JPH09227624A - Production of brominated petroleum resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a brominated petroleum resin having a good color tone, an excellent heat resistance, and a high bromine content by adding a bromination catalyst after partially or totally adding a brominating agent in brominating an arom. petroleum resin. SOLUTION: In producing a brominated petroleum resin by partially brominating a petroleum resin having arom. groups on side chains, a bromination catalyst is added after at least a part of a brominating agent is added to a soln. contg. the petroleum resin under such conditions that the bromination substantially occurs. A pref. example of the petroleum resin having arom. groups on side chains contains repeating units represented by the formula (wherein R is H or methyl) in an amt. of 30mol% based on the total repeating units. A pref. bromination catalyst is a Lewis acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for brominating petroleum resin. More specifically, it relates to a method for producing a brominated petroleum resin having improved heat resistance and color tone.

[0002]

2. Description of the Related Art For the purpose of flame retarding an organic polymer material, a flame retardant such as an inorganic compound such as a metal hydroxide, an organic halogen compound or an organic phosphate compound is blended with the organic polymer material. Is widely used.
Among them, the organic bromine-based compound has a large flame retardant effect with respect to the compounding amount, has a small effect on the moldability of the material, is compatible with the material, and has little deterioration in the physical properties of the material due to compounding. It is most often used due to its excellent properties.

However, when a low-molecular weight organic bromine compound is used, such a low-molecular weight organic bromine compound may generate a gaseous substance due to sublimation or decomposition during resin molding, or may be soaked with time from a resin molded product after molding. There is a drawback that undesirable phenomena such as bleeding out and generation of extremely harmful substances during combustion often occur. On the other hand, a high molecular weight organic bromine compound, for example, brominated polystyrene obtained by brominating polystyrene (for example, see JP-A-53-60986),
Such high molecular weight organic bromine compounds have problems in compatibility with resins and fluidity during molding. Further, as for bromides of organic compounds having an intermediate molecular weight, polycarbonate oligomers of tetrabromobisphenol A, epoxy oligomers of tetrabromobisphenol A and the like are used, but the performance as a flame retardant is still insufficient, Further improvement is desired in terms of price-to-performance ratio. Further, among petroleum resins used for applications such as pressure-sensitive adhesive tapes and hot-melt adhesives, there is also a need for flame-retardant petroleum resins which themselves have flame retardancy.

To this end, the present inventor has proposed a brominated petroleum resin which has excellent flame retardancy and is suitable as a flame retardant for a thermoplastic resin, and a method for producing the same (Japanese Patent Application No. Hei 8).
-1609). However, the brominated petroleum resin obtained by such a proposed technique still has problems to be improved in terms of color tone and heat resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a brominated petroleum resin having a good color tone and excellent heat resistance. As a result of intensive studies to solve the above problems, the present inventor has found that when brominating a petroleum resin having an aromatic group, a bromination catalyst is added after a part or all of a brominating agent is added. It was found that a brominated petroleum resin having a good color tone and excellent heat resistance and a high bromine content can be obtained by the above method, and the present invention has been accomplished.

[0006]

That is, according to the present invention, in a method for partially brominated a petroleum resin having a side chain aromatic group in the molecule to produce a brominated petroleum resin, the petroleum resin is Provided is a method for producing a brominated petroleum resin, which comprises adding a part or all of a brominating agent to a solution containing the brominating agent under a reaction condition in which bromination substantially occurs, and then adding a bromination catalyst.

The petroleum resin is obtained by fractionating the main products of naphtha decomposition products, such as ethylene and propylene, and then polymerizing them, usually using C5 and C9 fractions for fuel evaluation as raw materials. The C5 cut contains 1-pentene, 2
-Pentene, 1-isopentene, 2-isopentene, 3
-Isopentene, isoprene, 1,3-pentadiene,
It contains olefin compounds such as cyclopentene and cyclopentadiene, and the C9 fraction contains styrene and α-
Methylstyrene, β-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-
Isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, indene, 1-methylindene, 2-methylindene, 3-methylindene, 4-methylindene, 5-methylindene, 6-methylindene, 7- Olefinic compounds such as methylindene are included.

The petroleum resin used in the present invention is a petroleum resin having an aromatic group, and is a C9 petroleum resin obtained by polymerizing at least one monomer selected from aromatic olefins in the C9 fraction. , At least one monomer selected from aromatic olefins in the C9 fraction and C5
It is a C5-C9 petroleum resin obtained by copolymerizing at least one monomer selected from aliphatic olefins and alicyclic olefins of a fraction. Both the C9-based petroleum resin and the C5-C9-based petroleum resin are usually produced by cationic polymerization, but can also be produced by other polymerization methods such as radical polymerization and thermal polymerization.

Examples of the C9 petroleum resin include homopolymers and copolymers obtained by polymerizing monomer units represented by the following formula. The copolymer represented by the following formula may be a random copolymer or a block copolymer.

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

[Chemical 6]

[0015]

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Examples of the C5-C9 petroleum resin include the above C9 resin and the following formula

[0017]

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Examples of the repeating unit include one or more of the monomer units represented by:

The C5-C9 type petroleum resin has a C
The monomer unit of 9 fractions is preferably 50 mol% or more, and 7
0 mol% or more is particularly preferred. In view of the performance of the brominated petroleum resin obtained in the present invention, the C9 petroleum resin and the C5-C9 petroleum resin preferably contain vinyl toluene or isopropenyl toluene as a monomer unit in a total amount of 30 mol% or more, and 40 mol% or more. %, More preferably at least 50 mol%. The C9-based petroleum resin and the C5-C9-based petroleum resin can include a partially hydrogenated resin in which the olefinic double bond in the resin is partially hydrogenated. These petroleum resins can be used alone or in combination of two or more.

The C9 petroleum resin and C5-C9
In the petroleum-based petroleum resin, other olefinic compounds may be used as a copolymerization component for the purpose of reforming the petroleum-based resin.
It is preferably used in an amount of less than or equal to mol%. The olefin compound may be a copolymerizable monomer, for example, ethylene, propylene, isobutene,
Examples thereof include butadiene, divinylbenzene, vinyl methyl ether, vinyl isopropyl ether, vinyl n-amyl ether and vinyl n-octadecyl ether. The weight average molecular weights of the C9-based petroleum resin and the C5-C9-based petroleum resin are determined by the GPC measurement method, and the molecular weight range is preferably 300 to 10,000.
00-6,000 are more preferable, and 500-4,000 are still more preferable.

C9 petroleum resin and C5 in the present invention
-C9 petroleum resin is easily available from the market, for example, FTR-6000 petroleum resin, FTR-7000 petroleum resin and FTR-800 manufactured by Mitsui Petrochemical Industry Co., Ltd.
0 series petroleum resin, Quintone manufactured by Nippon Zeon Co., Ltd.
Examples include petroleum resins having an aromatic group such as 100 series petroleum resins, which can be preferably used in the present invention.

The bromination reaction of the petroleum resin according to the present invention is carried out by adding a part or all of the brominating agent to a solution containing the petroleum resin under a reaction condition in which bromination substantially occurs, and then adding a bromination catalyst. It is made by adding. When the brominating agent is partially added, the remaining brominating agent is further added simultaneously with or after the addition of the bromination catalyst.

In the present invention, the bromination catalyst is added after the addition of a part or all of the brominating agent under the reaction conditions in which bromination substantially occurs. The preferable addition timing of the bromination catalyst is After bromine substitution of 0.3 to 1 mol, preferably 0.5 to 1 mol, and more preferably 0.7 to 1 mol of bromine atom with respect to 1 mol of the aromatic group of the side chain of the petroleum resin. .

In the bromination reaction of the petroleum resin of the present invention, first, by adding a brominating agent in the absence of a catalyst, a particularly highly reactive site in the aromatic group of the side chain of the petroleum resin is replaced by bromine,
Then, the addition of the bromination catalyst advances the bromine substitution to other sites. In the former reaction without catalyst,
In the petroleum resin, a highly reactive aromatic moiety, particularly one moiety of the aromatic group substituted with two or more aliphatic groups containing a cyclized structure, is bromine-substituted, so that a bromination catalyst is added thereafter. Even if the main chain is cleaved or the bromine substitution with the aliphatic group hydrogen atom due to the reaction with the petroleum resin is suppressed, a brominated petroleum resin having excellent color tone and heat resistance can be obtained as a result. Presumed. In addition, as a monomer unit which gives an aromatic group substituted by two or more aliphatic groups having the above-mentioned cyclized structure, representative examples thereof include vinyltoluene, isopropenyltoluene, indene, methylindene and the like.

Therefore, the particularly preferable time of addition of the bromination catalyst is 0.6 to 1 with respect to 1 mol of the aromatic group substituted with two or more aliphatic groups containing a cyclized structure of the side chain of the petroleum resin. After more than 0.8 to 1 mole of bromine atoms have been bromine replaced. The timing of adding the bromination catalyst can be determined by measuring the bromine content in advance by the method described below and calculating the bromine substitution amount.

The solvent used for the bromination may be any solvent which dissolves the petroleum resin and does not react with the bromination catalyst and the brominating agent. Examples of the solvent include hydrocarbons such as petroleum ether, n-hexane, kerosene and cyclohexane, dichloromethane, 1,2-dichloroethane, sym-trichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene and o-dichlorobenzene. , M-dichlorobenzene, o-chlorotoluene, and other halogenated hydrocarbons, and the like. Chlorinated hydrocarbons are preferred from the viewpoints of solubility of petroleum resin, ease of bromination reaction, and the like.
Particularly, dichloromethane and 1,2-dichloroethane are preferable. These solvents may be used as a mixture of two or more.

The concentration of the petroleum resin solution in the bromination reaction is preferably in the range of 3 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. If the concentration is too low, productivity decreases, which is not preferable. On the other hand, if the concentration is too high, it is difficult to control the reaction, and the resulting product may be darkly colored or may be unfavorable in performance.

As the brominating agent, bromine itself is preferably used, but chlorinated bromine and the like can also be used,
Two or more brominating agents may be used. The brominating agent may be diluted with the above solvent before use. Such a brominating agent is used in an amount of preferably 20 to 500% by weight, more preferably 100 to 300% by weight, based on the petroleum resin. If the amount is less than 20% by weight, the resulting product has a low bromine content. If the amount is more than 500% by weight, undesired phenomena such as a decrease in the degree of polymerization of the resin, bromination of aliphatic groups other than aromatic groups, and coloring of the product. Is easy to occur.

In the present invention, the amount of the brominating agent added before the bromination catalyst is determined by the abundance ratio of the aromatic group substituted with two or more aliphatic groups including the cyclized structure in the petroleum resin used. It is preferably 20% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more of the brominating agent used.

As the bromination catalyst, usually a Lewis acid such as a metal halide is preferably used. For example, aluminum chloride, aluminum bromide, ferric chloride, ferric bromide, ferrous chloride, antimony (III) chloride, antimony (V) chloride, boron trifluoride, boron trifluoride diethyl etherate, tetra Examples thereof include titanium chloride, stannic chloride, zinc chloride, cupric chloride, cuprous bromide and the like. Further, the Lewis acid catalyst may be one produced during the bromination reaction, and examples thereof include simple metals such as aluminum, iron, zinc and tin. Among them, ferric chloride, ferric bromide,
Ferrous chloride and iron are preferably used. These catalysts can be used alone or in combination of two or more. Further, the bromination catalyst may be diluted with the above solvent before use.

The catalyst is preferably 0.001 to 20% by weight, more preferably 0.01 to 1% by weight based on the petroleum resin.
Used in the range of 0% by weight. If the amount of the catalyst is less than 0.001% by weight, the catalytic effect is poor. If the amount is more than 20% by weight, undesired phenomena such as a decrease in the degree of polymerization of the resin, bromination of aliphatic groups other than aromatic groups, and coloring of the product. Is easy to occur.

Further, for the purpose of controlling the catalytic activity of the bromination catalyst, a substance that reacts with the bromination catalyst, such as water,
Alcohols such as ammonia, methanol, ethanol, n-butanol, sec-butanol, ethylene glycol, ethyl cellosolve, formic acid, acetic acid, oxalic acid,
Carboxylic acids such as succinic acid and benzoic acid, ethylamine,
Amines such as triethylamine, ethylenediamine, morpholine, benzylamine, pyridine and imidazole can be used. The amount of addition of these substances depends on the catalyst
The amount is preferably 2.5 mol or less, more preferably 1.5 mol or less, based on mol.

The above bromination reaction is usually carried out at -40 to 50 ° C,
Preferably, it is carried out at -10 to 30C. When the temperature is lower than -40 ° C, the reaction rate is slow and not practical. When the temperature is higher than 50 ° C, undesired phenomena such as reduction of the polymerization degree of the resin, bromination of aliphatic groups other than aromatic groups, and coloring of the product occur. Cheap. The reaction time of the bromination depends on the petroleum resin concentration, the reaction temperature,
Although it largely depends on the type and amount of the catalyst, it is usually 1
It is 0 minutes to 10 hours.

After completion of the bromination reaction, it is desirable to add water to the reaction system to inactivate the catalyst, and then wash and remove. When the brominating agent remains, it is preferable to add a reducing agent such as sodium sulfite, sodium hydrogen sulfite, sodium dithionite, sodium thiosulfate, etc. to the water to decompose the residual bromine. Then, if necessary,
Sodium hydrogen carbonate, sodium carbonate, potassium carbonate,
It is preferable to wash with a diluted aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. Further, by sufficiently washing with water, a reaction product which is neutral and has little residual salt can be obtained.

Then, the solvent is removed from the reaction solution after the water washing treatment to obtain the brominated petroleum resin in the method of the present invention as a solid. As a method for removing the solvent, a known method used for recovering a solid from a solution may be used, and usually, a distillation method under normal pressure or a reduced pressure, a spray drying method and the like are used. Alternatively, the reaction solution is about 3 by volume.
Brominated petroleum is obtained by pouring into a poor solvent such as methanol or ethanol in an amount of ˜20 times to precipitate the desired product, separating the resulting precipitate by filtration or centrifugation, and drying by a known method. A resin can be obtained.

The solid product thus obtained has a white, light yellow or light brown color and is subjected to halogen analysis, ¹ H-
By analysis of NMR, ¹³ C-NMR, etc., it can be confirmed that the petroleum resin is brominated.

The bromine content of the brominated petroleum resin obtained by the method of the present invention reaches a maximum of about 75% by weight depending on the structure of the petroleum resin used (the type and composition of the monomer used for polymerization) and the reaction conditions. In terms of performance as a petroleum resin and a flame retardant, it is preferably in the range of 40 to 70% by weight. Also, the bromine substitution site in the brominated petroleum resin is ¹ H-NMR
The proportion of bromine substitution of the hydrogen atoms of the aliphatic groups, which is obtained by analysis, is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 2 mol% or less, based on the total hydrogen atoms of the aliphatic groups. When the proportion of bromine substitution of the hydrogen atom of the aliphatic group increases, the thermal stability of the compound generally tends to decrease depending on the degree of the proportion, but the decreasing rate depends on the structure and other factors. It depends.

The brominated petroleum resin obtained according to the present invention is
It has a suitable molecular weight, exhibits excellent flame retardancy, and due to its good color tone and excellent heat resistance, it is widely and preferably used as a flame retardant for polymer molding materials and paints. Examples of the polymer molding material include thermoplastic resins, such as polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyoxymethylene, acrylic resin, nylon resin, polyester resin, and polycarbonate resin. Is mentioned.

[0039]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Unless otherwise specified, parts in Examples are parts by weight, and% is% by weight.
It is. The evaluation was performed according to the following methods (1) to (4).

(1) The weight average molecular weight was determined by GPC measurement. (Measurement conditions are as follows: Apparatus: Tosoh Corp. GPC-8000 type, Column: Tosoh Corp. G-MHXL, G-3000HXL 1 each and G-20
00HXL 2 pieces are connected in series, detector: differential refraction detector or ultraviolet spectroscopic detector (measurement wavelength 254 nm), eluent:
(Tetrahydrofuran, flow rate: 1.0 ml / min) (2) To measure the bromine content of the brominated petroleum resin, a certain amount of the sample is completely combusted, and the combustion gas generated at that time is absorbed in a dilute aqueous sodium nitrite solution to obtain a solution. Was calculated by potentiometric titration with 0.01N silver nitrate aqueous solution and calculated from it. (3) The ratio of bromine substitution of aliphatic group hydrogen atoms (aliphatic group bromine substitution ratio) can be determined by a simple method using ¹ H-N of brominated petroleum resin.
From the MR spectrum, the peak area at a chemical shift of 0 to 3.0 ppm was designated as A, and the peak area at a chemical shift of 3.4 to 4.5 ppm was designated as B using the following formula. Aliphatic group bromine substitution rate (mol%) = 100 × B / (A + 2)
B) (4) A 5% weight loss temperature is obtained by flowing the brominated petroleum resin at a flow rate of 40%.
It was determined by thermogravimetric analysis (TGA) measurement under the condition of temperature rising rate of 20 ° C./min under nitrogen flow of ml / min.

Example 1 The following formula (2)

[0042]

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Petroleum resin FTR-8080 (manufactured by Mitsui Petrochemical Industry Co., Ltd., weight average molecular weight 800) 20
g of dichloromethane and 60 g of dichloromethane was cooled to about 5 ° C., and 60 g of bromine was added to the solution while maintaining the reaction system at about 5 ° C. or less.
The mixture was added over 5 minutes with stirring (0.84 mol of bromine atom was substituted for 1 mol of the aromatic group of the side chain of the petroleum resin). Subsequently, 0.5 g of ferric chloride was added. After addition of the catalyst, stirring was continued at this temperature for a further 30 minutes. afterwards,
Water is added to the reaction system to inactivate the catalyst, and further 1
After decomposing excess bromine with a 0% aqueous sodium hydrogen sulfite solution, the reaction system was thoroughly washed with water, and then the organic layer was separated from the reaction system. Dichloromethane was distilled off from the reaction solution to obtain 49 g of pale pale yellow brominated petroleum resin.

The bromine content of the brominated petroleum resin was 60%, of which the aliphatic group bromine substitution rate was 1.0 mol%. Also, the 5% weight loss temperature of the brominated petroleum resin is 2
It was 85 ° C.

Comparative Example 1 A solution consisting of 20 g of the petroleum resin FTR-8080 and 60 g of dichloromethane was cooled to about 5 ° C., 0.5 g of ferric chloride was added, and then 60 g of bromine was added to the reaction system at about 5 ° C.
It was added under stirring over 15 minutes while maintaining:
After the addition of bromine, stirring was continued at this temperature for a further 30 minutes. Thereafter, water is added to the reaction system to inactivate the catalyst, and excess bromine is decomposed using a 10% aqueous sodium bisulfite solution. The layers were separated. Dichloromethane was distilled off from the reaction solution to obtain 49 g of pale yellow brominated petroleum resin.
The bromine content of the brominated petroleum resin was 60%, of which the aliphatic group bromine substitution rate was 2.0 mol%. The 5% weight loss temperature of the brominated petroleum resin was 230 ° C.

Example 2 A solution consisting of 20 g of the petroleum resin FTR-8080 and 60 g of dichloromethane was cooled to about 5 ° C., and then 30 g of bromine was added with stirring over 8 minutes while maintaining the reaction system at about 5 ° C. or lower. (0.82 mol of bromine atom was substituted for 1 mol of the aromatic group of the side chain of the petroleum resin). Subsequently, 0.5 g of ferric chloride was added. After the catalyst was added, 30 g of bromine was added with stirring for another 8 minutes while maintaining the temperature, and then the stirring was continued for 30 minutes. Thereafter, water is added to the reaction system to inactivate the catalyst, and excess bromine is decomposed using a 10% aqueous sodium bisulfite solution. The layers were separated. Dichloromethane was distilled off from the reaction solution,
48 g of a pale pale yellow brominated petroleum resin was obtained. The bromine content of the brominated petroleum resin was 60%, in which the bromine substitution rate of the aliphatic group was 1.2 mol%. The 5% weight loss temperature of the brominated petroleum resin was 276 ° C.

Example 3 A solution consisting of 20 g of the above petroleum resin FTR-8080 and 60 g of dichloromethane was cooled to about 5 ° C., and then 60 g of bromine was added with stirring over 15 minutes while maintaining the reaction system at about 5 ° C. or lower. After the addition of bromine, stirring was continued for 30 minutes at that temperature (0.8 mol to 1 mol of the aromatic group of the side chain of petroleum resin).
6 mol of bromine atoms were replaced. ). Then 0.5 g of ferric chloride was added. After addition of the catalyst, another 30 at that temperature
Stirring was continued for minutes. Thereafter, water is added to the reaction system to inactivate the catalyst, and excess bromine is decomposed using a 10% aqueous sodium bisulfite solution. The layers were separated. Dichloromethane was distilled off from the reaction solution to obtain 49 g of pale pale yellow brominated petroleum resin. The bromine content of the brominated petroleum resin is 60%, of which the aliphatic group bromine substitution rate is 0.
8 mol%. The 5% weight loss temperature of the brominated petroleum resin was 283 ° C.

Examples 4-5, Comparative Examples 2-3 Using 20 g of the above petroleum resin FTR-8080, Table 1
Bromination was carried out in the same manner as in Example 1 or Comparative Example 1 except that the brominated conditions shown in Table 1 were used to obtain brominated petroleum resins as shown in Table 1.

[0049]

[Table 1]

Example 6 The following formula (3)

[0051]

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Petroleum resin FTR-6110 (Mitsui Petrochemical Industry Co., Ltd.) represented by (in the formula, numbers represent mol%)
Made, weight average molecular weight 1,630) 20 g and 1,2-dichloroethane 60 g solution cooled to about 5 ℃, bromine 5
0 g was added with stirring over 15 minutes while maintaining the reaction system at about 5 ° C. or lower (0.84 mol of bromine atom was substituted for 1 mol of the aromatic group of the side chain of the petroleum resin). . Then 0.5 g of ferric chloride was added. After addition of the catalyst, stirring was continued at this temperature for a further 30 minutes. Then, the same operation as in Example 1 was performed to obtain 42 g of a light brown brominated petroleum resin. The brominated petroleum resin has a bromine content of 53%,
The bromine substitution rate of the aliphatic groups was 2.3 mol%.
The 5% weight loss temperature of the brominated petroleum resin is 230 ° C.
Met.

Comparative Example 4 Bromination was carried out in the same manner as in Comparative Example 1 except that a solution consisting of 20 g of the above petroleum resin FTR-6110 and 60 g of 1,2-dichloroethane and 50 g of bromine were used. 41 g of resin was obtained. The bromine content of this brominated petroleum resin was 51%, of which the aliphatic bromine substitution rate was 2.7 mol%. The 5% weight loss temperature of the brominated petroleum resin was 200 ° C.

Example 7 26 g of vinyltoluene (a mixture of meta and para compounds), 10 g of indene and 14 g of styrene were dissolved in 195 g of dichloromethane, and this solution was cooled to 10 ° C. under a nitrogen stream. 1.8 g of boron trifluoride diethyl etherate was added to the solution with stirring, and stirring was continued at 10 to 20 ° C. for 3 hours. Then, 3.0 g of methanol was added to deactivate the catalyst. This reaction solution was dropped into 1000 g of methanol to produce a white precipitate. The precipitate was collected by filtration and dried at about 80 ° C. under reduced pressure to obtain 45 g of a polymer as a white powder. The obtained polymer was redissolved in dichloromethane and purified by reprecipitation in methanol. The composition of the polymer was vinyltoluene 50 mol%, indene 20 mol%, styrene 30 mol%, and the weight average molecular weight was 3,
It was 700. Bromination was performed in the same manner as in Example 1 except that 20 g of the polymer was used (0.63 mol of bromine atom was substituted for 1 mol of the aromatic group of the side chain of the petroleum resin before the catalyst was added). , Pale pale yellow brominated petroleum resin 48
g was obtained. The bromine content of the brominated petroleum resin was 58%, in which the bromine substitution rate of the aliphatic group was almost 0 mol%. Also, the 5% weight loss temperature of the brominated petroleum resin is 3
It was 75 ° C.

[0055]

According to the bromination method of the present invention, a brominated petroleum resin having a good color tone, excellent heat resistance and a high bromine content can be obtained.

Claims (3)

[Claims] 1. A method for partially brominating a petroleum resin having a side chain aromatic group in the molecule to produce a brominated petroleum resin, a reaction in which bromination substantially occurs in a solution containing the petroleum resin. A method for producing a brominated petroleum resin, which comprises adding a part or all of a brominating agent under conditions and then adding a bromination catalyst. 2. A petroleum resin having a side chain aromatic group in its molecule has a repeating unit represented by the following formula (1): The method for producing a brominated petroleum resin according to claim 1, which is a petroleum resin containing 30 mol% or more of a unit represented by the formula (wherein R represents a hydrogen atom or a methyl group) based on all repeating units. 3. The method for producing a brominated petroleum resin according to claim 1, wherein the brominated catalyst is a Lewis acid.