JPH1180051A - Brominated 1,3-dimethyl-3-phenyl-1-(2-methyl-2-phenylpropyl)indan and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of expressing excellent flame retardance and molding processability and preventing the generation of brominated dioxins during burning and useful for flame-retarding various resins by brominating a specific trimer of α-methylstyrene. SOLUTION: This invention relates to a compound of the formula [(x) and (z) are each 0-5: (y) is 0-4; x+y+z>=1, preferably x+y+z>=11]. The compound is obtained, e.g. by reacting 1,3-dimethyl-3-phenyl-1-(2-methyl-2-phenylpropyl)indan with a brominating agent such as bromine, etc., in an organic solvent such as dibromomethane, dibromoethane, etc., in the presence of a catalyst such as a metal catalyst, a Lewis acid catalyst, etc., at 0-70 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in order to impart flame retardancy to various thermoplastic resins and thermosetting resins, bromine compounds having high heat resistance and good various properties such as electrical insulation properties have been used. Above all, in the field where addition type is required to have heat resistance, decabromodiphenyl ether, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A polycarbonate oligomer, bromine excellent in thermal decomposition characteristics Brominated aromatic compounds such as polystyrene and ethylenebistetrabromophthalimide, that is, compounds in which bromine is directly bonded to an aromatic ring have been used. Also, JP-A-6-12
Compounds such as brominated 1,1,3-trimethyl-3-phenylindane disclosed in No. 2637 have been newly developed.

[0003] As an additive type flame retardant, the thermal decomposition temperature is high,
It is required that the moldability is good, that is, it has an appropriate melting point to uniformly knead with the base resin. Flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A polycarbonate oligomer, brominated polystyrene and ethylenebistetrabromophthalimide mentioned above are thermally decomposed. Compounds having a temperature of 300 ° C. or higher but a bromine content of 70% or higher are narrowed down to decabromodiphenyl ether. However, decabromodiphenyl ether has a problem that the melting point is as high as 306 ° C. and the molding temperature must be raised to 306 ° C. or higher to make it uniform with the base resin. The technique of dispersing to was adopted. In addition, it was reported that polybromobiphenyl ethers generate brominated dioxins and brominated dibenzofurans when burned at a specific temperature (Environ. Sci. Technol., 20, 4, 404-408 (1986)). It has become. Also, octabromo-1,
1,3-Trimethyl-3-phenylindane has a slightly lower thermal decomposition temperature of 296 ° C., and a flame retardant having a higher thermal decomposition temperature has been demanded.

[0004]

SUMMARY OF THE INVENTION The invention of claim 1 provides 1,3-dimethyl-3-phenyl-1- (2) having excellent flame retardancy, high thermal decomposition temperature and excellent moldability. −
Methyl-2-phenylpropyl) indane bromide. The invention according to claim 2 provides, in addition to the effect of the invention according to claim 1, 1,3-dimethyl-3-phenyl-1- (2-methyl-) which is particularly excellent in moldability.
2-phenylpropyl) indane bromide. The invention according to claim 3 provides, in addition to the effect of the invention according to claim 1, in particular 1,3-dimethyl-3-phenyl-1- (2-methyl-) which is excellent in flame retardancy and has a high thermal decomposition temperature.
2-phenylpropyl) indane bromide.

The invention according to claim 4 provides 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropionate) having excellent flame retardancy, high thermal decomposition temperature and excellent moldability. G) a process for producing indane bromide. The invention according to claim 5 provides, in addition to the effects of the invention according to claim 4, 1,3-, which can be produced in a shorter time and with higher yield.
It is intended to provide a method for producing dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide. The invention according to claim 6 provides, in addition to the effects of the invention according to claim 4 or 5, a 1,3-dimethyl-3-phenyl-1- (2-methyl-
2-phenylpropyl) indane bromide. The invention according to claim 7 is based on claim 4,
In addition to the effects of the invention described in 5 or 6, 1,3-dimethyl-3-phenyl-1-phenyl which can be produced in a shorter time and in a higher yield.
It is intended to provide a method for producing (2-methyl-2-phenylpropyl) indane bromide.

[0006]

The present invention provides a compound represented by the general formula (I):

Embedded image (Where x and z are each independently an integer from 0 to 5, and y
Is an integer of 0 to 4 and x + y + z ≧ 1), and relates to 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide. Further, the present invention provides a compound represented by the formula (I) wherein x + y +
1,3-dimethyl-3-phenyl-1 wherein z ≧ 3
-(2-methyl-2-phenylpropyl) indane bromide; Further, the present invention provides the above-mentioned 1,3-dimethyl-3 wherein x + y + z ≧ 11 in the general formula (I).
-Phenyl-1- (2-methyl-2-phenylpropyl) indane bromide.

[0007] The present invention also relates to 1,3-dimethyl-3-.
Phenyl-1- (2-methyl-2-phenylpropyl)
Reacting indane with a brominating agent, characterized in that 1,3-dimethyl-3-phenyl-1- (2-methyl-
The present invention relates to a method for producing 2-phenylpropyl) indane bromide. In the present invention, the reaction temperature of bromination when reacting 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane with a brominating agent is 0.
The present invention relates to a method for producing the above-mentioned 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide having a temperature range of from 70C to 70C. The present invention also relates to a method for producing the 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide wherein the brominating agent is bromine. Further, the present invention relates to 1,3
-Dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane and a brominating agent are reacted with each other in an organic solvent in the presence of a catalyst.
-Phenyl-1- (2-methyl-2-phenylpropyl) indan bromide.

[0008]

DETAILED DESCRIPTION OF THE INVENTION 1,3-Dimethyl-3- of the present invention
Phenyl-1- (2-methyl-2-phenylpropyl)
Indane bromide (hereinafter abbreviated as MPIB) is represented by the above general formula (I).
x and z are each independently an integer of 0 to 5;
4 and x + y + z ≧ 1. Preferably x
+ Y + z ≧ 3, more preferably x + y + z
≧ 11. The larger the value of x + y + z, that is, the higher the bromine content, the higher the flame retardancy as a flame retardant. However, the MPIB of the present invention may be used in combination with other flame retardants or flame retardant aids, and the value of x + y + z may be small when a plasticizing effect is expected even if the bromine content is low.

The process for producing MPIB of the present invention comprises the steps of (A)
3-dimethyl-3-phenyl-1- (2-methyl-2-
Phenylpropyl) indane (hereinafter abbreviated as MPI) and (B) a brominating agent. MP
I is obtained by trimerizing α-methylstyrene. Typical synthesis conditions are disclosed in JP-B-57-10851, but under these conditions, a mixture of dimeric and tetrameric linear and cyclic compounds is obtained. MPI can be obtained by fractionating this mixture by vacuum distillation.

As the brominating agent, bromine, bromate, hydrogen bromide and the like are used, but bromine is preferred from the viewpoint of inexpensiveness. M
The mixing ratio of PI to the brominating agent is determined by the desired bromination ratio, but the amount of the brominating agent is preferably slightly larger than the amount calculated from the stoichiometric ratio. In the bromination reaction, there are a method of dropping a brominating agent to MPI and a method of dropping MPI to the brominating agent. In the case of synthesizing MPIB having a higher bromine content, the brominating agent is added to MPI.
The method of dropping I is preferable. The reaction temperature for bromination varies depending on the brominating agent, but is preferably in the range of 0 to 70 ° C. If the reaction temperature is lower than 0 ° C., the reaction tends to take a long time, and if it is higher than 70 ° C., M
The backbone of PI tends to cleave.

The bromination reaction can be carried out in an organic solvent, and such an organic solvent is not particularly limited as long as it does not inhibit the bromination reaction. Examples thereof include dibromomethane, dibromoethane, and the like. Halogenated aliphatic hydrocarbons such as tribromoethane, tetrabromoethane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and tetrachloroethane are preferable, and dibromomethane and dibromoethane are more preferable.

The above-mentioned bromination reaction can be carried out in the presence of a catalyst. As such a catalyst, a metal catalyst or a Lewis acid catalyst is preferable, for example, Fe, AlCl ₃ , Al
Br ₃ , FeCl ₃ , FeBr ₃ , BF ₃ , BF ₃ derivative,
BCl ₃ , BBr ₃ , SbCl ₃ , SbBr ₃ , SnC
_{l 4, SnBr 4, ZrCl 4} , ZrBr 4 , and the like,
Among them, Fe and AlCl ₃ are preferable. The amount of the catalyst used is preferably 1 to 10 parts by weight, and more preferably 3 to 7 parts by weight based on 100 parts by weight of MPI. If the amount of the catalyst is less than 1 part by weight, the reaction rate of bromination tends to be remarkably reduced. If the amount is more than 10 parts by weight, a side reaction occurs and the yield of the target bromide tends to decrease.

The reaction time for bromination is preferably 3 to 24 hours, more preferably 4 to 12 hours, and particularly preferably 6 to 9 hours. If the reaction time is less than 3 hours, the reaction tends to be insufficient, and if it exceeds 24 hours, a side reaction such as cleavage of the main chain of MPI tends to occur. The pressure in the bromination reaction system
There is no particular limitation, and the reaction can usually be performed at normal pressure. In the above-mentioned production, MPI was converted to its structural isomer, 1,1-dimethyl-3-phenyl-3-.
When (2-methyl-2-phenylpropyl) indane is contained, the product MPIB contains its structural isomer, 1,1-dimethyl-3-phenyl-3- (2-methyl-2-phenylpropyl). ) Indone bromide is included, but it does not interfere with the performance as a flame retardant.

[0014]

The present invention will be described below with reference to examples. Example 1 [Synthesis of 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane (MPI)]
To a 2000 ml four-necked flask equipped with a stirrer, a dropping funnel, a Dimroth condenser and a thermometer, was added 1200 g of a toluene solution of 300.4 g of α-methylstyrene,
The temperature was set to 0 ° C. with ice water, and the catalyst AlCl _{3 was} 1.02 g.
The toluene solution 300ml plus -CH ₃ NO ₂ 2.5 ml was added dropwise under stirring slowly. The reaction solution at the end of the reaction was pale yellow. After completion of the reaction, water was slowly added dropwise to decompose the catalyst. The organic phase was washed with water, dried and concentrated. Further, 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane (MPI) 14 was obtained under the conditions of vacuum distillation at a degree of vacuum of 670 Pa and a temperature of 218 to 221 ° C.
0.0 g was obtained.

[1,3-dimethyl-3-phenyl-1-
Synthesis of (2-methyl-2-phenylpropyl) indane bromide (MPIB) 95 ml (1840) of bromine was placed in a 1000 ml three-necked flask equipped with a stirrer, a dropping funnel, a dimroth condenser, and a thermometer. Mmol), 125 ml of dibromoethane as a solvent, and AlCl ₃ as a catalyst.
1.67 g (12.52 mmol) were charged. Then, 1,3-dimethyl-3-phenyl-1-phenyl was added to the dropping funnel.
(2-methyl-2-phenylpropyl) indane (MP
I) A solution prepared by dissolving 35.45 g (100 mmol) in 125 ml of dibromoethane was charged. The liquid temperature was set to 35 ° C. by an oil bath, and the MPI solution was added dropwise over 1.33 minutes. Further, stirring is continued for 250 minutes from the start of dropping,
Thereafter, the liquid temperature was raised to 60 ° C. over 10 minutes, and stirring was continued for 240 minutes. After cooling the whole system to room temperature, water was added to stop the reaction. Further, a 10% by weight aqueous solution of sodium hydrogen sulfite was added to remove residual bromine, and after washing with water, the solvent was removed from the mixture of the precipitate and the solvent by filtration,
After washing with acetone and drying, a light yellow powdery product A
28.7 g (yield 23.5%) was obtained.

As a result of elemental analysis of product A, carbon was 2
6.24%, hydrogen was 1.32%, and bromine was 72.12%. The calculated value of the bromine 11-substituted product is 26.53 carbon
%, Hydrogen was 1.57%, and bromine was 71.90%, which were in good agreement. Further, as a result of analyzing the product A by HPLC, a main peak appeared at an elution retention time of 25.5 minutes. The HPLC measurement conditions were that the column used was TSK-
G1000HHR, the eluent was a mixed solvent of hexane / toluene (volume ratio 7/3 to 5/5), the flow rate was 1.0 ml / min, and the detector was a UV detector (measuring wavelength 282 nm).

The IR spectrum of the product A and the proton N
The MR spectrum was measured. Each spectrum is shown in FIG. 1 and FIG. In the IR spectrum (KBr method),
10 as absorption due to the bond between bromine and carbon in the aromatic ring
30cm ^-1, 870cm ^-1, the absorption at 739cm ^-1 was observed. 1.13 ppm, 1.27 ppm, 1.39 pp in proton NMR spectrum (solvent is deuterated chloroform)
m, a singlet absorption due to four methyl groups was observed at 1.74 ppm, and 2.03 ppm and 2.08 ppm at 3.08 ppm.
Quartet absorption due to two methylene groups is observed,
Three hydrogens of the aromatic ring were observed at 7.76 ppm and 7.72 ppm. The hydrogen in the methylene group is split into quartets because there are two optically active carbons in the molecule. The absorptions of 1.51 ppm, 3.60 ppm, and 7.17 ppm are absorptions of water, dibromoethane, and chloroform, which are residual solvents, respectively.

Further, as a result of mass analysis of the product A, m / z = 355 and m / z = 8 as fragment ion peaks
52 absorptions were observed. The fragment at m / z = 355 is considered to be a bromine tri-substituted product cleaved at the dimethylbenzyl group site, and the fragment at m / z = 852 is considered to be a bromine 8-substituted product cleaved at the indane ring site. From these results, it was found that the main product of the product A was a compound obtained by adding 11 bromine atoms to the aromatic ring of MPI. Product A
Was measured by DSC (differential scanning calorimetry) to find that the melting point was 295 ° C. Further, as a result of measuring the thermal decomposition characteristics of the product A by TGA (thermal balance), it was found that the thermal decomposition initiation temperature was 316 ° C., and the heat resistance was extremely high.

Example 2 In Example 1, 1.67 g of AlCl ₃ was used as a catalyst.
(12.52 mmol) instead of 0.70 g of iron (1
Product B was obtained in the same manner as in Example 1 except that 2.50 mmol) was used. As a result of mass analysis of the product B, m / z = 355 and m / z =
An absorption of 772 was observed. The fragment with m / z = 355 is considered to be a bromine tri-substituted product cleaved at the dimethylbenzyl group site, and the fragment with m / z = 772 is considered as a bromine 7-substituted product cleaved at the indane ring site. From these results, it was found that the main product of the product B was a compound in which 10 bromine atoms were added to the aromatic ring of MPI.

Example 3 1,3-Dimethyl-3-phenyl-1- (2-methyl-) was placed in a 200 ml three-necked flask equipped with a stirrer, a dropping funnel, a Dimroth condenser and a thermometer. 10.6 g (30 mmol) of 2-phenylpropyl) indane (MPI), 40 ml of dibromoethane as a solvent, and 0.33 g (2.5 mmol) of AlCl ₃ as a catalyst were charged. Then, a solution prepared by dissolving 20.0 g (125 mmol) of bromine in 15 ml of dibromoethane was charged to the dropping funnel. The liquid temperature was set at 22 ° C., and the bromine solution was added dropwise over 20 minutes. Further, stirring was continued for 70 minutes from the start of the dropping. Thereafter, water was added to stop the reaction. Further, a 10% by weight aqueous solution of sodium hydrogen sulfite was added to remove residual bromine, and after washing with water, the solvent was distilled off. The obtained reaction product was a brown highly viscous liquid. The highly viscous liquid is subjected to silica gel dry chromatography (Wako gel C200, eluent: hexane / toluene = 500/10 mixed solution).
And purified, and the solvent was distilled off to obtain 6.1 g (yield 33%) of a yellow solid product C.

As a result of elemental analysis of the product C, carbon was 5%.
2.64%, hydrogen was 4.31%, and bromine was 43.37%. 3.3 Calculated value of bromine-substituted product is 52.41 for carbon
%, Hydrogen was 4.34%, and bromine was 43.37%, which were in good agreement. Further, as a result of mass spectrometry of the product C, m / z = 197 and m / z = 379 were obtained as fragment peaks.
And m / z = 457 absorption were observed. m / z = 197
Is considered to be a bromine monosubstituted product cleaved at the site of the dimethylbenzyl group, a fragment with m / z = 379 is considered to be a bromine disubstituted product cleaved at the indane ring site, and a fragment with m / z = 457 is indane. It is considered to be a trisubstituted bromine cleaved at the ring site. From these results, it was found that the main product of the product C was a compound in which three or four bromine atoms were added to the aromatic ring of MPI.

Example 4 In a 200 ml three-necked flask equipped with a stirrer, a dropping funnel, a Dimroth condenser and a thermometer, 1,3-dimethyl-3-phenyl-1- (2-methyl- 10.6 g (30 mmol) of 2-phenylpropyl) indane (MPI), 40 ml of dibromoethane as a solvent, and 0.66 g (5 mmol) of AlCl ₃ as a catalyst were charged. Then, 50.4 g (315 mmol) of bromine was added to the dropping funnel.
Was dissolved in 15 ml of dibromoethane. The liquid temperature was set at 47 to 50 ° C, and the bromine solution was added dropwise over 40 minutes. Further, stirring was continued for 240 minutes from the start of the dropping.
Thereafter, water was added to stop the reaction. Further, a 10% by weight aqueous solution of sodium hydrogen sulfite was added to remove residual bromine, and after washing with water, the solvent was distilled off. The obtained reaction product was a brown highly viscous liquid. This highly viscous liquid is subjected to silica gel dry chromatography (Wako gel C20).
0, eluent: a mixed solution of hexane / toluene = 500/10) for purification, and the solvent was distilled off to obtain 4.9 g (16% yield) of a pale brown powdery product D. .

As a result of elemental analysis of the product D, carbon was found to be 3%.
2.43%, hydrogen 1.88%, and bromine 64.99%. The calculated value of the 8-bromine-substituted product is 32.77% of carbon,
Hydrogen was 2.24% and bromine was 64.99%, which were in good agreement. Further, as a result of mass spectrometry of the product D, m / z = 277 and m / z = 355 and m
Absorptions of / z = 537, m / z = 615, and m / z = 695 were observed. The fragment with m / z = 277 is considered to be a brominated disubstituted product at the dimethylbenzyl group site, the fragment with m / z = 355 is considered as a brominated trisubstituted product at the benzyl group site, and m / z = 537 is considered to be a brominated tetrasubstituted product at the indane ring site, m / z = 615 is considered to be a brominated 5-substituted product that is cleaved at the indane ring site, and m / z = 6.
The 95 fragment is bromine 6 cleaved at the indane ring site.
It is considered a substitute. From these results, product D is MP
Compounds obtained by adding 7 or 8 bromine atoms to the aromatic ring of I were found to be the main products.

[0024]

The 1,3-dimethyl-3- according to claim 1
Phenyl-1- (2-methyl-2-phenylpropyl)
Indane bromide has excellent flame retardancy, high thermal decomposition temperature, and there is no danger of producing brominated dioxin or brominated dibenzofuran during combustion, making it suitable for flame retarding various thermoplastic resins and thermosetting resins. It is. The 1,3-dimethyl-3-phenyl-1- (2-methyl-) according to claim 2.
2-phenylpropyl) indane bromide according to claim 1
It has the effects described, and has an appropriate melting point because it is uniformly kneaded with the base resin, so it has particularly good moldability and is suitable for flame retardancy of various thermoplastic resins and thermosetting resins. It is. The 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide according to the third aspect has the effect of the first aspect, and is particularly difficult because the bromine content is high. It has excellent flammability and is suitable for making various thermoplastic resins and thermosetting resins flame-retardant.

The production method according to claim 4 is a method according to claim 1, wherein the 1,3-dimethyl-3-phenyl-1- (2-methyl-
2-phenylpropyl) indane bromide,
It is suitable as a manufacturing method. The production method according to the fifth aspect has the effects described in the fourth aspect, and is suitable as a production method capable of producing in a short time and high yield. The production method according to claim 6 has the effects described in claim 4 or 5, and is suitable as a production method that can be produced at low cost and with high yield. The production method according to the seventh aspect has the effects of the fourth, fifth, or sixth aspect, and is suitable as a production method capable of producing a product in a short time and with high yield.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of 11-brominated MPI obtained in Example 1.

FIG. 2 is a proton NMR spectrum of 11-brominated MPI obtained in Example 1.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C09K 21/08 C09K 21/08 C07B 61/00 300 // C07B 61/00 300 B01J 23/74 301X (72) Inventor Akihiro Kobayashi 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant of Hitachi Chemical Co., Ltd. (72) Inventor Fumiaki Kanga 4-9-25 Shibaura, Minato-ku, Tokyo Within the Chemical Products Business Division

Claims (7)

[Claims] 1. A compound of the general formula (I) (Where x and z are each independently an integer from 0 to 5, and y
Is an integer of 0 to 4 and x + y + z ≧ 1), 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide. 2. In the general formula (I), x + y + z ≧ 3
The 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide according to claim 1, wherein 3. In the general formula (I), x + y + z ≧ 1
The 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide according to claim 1, which is 1. (4) 1,3-dimethyl-3-phenyl-1-
1,2-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide, characterized by reacting (2-methyl-2-phenylpropyl) indane with a brominating agent. Manufacturing method. (5) 1,3-dimethyl-3-phenyl-1-
The reaction temperature for bromination when reacting (2-methyl-2-phenylpropyl) indane with a brominating agent is 0 ° C to 70 ° C.
The 1,3-dimethyl-3- according to claim 4, which is in the range of ° C.
Phenyl-1- (2-methyl-2-phenylpropyl)
Production method of indane bromide. 6. The method for producing 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane bromide according to claim 4, wherein the brominating agent is bromine. 7. 1,3-dimethyl-3-phenyl-1-
7. The 1,3-dimethyl-3-phenyl-1 according to claim 4, wherein the (2-methyl-2-phenylpropyl) indane and the brominating agent are reacted in an organic solvent in the presence of a catalyst.
A method for producing-(2-methyl-2-phenylpropyl) indane bromide.