JPH0363574B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel modified polyamine.
More specifically, it relates to modified polyamines that exhibit excellent surfactant properties, are useful as surfactants, and can be widely used in textile processing agents, antistatic agents, paper processing agents, rust preventives, etc. . (Prior Art and Problems to be Solved by the Present Invention) Various modified polyamines have been known, and among them, polyamines with alkylene oxide added to polyethyleneimine are known to exhibit surface activity. It is being However, since the above-mentioned polyethyleneimine/alkylene oxide adduct has low surface activity, when used as an emulsifier for oily or resinous substances or as an emulsifier during emulsion polymerization, it is difficult to use the polyethyleneimine/alkylene oxide adduct to emulsify the object to be emulsified or the monomer that can be emulsion polymerized. It has the disadvantage of limited body range. The purpose of the present invention is to eliminate the above-mentioned drawbacks of conventional products, have high surfactant ability, and therefore be able to handle a wide range of oily substances.
The object of the present invention is to develop modified polyamines that can be used as emulsifiers for emulsion polymerization of resinous materials or polymerizable monomers. (Means and effects for solving the problem) The present inventors reacted a monoepoxy compound having a specific structure having a hydrophobic group and a hydrophilic group in the molecule with a polyamine and/or a polyamine derivative at a specific ratio. It was discovered that the modified polyamine obtained by the method of the present invention exhibits excellent surfactant ability, and the present invention was achieved based on this finding. That is, the present invention relates to polyamines and/or polyamine derivatives having at least two nitrogen atoms in the molecule and having at least two primary and/or secondary amino groups and an average molecular weight of 5,000 or less, and the general formula () (In the formula, R is a hydrocarbon group having 28 or less carbon atoms,
n is 0 or an integer from 1 to 30. ) and the amine hydrogen 1 in the polyamine and/or polyamine derivative.
Regarding modified polyamines having at least one structural unit represented by the general formula () in the molecule and having an average molecular weight of 200 to 200,000, obtained by reacting at a ratio of 0.01 to 1 monoepoxy compound per molecule. It is something. (A in the formula is a divalent organic group, and R and n are the same as in the above formula ().) The polyamine and/or polyamine derivative used in the present invention refers to at least two nitrogen atoms in the molecule. and at least two primary and/or secondary amine groups. Examples of polyamines include polyalkyleneimines such as polyethyleneimine obtained by polymerizing ethyleneimine, copolymers of ethyleneimine and propyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylene. (Poly)alkylene polyamines such as hexamine;
Polyamide polyamine obtained by condensation of polyalkylene imine and/or (poly) alkylene polyamine with polybasic acid such as adipic acid; Examples include polyurea polyamines obtained by reaction; polyamide polyester polyamines obtained by copolymerization of alkylene imine and acid anhydride such as phthalic acid. Examples of polyamine derivatives include those obtained by addition-reacting the polyamine with an alkylene oxide such as ethylene oxide or propylene oxide, or an α,β-unsaturated acid amide compound such as (meth)acrylamide. The monoepoxy compound used in the present invention is represented by the above general formula, and in the formula, the hydrocarbon group having 28 or less carbon atoms corresponding to R is a linear or branched hydrocarbon group having 28 or less carbon atoms. Examples include branched alkyl groups, (alkyl)aryl groups, (alkyl)hydrogenated aryl groups, and (alkyl)aralkyl groups. Specific examples of monoepoxy compounds include n-octyl polyoxyethylene glycidyl ether, n-nonyl polyoxyethylene glycidyl ether, lauryl polyoxyethylene glycidyl ether, and stearyl polyoxyethylene glycidyl ether having an ethylene oxide addition mole number of 1 to 30. , 2-ethylhexyl polyoxyethylene glycidyl ether and other primary alkyl polyoxyethylene glycidyl ethers; 1 to 30 moles of ethylene oxide is added to a mixture of secondary alcohols having 12 to 14 carbon atoms, and further glycidyl etherification is performed. Secondary alkyl polyoxyethylene glycidyl ethers such as those obtained by adding 1 to 30 moles of ethylene oxide to a mixture of secondary alcohols having 10 to 12 carbon atoms and further converting the mixture into glycyl diether; addition of ethylene oxide Phenyl polyoxyethylene glycidyl ether, octylphenyl polyoxyethylene glycidyl ether, nonylphenyl polyoxyethylene glycidyl ether, lauryl phenyl polyoxyethylene glycidyl ether, stearyl phenyl polyoxyethylene glycidyl ether with a mole number of 1 to 30 (Alkyl)phenyl polyoxyethylene glycidyl ethers such as; cyclopentyl polyoxyethylene glycidyl ether with an added mole of ethylene oxide of 1 to 30, cyclohexyl polyoxyethylene glycidyl ether, octylcyclopentyl polyoxyethylene glycidyl ether,
Octylcyclohexyl polyoxyethylene glycidyl ether, nonylcyclopentyl polyoxyethylene glycidyl ether, nonylcyclohexyl polyoxyethylene glycidyl ether,
(Alkyl)cycloalkyl polyoxyethylene glycidyl ethers such as lauryl cyclopentyl polyoxyethylene glycidyl ether, lauryl cyclohexyl polyoxyethylene glycidyl ether, stearyl cyclopentyl polyoxyethylene glycidyl ether, stearyl cyclohexyl polyoxyethylene glycidyl ether; addition of ethylene oxide; Such as benzyl polyoxyethylene glycidyl ether, octylbenzyl polyoxyethylene glycidyl ether, nonylbenzyl polyoxyethylene glycidyl ether, lauryl benzyl polyoxyethylene glycidyl ether, stearyl benzyl polyoxyethylene glycidyl ether, etc. with a mole number of 1 to 30 ( Alkyl) benzyl polyoxyethylene glycidyl ethers; glycidyl ethers of higher alcohols such as octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether, etc.; phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl Glycidyl ethers of (alkyl)phenols such as phenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether, etc.; diclopentyl glycidyl ether, cyclohexyl glycidyl ether, octyl cyclopentyl glycidyl ether, octyl cyclohexyl glycidyl ether, nonyl cyclopentyl Glycidyl ethers of (alkyl)cycloalkanols such as glycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, laurylcyclohexylglycidyl ether, stearylcyclopentylglycidyl ether, stearylcyclohexylglycidyl ether; benzylglycidyl ether, octylbenzylglycidyl ether,
Glycidyl ethers of (alkyl)benzyl alcohols such as nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether, and stearyl benzyl glycidyl ether can be mentioned, and one type or a mixture of two or more of these can be used. . The amount of the monoepoxy compound used to obtain the modified polyamine of the present invention is not particularly limited, but in order to express sufficient surfactant ability, it is necessary to use from 0.01 to 1 per amine hydrogen in the polyamine and/or polyamine derivative. The range is one molecule. If the amount of the monoepoxy compound used is outside this range, the surface active ability of the modified polyamine will decrease. The reaction conditions for obtaining the modified polyamine of the present invention are not particularly limited, but the reaction rate of the reaction between a polyamine and/or a polyamine derivative and a monoepoxy compound tends to be slow and the reaction time becomes long when diluted with a solvent. It is preferable to carry out without solvent and without dilution. Further, when carrying out the reaction without a solvent, it is preferable that the viscosity of the polyamine and/or polyamine derivative be as low as possible because stirring is easier, the reactants can be mixed uniformly, and heat can be easily removed. Therefore,
The average molecular weight of the polyamine and/or polyamine derivative is preferably 5,000 or less. That is, the modified polyamine of the present invention can most advantageously be obtained by reacting a polyamine and/or polyamine derivative having a molecular weight of 5,000 or less with a monoepoxy compound in the absence of a solvent at a temperature in the range of 20 to 150°C. The modified polyamine of the present invention has an average molecular weight of 200~
200000 range. If the average molecular weight is outside this range, there will be disadvantages such as a decrease in surfactant ability and difficulty in handling, which is not preferable. (Effects of the Invention) The modified polyamine of the present invention is obtained by adding a monoepoxy compound with a specific structure having both a hydrophobic group and a hydrophilic group in the molecule to a polyamine and/or a polyamine derivative. Therefore, it has a large surfactant ability, has excellent emulsifying power for various oily substances, resinous substances, etc., and can be used as an emulsifier for emulsion polymerization of various types of monomers. Furthermore,
Due to its structural characteristics, the modified polyamine of the present invention can be effectively used in applications such as fiber treatment agents, antistatic agents, paper processing agents, and rust preventive agents. The present invention will be explained in detail below with reference to Examples, but the scope of the present invention is not limited only to these Examples. In the examples, unless otherwise specified, % means % by weight and parts means parts by weight. Example 1 In a flafco equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, Epomin SP-006 (polyethyleneimine manufactured by Nippon Shokubai Chemical Co., Ltd., with an average molecular weight of approx.
600) 61 parts and Softanol 30 (Nippon Catalyst Chemical Industry)
Secondary alcohol manufactured by Co., Ltd. (mixture with 12 to 14 carbon atoms)
39 parts of glycidyl ether (3 mole adduct of ethylene oxide) was charged, and reacted by stirring at 80°C for 2 hours while nitrogen gas was slowly flowing, to obtain a pale yellow liquid reaction product (modified polyamine). Prepare a 0.1% aqueous solution of the obtained reaction product,
The surface tension at 25°C was measured using a Giunui surface tension meter and was found to be 43.6 dyne/cm. Examples 2 to 7 Modified polyamines were obtained by repeating the same operations as in Example 1, except that the polyamine and monoepoxy compound were as shown in Table 1. Further, the surface tension of the modified polyamine was measured in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 1 A modified polyamine for comparison was obtained by repeating the same operation as in Example 1, except that the monoepoxy compound was outside the scope of the present invention as shown in Table 1. Further, the surface tension of a modified polyamine for comparison was measured at the same time as in Example 1, and the results are shown in Table 1. As is clear from Table 1, the modified polyamine for comparison has inferior surface active ability compared to the modified polyamine of the present invention. Comparative Example 2 In Example 1, instead of the polyamine, 28 parts of stearylamine having only one nitrogen atom in the molecule, which is outside the scope of the present invention, and 72 parts of glycidyl ether of softanol 120 as the monoepoxy compound
A comparative compound was obtained by repeating the same operation as in Example 1. The surface tension of the obtained comparative compound was determined in Example 1.
When measured in the same manner as above, the surface activity was 65.2 dyne/cm, which is significantly inferior to the modified polyamine of the present invention.

【table】

[Table] 〓AOE−X24
CH ₃ (−CH ₂ )− _k −CH−CH ₂ k=9 and
11
\ /
O

Claims (1)

[Claims] 1. Having at least two nitrogen atoms in the molecule,
Furthermore, polyamines and/or polyamine derivatives having at least two primary and/or secondary amino groups and an average molecular weight of 5000 or less and the general formula () (In the formula, R is a hydrocarbon group having 28 or less carbon atoms,
n is 0 or an integer from 1 to 30. ) and the amine hydrogen 1 in the polyamine and/or polyamine derivative.
A modified polyamine having at least one structural unit represented by the general formula () in the molecule and having an average molecular weight of 200 to 200,000, obtained by reacting at a ratio of 0.01 to 1 monoepoxy compound per molecule. (A in the formula is a divalent organic group, and R and n are the same as in formula () above.) 2. A patent obtained by reacting a polyamine and/or a polyamine derivative with a monoepoxy compound in the absence of a solvent. The modified polyamine according to claim 1.