JPH0360324B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing members of the group of substances broadly known as reactive polymers. Specifically, the present invention relates to a method for producing a polymer compound having acid chloride in the benzene nucleus of a polymer compound having styrene units as a main component (hereinafter simply referred to as polystyrene).

The polymer compound of the present invention is a substance whose use has been significantly developed in recent years as a convenient polymer reagent in various organic syntheses. For example, acid chlorides can be used for partial protection of diphenols and diols [CCLeznoff et al., Can.J.Chem., 55, 3351]
(1977)], for the synthesis of peptides and oligonucleotides [RLLetsinger et al., J.Am.Chem.Soc., 87,
3526 (1965)], and also for the synthesis of porphyrins [C.
C. Leznoff et al., Angew.Chem., Int.Ed., Engl.
17, 947 (1978)].

Carboxylic acids derived from acid chlorides have also been used with hydrogen peroxide as epoxidizing agents for olefins [CR Harrison et al., J. Chem, Soc.
Perkin I, 1976, 605 (1976)], and as a phase transfer catalyst [SLRegen et al., J.Org.Chem., 44,
1961 (1979)] used. For such uses, crosslinked polymer compounds are preferred because they are convenient in both manufacturing and usage steps, processing, and handling.

The method for producing a polymer compound according to the present invention is conventionally obtained by reacting carboxylic acid-containing polystyrene with thionyl chloride. This manufacturing method is based on JT
Journal of Polymer by Ayres, CKMann
Science, Polymer Letters, 3, 505 (1965). However, in order to obtain carboxylic acid-containing polystyrene as a raw material through a polymer reaction as in the present invention, conventionally it has to be obtained from polystyrene through at least two steps of unit reactions. Therefore, in the conventional method, in order to obtain the acid chloride-containing polystyrene of the present invention, it was necessary to undergo at least three unit reactions in the entire process, which was extremely complicated.

The conventional method for producing carboxylic acid-containing polystyrene, which is an intermediate for introducing acid chloride into polystyrene, involves sequentially acetylating polystyrene and oxidizing it with hypobromite [synthesis of carboxylic acid; RL Letsinger et al. , J.of Am.
Chem.Soc., 86, 5163 (1964)], two-step oxidation method of chloromethylated polystyrene [synthesis of carboxylic acids;
JTAyres et al., J. Polymer Science, Polymer
Lett., 3505 (1965)], Lithiation of Polystyrene,
Method of sequential carbon dioxide insertion [synthesis of carboxylic acids, TMFyles et al., Canada.J.Chem.54, 935
(1976)] is known.

Therefore, the present invention provides a method for easily obtaining polystyrene containing acid chloride (2) by polymer reaction without going through the conventional complicated operations as described above.

The reaction for producing the acid chloride-containing polymer compound of the present invention requires four components: polystyrene, oxalyl chloride, an activator, and a solvent.

The polystyrene used as a starting material in the present invention contains 50 mol% or more of styrene units, may be linear, and known polystyrene-based polymers can be used. In addition to styrene homopolymers, linear polystyrenes include substituted styrenes having halogen, nitro, methoxy, etc. as cores, and copolymers with monomers such as α-methylstyrene, butadiene, isoprene, propylene, and ethylene. can be used. The molecular weight of the linear polystyrene used is not particularly limited, but
Usually in the range of 5,000 to 5,000,000. Further, as the crosslinked polystyrene, a copolymer with divinylbenzene, butadiene, etc. can be used.
Any of these various polystyrenes can be used regardless of the polymerization method used to produce them.

As the oxalyl chloride used in the present invention, a commercially available product (purity of 98% or more) can be used as is. If necessary, it can also be obtained by distillation from a reaction mixture of oxalic acid and phosphorus pentachloride for a long period of time at or below room temperature. The amount of oxalyl chloride to be used is determined depending on the rate of introduction of acid chloride into polystyrene, but is usually 0.02 to 5 mol, preferably 0.05 to 3.0 mol, per mol of benzene nuclei in polystyrene.

As the solvent used for producing the acid chloride-containing polystyrene of the present invention, solvents commonly used in Friedel-Crafts reactions, such as carbon disulfide, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, and nitrobenzene, can be used. . Such a solvent has the ability to dissolve or disperse the starting material polystyrene, and at the same time can dissolve oxalyl chloride.
The amount of solvent used is usually per 100g of polystyrene.
The proportion is 200-3000g.

The synthesis of the acid chloride-containing polystyrene of the present invention requires an activator for oxalyl chloride. As the activator, Lewis acids used in Friedel-Crafts reactions, ie, aluminum chloride, tin tetrachloride, zinc chloride, ferric chloride, titanium tetrachloride, zirconium tetrachloride, etc. can be used. The amount of the activator used depends on the amount of oxalyl chloride used, and is usually 0.5 to 2.0 mol, preferably 0.75 to 2.0 mol, per 1 mol of oxalyl chloride.
It is 1.25 mol.

The method for producing acid chloride-containing polystyrene according to the present invention is specifically shown in the Examples below, and the outline thereof will be explained as follows.

A predetermined amount of polystyrene is dissolved or dispersed in a solvent under stirring. Oxalyl chloride is added thereto, and the temperature is set to a predetermined temperature selected from the range of -10 to 65°C while stirring. Next, the activator is added in portions of the amount to be used, and the addition is usually completed within 2 minutes to 60 minutes. After continuing stirring for 1/4 hour to 10 hours depending on the reaction rate,
Terminate the reaction.

It should be noted that even if an operational change is made, such as adding the activator first and then adding oxalyl chloride, this does not in any way diminish the features of the production method of the present invention.

The reaction mixture thus obtained is mixed with 1 to 4 N hydrochloric acid, and if the product is dissolved, the mixture is separated; if the product is not dissolved, it is filtered as is.
Next, after repeated washing with water, the desired produced polymer can be obtained by applying known techniques depending on whether the product is soluble or insoluble. Also,
The acid chloride-containing polystyrene obtained by the present invention can be easily converted into carboxylic acid-containing polystyrene.

That is, in the method for producing acid chloride-containing polystyrene of the present invention, the reaction mixture after the completion of the reaction is treated with hydrochloric acid and repeatedly washed with water, or the product recovered without washing with water is hydrolyzed under heating in an aqueous alkaline solution, Thereafter, carboxylic acid-containing polystyrene can be obtained by neutralizing with acid. Usually, there are no particular limitations on the alkali used for hydrolysis, but 0.01 to 4 N caustic soda or caustic potash is preferred. Also, the temperature of hydrolysis is
The temperature is 60-100°C and the reaction time is 2-10 hours.

The acid chloride produced by the present invention, and the polystyrene containing the carboxylic acid derived therefrom, can usually have a functional group content in a wide range from 0.01 to 1 mole per mole of benzene nuclei in the polystyrene.

According to the present invention, the production of acid chloride-containing polystyrene using polystyrene as a raw material, which had the disadvantages of complicated operations and low content of functional groups in conventional production methods, has become significantly easier.

The manufacturing method of the present invention will be specifically illustrated below using Examples, but the present invention is not limited to the scope of these Examples.

Example 1 18.7 g of oxalyl chloride was added to a mixture of 10 g of porous granules of polystyrene crosslinked with 10% divinylbenzene dispersed in 100 ml of carbon disulfide.
(142 mmol) was added. While stirring this mixture, 19.0 g (142 mmol) of aluminum chloride was added little by little over 10 minutes. After continuing stirring at room temperature for 2 hours, the reaction was completed. The reaction mixture was shaken with 2N hydrochloric acid (100ml) and filtered. After repeating washing with water (100ml) and filtration three times, washing with acetone (100ml), and vacuum drying (60ml).
°C/15-18 mmHg for 16 hours). generated granules
13.5g was obtained.

Elemental analysis shows Cl; 15.54%, which is −
The content of COCl was 64% in mole fraction relative to all benzene nuclei in the product. The infrared absorption spectrum (KBr tablet) is as shown in Figure 2.
The absorption of carbonyl (>=0) derived from acid chloride, which was not observed in the raw polystyrene shown in FIG. 1, appears divided into 1770 cm ^-1 and 1727 cm ^-1 .

Example 2 10 g of polystyrene obtained by homopolymerization (average molecular weight
20.000) was dissolved in 150 ml of methylene chloride, and 25.4 g (200 mmol) of oxalyl chloride was added thereto. Add aluminum chloride to this solution while stirring.
29.4 g (220 mmol) was added in small portions over 20 minutes.
Then, the reaction was completed after stirring for 3 hours while heating and refluxing. The reaction mixture was diluted with 3N hydrochloric acid (100ml).
After shaking and liquid separation, washing with water (100 ml) was performed three times, and 100 ml of methanol was further added to precipitate the produced polymer. After passing, vacuum dry (60℃/15~
18 mmHg for 14 hours) to obtain 14.8 g of produced polymer.

Elemental analysis shows Cl; 19.06%, which is -
The content of COCl was 84 mol% based on the total benzene nuclei in the product.

Example 3 10 g of polystyrene popcorn polymer containing 8% butadiene was added to 30 ml of tetrachloroethane.
dispersed into There, 4.8g of ferric chloride (29.5m
mol), then 3.7 g of oxalyl chloride
(29.1 mmol) was added over 2 minutes. The mixture was stirred at room temperature for 1 hour to complete the reaction. The reaction mixture was shaken with 1N hydrochloric acid (50ml) and filtered. Furthermore, after washing with water (100 ml) three times and acetone (100 ml), vacuum drying was performed in the same manner as in Example 1. 10.3 g of product was obtained.

Elemental analysis shows Cl/; 2.18%, which is -
The content of COCl corresponded to 7.2 mol% relative to the total benzene nuclei in the product.

Example 4 4.1 g of oxalyl chloride was added to a mixture of 10 g of polystyrene copolymer containing 8% p-chlorostyrene dissolved in 40 ml of methylene chloride with stirring.
(32.3 mmol), followed by 8.4 g of tin tetrachloride.
(32.2 mmol) were added sequentially. Thereafter, the mixture was stirred at room temperature for 30 minutes, and then heated to reflux while stirring for another 2 hours to complete the reaction. The reaction mixture was shaken and separated with 1N hydrochloric acid (100 ml), and then washed with water (100 ml) three times. 100 ml of methanol was added to obtain 9.3 g of produced polymer from the methylene chloride solution.

Elemental analysis shows Cl; 9.80%, which is −
The content of COCl corresponded to 28 mol% relative to the total benzene nuclei in the product.

Example 5 5 g of the produced polymer obtained in Example 1 was heated with 100 ml of 2N caustic potash at 100° C. for 5 hours while stirring. After filtering the product, washing with 0.1N hydrochloric acid (50 ml) and water (50 ml) were repeated three times, and then with acetone (50 ml), followed by vacuum drying.

The infrared absorption spectrum (KBr tablet) is shown in Figure 3. Strong absorption of -CO ₂ H is seen at 1700 cm ^-1 , while at 1770 cm ^-1 and 1727 cm ^-1
The absorption of acid chloride (see Figure 2) completely disappeared.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the raw polystyrene of Example 1, Figure 2 shows the infrared absorption spectrum of the product granules obtained in Example 1, and Figure 3 shows the infrared absorption spectrum of the product treated in Example 5. be.

Claims (1)

[Claims] 1. By reacting oxalyl chloride with a polymer compound containing styrene as a main component under Friedel-Crafts reaction conditions, an acid chloride represented by the formula () is produced by -COCl () in the polymer. A method for producing a polymer compound having part or all of the benzene nucleus of.