JPS62903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel monomer having multiple nitrogen atoms and a method for producing the same. Polymers with basic nitrogen in their side chains have functionality in polymer electrolytes, ion exchange resins, adsorbents, etc. by utilizing the basicity of nitrogen, the ability to coordinate with metals, and the cationic nature of quaternary nitrogen. Widely used as a polymer. Among these, polyvinylamine, aminopolystyrene, aminomethylpolystyrene, and their derivatives are representative as polymers containing aliphatic nitrogen, but it is difficult to synthesize the corresponding monomers for all of them. Due to low polymerizability,
It cannot be produced by direct polymerization of monomers, and it is necessary to perform a polymer reaction on a polymer of other monomers. However, in this case, the process becomes complicated because it is necessary to isolate and purify the intermediate, and
In general, polymer reactions have many problems, such as slow reaction rates and long reaction times; especially in the case of three-dimensionally crosslinked polymers, the reaction is even slower and often does not go to completion. ing. As a result of repeated studies based on the above background, the present inventors discovered a monomer represented by the following structural formula (A) (hereinafter referred to as "monomer (A)"). Ivy. (Here, n represents an integer of 0 or more, and R represents an alkyl group having 4 or less carbon atoms.) Since this monomer (A) has a nitrogen-containing substituent, it cannot be polymerized or By copolymerizing with the monomer, a polymer having an aliphatic nitrogen in the side chain can be easily synthesized. Furthermore, monomer (A)
When n is large, the type has a high molecular weight side chain, and when this is polymerized, a graft polymer having polystyrene as the backbone is produced. In general, most methods for producing graft polymers involve synthesizing a trunk polymer and attaching branch polymers using various techniques, but such grafting reactions require activation of the trunk polymer. , polymerization is required under special conditions, which often requires more sophisticated operations than general polymerization reactions, and molecular design such as branch length and number of branches is not always easy. isn't it. On the other hand, the monomers of the present invention not only easily yield graft polymers through general radical polymerization, but also allow for more precise molecular design because the length of the branches is also controlled by the molecular weight of the starting monomer. Can be executed. The method for producing monomer (A) is to use a diamine represented by the following structural formula (B) (hereinafter referred to as "diamine (B)").
is reacted with divinylbenzene in the presence of the corresponding lithium amide. (Here, R represents an alkyl group having 4 or less carbon atoms.) In this reaction, a one-to-one adduct of divinylbenzene and diamine (B), that is, monomer (A)' [formula (A) Then, a polyadduct, that is, monomer (A)' [where n is a positive integer in formula (A)] is formed, and the molecular weight of the monomer is will increase. In this way, the rate of the first-stage addition reaction is higher than that of the second-stage polyaddition reaction, so depending on the conditions, it is possible to isolate the one-to-one adduct (A)'; By mixing the 1-adduct (A)′ and lithium dialkylamide, the polyadduct (A)′
can also be manufactured. A more preferred embodiment of the reaction method is a method using lithium amide prepared from diamine (B) and alkyllithium, lithium aluminum hydride, lithium hydride, or the like. Among these, alkyl lithiums are particularly preferred from the viewpoint of solubility in solvents, operability, and the like. Furthermore, when producing polyadduct (A)' using the above-mentioned one-to-one adduct (A)' as a starting material, it is necessary to use lithium dialkylamide with large steric hindrance, and preferably lithium diisopropylamide. It is. As divinylbenzene, p-divinylbenzene, m-divinylbenzene, or a mixture thereof can be used. Furthermore, although commercially available divinylbenzene contains ethylvinylbenzene as an impurity, such crude divinylbenzene can also be used.
However, when crude divinylbenzene is used as a starting material, a product derived from ethylvinylbenzene may be produced as a by-product. It is preferable to use p-divinylbenzene for the following reasons. First, this reaction is faster for p-divinylbenzene than for m-isomer, and is less likely to produce by-products, which will be described later. Furthermore, in the polymer of monomer (A), since the alkylaminoethyl group occupies a position farther from the polymer main chain, steric hindrance around nitrogen is small and the performance as a functional polymer is high. In the monomer (A) disclosed in the present invention, R is an alkyl group having 4 or less carbon atoms, but the smaller the carbon number of R, the more widely used as a starting material for polycondensates,
One-to-one adducts that also have high utility value as monomers
The boiling point of (A)' is lowered, making it easier to purify by distillation, and the nitrogen content per weight of monomer (A) is increased, improving its performance as a functional polymer. For these reasons, R is a methyl group,
Ethyl group is more preferred. In the reaction of the present invention, lithium amide performs a catalytic action. This is one of the major features of this reaction. It is sufficient to use lithium amide in an equimolar or less amount relative to divinylbenzene or the 1:1 adduct (A)′, preferably in a molar ratio of 0.001.
It is preferable to use an amount of 0.5 times to 0.5 times, more preferably 0.01 times to 0.2 times. At this time, it should be kept in mind that the concentration of lithium amide influences the reaction rate. Lithium amide is deactivated by reacting with substances containing active hydrogen such as water, alcohol, and acids that coexist in the reaction system, so it is preferable to dehydrate or otherwise purify the raw materials and solvents used beforehand. ,
When these active hydrogen-containing substances are mixed, it is desirable to use more than the intended amount of lithium amide. Lithium amide can be prepared, for example, by reacting an amine with a lithium compound of a substance less acidic than the amine used. As such a lithium compound, phenyllithium or alkyllithium such as methyllithium, ethyllithium, butyllithium, etc. is preferable. For example, by adding a hexane solution of n-butyllithium to diamine (B), lithium amide can be prepared immediately. Diamine (B) causes a stoichiometric reaction with divinylbenzene, but the amount used is preferably 0.3 to 2.5 times the molar ratio of divinylbenzene, and more preferably 0.6 to 1.3 times. be. If diamine (B) is in excess, a compound with secondary amines at both ends may be produced, and if divinylbenzene is in excess, a product with vinyl groups at both ends may be produced, which is undesirable. . In this point,
When obtaining the polyadduct (A)', the method of starting from the 1:1 adduct (A)' allows the divinylbenzene component and the diamine component to be set at exactly 1:1, so the above-mentioned problem does not occur. This is a recommended method because it reliably produces a monomer (A) structure. In particular, in order to obtain a high molecular weight monomer (A), it is necessary to maintain a strictly 1:1 molar ratio of divinylbenzene and diamine (B), starting from a 1:1 adduct (A)'. It is essential that There are no particular restrictions on the method of mixing the solution containing lithium amide and divinylbenzene or the one-to-one adduct (A)', but the method of adding the latter to the lithium amide solution allows the preparation and reaction of lithium amide to be carried out in the same container. This method is particularly preferable since it has advantages such as being able to be carried out using a lithium amide solution and eliminating the need for transferring the lithium amide solution. The reaction of the present invention can also be carried out in the presence of an inert solvent. Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and octane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, dioxane, and tetrahydrofuran, dimethyl sulfoxide, N,
Aprotic polar solvents such as N-dimethylformamide and hexamethylphosphoric triamide, etc.
Liquids that do not react with the lithium amide under the reaction conditions can be used. Among these, benzene, tetrahydrofuran and the like are preferred. However, when producing a high molecular weight monomer (A), aliphatic hydrocarbons are not preferred because the solubility of the product is low. The amount of solvent used is preferably 0.1 to 50 times, more preferably 0.5 to 20 times, the volume of divinylbenzene. The reaction generally slows down as the relative amount of solvent increases. In the present invention, the temperature at which the reaction is carried out is not particularly limited, but is preferably -78°C to 100°C, more preferably -30°C to 50°C. Although there is no restriction on the reaction time, in the case of producing a one-to-one adduct (A)', it is preferably 1 minute to 8 hours, particularly 5 minutes to 4 hours. When obtaining the polyadduct (A)'', it is preferable for 30 minutes to 1000 hours, and more preferably 20 minutes to 1000 hours.
Hours to 400 hours are preferred. In particular, in order to obtain a high molecular weight polyadduct, it is necessary to carry out the reaction at low temperature for a long time. The reaction rate is largely controlled by temperature, type of amine, concentration of raw materials, type of solvent, etc., so the reaction time should be set depending on the conditions. It is recommended to determine the end time of the reaction by quantifying the raw materials and products using chromatography or liquid chromatography. In order to stop the reaction, it is necessary to deactivate lithium amide with alcohol such as ethanol or propanol, water, or the like. The product can be isolated by distillation in the case of a one-to-one adduct (A)', but in the case of a higher molecular weight, column chromatography, reprecipitation method, etc. can be used. can. Also recommended is a method in which concentrated hydrochloric acid or hydrogen chloride gas is added to the reaction mixture to precipitate the hydrochloride. Isolation operations often become more efficient by adding water to the reaction mixture as a pretreatment and performing extraction and separation. In addition, to measure the molecular weight of monomer (A), viscosity method,
A vapor pressure osmometer or the like may also be used, but gel permeation chromatography is preferred. Using this, the molecular weight distribution can also be determined,
Moreover, the weight average molecular weight can be obtained from the position of the peak. Furthermore, since a small amount of the reaction solution can be sampled and measured as it is, it is possible to track the progress of the reaction while it is being carried out. Furthermore, by using the carbon-13 nuclear magnetic resonance spectrum, it is possible to determine the number average molecular weight. Specific measurement examples are shown in Examples. The novel monomer (A) obtained by the present invention is useful as a basic monomer, and the polymer or copolymer derived therefrom has a plurality of nitrogen atoms in the side chain, For example, it has excellent coordination ability for metals. Furthermore, the polymer of monomer (A) having a large molecular weight is a novel graft polymer. Examples of the present invention will be shown below, but the present invention is not limited to the scope of these Examples. Example 1 200 ml of benzene, N,
30ml of N'-diethylethylenediamine, plus n
6 ml of a 15% n-hexane solution of -butyllithium was added with magnetic stirring to prepare a solution containing N,N'-diethylethylenediamine and the corresponding lithium amide. Next, 26 g of p-divinylbenzene was added and the mixture was sealed. After stirring for an additional 30 minutes at room temperature, 0.2 ml of water was added. After separating the white precipitate generated at that time, 0.1 g of a polymerization inhibitor (Sumilyzer BBM-S, manufactured by Sumitomo Chemical Co., Ltd.) was added.
Distillation was performed under reduced pressure to obtain 30.6 g of a fraction at around 110°C at 0.1 mmHg. This product is p-(N,N'-diethylethylenediaminoethyl)styrene (structural formula (A); n=
0, R=C ₂ H ₅ ) was confirmed from the following spectrum data. Proton nuclear magnetic resonance spectrum (100MHz, solvent: deuterochloroform, reference material: tetramethylsilane), δ value: 1.02 (triplet, J = 7Hz, 6H),
1.4 (1H), 2.4-2.7 (multiplet, 12H), 5.15 (double line, J = 11Hz, 1H), 5.65 (double line, J = 18Hz,
1H), 6.67 (two sets of doublets, 1H), 7.05-7.4 (multiplet, 4H) Here, J represents a coupling constant, and nH represents that it corresponds to n protons. Carbon-13 nuclear magnetic resonance spectrum (25MHz, solvent;
Deuterium chloroform, reference material; tetramethylsilane, total proton irradiation conditions), δ value; 11.9, 15.3,
33.5, 44.2, 47.6, 53.3, 55.3, 112.9, 126.1,
128.9, 135.3, 136.7, 140.6ppm. Example 2 17.7 g of p-(N,N'-diethylethylenediaminoethyl)styrene produced in Example 1 was added to a 100 ml eggplant-shaped flask with a three-sided pot, and then,
50ml of tetrahydrofuran was added. Furthermore,
15% n-hexane solution of n-butyllithium 3.0
A mixed solution containing diisopropylamine and the corresponding lithium amide obtained by mixing 0.51 g of diisopropylamine and 0.51 g of diisopropylamine was added. Magnetic stirring was continued for 150 hours at room temperature. During this time, sampling was performed over time and analyzed using gel permeation chromatography. The analysis conditions are as follows. Equipment: HLC802-UR manufactured by Toyo Soda Kogyo Co., Ltd.
Mold, filler; TSK-GEL G-2000 2 pieces, G-
3000 1 bottle, G-4000 1 bottle, measurement temperature: room temperature, eluent: tetrahydrofuran. The measurement data is shown in the drawing. This data is
Monomer (A) (R
= C ₂ H ₅ ) is generated. Example 3 The same operation as in Example 2 was performed except that 78 ml of tetrahydrofuran was used. After stirring for one week at 0° C., analysis was performed by gel permeation chromatography in the same manner as in Example 2, and the weight average molecular weight was 5,400. On the other hand, after adding 0.2 ml of water to the reaction mixture and separating the white precipitate formed, the solvent was removed under reduced pressure, and further
It was dried under reduced pressure at 70°C for 5 hours. A portion of the viscous substance thus obtained was dissolved in deuterated chloroform and the carbon-13 nuclear magnetic resonance spectrum was measured.
The chemical shifts (δ values) based on TMS were as follows. 12.0, 33.2, 48.1, 51.8, 56.1, 128.7,
138.1ppm. In addition, 135ppm on both sides of the 138.1ppm peak,
A small peak at 141 ppm is observed, but this is absorption derived from the benzene nucleus adjacent to the terminal vinyl group, and the number average molecular weight can be determined from its relative integral value. The value obtained with this system was 3700. Examples 4 and 5 Reactions were carried out using the same apparatus and composition as in Example 3.
The reaction conditions and results are shown in Table 1, where M
_o is the number average molecular weight determined from carbon-13 nuclear magnetic resonance spectrum, and M _gpc is the weight average molecular weight obtained from gel permeation chromatography.

[Table] Example 6 Using the same apparatus as in Example 1, the following reagents were introduced in the following order. (1) 150ml of benzene, (2) N,N'-
10 ml of dimethylethylenediamine, (3) 3.0 ml of a 15% n-hexane solution of n-butyllithium, (4) 15 ml of p-divinylbenzene. In the above mixture, the corresponding lithium amide is immediately generated from N,N′-dimethylethylenediamine and n-butyllithium, and
The reaction for producing the target substance has started. After continuing stirring at room temperature for 1 hour and performing the same treatment as in Example 1,
Distilled. A distillate with a boiling point of 115℃ at 0.5mmHg
I got 6.5g. The proton nuclear magnetic resonance spectrum of this product gave the following chemical shifts. (Reference material; TMS) 1.18 (1H), 2.28 (double line, J = 7Hz, 6H),
2.4-2.8 (multiplet, 8E), 5.12 (doublet, J=11
Hz, 1H), 5.61 (double line, J=17Hz, 1H), 6.59
(two sets of doublets, 1H), 6.95-7.35 (multiplets,
4H). Example 7 A 500 ml four-necked flask equipped with a thermometer, stirrer, and dropping funnel is charged with 150 ml of n-hexane which has been dried and distilled with sodium metal added thereto. next
Add 60 ml of N,N'-diethylethylenediamine, followed by 21 ml of 15% n-butyllithium.
- Add the hexane solution while stirring. While stirring, 142 ml of a 1:1 (V/V) mixture of p-divinylbenzene and n-hexane was added dropwise from the dropping funnel. Stirring was continued for 3 hours while keeping the reaction system at 50°C, and then 0.7 ml of water was added, and treatment and distillation were carried out in the same manner as in Example 1 to obtain 51 g of product. Example 8 A reaction was conducted in exactly the same manner as in Example 7, except that m-divinylbenzene was used instead of p-divinylbenzene. Distillation resulted in 43 g of product. Example 9 57ml of tetrahydrofuran in a 100ml pressure bottle,
17.6 g of N,N'-dimethylethylenediamine was added, and while stirring, 3 ml of a 2N solution of methyllithium in ethyl ether was added. An additional 26.0g of p.
- Add divinylbenzene, seal the bottle and leave at room temperature for 1 hour.
Shake weekly. Gel permeation chromatography was carried out under the same conditions as in Example 2, and the weight average molecular weight was determined to be 1100.

[Brief explanation of the drawing]

The drawing is a graph showing the relationship between reaction time and molecular weight measured in Example 2 of the present invention.

Claims (1)

[Claims] 1. Weight average molecular weight represented by the following structural formula (A)
A new nitrogen-containing monomer of less than 10,000. (Here, n is an integer of 0 or more, and R represents an alkyl group having 4 or less carbon atoms.) 2. The monomer according to claim 1, wherein the substituent R is an ethyl group or a methyl group. 3. The monomer according to claim 1 or 2, wherein the disubstituent substituent on the benzene nucleus is at the para position. 4. The monomer according to any one of claims 1 to 3, wherein n is 0. 5. A novel nitrogen-containing monomer represented by the following structural formula (A), which is obtained by reacting a diamine represented by the following structural formula (B) with divinylbenzene in the presence of the corresponding lithium amide. manufacturing method. (Here, n is an integer of 0 or more, and R represents an alkyl group having 4 or less carbon atoms.) 6. Claims in which the lithium amide is prepared from a diamine represented by the structural formula (B) and an alkyl lithium. A method for producing the monomer according to item 5. 7. The method for producing a monomer according to claim 6, wherein the alkyllithium is n-butyllithium. 8. A method for producing a monomer according to any one of claims 5 to 7, wherein the reaction is carried out in the presence of an inert organic liquid. 9. The method for producing a monomer according to claim 8, wherein the inert organic liquid is benzene, tetrahydrofuran, n-hexane, cyclohexane, or a mixture of two or more of these liquids. 10. A method for producing a monomer represented by the following structural formula (A)'', which comprises reacting an amine represented by the following structural formula (A)' with a lithium dialkylamide. (Here, R is an alkyl group having 4 or less carbon atoms, m
represents a positive integer. 11. The method for producing a monomer according to claim 10, wherein the lithium dialkylamide is lithium diisopropylamide.