JPH029623B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel amphoteric surfactant. More specifically, the active hydrogen bonded to nitrogen in polyethyleneimine has the following general formula: (where m is an integer from 9 to 15) is subjected to an addition reaction with an epoxy alkane, and then the reaction product is subjected to a Michael addition reaction with an ethylenically unsaturated monomer, and the resulting reaction It relates to an amphoteric surfactant consisting of a compound obtained by saponifying a product with an acid or an alkali. [Prior art] Amphoteric polymers using polyethyleneimine as a starting material include poly-N-ethylene glycine salts such as poly-(N-propionic acid)-ethyleneimine and poly-(N-methylenesuccinic acid)-ethyleneimine. , poly-(N-succinic acid)-ethyleneimine, poly-(N-methyleneglutaric acid)-ethyleneimine, poly-(N-tricarballylic acid)-
On ethyleneimine, etc., Journal of the American Chemist Society, Vol. 77, No.
4743 (1955) and Japanese Patent Publication No. 48-20203, and further describes polymers with dithiocarbamate groups obtained by reacting polyethyleneimine, sodium hydroxide, and carbon disulfide, Koka Journal Vol. 69,
There is a report on page 716 (1966). Applications of these amphoteric polymer compounds include applications in cleaning agents, bleaching agents, etc. according to Japanese Patent Publication No. 48-20203, applications in adhesion promoters according to Japanese Patent Publication No. 48-3644, and cosmetic compositions according to Japanese Patent Publication No. 54-23135. and so on. [Problems with the prior art] However, these compounds are characterized by a high content ratio of nitrogen and carboxylic acid in the molecule, which makes them highly hydrophilic and highly stable as an aqueous solution. Because it does not contain any substances, it can only be used within an extremely limited range in terms of performance or application. [Means for solving the problems] The present inventors focused on these problems and, as a result of intensive research, succeeded in introducing a β-hydroxyalkyl group and a carboxyalkyl group into the polyethyleneimine molecule. imparts lipophilicity,
It was discovered that by changing the hydrophilicity-lipophilic balance with carboxyl groups or their salts (hydrophilicity), the properties can be broadened and applied to a wide range of applications. . That is, the present invention provides polyethyleneimine having an average molecular weight of 200 to 100,000, and the following general formula (1). (where m is an integer of 9 to 15) is subjected to an addition reaction, and the reaction product is further added with an ethylenically unsaturated monomer having an ester bond or nitrile group in one molecule The reaction product obtained by the addition reaction [However, the amount of both added is 1 mole or more of epoxy alkane and 1 mole of ethylenically unsaturated monomer per 1 mole of polyethyleneimine.
an amphoteric surfactant consisting of a compound obtained by saponifying with an acid or an alkali the number of moles or more of epoxy alkane + the number of moles of added ethylenically unsaturated monomer/degree of polymerization of polyethyleneimine ≦1] . To explain the present invention in more detail, first, polyethyleneimine and epoxy alkane were heated at 50 to 150°C.
The mixture is reacted 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
When using a molecular weight of ~20,000, it is preferable to conduct the reaction without a solvent, and when using a molecular weight of 20,000 to 100,000, it is preferable to conduct the reaction in a solvent. Then, the Michael addition reaction between the poly-N-β-hydroxyalkyl polyethyleneimine obtained above and the ethylenically unsaturated monomer is carried out without or in a solvent at 50 to 150°C for 1 to 20 hours. This completes the process. 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 as a solution. Furthermore, the subsequent saponification reaction is carried out at 90 to 120° C. for 1 hour or more with an acid or alkali in an amount of 1.0 to 1.2 times the mole of the ethylenically unsaturated monomer used. 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 both the stage 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 or more of epoxy alkane, 1 mole or more of ethylenically unsaturated monomer, and (epoxy Number of moles added of alkane + number of moles added of ethylenically unsaturated monomer)/
The degree of polymerization of polyethyleneimine is ≦1, and the compound obtained by reacting within this range has a good balance between hydrophilicity and lipophilicity, and exhibits amphoteric surfactant ability. When the amount of epoxy alkane added to polyethyleneimine is less than 1 mol, the resulting compound has no lipophilic property, and when the amount of ethylenically unsaturated monomer added is less than 1 mol, the obtained compound has no hydrophilic property. . The amount of epoxy alkane and ethylenically unsaturated monomer added is the sum of the number of moles of both added/degree of polymerization of polyethyleneimine ≦1
, and it is not possible to add more than this. The polyethyleneimine used in the present invention has an average molecular weight of 200 to 100,000. As the epoxyalkane, 1.2-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, it will not be possible to obtain a compound with a good hydrophilic-lipophilic balance, and if it exceeds 100,000, the viscosity will be high.
This is not preferred because the addition reaction between the epoxy alkane and the ethylenically unsaturated monomer cannot be uniformly carried out. In addition, the solvents used in the present invention include benzene, toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, n-
Examples include hexane, chloroform, carbon tetrachloride, etc., and these 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,
Examples include, but are not limited to, methacryl nitrile, crotonic acid alkyl ester, itaconic acid alkyl ester, maleic acid alkyl ester, and fumaric acid alkyl ester. These may be used alone or in combination of two or more. The alkyl group used here has 1 to 5 carbon atoms.
It is preferable to use 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,
Examples include calcium hydroxide and magnesium hydroxide, and these acids or alkalis may be used alone or in combination of two or more alkalis. [Effect of the invention] The compound obtained as described above has a β-hydroxyalkyl group, an amino group and a carboxyl group in its molecule, the β-hydroxyalkyl group has lipophilicity, and the amino group and carboxyl group have amphoteric properties. It is an activator that exhibits natural hydrophilicity and has better amphoteric surfactant ability than conventional polyethyleneimine compounds without lipophilicity, and is useful as a paper strengthening agent, paper quality improver, sizing agent, etc. in the paper manufacturing industry. Various fillers,
As a retention improver for pigments, dyes, etc., as an adhesion promoter in the adhesive industry, for improving the dyeability of various fibers in the textile industry, for shrink-proofing, flame-retardant treatment, antistatic treatment, etc., as well as for cosmetic compositions and cleaning agent compositions. It is extremely useful as a lubricating oil additive, rust preventive, and antifogging agent. [Example] Next, Examples of the present invention will be shown, but these are not intended to limit the scope of the present invention. Example 1 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight: about 1000,
C ₁₄ -Epoxyalkane (oxirane oxygen content: 7.48%) was added to 150.7 parts (nitrogen content: 32.6%) at 80-85°C under stirring and nitrogen flow.
299.5 parts of methyl acrylate was added dropwise over 1 hour, the aging reaction was carried out for 4 hours, and 120.5 parts of methyl acrylate was added dropwise to 75-80 parts of methyl acrylate.
℃ for 1 hour to carry out the Michael addition reaction.
Aging reaction was carried out for 3 hours, and then again at 95-100℃.
616 parts of a 10% caustic soda aqueous solution was added dropwise over 2 hours to carry out a saponification reaction, and the mixture was aged at the same temperature for 2 hours. After aging, the reaction solution was cooled to room temperature and the pH of the reaction solution was adjusted to 4.5 with 5% hydrochloric acid. A white precipitate was formed. The precipitate was separated, washed with acetone, and dissolved in methanol. , and reprecipitated in acetone. Repeat this operation twice and leave at room temperature.
After drying under reduced pressure for 48 hours, a white amphoteric compound was obtained with a yield of 85.5%. The nitrogen content (hereinafter referred to as N%) by Kjeldahl method is 8.85% (theoretical value: 8.94%),
The average molecular weight (described below) was 3,700.
The surfactant ability of the obtained compound was measured and the results are shown in Table-1. Example 2 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight:
1000) 150.7 parts (ii) C ₁₆ -epoxyalkane (oxirane oxygen content: 6.55%) 266.1 parts (iii) Methyl acrylate 150.7 parts (iv) 770 parts of 10% caustic soda aqueous solution After the reaction was completed, the same procedure as in Example 1 was carried out. Reprecipitation was performed twice in a methanol-acetone system to obtain a white purified product (yield: 90.8%). N%: 9.12% (theoretical value: 9.27%): 3500 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 3 The reaction was carried out in much the same manner as in Example 1, using the following reagents in the order below. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-006, average molecular weight: approx.
600, N%: 32.5) 150.7 parts (ii) C ₁₈ -epoxyalkane (oxirane oxygen content: 5.85%) 191.5 parts (iii) Methyl acrylate 180.8 parts (iv) 924 parts of 10% caustic soda aqueous solution Performed after completion of reaction Similar to Example 1, reprecipitation was performed twice using a methanol-acetone system to obtain a white purified product (yield: 92.5%). N%: 9.81% (theoretical value: 10.02%): 2000 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 4 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-018, average molecular weight: approx.
1800, N%: 32.6) 258.4 parts (ii) Mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd.,
Oxirane oxygen content: 7.75%) 247.8 parts (iii) Methyl acrylate 309.6 parts (iv) 530 parts of 30% caustic soda aqueous solution After the reaction was completed, the same treatment as in Example 1 was carried out to obtain a pale yellow purified product ( Rate: 85.5%). N%: 10.45% (theoretical value: 10.98%): 5600 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 5 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight: approx.
1000) 172.3 parts (ii) Mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd.,
Oxirane oxygen content: 7.75%) 330.4 parts (iii) Butyl acrylate 205.1 parts (iv) 235 parts of 30% caustic soda aqueous solution After the reaction was completed, the same treatment as in Example 1 was carried out to obtain a pale yellow purified product ( Rate: 86.9%). N%: 8.96% (theoretical value: 9.07%): 3600 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 6 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight: about 1000)
215.4 parts at 80-85℃ under stirring and nitrogen flow
, 309.8 parts of a mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd., oxirane oxygen content: 7.75%) was added.
It was added dropwise over 1.5 hours, the aging reaction was carried out for 4 hours, 132.6 parts of acrylonitrile was added dropwise at 80°C over 1 hour to carry out the Michael addition reaction, the aging reaction was carried out for 3 hours, and then 10% caustic soda aqueous solution was added.
1,100 parts were added dropwise at 95 to 100°C over 2 hours to carry out a saponification reaction, and the mixture was aged for 2 hours. The reaction solution was cooled to room temperature, diluted 3 times with water,
When the pH of the reaction solution was adjusted to 5.0 with 5% hydrochloric acid, a white precipitate was formed, and the precipitate was separated and thoroughly washed with acetone. The precipitate was dissolved in methanol and reprecipitated by pouring it into a large amount of acetone, and this operation was repeated twice.
A purified product was obtained (yield: 85.5%). N%: 9.72% (theoretical value: 9.93%): 3300 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 7 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-200, average molecular weight: approx.
20000, N%: 32.5) 215.4 parts (ii) Mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd.,
Oxirane oxygen content: 7.75%) 309.8 parts (iii) Dimethyl itaconate 395 parts (iv) 10% caustic soda aqueous solution 1100 parts After the reaction was completed, the same treatment as in Example 1 was carried out to obtain a pale yellow purified product ( Rate: 78.5%). N%: 8.10% (theoretical value: 8.23%): 71000 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 8 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-300, average molecular weight: approx.
30000) 150.7 parts (ii) Mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd.,
Oxirane oxygen content: 7.75%) 50.6 parts (iii) Methyl acrylate 189.8 parts (iv) 883 parts of 10% caustic soda aqueous solution After the reaction, reprecipitation was performed twice with methanol-acetone system as in Example 1, and a white A purified product was obtained (yield: 91.8%). N%: 11.82% (theoretical value: 11.84%): 81800 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Example 9 The reaction was carried out in substantially the same manner as in Example 1, using the following reagents in the following order. (i) Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-1020, average molecular weight: approx.
100,000) 150.7 parts (ii) 500 parts of benzene (iii) Mixture of C ₁₂ -epoxy alkane and C ₁₄ -epoxy alkane (manufactured by Daicel Chemical Industries, Ltd.,
Oxirane oxygen content: 7.75%) 271.3 parts (iv) Methyl acrylate 37.7 parts (v) 175 parts of 10% caustic soda aqueous solution After the reaction, reprecipitation was performed twice with methanol-acetone system in the same manner as in Example 1, and a white color was obtained. A purified product was obtained (yield: 88.4%). N%: 10.39% (theoretical value: 10.58%): 302000 The surface active ability of the obtained compound was measured, and the results are shown in Table-1. Comparative Example 1 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight: approximately 1000)
120.5 parts of methyl acrylate was added dropwise to 150.7 parts at 75 to 80°C over 1 hour while stirring and under a stream of nitrogen.
A Michael addition reaction was carried out, an aging reaction was carried out for 3 hours, the mixture was further heated to 95-100°C, 616 parts of a 10% aqueous sodium hydroxide solution was added dropwise over 2 hours, a saponification reaction was carried out, and the mixture was aged for 2 hours at the same temperature. After aging, the reaction solution was cooled to room temperature, and the pH of the reaction solution was adjusted to 4.5 with 5% hydrochloric acid. A white precipitate was formed. The precipitate was separated, washed with acetone, dissolved in methanol, and dissolved in acetone. and re-sedimentation.
This operation was repeated twice and dried under reduced pressure at room temperature for 48 hours to obtain a white amphoteric compound with a yield of 80.2%. The nitrogen content by Kjeldahl method was 19.1% (theoretical value: 19.5%), and the average molecular weight was 1700. The surfactant ability of the obtained compound was measured and the results are shown in Table-1.

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Claims (1)

[Claims] 1 Polyethyleneimine having an average molecular weight of 200 to 100,000, and the following general formula (1) (where m is an integer of 9 to 15) is subjected to an addition reaction, and the reaction product is further added with an ethylenically unsaturated monomer having an ester bond or nitrile group in one molecule The reaction product obtained by the addition reaction [However, the amount of both added is 1 mole or more of epoxy alkane and 1 mole of ethylenically unsaturated monomer per 1 mole of polyethyleneimine.
an amphoteric surfactant consisting of a compound obtained by saponifying with an acid or an alkali the number of moles or more of epoxy alkane + the number of moles of added ethylenically unsaturated monomer/degree of polymerization of polyethyleneimine ≦1] . 2 The ethylenically unsaturated monomer is an acrylic acid alkyl ester, a methacrylic acid alkyl ester, a crotonic acid alkyl ester, an itaconic acid alkyl ester, a maleic acid alkyl ester, a fumaric acid alkyl ester (all of the above alkyl groups have 1 to 5 carbon atoms) ), acrylonitrile, and methacrylonitrile.