JPS59161368A - Novel halogenated 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride and its preparation - Google Patents

Abstract

NEW MATERIAL:The novel halogenated 3,3',4,4'-benzophenonetetracarboxylic acid anhydride of formula I (R1 is halogen; R2 is H or halogen; R3 is H or halogen). EXAMPLE:2,2'-Dibromo-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride. USE:Raw material of flame retardant, curing agent of epoxy resin, stabilizer of plastics against ultraviolet radiation, and reactive flame-retardant. PREPARATION:The objective compound of formula I can be prepared by the halogenation reaction of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride of formula II in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel... halogenated 3.3',4.4'-benzophenone tetracarboxylic dianhydride (hereinafter halogenated B
Regarding 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) represented by the following general formula (1), and its production method,
By carrying out a halogenation reaction in a solvent, a new compound, halogenated BT represented by the following general formula (n), is produced.
DA(r heading) and the establishment of its manufacturing method.

(In the formula, R1 is a halogen atom, and R2 and R3 each independently represent a halogen atom after removing a hydrogen atom.) Conventionally, tetrapromofucuric acid anhydride, which has a similar structure to BTDA, is used as a flame retardant for unsaturated polyester resins. Although it has been
It is not preferred because it has a drawback of very low solubility in the resin and deteriorates the physical properties of the resin. The present inventors have conducted extensive research to find a flame retardant and a flame-retardant curing agent for epoxy that do not have these drawbacks, and have developed a new halogenated BTDA'e.

The new halogenated BTDA is flame retardant on its own, and has a wide range of applications such as a curing agent for epoxy resins and a stabilizer for ultraviolet rays in plastic processing. It is a compound that is expected to be applied as a raw material for reactive flame retardants by fully deriving the ester. 1. Demand for polymeric materials with excellent heat resistance, such as polyesternovepolyimide, has been increasing in recent years, and low-halogenated BTDA is a compound that is expected to be widely applied as this material.

In the general formula (n), the halogenated BTDA of the present invention is a dihalogenated BTDA in which R no 1 is substituted with a halogen atom, R, 2, and R's are hydrogen atoms, and R1 and R2 are
Logen atom substitution, tetrahalogenation B where R1 is a hydrogen atom
T DA , Rs , R2, and R3 are obtained as hexa/.-halogenated BTDA in which halogens are substituted. Desired compounds can be obtained by adjusting reaction factors such as the oxidation conditions, such as reaction temperature, reaction time, type of solvent, and amount of catalyst and oxidation agent. Furthermore, as the degree of halogen substitution of BTDA increases, the original ultraviolet absorption power decreases, and the hexa-isomer no longer exhibits absorption. Infrared absorption spectrum is 3050-31
The absorption of -CH stretching vibration at 50 cm-' decreases as halogen substitution increases, and absorption disappears in the hexa-isomer. Therefore, by detecting these, the halogenation reaction can be controlled.

The halogenated BTDA of the present invention can be obtained by carrying out a halogenation reaction in a BTDAk solvent.

As the halogenating agent used in the halogenation reaction, it is preferable to use chlorine or bromine alone, but bromine chloride, sulfur chloride, sulfuryl chloride, other halogenating agents, or solutions thereof may also be used. Bromine chloride can be obtained by reacting approximately equimolar amounts of chlorine and bromine, but it may also be a mixture of approximately equimolar amounts of chlorine and bromine or a mixed solution thereof. It can also be obtained by reacting a bromide such as potassium bromide with hydrogen chloride in water. Ultraviolet light and/or catalysts are used as necessary for the halogenation reaction, and examples of catalysts include organic peroxides, phosphorus, sulfur, iron powder, iodine, Friedel graft catalysts such as ferric chloride, etc. A composite system of these can also be used.

As the solvent, a protic solvent or an organic solvent can be used. As a protic solvent, sulfur chloride IJ)
Persulfuric acid, chlorosulfuric acid, fuming sulfuric acid, acetic acid, etc. are used. Examples of organic solvents include chlorogenated aliphatic hydrocarbons containing chlorine and/or bromine and having carbon atoms of 4 or less, such as carbon tetrachloride, chloroform, and trichloroethane.

Even if the solvent is a heterogeneous solvent system of a protic solvent and an organic solvent, the halogenation reaction can be caused.

The mixing ratio of the heterogeneous solvent system is not particularly limited.

The halogenation reaction is usually carried out in a solvent system containing BTDAk by adding a halogenating agent while stirring.

The reaction temperature can be 0 to 150°C. In a protic solvent, the temperature is usually 40 to 80°C. When carrying out a halogenation reaction in a heterogeneous solvent system, it is preferable to carry out the reaction near the boiling point of the organic solvent.

After the reaction is complete, the halogenated BTDAkF is separated by injecting the reaction mixture into ice water.4 Because the reaction mixture contains unreacted halogenating agent, when injecting the reaction mixture into ice water, excess In order to reduce the halogenating agent, a reducing agent such as sulfite, sodium thiosulfate, etc. can be added to prevent coloring of the product. The crude halogenated B TDA separated from each household is purified using dilute sulfuric acid, ice water, organic solvents, washing and recrystallization, or other methods. For example, crude 2.2', 5.5'.

6.6'-Hexabromo-3,3',4,4'-benzophenonetetracarboxylic dianhydride can be obtained in high purity (99.9% or more) by recrystallization in acetic acid. .

The present invention will be explained in detail below using all Examples, but the present invention is not limited only to these Examples.

Example 1゜Volume 1. 700ml of acetic acid was added to a reactor equipped with a four-eye flask, a thermometer, a condenser, an addition funnel, and a stirrer.
1. Add 100 y of BTDA @, add 1.0 g of anhydrous ferric chloride and 1.51 g of iodine as a catalyst and mix at 40-45°C.
Add bromine 11 (1'r, 2'r) for about 60 minutes while maintaining
The time bromination reaction was carried out. After concentrating this reaction solution,
When recrystallized from acetic acid, highly pure 2,2'-dibromo 3°3', 4
, 4'-benzophenonetetracarboxylic dianhydride 1
08.9′? was obtained (73.2% of theoretical yield).

The elemental analysis values, mp, and ultraviolet absorption spectrum of this product are shown in Table 1.

Example 2゜In the same reactor as in Example 1, 30% oleum 8007,
BTDAIO (1 completely dissolved, 3,07% of sulfur monochloride as a catalyst, 1,0% of liquid chlorine added, treated with crystals kept at 50-55°C, washed with ice water and acetone, then acetic acid -
Recrystallization from dimethyl sulfoxide gives highly pure 2
,2',5,5'-tetrabromo-3,3',4
．． 4'-benzophenonetetracarboxylic dianhydride 17
11 (yield 86.5% relative to theory).

The elemental analysis values, mp, and ultraviolet absorption spectrum of this product are all shown in Table 1.

Implementation fylJ 3゜In the same reactor as in Example 1, 100 f of BTDA was completely dissolved in 60% oleum 6002, and iron 4.07 was added as a catalyst.
~bromine chloride5. Ofi was added thereto, and bromine was added to 300 f' for about 60 minutes while maintaining the temperature at 60 to 65° C., and then bromination reaction was carried out for 8 hours. High purity 2゜2', 5.5', 6.6'-hexabromo 3.3', 4 was obtained by the same post-treatment as in Example 2.
．． 4'-benzophenonetetracarboxylic dianhydride 22
4′? was obtained (90.5% of theoretical yield).

The elemental analysis value, rnp, and ultraviolet absorption spectrum of this product are shown in Table 1, and the infrared absorption spectrum (
KBr method) All shown in Figure 2. FIG. 1 shows an infrared absorption spectrum of the raw material BTDA using the CKBr method, which is shown for reference.

Example 4 In the same reactor as in Example 1, BTDAloof was bath-dissolved in 600 g of 60% oleum, and 0.5 g of phosphorus was added as a catalyst.

Iron powder5. After introducing liquefied chlorine (L501) for about 60 minutes while maintaining the temperature at 45 to 50°C, the chlorination reaction was carried out for 6 hours.
, 2', 5, 5', 6, 6'-hexachloro 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride (1391 total) was obtained (theoretical yield: 84
．． 6%].

The elemental analysis values, rnp, and ultraviolet absorption spectrum of this product are all shown in Table 1.

Table 1 Example 5 60 d of concentrated sulfuric acid was added to a 500° volume four-tube flask equipped with a stirrer, condenser, thermometer and addition funnel.

250ml of carbon tetrachloride was added, and 1.07ml of acetic acid as a catalyst, and 2.0ml of iodine chloride. Of and BTDA60
While maintaining the heterogeneous suspension containing f at 30 to 40°C,
A total of 150 g of bromine was added in about 30 minutes, the temperature was raised to 55-60°C, and the bromination reaction was carried out for 6 hours. When the same post-treatment as in Example 2 was carried out, highly pure 2.2', 5.5', 6°a 6'-hexabromo BTDA 139 was obtained.
．． I got 4 r.

[Brief explanation of the drawing]

Figure 1 shows the raw material BTDA used in Example 3 of the present invention. FIG. 2 shows infrared absorption spectra of the produced hexabromo BTDA obtained by the KBr method. Procedure 7 Ichi Masakawa, (self-motivated) April 5, 1981 1, Indication of the case 1988 Patent Axis No. 3"183/i No. 2, Name of invention New halogenation 3.3', 4.4 '-Hensifhenonetetracarboxylic dianhydride and its manufacturing method 3. Relationship with the amendment case
Tokyofli1chiyo1. L1 Ward Marunouchi 1-. 4 5 Name (234) Sanyo Kokusaku Valve Co., Ltd. 4, Agent Address 16 FlJ, Kanda Higashimono, Chiyoda-ku, Tokyo, 3rd Floor 5, Ei Building, 101, Subject of amendment @ 閠 and specification (detailed description of the invention) Contents A: The following matters in the application are corrected. 1. To the right of the "patent axis" on the first page, [(Patent Law No. 38)
2, and between the ``Title of the Invention'' column and the ``Inventor'' column on the first page, ``Patent application pursuant to the provisions of the Prospectus'' has been added. 2" has been added, and the following matters in the detailed description of the invention section of the specification have been corrected. 1. On the last line of page 6 of the specification [MaIc B T D A J
``In addition, regarding the ultraviolet absorption spectrum, halogenated BTDAJ and correction 2, added [(λmax x 262.5 nm) J'' between ``yield'' and ``decreased'' on the second line of page 7 of the specification cylinder. The following matters in the brief description of drawings section of C9 specification are corrected. 1. At the end of page 13 of the specification [In the drawings, the upper side of the horizontal axis indicates nll+, the lower side of Ic indicates Cm -1, and the vertical axis indicates %. 1 + IF] person.

Claims (1)

[Scope of Claims] (In the formula, R1 is a halogen atom, R2 is a hydrogen atom or a halogen atom, and R3 is a hydrogen atom or a halogen atom, respectively.) Novel halogenated 3, 3', 4, 4'
-benzophenonetetracarboxylic dianhydride. (2) 2.2' dihalogen 3, 3', 4, where R1 is a halogen atom and R2 and R3 are both hydrogen atoms;
Novel halogenated 3.3' according to claim 1, which is 4'-benzophenone tetracarboxylic dianhydride;
4.4'-benzophenonetetracarboxylic dianhydride. (3) In the formula, R,,R, are all halogen atoms, R3 is hydrogen atom, 2.2',,5.5'-tetrahalogen 3
, 3', 4, 4'-benzophenone tetracarboxylic dianhydride. , 4,4'-benzophenone tetracarboxylic dianhydride, the novel halogenated 3,3',4,4'-benzophenone tetracarboxylic dianhydride according to claim 1. (5) Chlorination of chlorine in which the halogen atom in the formula is 3.3', 4
゜4'-benzophenonetetracarboxylic dianhydride)
A novel halogenated 3.3',4.4'-benzophenonetetracarboxylic dianhydride according to any one of claims 1 to 4. . (6) In the formula, the rogen atom is brominated 3,3'
, 4. The novel halogenated 3,3',4,4'-benzophenonetetracarboxylic dianhydride according to any one of claims 1 to 4, which is 4'-benzophenonetetracarboxylic dianhydride. Anhydrous. (7) It is characterized by subjecting 3,3',4,4'-benzophenonetetracarboxylic dianhydride represented by the general formula to a halogenation reaction in a solvent (in the formula, R+ is a halogen atom and R2 is a hydrogen atom). or a halogen atom, and R3 represents a hydrogen atom or all halogen atoms, respectively). (8) Regulation halogenation 3 according to claim 7, wherein the halogenation reaction is a chlorination and/or bromination reaction
, 3', 4, 4'-benzophenonetetracarboxylic dianhydride production method. (9) The novel halogenated compound 3 according to claim 7 or 8, wherein the @ medium is a halogenated aliphatic hydrocarbon with a carbon range of 4 or less containing chlorine and/or bromine, and/or a protic solvent. .3',4,4'-benzophenonetetracarboxylic dianhydride production method. (10) Halogenated 3.3',4゜4'-benzophenone tetra according to any one of claims 7 to 9, wherein the halogenation reaction is carried out in the presence of ultraviolet rays and/or a catalyst. Method for producing carboxylic dianhydride. (11) The novel halogen according to any one of claims 7 to 10, wherein the catalyst is any one of organic peroxide, phosphorus, sulfur, iron powder, iodine, and free chill craft catalyst. Chemical formula 3.3', 4.4'-Method for producing benzophenonetetracarboxylic dianhydride.