JPS59184140A - Novel monomer and production thereof - Google Patents

Abstract

NEW MATERIAL:A monomer of the formula (X1 and X2 are halogen; R is H, 1-10C alkyl, aryl or aralkyl). EXAMPLE:3-(1,2-Dibromoethyl)styrene. USE:Capable of synthesizing a high polymer by homopolymerization or copolymerization with another monomer. The high polymer has 1,2-dihalogenoethylphenyl groups in the side chain thereof, is capable of converting the above-mentioned groups into various functional groups by various reactions and useful as a functional high polymer. For example, the introduction of iminodiacetyl groups permits the synthesis of chelate high polymers useful as a metal removing agent or high polymers useful as flame retardant high polymers. PREPARATION:Divinylbenzene or a substitution product thereof is reacted with an inactivated halogenating agent to give the compound of the formula. The molar amount of the halogenating agent to be used is preferably 0.4-0.9 times that of the benzene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel monomer and a method for producing the same, and more particularly to a novel styrene derivative having a 1,2-dihalogenoethyl group and a method for producing the same.

Many styrene derivatives have been developed and synthesized and are widely used in the synthesis of functional polymers. For example, cyanostyrene, aminostyrene, etc. are easily polymerized by radical polymerization to provide polymers having various functional groups.

In addition, styrene derivatives and siteha having halogen atoms,
Chlorostyrene, bromostyrene, chloromethylstyrene, per-5-(2-bromoethyl)styrene, and the like are known. In addition, bis-(1,2-dihalogenoethyl)benzene, which has four halogen atoms added to two vinyl groups of divinylbenzene, is well known and has a 1/4 The existence of 2-dihalogenoethylstyrene, which has both groups ], has been completely unknown so far.

As a result of repeated studies under various experimental conditions regarding the reaction of divinylbenzene and its substituted products with halogenating agents, the present inventor synthesized and isolated a novel monomer represented by the following structural formula (1). reached.

(In the formula, X represents halogen, R is hydrogen,
Represents an alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. ) A preferred embodiment of XI, X is the same or different combinations of chlorine, bromine and iodine.

The preferable positional relationship between the vinyl group and the 1,2-dihalogenoethyl group is the meta or para position.

The 1,2-dihalogenoethylstyrene and its substituted product of the present invention are produced by reacting divinylbenzene and its substituted product with a halogen molecule or a halogenating agent that has inactivated the halogen molecule.

As divinylbenzene, it is desirable to use one or a mixture of two of meta-divinylbenzene and para-divinylbenzene.

It is also possible to use substituted divinylbenzenes having an alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms and commercially available divinylbenzene.

As the halogenating agent, halogen molecules such as chlorine, bromine, and iodine can be used, but in order to control the reaction rate and selectivity, it is preferable to use a halogenating agent with inactivated halogen molecules. When using halogen molecules, particular attention must be paid to temperature, addition rate and amount. As the halogenating agent that has inactivated the halogen molecule, for example, an iodinated aromatic compound or an adduct of a nitrogen compound and a halogen molecule is used. Preferably, an adduct of a nitrogen compound, a halogen molecule, and a hydrogen halide is used, and a more preferable example of the adduct is pyridinium hydroprodoberproεd○○ ammoniumpromide perchlorite ((OHJ4N B
r011) etc.

The amount of the halogenating agent used is usually 0.1 to 2.0 times the mole of divinylbenzene, but preferably,
It is from 0.4 times mole to 0.9 times mole.

This reaction can also be carried out in the presence of an inert liquid. Any inert liquid may be used as long as it does not undergo the halogenation reaction itself and does not inhibit the addition reaction of halogen to divinylbenzene.

Preferably, aliphatic hydrocarbons such as pentane, hexane and heptane, alcohols such as methanol, ethanol and Improvyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, ethyl acetate and ethyl benzoate, etc. esters, dimethylformamide,
Amides including dimethylacetamide; halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethylene; ketones such as acetone methyl ethyl ketone and diethyl ketone; ethers such as diethyl ether and methyl ethyl ether dioxane; acetic acid, propionic acid, etc. carboxylic acids, etc. can be used. More preferably, aliphatic hydrocarbons such as hexane and heptane,
Halogenated hydrocarbons such as methylene chloride 7 and carbon tetrachloride,
It is any one type or a mixture of two or more types of carboxylic acids such as acetic acid and propionic acid.

Although the appropriate reaction temperature varies depending on the halogenating agent, it is generally in the range of -100'C to 100C. When using an inactivated halogenating agent, the temperature is preferably -50°C to 30°C. In order to carry out the reaction selectively and efficiently, the temperature of K is particularly preferably from -20°C to 10°C. When using a halogen molecule directly as a halogenating agent,
-70°C to 0°C is preferred.

In the addition reaction using a halogen molecule to divinylbenzene, under the conventional conditions, bis-(1,2-dihalogenoethyl)benzene, in which halogen molecules are added to both of the two vinyl groups, is produced. Quantitative generation. On the other hand, as a result of examining various reaction conditions, we found that when using a halogen molecule, not only mono-his-(1,2-dihalogenoethyl)benzene but also its synthetic intermediate 1,2-
It has become clear that dihalogenoethylstyrene can also be produced. However, when halogen molecules were used, the yield was low and it was not very practical. On the other hand, it has been surprisingly revealed that <1,2-dihalogenoethylstyrene can be synthesized with a very high yield using a halogenating agent in which halogen molecules are inactivated.

The reaction time is not particularly limited, but the reaction rate varies depending on the type of inert liquid, the type of halogenating agent, and its addition rate, so the amount of product can be determined by monitoring the progress of the reaction using gas chromatography etc. It is desirable to take a method to confirm the following.

To describe a specific reaction method that is recommended, put an inert liquid containing divinylbenzene into a flask, and cool it sufficiently while stirring well. Add the halogenating agent little by little to this while being careful not to raise the internal temperature. The reaction is monitored using gas chromatography, etc., and the reaction is stopped after confirming that the reaction has completed. General separation methods such as extraction and distillation can be used to isolate and purify the product from the reaction mixture.

Polymers can be easily synthesized from the seven polymers (I) of the present invention by homopolymerization or copolymerization with other monomers. The polymer has an alkyl-substituted phenyl group with one halogen on an adjacent carbon, that is, a 1,2-dihalogenoethyl phenyl group, in its side chain, and can be converted into various functional groups by various reactions. It is very useful as a functional polymer. For example, it is possible to produce a polymer having the ability to chelate various metals from Shimoto K, which has produced a polymer having an anion exchange ability by reaction with a nitrogen compound. In this case, it is also possible to synthesize a similar polymer using a copolymer of alkyl-substituted styrene having one -.logen atom, such as para-(2-bromoethyl)styrene or chloromethylstyrene. However, there are very large qualitative differences in the performance of the synthesized polymers. For example, the difference is obvious in chelate polymers into which iminodiacetic acid groups have been introduced. When iminodiacetic acid groups are introduced into a polymer produced from 1,2-dihalogenoethylstyrene, a side chain with two iminodiacetic acid groups arranged side by side is produced. It is represented by the following structural formula (10).

On the other hand, when an iminodiacetic acid group is introduced into a polymer produced by, for example, chloromethylstyrene, the following structural formula (1) is obtained.

Comparing the side chains of structural formulas (It) and (III), it is found that ([0 has a greater ability to form complexes with various metals (,]
, ] 2-dihalogenoethyl styrene The chelate polymer synthesized from 2-dihalogenoethyl styrene has been found to be very useful as a metal removal agent.

Furthermore, the polymer produced from 1,2-dihalogenoethylstyrene has two halogen atoms in the side chain, so it is useful as a flame-retardant polymer.

Examples of the present invention will be shown below, but these are not intended to limit the present invention.

Example 1 1 ton of methylene monochloride and 130 liters of meta-divinylbenzene are added to a 2 ton four-loaf flask equipped with a thermometer, reflux, and stirrer. Of (1.0 mol) was introduced. 255.8 f (0.8 mol) of pyridinium hydropromide perpromide (pyridinium hydropromide perpromi) was added in 10 portions at the same temperature for about 2 hours while maintaining the internal temperature at -5°C and stirring. Stirring was continued. 1 lNHCl was added to the reaction product.
was added to remove pyridinium hydropromide. Thereafter, the reaction product was washed twice with 500-pure water. After removing methylene chloride from this liquid using an evaporator, vacuum distillation was performed. If the internal temperature is increased by increasing the internal pressure by 1 sieve, first 33
Unreacted meta-divinylbenzene was distilled off at . Subsequently, a pale yellow-green liquid was distilled out at 101°C. The yield of this liquid was 204.7 tons (71%). Analysis by gas chromatography and liquid chromatography revealed that it was a single substance. Using common organic chemical analysis methods including spectroscopic analysis, it was concluded that this single substance was 3-(1,2-dibromoethyl)styrene.

The analysis results are as follows.

Elemental analysis; C: 41.13 (41,42),
H: 3.65 (3,48), Br: 55-22
(55, 11) However, the numerical values in parentheses here indicate theoretical values.

Mass spectrum; 292 (P+4), 290 (
P+2), 288 (M”/e), 261
(MC2H3), 103 (MCJaBr2
)76(C8H4) Infrared absorption spectrum; 3020.2970.1630
．． 1510.1480.1215.1155.980.
910.800 α, -1 proton nuclear magnetic resonance spectrum (60 MHz % solvent; deuterium chloroform, reference material: tetramethylsilane) δ value; 3.97 (double line, 2H)
, 4.9-5.4 (multiplet, 2H) , 5.73 (4
Double line, IH), 6.67 (Quadruple line, IH), 7.0
~7.7 (Multiplet, 4H) Example 2 Into an IL four-loaf flask equipped with a thermometer, reflux, and stirrer, 500% of methylene chloride and 65% of para-divinylbenzene were charged. Or (0.5 mol) was added. While stirring while maintaining the internal temperature at -10° C., 125.69 (0.4 mol) of tetramethylammonium bromide perpromide was added in 15 portions of about 8 f each.

Thereafter, stirring was continued for about 2 hours at the same temperature. 500-1N HCl was added to the reaction product to remove tetramethylammonium bromide. After that, 250 t of reaction product
Washed twice with nl of pure water. This liquid was applied to an evaporator to remove methylene chloride, and then distilled under reduced pressure.

The internal temperature was raised at an internal pressure of 1 ttmHg, and unreacted para-divinylbenzene was distilled off at 42°C. After that 200
Although the temperature was raised to ℃, no distillate was obtained. When this residual liquid was cooled to room temperature, it became a white solid. The melting point of this solid was 107°C to 110°C. The yield of this solid was 92.4f (64%). As a result of analysis by gas chromatography and liquid chromatography,
This thing turned out to be a single substance. General organic chemical analytical techniques including spectroscopic analysis concluded that this single substance was 4-(1,2-dibromoethyl)styrene.

The analysis results are as follows.

Elemental analysis; C: 41.21 (41,42), H
: 3.40 (3-48), Br:55.18 (5
5, 11) However, the numerical values in parentheses here indicate theoretical values.

Mass spectrum; 292 (P+4 >, 290 (
P+2), 288 (M"◆-/e), 261 (
M C2H3), 103 (M-CtHsBrt
), 76 (C'6H4 infrared absorption spectrum; 3
020.2910.1625.1600.1510.1
430.1130.985.910, sa5, C11 1' proton nuclear magnetic resonance spectrum (60 MHz, solvent: deuterated chloroform, reference material: tetramethylsilane) δ
Value; 3.97 (doublet, 2H), 4.9-5.4 (multiplet, 2H), 5.73 (quadruplet, IH), 6.67
(quadruplet, IH), 7.0-7.6 (multiplet, 4H).

Example 3 1t equipped with thermometer, reflux, dropping funnel and stirrer
500-methylene monochloride and 65% meta-divinylbenzene in a four-bottle flask. Of (0.5 mol) was added. 63.9 f (0.4 mol) of bromine was added dropwise using the dropping funnel while stirring while keeping the internal temperature at -40°C. The dropping rate was about 1 f per minute. After the dropwise addition, stirring was continued for 1 hour at the same temperature.The solution was evaporated to remove methylene chloride, and then treated in the same manner as in Example 1 to obtain a 21.8F (15%) product. The analytical results of this product were consistent with those of the product obtained in Example 1,
It was confirmed to be 3-(1,2-dibromoethyl)styrene.

Example 4 Hexane and 130 ml of meta-divinylbenzene were added to a 2 ton four-loaf flask equipped with a thermometer, reflux and stirrer.
．． Of (1.0 mol) was added. Tetramethylammonium promide perpromide 277.3 F (about 28
The mixture was added in 10 portions of t each. Thereafter, stirring was continued for 2 hours at the same temperature. The product was obtained from this reaction solution in the same manner as in Example 1, and 175.89 (61%) was obtained.

The analytical results of this product were consistent with those of the product obtained in Example 1, and it was confirmed to be 3-(1,2-dibromoethyl)styrene.

Subsequently, in a 500° four-bottle flask equipped with a thermometer, refluxer, and stirrer, 0.5 parts of commercially available polyvinyl alcohol (average molecular weight approximately 1800) and 1 part of sodium chloride were added.
3-(1,2-dibromoethyl)styrene 16.4
t, divinylbenzene (purity 56%, meta form: para form = 773.44% ethylstyrene) 3.6
A mixture of 2.2,2'-azobisisobutyronitrile (0.22%) was added, and stirring was continued at 60°C for 1 hour, at 70°C for 2 hours, and further at 80°C for 4 hours. Subsequently, 20.2 t of dipropylamine was dissolved in 100 ml of ethanol, added to the polymerization solution, and stirring was continued for 8 hours while keeping the internal temperature at 80°C. The produced polymer was spherical particles with a particle size of 0.1 to 1.

After washing the particles with water, they were packed approximately 4 times in a glass column equipped with a glass filter and having an inner diameter of 1.21 mm. A separatory funnel was attached to this glass column, and 200% of IN hydrochloric acid was poured into the column, followed by 100% of acetone, and then 100% of IN potassium nitrate was poured into the column.
ml! It flowed.

At this time, chloride ions in the potassium nitrate solution that had passed through the column were determined by silver nitrate titration. Furthermore, column ni 20
0-IN hydrochloric acid, followed by acetone 100 l11
7! After flowing, the particles were taken out and vacuum dried at 60° C. for 15 hours, and their weight was determined. As a result, the anion exchange capacity of the synthesized particles per dry weight was 4.03 meq.
/l.

Example 5 Commercially available polyvinyl alcohol (average molecular weight approx.
800) 2. Or, 400v of pure water in which 25f of sodium chloride was dissolved was added, and while stirring, 32.8% of the 3-(1,2-dibromoethyl)styrene synthesized in Example 1 was added.
F, divinylbenzene (pure i56% meta form: para form = 7: containing 3.44% ethylstyrene tr) 7.2
f, m-xy Lz750. Of, 2.2'-77
'Add a mixture of 0.42 bisisobutyronitrile,
Stirring was continued at 60°C for 1 hour, at 70°C for 2 hours, and further at 80°C for 4 hours. The particles obtained after cooling-washing are 0.1-1
．． They were spherical particles with a particle size of 0m+.

This particle 30. Of was placed in a 5001Rt four-loof flask equipped with a thermometer, reflux, and stirrer, then 35. A 200-mL ethanol solution in which Of was dissolved was added, and stirring was continued at 70°C for 24 hours. Next, 100% pure water in which sodium hydroxide S, Ot was dissolved.
m was added thereto, and stirring was continued at 90°C for 5 hours. After cooling and washing with water, metal removal ability was examined as shown below. Divalent chloride of Cu and trivalent chloride of F'e were dissolved in pure water, and 10% of each metal was dissolved.
1 ton of an aqueous solution containing 0.0 mm was prepared. Particles synthesized above in this aqueous solution 5. When the amount of metal ions remaining in the aqueous solution was measured after adding Of and soaking for 24 hours, Cu, Fe
Both values were 0.1■ or less.

Patent applicant: Asahi Kasei Industries, Ltd. Representative Patent Attorney Toru Hoshino 347

Claims (1)

[Claims] 1. A novel monomer represented by the following structural formula (1). (wherein, 1. A method for producing a novel monomer represented by structural formula (1), which comprises reacting the monomer with a polymerizing agent.