JPH0522727B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated amide-substituted polyoxyalkylene compound and a method for producing the same. More specifically, the present invention relates to an unsaturated amide-substituted polyoxyalkylene compound in which at least one hydroxyl group of the polyoxyalkylene compound is substituted with an ω-unsaturated amide polymethyleneoxy group, and a method for producing the same. The compounds of the present invention have the general formula (However, A is a hydrogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an ω-unsaturated amide polymethylene group (however,

[Formula]), an acyloxy group or an aminoalkyl group, R is a hydrogen atom or a methyl group, α is an integer of 2 to 10, β is an integer of 3 to 50, m is an integer of 4 to 20 It is. ) is an unsaturated amide-substituted polyoxyalkylene compound, and is a new compound that has not been described in any literature. The compound of the present invention has the general formula B(-O- _C〓H2〓 )〓-O( _-CH2 ) _n --X...(2) (However, B is a hydrogen atom, an alkyl group, an alkenyl group, It represents a haloalkyl group, acyloxy group, or aminoalkyl group, X is a halogen atom, and α, β, and m are the same as in the above general formula.)
Polyoxyalkylene compound and general formula represented by (R is the same as the general formula above.) It can be produced by reacting an unsaturated amide compound represented by the following in an aprotic polar solvent in the presence of a strong basic substance. The compound of the present invention represented by the general formula (1) is a polyoxyalkylene compound in which at least one hydroxyl group is substituted with an ω-unsaturated amide polymethylene group. The halogen atoms in the group are chlorine, bromine, iodine or fluorine, and the general formula
In (2), the halogen represented by X is, for example, chlorine,
Bromine or iodine. Furthermore, among the various groups represented by A in the present invention, the acyloxy group and the aminoalkyl group have the general formulas RCOO-,

It is represented by the following formula, where R includes not only an alkyl group but also an alkenyl group and an aryl group. Further, R' and R'' are a hydrogen atom, a lower alkyl group, or an ω-unsaturated amide polymethylene group, and may be different, and R is an alkylene group. More specifically, ethylene glycol, propylene glycol, At least one of the two hydroxyl groups of a polyoxyalkylene compound whose basic skeleton is a trimer to 50-mer of alkylene glycol such as butylene glycol is substituted with an ω-unsaturated amide polymethyleneoxy group, and the remaining One is a hydroxyl group as it is, but instead of the hydrogen atom, an alkyl group, an alkenyl group, a haloalkyl group,
Also included are those substituted with an acyloxy group or an aminoalkyl group. Representative examples of the compounds of the present invention are illustrated below. However, in order to simplify the illustration, first m=4 and R are fixed to hydrogen atoms in the general formula (1), and A, α, and β are variously changed and exemplified. Then, A is an ω-unsaturated amide polymethylene group, α=
2. An example will be given by fixing β=3, changing R to a hydrogen atom or a methyl group, and changing m to 4 to 20. Examples of the above compounds include N-[4-(3,
6,9-trioxadecyloxy)butyl]acrylamide, N-[4-(3,6,9-trioxaundecyloxy)butyl]acrylamide, N
-[4-(3,6,9-trioxatridecyloxy)butyl]acrylamide, N-[4-(1,
4,7-trimethyl-3,6,9-trioxadecyloxy)butyl]acrylamide, N-[4
-(1,5,8-trimethyl-3,6,9-trioxadecyloxy)butyl]acrylamide,
N-[4-(2,4,8-trimethyl-3,6,9
-trioxadecyloxy)butyl]acrylamide, N-[4-(2,5,7-trimethyl-3,
6,9-trioxadecyloxy)butyl]acrylamide, N-[4-(2,5,8-trimethyl-3,6,9-trioxadecyloxy)butyl]acrylamide, N-[4-(3, 6,9-trioxaheneeicosyloxy)butyl]acrylamide, N-[4-(3,6,9,12-tetraoxatetracosyloxy)butyl]acrylamide, N-[4-(3,6, 9,12,15-pentaoxaheptacocyloxy)butyl]acrylamide, N-[4-(3,6,9,12,15,18-hexaoxatriacontyloxy)butyl]acrylamide, N-[4 -(3, 6, 9, 12, 15, 18, 21
-hepuoxatritriacontyloxy)butyl]acrylamide, N-[4-(3,6,9,
12,15,18,21,24-octaoxahexatriacontyloxy)butyl]acrylamide, N-
[4-(dodecyloxy)polyethoxy]butylacrylamide {CH ₂ =CH-CONH(-CH ₂ ) ₄ --O(-
CH ₂ CH ₂ −O) _o --C ₁₂ H ₂₅ ; n=25}, N-[4-lauroyloxy)polyethoxy]butylacrylamide {CH ₂ =CH−CONH(—CH ₂ ) ₄ O—(—
CH ₂ CH ₂ −O) _o --CO(-CH ₂ ) ₁₀ --C ₃ ; n=10},
N-[4-(oleyloxy)polyethoxy]butylacrylamide { _CH2 =CH-CONH( _-CH2
) ₄ O――(-CH ₂ CH ₂ -O) _o ――C ₁₈ H ₃₅ ; n=6,7
，
10,20,50}, N-[4-stearoyloxy)polyethoxy]butylacrylamide CH ₂ =CH-
CONH(-CH ₂ ) ₄ --O(-CH ₂ CH ₂ -O) _o --CO・
C ₁₇ H ₃₅ ; n = 4, 10, 25, 40, 45, triethylene glycol mono(4-acrylamidobutyl)
ether, triethylene glycol bis(4-acrylamidobutyl) ether, tetraethylene glycol mono(4-acrylamidobutyl) ether, tetraethylene glycol bis(4-acrylamidobutyl) ether, tripropylene glycol mono(4-acrylamidobutyl) ether, Tripropylene glycol bis(4-acrylamidobutyl) ether, polyethylene glycol mono(4-acrylamidobutyl) ether, polyethylene glycol bis(4-acrylamidobutyl) ether, polypropylene glycol mono(4-acrylamidobutyl) ether, polypropylene glycol mono(4-acrylamidobutyl) ether -acrylamidobutyl) ether, etc. Next, in the general formula (1), A is fixed to an ω-unsaturated amide polymethylene group, α=2, β=3, R is a hydrogen atom or a methyl group, and m is changed to 4 to 20. do. Examples of these compounds include triethylene glycol bis(4-acrylamidobutyl) ether, triethylene glycol bis(4-methacrylamidobutyl) ether, triethylene glycol bis(5-acrylamidopentyl) ether, and triethylene glycol bis(5-acrylamidobutyl) ether. methacrylamide pentyl) ether, triethylene glycol bis(6-acrylamidohexyl) ether, triethylene glycol bis(6-methacrylamidohexyl) ether, triethylene glycol bis(8-acrylamidooctyl)
Ether, triethylene glycol bis(8-methacrylamidooctyl) ether, triethylene glycol bis(10-acrylamidodecyl)
Ether, triethylene glycol bis(10-methacrylamidodecyl) ether, triethylene glycol bis(12-methacrylamidodecyl) ether, triethylene glycol bis(12-methacrylamidododecyl) ether, triethylene glycol bis(14-acrylamidotetradecyl) ) ether, triethylene glycol bis(14
-methacrylamidotetradecyl) ether, triethylene glycol bis(16-acrylamidohexadecyl) ether, triethylene glycol bis(16-methacrylamidohexadecyl) ether, triethylene glycol bis(18-acrylamidooctadecyl) ether, triethylene glycol These include bis(18-methacrylamidooctadecyl) ether, triethylene glycol bis(20-acrylamidoeicosyl) ether, triethylene glycol bis(20-methacrylamidoeicosyl) ether, and the like. The method for producing the above-mentioned unsaturated amide-substituted polyoxyalkylene compound involves combining a polyoxyalkylene compound represented by the following general formula (2) and an unsaturated amide compound represented by the above-mentioned general formula (3) in an aprotic polar solvent. Manufactured by reaction in the presence of a strong basic substance. The structures of the polyoxyalkylene compounds and unsaturated amide compounds targeted by the method of the present invention are exactly the same as those of the general formulas detailed in the description of the unsaturated amide-substituted polyoxyalkylene compounds, so they will be described in detail. However, polyoxyalkylene compounds in which at least one hydroxyl group is substituted with a halogen-substituted ether group are targeted. The above general formula (2)
Among the various groups represented by B in the above, the haloalkyl group includes an ω-halopolymethylene group ((—CH ₂ ) _n —
X), and the acyloxy group and aminoalkyl group have the general formula RCOO-,

It is represented by the following formula, where R includes not only an alkyl group but also an alkenyl group and an aryl group. Further, R' and R'' are hydrogen, a lower alkyl group, or an ω-halopolymethylene group, and may be different from each other, and R is an alkylene group.In addition, unsaturated amide compounds include acrylamide and methacrylamide The polyoxyalkylene compound represented by the general formula (2) is described, for example, in U.S. Pat.
It can be easily obtained by the methods known per se described in columns to column 6. That is, a corresponding hydroxyl group-substituted compound and a disubstituted halogen compound may be reacted in an aprotic solvent such as acetone or DMF in the presence of a strong basic substance such as caustic potash or potassium carbonate. For example, as shown in Example 1 below, the compound represented by general formula (2) is 1-bromo-5,8,
In the case of 11,14-tetraoxahexadecane, triethylene glycol monoethyl ether and 1,
In the case of 4-bromobutane and triethylene glycol mono(4-bromobutyl) ether, as shown in Example 2,
Triethylene glycol and 1,4-dibromobutane, and in the case of triethylene glycol di(4-bromobutyl) ether in Example 3, triethylene glycol and 1,4-dibromobutane in the presence of potassium hydroxide in a DMF solvent. It can be obtained by reacting with In the present invention, specific methods for causing the reaction in the presence of a strong basic substance include a method in which the reaction is started by dissolving the strong basic substance in the reaction solution, and a method in which the reaction is started in the suspension of the strong basic substance. There is a way. In the case of the present invention, any method can be employed, but surprisingly, starting the reaction under suspension of a strongly basic substance is preferable in terms of reaction efficiency such as suppression of side reactions.
More specifically, as a method to start the reaction while a strongly basic substance is suspended, there is a method in which the three substances are simultaneously supplied and mixed in an aprotic polar solvent to suspend the strongly basic substance and react. A method in which a strongly basic substance is suspended in an aprotic polar solvent, and then a polyoxyalkylene compound and an unsaturated amide compound are simultaneously supplied and reacted, and a polyoxyalkylene compound and an unsaturated amide compound are suspended in an aprotic polar solvent. An appropriate method may be employed, such as dissolving or suspending the compound and then adding and suspending a strong basic substance. The reaction solvent used in the present invention may be any aprotic polar solvent, such as acetonitrile,
Examples include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolane, tetrabrime, dioxane, and N-methylpyrrolidone. In the reaction system in the method of the present invention, it is preferable to start the reaction in a state where at least a part of the strong basic substance is suspended, and the amount of water in such a state is the amount of water in the reaction system. It is usually about 6% by weight. If the amount of water exceeds this value, side reactions such as hydrolysis of the dihalogen-substituted compound are likely to occur, resulting in a significant decrease in yield. In order to carry out the reaction efficiently and increase the yield of the desired product, it is preferable that the water content in the reaction system is 5% by weight or less. The amount of the solvent to be used is not particularly limited, but is in the range of 5 to 95% by weight, preferably 10 to 90% by weight, based on the total amount of the reactants including the solvent. Next, the strong basic substance used in the present invention is a solid substance, and can be used as long as the pH of the aqueous solution when dissolved or suspended in water is 10 or more, preferably 11 or more. Such basic substances include, for example, alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal oxides, alkali metal hydrides, alkaline earth metal hydrogens. compounds, alkali metal amides, alkali metal alkoxides, etc. Examples of the above substances include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of the alkali metal oxide include sodium oxide, potassium oxide, lithium oxide, rubidium oxide, and cesium oxide. Alkali metal carbonates are, for example, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of alkaline earth metal hydroxides are beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Examples of alkaline earth metal oxides include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. Examples of the alkali metal hydride include sodium hydride, potassium hydride, and lithium hydride. Examples of alkaline earth metal hydrides include beryllium hydride, magnesium hydride, and calcium hydride. Alkali metal amides are alkali metal substituted compounds of ammonia, such as sodium amide, potassium amide, lithium amide, and the like. Alkali metal alkoxides are compounds in which the protons of the hydroxyl groups of alcohols are replaced with alkali metals, such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and the like. Among the above-mentioned basic substances, those suitable for carrying out the method of the present invention include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal Carbonates, etc. These strongly basic substances are usually used in the reaction in solid form, and the reaction is initiated while at least a portion of them is suspended in the reaction solution. In carrying out the present invention, the relative usage amounts of the raw materials polyoxyalkylene compound, unsaturated amide compound, and strong basic substance vary depending on the reactivity of the polyoxyalkylene compound and the unsaturated amide compound, etc., and are uniformly used. Cannot be specified. However, the amount of polyoxyalkylene compound used is generally 0.2-20% relative to the unsaturated amide compound.
preferably in the range of 0.3 to 10 times the mole,
The amount of strong basic substance used is 0.2 per amide compound.
-15 times by mole, preferably in the range of 0.5-10 times by mole. Furthermore, a polymerization inhibitor may be added to prevent polymerization of raw materials and products during reaction and purification steps. In this case, the polymerization inhibitor is not particularly limited, but phenolic inhibitors, amine inhibitors, mercaptan inhibitors, copper powder, and the like are generally used. For the reaction method, a normal reaction vessel may be used, or if a strongly basic substance with low solubility is used, it is packed in a column and the polyoxyalkylene compound and unsaturated amide compound are combined. A flow type method may also be used in which a mixed solution of is passed through and circulated.
However, a reaction vessel is more convenient for equipment maintenance and management. The reaction temperature depends on the reactivity of the polyoxyalkylene compound and unsaturated amide compound used, but if the reaction temperature is low, the reaction progresses slowly;
On the other hand, if the temperature is high, side reactions such as hydrolysis of the unsaturated amide compound occur and the yield of the product decreases. Therefore, it is usually carried out at a temperature range of -30 to 100°C, preferably -20 to 70°C. As long as it is within this temperature range, it is not necessarily necessary to keep the temperature constant during the reaction, but it is sufficient to monitor the progress of the reaction and appropriately set the reaction temperature to carry out the reaction efficiently. Further, the reaction time also varies depending on the polyoxyalkylene compound and unsaturated amide compound used, as well as the reaction temperature, but it is 30 hours at the longest, and usually within 20 hours. The progress of the reaction can be understood by observing changes in the properties of the reaction system and the concentrations of raw materials and target products in the reaction solution using gas chromatography or high performance liquid gas chromatography. After the reaction, by-produced metal halides are filtered off and distilled under reduced pressure using a conventional method to obtain a highly pure target product. However, if the metal halide is dissolved in the reaction solution, after distilling off the solvent,
After removing the above substances with a combination of solvents forming two layers, such as water, benzene-water, or chloroform-water, the desired product can be obtained with high purity by distillation under reduced pressure. However, many of the compounds of the present invention generally have a high boiling point and are nonvolatile, and furthermore, they have highly polymerizable double bonds in their molecules, so distillation purification may not be possible in some cases. many. In such cases, the target product can be separated with high purity by a method using solvent extraction, recrystallization, or a purification method using an adsorbent such as silica gel, alumina, activated carbon, ion exchange resin, or adsorption resin.
Further, these methods described above may be combined. The reaction solvent is dimethyl sulfoxide, N,
When the target product has high affinity for water and is highly lipophilic, such as N-dimethylformamide,
After the reaction, a method of adding an aliphatic hydrocarbon solvent such as hexane to the reaction solution to extract the target product, a method of adding water to the reaction solution and separating the target product as an oil layer, or a method of adding an aliphatic hydrocarbon solvent such as hexane to the reaction solution and separating the target product as an oil layer, or a method such as benzene, toluene, chloroform, etc. A method of extracting and separating the target substance using a solvent that forms two layers with water can also be applied. According to the present invention, a wide variety of unsaturated amide-substituted polyoxyalkylene compounds can be produced in the same reactor using the same reaction mode, and is suitable for producing a wide variety of products in small quantities. As shown in the compound examples, the unsaturated amide-substituted polyoxyalkylene compound of the present invention has various polyoxyalkylene groups or derivative groups thereof introduced into the side chain, and can be used in various ways depending on the introduced substituents. It can be applied to Specific applications include adhesives, paint and paper processing agents, fiber processing agents, emulsions, urethane curing agents, pigment dispersants, plastic additives, polymer flocculants, ion exchange resins, adsorption separation resins, chelate resins, optical lenses, Main raw materials, auxiliary raw materials, crosslinking agents, etc. for photosensitive resins, soft contact lenses, water absorbing resins, magnetic material binders, water absorbing resins, polymer catalysts, clinical trials, biocompatible materials, enzyme immobilization base materials, etc. It can be applied in many fields. Next, the present invention will be further explained by examples. Example 1 0.06 g of acrylamide and 1-bromo-5,8,11,14- in 20 ml of N,N-dimethylformamide
2.0 g of tetraoxahexadecane was added, and while stirring, 0.38 g of flaky potassium hydroxide ground in a mortar was added and reacted at 0-5°C for 6 hours.
In addition, the difference between phenothiazine and acrylamide is
Added 0.5%. After reacting for a predetermined time, insoluble substances in the reaction solution were separated, and the solvent and unreacted raw materials were distilled off from the solution. The residue was extracted with benzene-water to obtain the desired product in the benzene layer. Benzene was distilled off from the benzene layer to obtain 1.49 g (yield 77%) of N-(4(3,6,9-trioxaundecyloxy)butyl). This product was further purified by column chromatography using silica gel as an adsorbent and a benzene-methanol mixed solvent as a developing solvent, and the refractive index was measured at 25°C and elemental analysis was performed.
1.4715 and elemental analysis value: Carbon 59.71% (calculated value
59.36%), hydrogen 9.87% (9.65%), nitrogen 4.90%
(4.61%) results were obtained. Examples 2 and 3 Reactions were carried out using the combinations of raw materials, strong basic substances, and solvents listed in Table 1 under the conditions listed in Table 1. After the reaction, treatment was carried out in exactly the same manner as in Example 1, and the results shown in Table 2 were obtained.

【table】

[Table] Example 4 Production of water-absorbing resin; 1% tert.-butylperoxy-2-ethylhexanoate was added to N-acryloylpyrrolidine containing 0.2% triethylene glycol di(4-acrylamidobutyl) ether. Solventless polymerization was performed by standing at 40°C for 50 hours to obtain a block-shaped polymer. The polymer was pulverized to obtain a product as a powder. 1.0 g of this product powder was put into a graduated cylinder containing 50 ml of distilled water, and the water absorption volume of the resin was measured at 25°C, and it was found to be 23 ml.

Claims (1)

[Claims] 1. General formula (However, A is a hydrogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an ω-unsaturated amide polymethylene group (represented by the formula), an acyloxy group, or an aminoalkyl group, and R is a hydrogen atom or a methyl group. , α is an integer of 2 to 10, β is an integer of 3 to 50, and m is an integer of 4 to 20. 2 General formula B(-O-C〓H ₂ 〓)〓-O(-CH ₂ ) _n --X (2) (However, B is a hydrogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an acyloxy group, or an amino is an alkyl group, X is a halogen atom, α is an integer of 2 to 10, β is an integer of 3 to 50, and m is an integer of 4 to 20. and general formula (R is a hydrogen atom or a methyl group.) A general formula characterized by reacting an unsaturated amide compound represented by (R is a hydrogen atom or a methyl group) in an aprotic polar solvent in the presence of a strong basic substance (However, A is a hydrogen atom, an alkyl group, an alkenyl group, a haloalkyl group, an ω-unsaturated amide polymethylene group (represented by the formula), an acyloxy group, or an aminoalkyl group, and R is a hydrogen atom or a methyl group. , α is an integer of 2 to 10, β is an integer of 3 to 50, and m is an integer of 4 to 20.