JPH0363575B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel modified polyamine compound. More specifically, it has surfactant and curability, surfactant, fiber treatment agent,
This invention relates to modified polyamines useful in paper processing agents, sizing agents, adhesives, coating agents, and the like. (Prior art and problems to be solved by the present invention) A variety of modified polyamines have been synthesized in the past, and polyethyleneimine, α-olefin epoxide, etc. have hydrophobic groups and hydrophilic groups in the molecule. and a compound obtained by adding epihalohydrin to a polyamide polyamine resin (Japanese Patent Publication No. 22922/1989). However, when an α-olefin epoxide adduct of polyethyleneimine is used, for example, as an emulsifier in emulsion polymerization, it is difficult to carry out stable emulsion polymerization due to a lack of surfactant ability, and it also has curable properties. As a result, the water resistance of emulsion films and coatings obtained by emulsion polymerization is poor. Epihalohydrin adducts of polyamide polyamine resins also lack surface active ability, making it difficult to stably carry out emulsion polymerization. An object of the present invention is to develop a modified polyamine having excellent surface activity and curing reactivity. (Means and effects for solving the problems) The present inventors have developed a modified polyamine and/or its derivatives by reacting a monoepoxy compound and epihalohydrin having a hydrophobic group and a hydrophilic group in the molecule in a specific ratio. The present invention was achieved by discovering that polyamine compounds have greater surface activity than conventionally known modified polyamine compounds, are therefore suitable as emulsifiers, and have excellent crosslinking properties. That is, the present invention provides a compound having an average molecular weight of at least two nitrogen atoms and at least two primary and/or secondary amino groups in the molecule.
General formula for polyamines and/or their derivatives below 5000 (In the formula, R is a hydrocarbon group having 28 or less carbon atoms,
n is 0 or an integer from 1 to 30. The average molecular weight obtained by reacting a monoepoxy compound represented by 250～
200,000 for a modified polyamine. The polyamine and/or its derivative used in the present invention has at least two nitrogen atoms in the molecule and also has at least two primary and/or secondary amino groups. Examples of polyamines include polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine,
(Poly)alkylene polyamines such as tetraethylene pentamine, pentaethylene hexamine, etc.; polyamide polyamines obtained by condensation of polyalkylene imines and/or (poly) alkylene polyamines with polybasic acids such as adipic acid; polyalkylenes; A polyurepolyamine obtained by reacting an imine and/or a (poly)alkylene polyamine and/or an alkylene imine with urea; a polyamide polyester polyamine obtained by copolymerizing an alkylene imine with an acid anhydride such as phthalic acid, etc. can be mentioned. 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-ethylhexylpolyoxyethylene 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 glycidyl ether; added moles 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, etc. having a number of 1 to 30 (Alkyl)phenyl polyoxyethylene glycidyl ethers such as; cyclopentyl polyoxyethylene glycidyl ether, cyclohexyl polyoxyethylene glycidyl ether, octyl cyclopentypolyoxyethylene glycidyl ether, octyl cyclohexyl with an added mole number of ethylene oxide of 1 to 30; Polyoxyethylene glycidyl ether, nonylcyclopentyl polyoxyethylene glycidyl ether, nonylcyclohexyl polyoxyethylene glycidyl ether, lauryl cyclopentyl polyoxyethylene glycidyl ether, lauryl cyclohexyl polyoxyethylene glycidyl ether, stearyl cyclopentyl polyoxyethylene glycidyl ether, stearyl cyclohexyl polyoxy (alkyl) such as ethylene glycidyl ether, etc.
Cycloalkyl polyoxyethylene glycidyl ethers; benzyl polyoxyethylene glycidyl ether with an added mole of ethylene oxide of 1 to 30, octylbenzyl polyoxyethylene glycidyl ether, nonylbenzyl polyoxyethylene glycidyl ether, laurylbenzyl polyoxyethylene glycidyl ether, (Alkyl)benzyl polyoxyethylene glycidyl ethers such as stearyl benzyl polyoxyethylene glycidyl ether; glycidyl ethers of higher alcohols such as octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether; Glycidyl ethers of (alkyl)phenols such as phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether, etc.; cyclopentyl glycidyl ether, cyclohexyl glycidyl ether, octyl Glycidyl ethers of (alkyl)cycloalkanols such as cyclopentyl glycidyl ether, octyl cyclohexyl glycidyl ether, nonyl cyclopentyl glycidyl ether, nonyl cyclohexyl glycidyl ether, lauryl cyclopentyl glycidyl ether, lauryl cyclohexyl glycidyl ether, stearyl cyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether, etc. Class; benzyl glycidyl ether, octyl benzyl glycidyl ether,
Examples include glycidyl ethers of (alkyl)benzyl alcohols such as nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether, and stearyl benzyl glycidyl ether, 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 in the range of 0.01 to 1 molecule per amine hydrogen in the polyamine and/or its derivative. As the epihalohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, etc. can be used, but epichlorohydrin is preferable. In the present invention, the amount of epihalohydrin used to obtain a modified polyamine is in the range of 0.1 to 2 molecules per amine hydrogen in the polyamine and/or its derivative. The reaction conditions for obtaining the compound of the present invention are not particularly limited, but the reaction rate of polyamine and/or its derivative with monoepoxy compound is slow in the presence of a solvent, and the reaction of polyamine and/or its derivative with epihalohydrin is slow in the presence of a solvent. Since the reaction generates a large amount of heat, it is difficult to control the temperature without dilution. Therefore, a polyamine and/or its derivative and a monoepoxy compound are mixed and reacted without a solvent at a temperature of 20 to 150°C, the resulting reaction product is diluted with a solvent, and then epihalohydrin is mixed with a monoepoxy compound at a temperature of 20 to 150°C.
Preferably, the reaction is carried out at a temperature of 100°C. The solvent is not particularly limited as long as it is an inert solvent that can dissolve the reactants of the polyamine and/or its derivative and the monoepoxy compound. (Effect of the invention) The modified polyamine obtained by the present invention has a basic skeleton in which a monoepoxy compound with a specific structure having a hydrophobic group and a hydrophilic group is added to a polyamine and/or a derivative thereof. It has a large ability to reduce interfacial tension and has excellent emulsifying power for various oily substances and resinous substances, and furthermore, epihalohydrin is added to the basic skeleton to introduce an epoxy group and/or a group that can generate an epoxy group. Therefore, it has self-curing properties and the property of curing by reacting with compounds that can react with other epoxy groups. The modified polyamine of the present invention can be used for various industrial applications by taking advantage of the above-mentioned features, but
It is particularly useful as a reactive polymer emulsifier for emulsion polymerization of vinyl monomers, and various emulsions can be produced stably. has high film strength and excellent water resistance. Furthermore, the modified polyalline of the present invention can be effectively used alone or in combination with a compound capable of reacting with an epoxy group for applications such as fiber processing agents, paper processing agents, sizing agents, adhesives, and coating agents. . Examples of the present invention are shown below, but these are given for illustrative purposes and are not intended to limit the scope of the present invention. Further, in the following, parts and % represent parts by weight and % by weight, respectively. Example 1 Into a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 43.1 parts of polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight approximately 600) and a second 27.6 parts of glycidyl ether of 3 moles of ethylene oxide adduct (Softanol 30, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) of alcohol (mixture of 12 to 14 carbon atoms) were charged and reacted at 80°C for 2 hours with stirring under a nitrogen stream. Ta. Add 282.8 parts of water to the obtained reaction product
After making a 20% aqueous solution, add epichlorohydrin at room temperature.
When 92.5 parts were added and reacted at 80℃ for 5 hours, the resin content was 36
A pale yellow viscous aqueous solution was obtained containing %. The surface tension (25℃) at 0.1% resin content is 40.6dyne/
It was cm. Examples 2 to 7 A polyamine, a monoepoxy compound, and epichlorohydrin were reacted in the same manner as in Example 1 to obtain a modified polyamine. The results are summarized in Table 1. Comparative Example 1 In the same flask as used in Example 1, 43.1 parts of polyethyleneimine used in Example 1 and 12 carbon atoms were added.
and a mixture of 14 α-olefin epoxides (AOE-X24, manufactured by Daicel Chemical Industries, Ltd.)
14.0 parts and heated to 80℃ while stirring under nitrogen stream.
The mixture was allowed to react for 2 hours. The surface tension of the obtained modified polyethyleneimine at a resin content of 0.1% is
It was 65.7dyne/cm. Comparative Example 2 112.5 parts of diethylenetriamine and adipic acid
634.1 parts of water was added to 42.7 parts of polyamide polyamine synthesized from 146.1 parts of polyamine by dehydration condensation, and the mixture was further reacted with 27.8 parts of epichlorohydrin at 80°C for 5 hours. The surface tension of the obtained polyamide polyamine-epichlorohydrin resin at a resin content of 0.1% was 67.0 dyne/cm. Example 8 For each of the modified polyamines and modified polyethyleneimine obtained in Examples 1 to 7 and Comparative Example 1, an aqueous ammonium polyacrylate solution was mixed so that the resin content of each was the same, and then applied to a glass plate. It was left at room temperature. Cured films were obtained with the modified polyamines of Examples 1 to 7, but were not cured with the modified polyethyleneimine of Comparative Example 1.

【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,
Moreover, polyamines and/or derivatives thereof having at least two primary and/or secondary amino groups and an average molecular weight of 5,000 or less have 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 an epihalohydrin in a ratio of 0.01 to 1 molecule of monoepoxy compound and 0.1 to 2 molecules of epihalohydrin per amine hydrogen in the polyamine and/or its derivative, and the average molecular weight obtained is 250. ~
200000 modified polyamine. 2. The modified polyamine according to claim 1, which is obtained by reacting a polyamine and/or its derivative with a monoepoxy compound in the absence of a solvent.