be carried out without a solvent, but when the molecular weight is 20,000 or more, the viscosity is high, so it is preferable to carry out the reaction in a solvent in order to carry out the reaction smoothly. Then the poly-N-β- obtained above
The Michael addition reaction of an ethylenically unsaturated monomer to hydroxyalkyl polyethylene is completed by carrying out the reaction at 50 to 150° C. for 1 to 20 hours without or in a solvent. Regarding the solvent used in the Michael addition reaction, when a solvent is used in the first stage reaction, the second stage reaction is generally carried out using that solvent. Furthermore, the saponification reaction to be carried out next is carried out at a rate of 1.
The treatment is carried out with 0 to 1.2 times the mole of acid or alkali at 90 to 120°C for 1 hour or more. This reaction is also carried out without or in a solvent. When a solvent is used in this reaction, the solvent is
The solvent used in the first and second stage reactions can be used in common.

In the above reaction, the reaction ratio of epoxy alkane and ethylenically unsaturated monomer to polyethyleneimine is 1 mole of epoxy alkane to 8 moles of Pxo and 1 mole of ethylenically unsaturated monomer to 1 mole of polyethyleneimine. PXo is preferably 99 mol, and the compound obtained by reacting within this range has a good balance between hydrophilicity and lipophilicity and exhibits amphoteric surfactant ability. The amount of epoxy alkane added to 1 mole of polyethyleneimine is 1
If the amount is less than molar, the resulting compound has no lipophilicity, and P
If X exceeds 0.8 mol, it becomes water-insoluble, which is not preferable.

If the amount of ethylenically unsaturated monomer added to 1 mole of polyethyleneimine is less than 1 mole, the resulting compound will not have hydrophilicity and will be difficult to dissolve in water, and if it exceeds 99 moles of PXo, the surface active ability will decrease. I don't like it.

The polyethyleneimine used in the present invention has an average molecular weight of 2
Values from 00 to 100.000 are used.

Epoxyalkanes having a total carbon number of 12 to 18 can be used alone or in combination.

If the molecular weight of the polyethyleneimine used is less than 200, a compound with a good hydrophilic-lipophilic balance cannot be obtained,
Moreover, if it exceeds 100,000, the viscosity becomes high and the addition reaction of the epoxy alkane and the ethylenically unsaturated monomer cannot be carried out uniformly, which is not preferable.

Further, examples of the solvent used in the present invention include benzene, toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, n-hexane, chloroform, and carbon tetrachloride, which may be used alone or in combination.

In addition, examples of the ethylenically unsaturated monomer used in the present invention include acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylonitrile, methacrylnitrile,
Examples include, but are not limited to, crotonic acid alkyl esters, itaconic acid alkyl esters, maleic acid alkyl esters, and fumaric acid alkyl esters. These may be used alone or in combination of two or more. The alkyl group used here preferably has 1 to 5 carbon atoms.

In addition, acids used in the present invention include sulfuric acid, hydrochloric acid, nitric acid, etc., and alkalis include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc. Alkali may be used alone or in combination.

The polymer compound of the present invention can be used as a paper reinforcing agent, a paper quality improver, a sizing agent, a retention improver for various fillers, pigments, dyes, etc. in the paper manufacturing industry, as an adhesion promoter in the adhesive industry, and as an adhesion promoter in the textile industry. It is extremely useful for improving the dyeability of various fibers, shrink-proofing, flame-retardant processing, antistatic processing, etc., and as a cosmetic composition, detergent composition, lubricating oil additive, rust preventive, and antifogging agent.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 To 150 parts of polyethyleneimine (average molecular weight 1070, average degree of polymerization approximately 25, nitrogen content 32.55%), 80 parts
~85°C While stirring under nitrogen flow, epoxyalkane having 16 total carbon atoms (oxirane oxygen content 6.67%)
627.9 parts were added dropwise over 1 hour, and then an aging reaction was carried out for 2 hours. Next, 75 parts of methyl acrylate was added dropwise to the mixture at 75 to 80° C. over 1 hour, followed by an aging reaction for 6 hours to obtain reaction product A1. This was dissolved in methanol and then poured into n-hexane to obtain a precipitate, which was filtered. The precipitate was again dissolved in methanol and then poured into n-hexane to obtain a precipitate, which was filtered. n
-Remove hexane to obtain purified reaction product A1 in 87% yield
I got it from

Purified reaction product A was dissolved in methanol, and 10
% hydrochloric acid was added and the reaction was carried out for 6 hours under reflux,
A white precipitate formed. After filtering this and washing it with acetone, add a mixture of ethanol and water (1:1) to dissolve it, and then pour it into acetone again to form a precipitate.
Filter. After washing with acetone, it was dried under reduced pressure at room temperature for 18 hours to obtain a white purified reaction product B. Elemental analysis and molecular weight measurements were performed on the purified reaction product B1, and the results are shown in Table 1. All elemental analysis values showed extremely good agreement with the theoretical values.

In addition, as a result of measuring the IR spectrum of the purified reaction products '4iA, , B, the reaction product A1 has a 3360 cm
-', 2980cm-', 2860cm-', 1735
Absorption was observed at C11-', 1575cm-', and 1180cm-', and the ethyleneimine chain contained a hydroxyl group,
Introduction of alkyl groups and ester groups was observed.

In addition, reaction product B1 has 3380cm-', 2980c
m-', 2860cm-', 1695eni-', 15
Strong absorption was observed at 75 cm-' and 1180 cm-', and the ester group of reaction product A was changed to a carboxyl group, and the accompanying hydroxyl group was characterized by even stronger absorption. It was observed that a compound was produced.

Table 1 Example 2 140 parts of polyethyleneimine (average molecular weight 20,500, average degree of polymerization 476, nitrogen content 32.55%),
1335 parts of epoxyalkane having a total carbon number of 12 (oxirane oxygen content 9.76%) and 129 parts of dimethyl itaconate
．． Using 4 parts, the reaction was carried out in the same manner as in Example 1, and the reaction product A! I got it. This was purified in the same manner as in Example 1 to obtain purified reaction product A2 with a yield of 93%. Purified reaction product A2 was dissolved in methanol, and 685 parts of 10% alcoholic caustic soda was added thereto for saponification to obtain a white precipitate, which was filtered and washed with acetone. Example 1
Similarly, reprecipitation was performed twice using an ethanol-water (1:1) mixture and acetone, followed by drying under reduced pressure to obtain a white purified reaction product B2 in a yield of 87%. Elemental analysis and molecular weight measurement were performed on the purified reaction product B2, and the results are shown in Table 2. All elemental analysis values showed extremely good agreement with the theoretical values.

Table 2 We also measured the Nikki IR spectra of purified reaction products A, B, and found that reaction product A2 had the same characteristic absorption as reaction product A, and reaction product B, 3380c11-', 2980c11-', 2860
ca+-', 1640cm-', 1575cm-', 1
Strong absorption was observed at 180c+a-', and reaction product A
2 was saponified and turned into a carboxylic acid salt, and as a result, stronger absorption was observed in the hydroxyl group, indicating that a metal salt-type polymer compound was being produced.

Example 3 To 100 parts of polyethyleneimine (average molecular weight 99800, average degree of polymerization 2320, nitrogen content 32.55%),
Add 500 parts of benzene, stir well to disperse polyethyleneimine, and add 4.9 parts of epoxyalkane having a total of 14 carbon atoms (oxirane oxygen content 7.55%).
was added dropwise over a period of 1° to refluxing benzene in a nitrogen gas stream, and then stirring and heating were continued for 5 hours to complete the reaction. Next, add 60 to 267.9 parts of butyl acrylate to this.
The mixture was added dropwise at 65°C over 1 hour, and the reaction was continued for 8 hours, after which benzene was removed to obtain reaction product A3. This was dissolved in methanol and poured into n-hexane to obtain a white precipitate, which was filtered. This is again subjected to precipitation and filtration using methanol and n-hexane, and this process is repeated twice in total.Finally, the solvent is removed under reduced pressure to obtain purified reaction product A3.
was obtained in a yield of 91%.

Purified reaction product A3 was dissolved in methanol, and 10
Add 921 parts of alcoholic caustic soda and add 921 parts of alcoholic caustic soda to
After a period of reaction, a white precipitate was obtained, which was filtered off and washed with acetone. This was reprecipitated twice using an ethanol-water (1:1) mixture and acetone in the same manner as in Example 1, and then dried under reduced pressure to obtain a white purified reaction product B3 with a yield of 85%. Obtained. Purified reaction product B
Elemental analysis and molecular weight measurement were conducted for No. 3, and the results are shown in Table 3. All of the 0 elemental analysis values showed extremely good agreement with the theoretical values.

Table 3 In addition, as a result of measuring the IR spectrum for purified reaction product A3.8:l, reaction product A,
A characteristic absorption similar to that of the reaction product B3 was observed.
3380cn+-', 2980cm-', 286
0C11-', 1635C111-', 1575 (Jl
-', 1180 (J-'), the reaction product A is saponified and turns into a carboxylic acid salt, and as a result, a stronger absorption is observed in the hydroxyl group. It was observed that an acid salt type polymer compound was produced.

C Effect of the invention] The present invention is a novel polymer compound having a repeating unit of the general formula shown above, which has a β-hydroxyalkyl group and a carboxyalkyl group in its molecule, and which is treated with an acid or alkali. By doing this, the polymer compound itself has amphoteric surface activity, making it possible to provide a unique new polymer surfactant that has both lipophilic and hydrophilic groups, which is unprecedented. By using it as a processing agent in various industries, it has the effect of imparting distinctive effects not found in conventional low-molecular-weight surfactants.

Patent applicant: Miyoshi Yushi Co., Ltd.

Claims (1)

[Claims] 1. A polymer compound having a repeating unit of the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) However, in the above formula, X is -CH_2CH_2CO
OM, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Selected from the group consisting of M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, a calcium atom distributed according to valence, or a magnesium atom distributed according to valence. In addition, R_1 is an alkyl group having 10 to 16 carbon atoms, and l, m, and n are each 1 to 2330, 0 or 1.
-1400, an integer of 1-1880, and the sum of l, m, and n is 5-2350.