WO2012111594A1 - High fluidity brominated polystyrene composition and method of producing same - Google Patents

High fluidity brominated polystyrene composition and method of producing same Download PDF

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Publication number
WO2012111594A1
WO2012111594A1 PCT/JP2012/053235 JP2012053235W WO2012111594A1 WO 2012111594 A1 WO2012111594 A1 WO 2012111594A1 JP 2012053235 W JP2012053235 W JP 2012053235W WO 2012111594 A1 WO2012111594 A1 WO 2012111594A1
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polystyrene
molecular weight
weight
average molecular
brominated
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PCT/JP2012/053235
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French (fr)
Japanese (ja)
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勝頼 屋敷
角光 横田
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マナック株式会社
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Priority to JP2012557942A priority Critical patent/JP5829630B2/en
Priority to CN2012800087945A priority patent/CN103370370A/en
Publication of WO2012111594A1 publication Critical patent/WO2012111594A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to a brominated polystyrene composition having improved fluidity while maintaining heat resistance, and a method for producing the same.
  • brominated polystyrene As a flame retardant for synthetic resins, it is required that the resin itself be given flame retardancy without losing its physical properties such as mechanical properties, electrical properties, and appearance such as hue. Needless to say, since it is kneaded into a resin at a high temperature and used, it is required to have excellent heat resistance and compatibility with the resin. In recent years, from the viewpoint of disaster prevention, the use of flame retardants has become more widespread, and the low fluidity of brominated polystyrene during kneading into resins has become a problem. Therefore, in addition to the above-described properties, brominated polystyrene has been strongly required to improve fluidity.
  • brominated polystyrene As a method for producing such brominated polystyrene, a method of brominating polystyrene and a method of polymerizing brominated styrene into a polymer are known, but industrially, a method of brominating polystyrene is generally used. is there. By the way, it is well known that the fluidity of a polymer compound is determined by the molecular weight, but brominated polystyrene is no exception. However, in brominated polystyrene, there is a problem that heat resistance at high temperatures is lowered although fluidity is improved as the molecular weight is lowered.
  • Patent Document 3 a method of bromination with bromine chloride using antimony oxide as a catalyst in a halogenated hydrocarbon solvent has been proposed by the present applicant (for example, Patent Document 3).
  • various improvement of the physical property of the obtained brominated polystyrene is also examined.
  • flame retardants in which brominated polystyrenes having different molecular weights are mixed have been proposed (for example, Patent Document 4).
  • Patent Document 4 for the purpose of improving fluidity and color value, a method has been proposed in which aluminum halide is used as a catalyst in an organic solvent, bromination is carried out with bromine, and bromination is stopped in 20 minutes or less (Patent Document). 5).
  • Patent Document 5 Only the method of Patent Document 5 has improved flowability, but since it is necessary to feed the whole amount of brominating agent in a short time, it is difficult to scale up, difficult to control reaction temperature, and rapidly react. There are many problems when trying to implement industrially because there is concern about the dangers of progressing.
  • an object of the present invention is to provide a brominated polystyrene composition having high fluidity that has high flame retardancy and does not impair heat resistance. Furthermore, an object of the present invention is to provide a method for producing such a brominated polystyrene composition inexpensively and easily industrially.
  • the present inventors have found that a brominated polystyrene composition having a specific molecular weight distribution has both excellent fluidity and heat resistance that could not be achieved conventionally. Furthermore, the present inventors have completed the present invention by discovering an industrially inexpensive and usable production method for such brominated polystyrene compositions. That is, the present invention is as follows. [1] A high molecular weight brominated polystyrene obtained by bromination of polystyrene having a weight average molecular weight of 10,000 to 70,000, and a low molecular weight brominated polystyrene obtained by brominating polystyrene having a weight average molecular weight of 500 to 5,000.
  • a brominated polystyrene composition in which the polystyrene having a weight average molecular weight of 10,000 to 70,000 is 70 to 99% by weight, and the polystyrene having a weight average molecular weight of 500 to 5,000 is 1 to 30% by weight.
  • the brominated polystyrene composition characterized by the above-mentioned.
  • (a1) A step of mixing 70 to 99% by weight of polystyrene having a weight average molecular weight of 10,000 to 70,000 and 1 to 30% by weight of polystyrene having a weight average molecular weight of 500 to 5,000 to obtain a polystyrene mixture; b1) A method for producing a brominated polystyrene composition, comprising a step of brominating the polystyrene mixture obtained in the step (a1) in the presence of a catalyst and a brominating agent.
  • (a2) a step of brominating a polystyrene having a weight average molecular weight of 10,000 to 70,000 in the presence of a catalyst and a brominating agent to obtain a high molecular weight brominated polystyrene; (b2) a weight average molecular weight of 500 to 5, 000 polystyrenes in the presence of a catalyst and a brominating agent to obtain low molecular weight brominated polystyrene, and (c2) 70-99% by weight of the high molecular weight brominated polystyrene obtained in step (a2) and A method for producing a brominated polystyrene composition, comprising a step of mixing 1 to 30% by weight of the low molecular weight brominated polystyrene obtained in the step (b2).
  • the present invention provides a brominated polystyrene composition having high fluidity and high flame retardancy that does not impair heat resistance, which is useful as a flame retardant for various engineering plastics. Moreover, according to the production method of the present invention, it is possible to provide a brominated polystyrene composition having excellent fluidity while maintaining high heat resistance by an industrially available method.
  • the brominated polystyrene composition of the present invention is a brominated high molecular weight brominated polystyrene obtained by brominating a high molecular weight polystyrene having a weight average molecular weight of 10,000 to 70,000 and a low molecular weight polystyrene having a weight average molecular weight of 500 to 5,000.
  • a brominated polystyrene composition comprising a low molecular weight brominated polystyrene obtained in the above manner, wherein the high molecular weight polystyrene having a weight average molecular weight of 10,000 to 70,000 is 70 to 99% by weight and the weight average molecular weight is 500 It is characterized by 1 to 30% by weight of ⁇ 5,000 polystyrene.
  • the weight average molecular weight of the brominated polystyrene composition is preferably 7,000 to 80,000, and more preferably 30,000 to 50,000.
  • the molecular weight dispersity of the brominated polystyrene composition that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the brominated polystyrene composition is 2.0 to 5.0 is preferable. If it is such a range, it is preferable at the point from which high fluidity
  • the weight average molecular weight and the number average molecular weight are values obtained by measurement by gel permeation chromatography (GPC).
  • the bromine content of the brominated polystyrene composition is 60% by weight or more, preferably 60 to 75% by weight, and 65% to 75% by weight. More preferred.
  • the high molecular weight brominated polystyrene of the present invention can be obtained by brominating polystyrene (high molecular weight polystyrene) having a weight average molecular weight of 10,000 to 70,000.
  • polystyrene having a weight average molecular weight exceeding 70,000 heat resistance is maintained, but fluidity is not improved.
  • polystyrene having a weight average molecular weight of less than 10,000 is used, the fluidity is improved, but the heat resistance as a flame retardant is significantly reduced.
  • polystyrene having a weight average molecular weight of 30,000 to 70,000 is preferable.
  • the high molecular weight polystyrene of the present invention has a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of 1.5 to 4.0, preferably 1.5 to 3.5. Polystyrene in such a range is easily available, and heat resistance after bromination is maintained. Such high molecular weight polystyrenes are readily available as commercial products from suppliers such as, for example, polystyrene from Aldrich and elastyrene 200 from DIC Corporation.
  • the low molecular weight brominated polystyrene of the present invention can be obtained by brominating polystyrene having a weight average molecular weight of 500 to 5,000 (low molecular weight polystyrene).
  • polystyrene having a weight average molecular weight of more than 5,000 it is necessary to mix a large amount in order to improve fluidity, thereby causing a decrease in heat resistance.
  • the polystyrene whose weight average molecular weight is less than 500 is used, the heat resistance as a flame retardant falls remarkably.
  • polystyrene having a weight average molecular weight of 1,000 to 3,000 is preferred.
  • the low molecular weight polystyrene of the present invention preferably has a ratio of number average molecular weight to weight average molecular weight (Mw / Mn) of 2.5 to 4.5, more preferably 3.0 to 4.0. preferable. Polystyrene in such a range is easily available, and heat resistance after bromination is maintained. Such low molecular weight polystyrene is readily available as a commercial product from a supplier, such as, for example, SYO94, Sanyo Chemical Co., Ltd.
  • the content of high molecular weight polystyrene and low molecular weight polystyrene, which are raw materials of polystyrene for bromination reaction, is such that the high molecular weight polystyrene is based on the total polystyrene used, that is, the total amount of polystyrene before bromination. 99 to 70% by weight, and low molecular weight polystyrene is 1 to 30% by weight.
  • liquidity is obtained, maintaining heat resistance.
  • the high molecular weight polystyrene is preferably 80 to 95% by weight
  • the low molecular weight polystyrene is preferably 5 to 20% by weight
  • the high molecular weight polystyrene is 80 to 85% by weight. More preferably, the low molecular weight polystyrene is 15 to 20% by weight.
  • the present invention provides an inexpensive and easy method for producing such brominated polystyrene compositions.
  • the brominated polystyrene composition of the present invention can be obtained by a method in which high molecular weight polystyrene and low molecular weight polystyrene are mixed in advance at a predetermined ratio and then brominated, or high molecular weight polystyrene and low molecular weight polystyrene are separately brominated. And then mixed at a predetermined ratio. Any method may be used, but the method of bromination after mixing high molecular weight polystyrene and low molecular weight polystyrene in a predetermined ratio in advance is more preferable from an industrial viewpoint because bromination can be completed in one step. .
  • a method for producing a brominated polystyrene composition obtained by a method in which a high molecular weight polystyrene and a low molecular weight polystyrene are previously mixed at a predetermined ratio and then brominated is obtained by the following steps (a1) to (b1): (A1) mixing 1 to 30% by weight of polystyrene having a weight average molecular weight of 10,000 to 70,000 and 70 to 99% by weight of polystyrene having a weight average molecular weight of 500 to 5,000 to obtain a polystyrene mixture, and (b1) And a step of brominating the polystyrene mixture obtained in (a1) in the presence of a catalyst and a brominating agent.
  • Step (a1) is a step of obtaining a mixture of high molecular weight polystyrene and low molecular weight polystyrene as raw materials.
  • the polystyrene having a weight average molecular weight of 10,000 to 70,000, that is, high molecular weight polystyrene is as described above, including preferable ones.
  • the polystyrene having a weight average molecular weight of 500 to 5,000, that is, a low molecular weight polystyrene is as described above including preferable ones.
  • the content of polystyrene having a weight average molecular weight of 10,000 to 70,000 and polystyrene having a weight average molecular weight of 500 to 5,000, that is, high molecular weight polystyrene and low molecular weight polystyrene is 5 to 20% by weight of low molecular weight polystyrene.
  • the high molecular weight polystyrene is preferably 80 to 95% by weight
  • the low molecular weight polystyrene is 15 to 20% by weight
  • the method for mixing the raw material polystyrene is not particularly limited as long as it is a known method. Since it can mix uniformly, it is preferable to dissolve / mix in advance in the reaction solvent.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction, but a halogenated hydrocarbon solvent is preferable.
  • halogenated hydrocarbon solvents include chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and monochlorobenzene; methylene bromide and ethylene dibromide.
  • Brominated hydrocarbons such as methylene chloride are preferred. These may be used alone or as a mixture of two or more kinds of solvents at an arbitrary ratio.
  • the amount of the reaction solvent used is preferably 100 to 1,000% by weight, more preferably 350 to 750% by weight, based on the total polystyrene (high molecular weight polystyrene and low molecular weight polystyrene).
  • Step (b1) is a step for bromination reaction of the polystyrene mixture.
  • the bromination reaction of the present invention can be carried out in the presence of a catalyst and a brominating agent.
  • a catalyst a general Lewis acid catalyst or antimony oxide catalyst can be used.
  • Antimony oxide catalysts such as antimony trioxide, diantimony tetroxide, and diantimony pentoxide are preferred because water in the system does not affect the reaction. These catalysts may be used alone or in admixture of two or more at any ratio.
  • the catalyst is used in an amount of 1 to 30 mol%, preferably 3 to 10 mol%, based on the styrene units of all polystyrene used in the bromination reaction.
  • brominating agent examples include bromine (Br 2 ), bromine chloride, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and sulfuryl bromide. From the viewpoint of reactivity with polystyrene, bromine chloride is preferred.
  • the amount of the brominating agent used can be appropriately adjusted depending on the bromine content of the desired brominated polystyrene, but is preferably 100 to 350 mol% based on the styrene units of all polystyrene used in the bromination reaction.
  • the amount of brominating agent used is the styrene of all polystyrene used. More preferably, it is 200 to 350 mol% based on the unit.
  • a solvent may be used.
  • the solvent include those exemplified as the reaction solvent in the step (a1) including preferable ones.
  • the amount of the solvent used is the total amount of the reaction solvent used in step (a1) and the solvent used in step (b1) relative to the total polystyrene (high molecular weight polystyrene and low molecular weight polystyrene) used in the bromination step.
  • the amount is preferably 100 to 1,000% by weight, and more preferably 350 to 750% by weight.
  • the reaction temperature for bromination can vary depending on the type of solvent selected. From the viewpoint of the hue of the resulting brominated polystyrene composition, a range of ⁇ 10 to 50 ° C. is preferable, and a range of ⁇ 10 to 30 ° C. is more preferable.
  • the reaction time for bromination can vary depending on the type and amount of the solvent or catalyst selected, and is preferably 1 to 24 hours, more preferably 3 to 12 hours.
  • the excess brominating agent is reduced with a general reducing agent such as hydrazine and further washed with water, and then the reaction solvent is concentrated and distilled off from the resulting brominated polystyrene solution, or By adding the brominated polystyrene solution in a poor solvent such as methanol, a solid or powder of the brominated polystyrene composition can be obtained.
  • a method for producing a brominated polystyrene composition obtained by separately brominating high molecular weight polystyrene and low molecular weight polystyrene and then mixing them at a predetermined ratio is specifically described in the following step (a2).
  • step (A2) a step of brominating a polystyrene having a weight average molecular weight of 10,000 to 70,000 in the presence of a catalyst and a brominating agent to obtain a high molecular weight brominated polystyrene
  • step (B2) a step of brominating a polystyrene having a weight average molecular weight of 500 to 5,000 in the presence of a catalyst and a brominating agent to obtain a low molecular weight brominated polystyrene
  • step (c2) a high molecular weight obtained in step (a2).
  • a method for producing a brominated polystyrene composition comprising a step of mixing 70 to 99% by weight of a molecular weight brominated polystyrene and 1 to 30% by weight of a low molecular weight brominated polystyrene obtained in step (b2).
  • Step (a2) and step (b2) may be performed separately. That is, after brominating high molecular weight polystyrene, the low molecular weight polystyrene may be brominated, and after low molecular weight polystyrene is brominated, the low molecular weight polystyrene may be brominated.
  • polystyrene having a weight average molecular weight of 10,000 to 70,000 (high molecular weight polystyrene) and polystyrene having a weight average molecular weight of 500 to 5,000 (low molecular weight polystyrene) include those including preferable ones (
  • the conditions for the bromination reaction are as described in step (b1), including the preferred ones, as described in a1).
  • the high molecular weight brominated polystyrene has a weight average molecular weight of 15,000 to 90,000, and a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.5 to 4. 0 is preferred.
  • the low molecular weight brominated polystyrene has a weight average molecular weight of 600 to 7,000, and a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 3.0 to 4. 0 is preferred.
  • the mixing method of the high molecular weight brominated polystyrene and the low molecular weight brominated polystyrene in the step (c2) is not particularly limited as long as it is a known method.
  • the contents of the high molecular weight brominated polystyrene and the low molecular weight brominated polystyrene are 70 to 99% by weight for the high molecular weight brominated polystyrene, 1 to 30% by weight for the low molecular weight brominated polystyrene, and 80% for the high molecular weight brominated polystyrene.
  • the brominated polystyrene composition by which fluidity
  • the brominated polystyrene composition of the present invention is a brominated polystyrene composition having improved fluidity while maintaining heat resistance. Therefore, the brominated polystyrene composition of the present invention is useful as a flame retardant for various engineering plastics such as polystyrene, ABS, polyamide, polycarbonate, polyacetal, modified polyphenylene ether, and polyester.
  • the measurement methods of the molecular weight, bromine content, melt flow rate (MFR) and loss on heating of the brominated polystyrene obtained in Examples and Comparative Examples are as follows.
  • Weight average molecular weight Measured by gel permeation chromatography. A calibration curve with a molecular weight of up to about 1.2 million was prepared in advance using Tosoh standard polystyrene. Next, 0.01 g of a sample was dissolved in 10 ml of tetrahydrofuran, and 10 ⁇ l thereof was injected into a Tosoh CCPM system. The weight average molecular weight in terms of standard polystyrene was calculated using a data processor. The analysis conditions are as follows.
  • Synthesis example 1 To a 1 L glass four-necked flask equipped with a stirrer, a condenser, a thermometer and a chlorine inlet tube, 450 ml of methylene chloride and 617.8 g of bromine were added and stirred, and the internal temperature was cooled to 5 ° C. or lower. Next, 1.0 g / min. Chlorine was introduced at a rate of, and a total of 288.5 g of chlorine was added over 4.8 hours to obtain 1497.3 g of bromine chloride / methylene chloride solution. The reaction temperature during the introduction of chlorine was 0 to 5 ° C.
  • polystyrene polystyrene made by Al
  • Table 1 shows the analysis results of the resulting brominated polystyrene (high molecular weight Br—PS).
  • Example 7 A mixture of brominated polystyrene was obtained in the same manner as in Example 6 except that the mixing ratio of the high molecular weight Br-PS and the low molecular weight Br-PS was changed to 85:15 by weight. Table 2 shows the analysis results of the obtained mixture.
  • Example 8 A mixture of brominated polystyrene was obtained in the same manner as in Example 6 except that the mixing ratio of the high molecular weight Br-PS and the low molecular weight Br-PS was changed to 80:20 by weight. Table 2 shows the analysis results of the obtained mixture.
  • the brominated polystyrene of the present invention has excellent fluidity and heat resistance. Therefore, the brominated polystyrene composition of the present invention is useful as a flame retardant for various engineering plastics. Moreover, according to the manufacturing method of this invention, it becomes possible to provide the brominated polystyrene composition which has the outstanding fluidity

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Abstract

Provided is a brominated polystyrene composition which, useful as a flame retardant for various engineering plastics, has high liquidity and high flame retardancy, and which does not lose heat resistance; also provided is a method of producing the same. This brominated polystyrene composition comprises a high molecular weight brominated polystyrene obtained by brominating polystyrene of a 10k-70k weight-average molecular weight, and a low molecular weight brominated polystyrene obtained by brominating polystyrene of a 500-5000 weight-average molecular weight, wherein said brominated polystyrene composition is characterized in that the polystyrene of the 10k-70k weight-average molecular weight accounts for 70-99 weight% of the raw polystyrene and the polystyrene of the 500-5000 weight-average molecular weight accounts for 1-30 weight% of the raw polystyrene. This method of producing the brominated polystyrene composition involves a step for brominating the raw material polystyrene of said composition in the presence of a catalyst and a brominating agent.

Description

高流動性臭素化ポリスチレン組成物及びその製造方法High fluidity brominated polystyrene composition and process for producing the same
　本発明は、耐熱性を維持しながらも流動性が改善された臭素化ポリスチレン組成物及びその製造方法に関する。 The present invention relates to a brominated polystyrene composition having improved fluidity while maintaining heat resistance, and a method for producing the same.
　ポリスチレン、ABS（アクリロニトリル・ブタジエン・スチレン共重合体）をはじめとする各種のエンジニアリング樹脂は、自動車、電気分野、建築材料、家具、包装・雑貨など幅広く使用されている。しかし、これらの樹脂は燃えやすいという欠点を有しており、防災上の見地から難燃性を付与することが強く求められている。かかる観点から各種の難燃剤が開発され、使用されている。
　臭素化ポリスチレンは、安価で物性、外観及び成形性が優れ、電気特性、機械特性にも優れているため、難燃性を付与する難燃剤として幅広く使用されている。臭素化ポリスチレンを合成樹脂の難燃剤として使用する場合、樹脂自身の機械特性、電気特性などの物理特性、色相などの外観を失うことなく、樹脂に難燃性を付与できることが要求されることは言うまでもないことであるが、高温で樹脂に練り込んで使用することから、耐熱性、樹脂との相溶性などにおいても、優れていることが要求される。
　近年、防災上の観点から、難燃剤の使用はさらに広範囲に及んでおり、樹脂への練り込みに際しての臭素化ポリスチレンの低流動性が問題になっている。よって、臭素化ポリスチレンには、前述した特性に加えて、流動性の改善が強く求められるようになってきた。
　このような臭素化ポリスチレンの製造方法として、ポリスチレンを臭素化する方法と臭素化スチレンを重合してポリマーとする方法が知られているが、工業的にはポリスチレンを臭素化する方法が一般的である。
　ところで、高分子化合物の流動性は、分子量によって決定されることはよく知られているが、臭素化ポリスチレンにおいても、例外ではない。しかしながら、臭素化ポリスチレンにおいて、分子量を下げていくと流動性は改善されるものの、高温での耐熱性が低下するという問題がある。そこで、臭素化により流動性と耐熱性を兼ね備えた臭素化ポリスチレンを得るためには、最適な分子量のポリスチレンを選択し、臭素化することが必要とされるが、市販品として安価に入手可能な分子量のポリスチレンは限られており、これらの要求性能を満たす安価な臭素化ポリスチレンを工業的に得ることは従来の方法では困難であった。
　従来、ポリスチレンを臭素化して臭素化ポリスチレンを得る方法としては、有機溶媒中、触媒として二価及び／又は三価の鉄塩を用い、臭素により臭素化を行う方法（例えば、特許文献１）、又は三塩化アンチモンと同等の活性を有するルイス酸触媒を用いる方法（例えば、特許文献２）等が知られている。
　また、ハロゲン系炭化水素溶媒中、触媒として酸化アンチモンを用い、塩化臭素により臭素化を行う方法が本出願人により提案されている（例えば、特許文献３）。
　一方で、得られた臭素化ポリスチレンの物性の改善も種々検討されている。スチレン系樹脂との相溶性を改善する目的で、分子量の異なる臭素化ポリスチレンを混合した難燃剤が提案されている（例えば、特許文献４）。
　さらに、流動性及び色値を改善する目的で、有機溶媒中、触媒としてハロゲン化アルミニウムを用い、臭素により臭素化を行い、２０分以下で臭素化を停止する方法が提案されている（特許文献５）。
　しかし、これらの従来技術は、いずれも高流動性を得ることを主な目的とするものではなく、上述のような臭素化ポリスチレンの流動性の問題の解決に関して何ら示唆を与えるものではない。唯一、特許文献５の方法では、流動性が改善されているものの、短時間で臭素化剤を全量フィードする必要があることから、スケールアップの困難性、反応温度制御の困難性及び急速に反応が進行した場合の危険性が懸念され、工業的に実施しようとする場合、多くの問題がある。 Various engineering resins such as polystyrene and ABS (acrylonitrile butadiene styrene copolymer) are widely used in automobiles, electrical fields, building materials, furniture, packaging and general goods. However, these resins have a drawback that they are easily flammable, and there is a strong demand for imparting flame retardancy from the standpoint of disaster prevention. From this viewpoint, various flame retardants have been developed and used.
Brominated polystyrene is widely used as a flame retardant imparting flame retardancy because it is inexpensive, excellent in physical properties, appearance and moldability, and excellent in electrical properties and mechanical properties. When using brominated polystyrene as a flame retardant for synthetic resins, it is required that the resin itself be given flame retardancy without losing its physical properties such as mechanical properties, electrical properties, and appearance such as hue. Needless to say, since it is kneaded into a resin at a high temperature and used, it is required to have excellent heat resistance and compatibility with the resin.
In recent years, from the viewpoint of disaster prevention, the use of flame retardants has become more widespread, and the low fluidity of brominated polystyrene during kneading into resins has become a problem. Therefore, in addition to the above-described properties, brominated polystyrene has been strongly required to improve fluidity.
As a method for producing such brominated polystyrene, a method of brominating polystyrene and a method of polymerizing brominated styrene into a polymer are known, but industrially, a method of brominating polystyrene is generally used. is there.
By the way, it is well known that the fluidity of a polymer compound is determined by the molecular weight, but brominated polystyrene is no exception. However, in brominated polystyrene, there is a problem that heat resistance at high temperatures is lowered although fluidity is improved as the molecular weight is lowered. Therefore, in order to obtain brominated polystyrene having both fluidity and heat resistance by bromination, it is necessary to select and bromine polystyrene having the optimum molecular weight. Molecular weight polystyrene is limited, and it has been difficult to obtain inexpensive brominated polystyrene industrially satisfying these required performances by conventional methods.
Conventionally, as a method of brominating polystyrene to obtain brominated polystyrene, a method of brominating with bromine using a divalent and / or trivalent iron salt as a catalyst in an organic solvent (for example, Patent Document 1), Alternatively, a method using a Lewis acid catalyst having an activity equivalent to that of antimony trichloride (for example, Patent Document 2) is known.
In addition, a method of bromination with bromine chloride using antimony oxide as a catalyst in a halogenated hydrocarbon solvent has been proposed by the present applicant (for example, Patent Document 3).
On the other hand, various improvement of the physical property of the obtained brominated polystyrene is also examined. For the purpose of improving compatibility with styrene resins, flame retardants in which brominated polystyrenes having different molecular weights are mixed have been proposed (for example, Patent Document 4).
Furthermore, for the purpose of improving fluidity and color value, a method has been proposed in which aluminum halide is used as a catalyst in an organic solvent, bromination is carried out with bromine, and bromination is stopped in 20 minutes or less (Patent Document). 5).
However, none of these prior arts is mainly intended to obtain high fluidity, and does not provide any suggestion regarding the solution of the fluidity problem of brominated polystyrene as described above. Only the method of Patent Document 5 has improved flowability, but since it is necessary to feed the whole amount of brominating agent in a short time, it is difficult to scale up, difficult to control reaction temperature, and rapidly react. There are many problems when trying to implement industrially because there is concern about the dangers of progressing.
特開昭５５－１５１００７号公報Japanese Patent Laid-Open No. 55-151007 特公平１－５７６８４号公報Japanese Patent Publication No. 1-57684 特開平７－２９２０２６号公報JP-A-7-292026 特開平７－１２６４６３号公報JP-A-7-126463 特表２００９－５００４７０号公報Special table 2009-500470
　本発明は、上述のような問題に鑑みてなされたものである。即ち、本発明は、高難燃性で、耐熱性を損なうことがない、高い流動性を有する臭素化ポリスチレン組成物を提供することを目的とする。更には、本発明は、このような臭素化ポリスチレン組成物を安価で工業的にも容易に製造する方法を提供することを目的とする。 The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a brominated polystyrene composition having high fluidity that has high flame retardancy and does not impair heat resistance. Furthermore, an object of the present invention is to provide a method for producing such a brominated polystyrene composition inexpensively and easily industrially.
　上記課題を解決するため鋭意研究を重ねた結果、本発明者らは、特定の分子量分布を有する臭素化ポリスチレン組成物が、従来では成し得なかった、優れた流動性及び耐熱性を併せ持つことを見出し、さらにはかかる臭素化ポリスチレン組成物の工業的に安価で利用可能な製造方法を見出し、本発明を完成した。
　即ち、本発明は、以下のとおりである。
［１］重量平均分子量１万～７万のポリスチレンを臭素化して得られる高分子量臭素化ポリスチレンと、重量平均分子量５００～５，０００のポリスチレンを臭素化して得られる低分子量臭素化ポリスチレンとからなる臭素化ポリスチレン組成物であって、原料ポリスチレンにおいて、重量平均分子量１万～７万のポリスチレンが７０～９９重量％であり、重量平均分子量５００～５，０００のポリスチレンが１～３０重量％であることを特徴とする、臭素化ポリスチレン組成物。
［２］臭素化ポリスチレン組成物の重量平均分子量が、７，０００～８０，０００である、［１］記載の臭素化ポリスチレン組成物。
［３］臭素化ポリスチレン組成物の重量平均分子量と数平均分子量との比（Ｍｗ／Ｍｎ）が、２．０～５．０である、［１］又は［２］記載の臭素化ポリスチレン組成物。
［４］重量平均分子量１万～７万のポリスチレンのＭｗ／Ｍｎが、１．５～４．０である、［１］～［３］いずれかに記載の臭素化ポリスチレン組成物。
［５］重量平均分子量５００～５，０００のポリスチレンのＭｗ／Ｍｎが、２．５～４．５である、［１］～［４］いずれかに記載の臭素化ポリスチレン組成物。
［６］重量平均分子量１万～７万のポリスチレンが８０～８５重量％であり、重量平均分子量５００～５，０００のポリスチレンが１５～２０重量％である、［１］～［５］いずれかに記載の臭素化ポリスチレン組成物。
［７］（ａ１）重量平均分子量１万～７万のポリスチレン７０～９９重量％及び重量平均分子量５００～５，０００のポリスチレン１～３０重量％を混合して、ポリスチレン混合物を得る工程、及び（ｂ１）工程（ａ１）で得られたポリスチレン混合物を、触媒及び臭素化剤の存在下で臭素化する工程を含む、臭素化ポリスチレン組成物の製造方法。
［８］重量平均分子量１万～７万のポリスチレンが８０～８５重量％であり、重量平均分子量５００～５，０００のポリスチレンが１５～２０重量％である、［７］記載の製造方法。
［９］（ａ２）重量平均分子量１万～７万のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、高分子量臭素化ポリスチレンを得る工程、（ｂ２）重量平均分子量５００～５，０００のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、低分子量臭素化ポリスチレンを得る工程、及び（ｃ２）工程（ａ２）で得られた高分子量臭素化ポリスチレン７０～９９重量％及び工程（ｂ２）で得られた低分子量臭素化ポリスチレン１～３０重量％を混合する工程を含む、臭素化ポリスチレン組成物の製造方法。
［１０］高分子量臭素化ポリスチレンが８０～８５重量％であり、低分子量臭素化ポリスチレンが１５～２０重量％である、［９］記載の製造方法。
［１１］重量平均分子量１万～７万のポリスチレンのＭｗ／Ｍｎが、１．５～４．０である、［７］～［１０］いずれかに記載の製造方法。
［１２］重量平均分子量５００～５，０００のポリスチレンのＭｗ／Ｍｎが、２．５～４．５である、［７］～［１１］いずれかに記載の製造方法。
［１３］触媒が酸化アンチモンである、［７］～［１２］いずれかに記載の製造方法。
［１４］臭素化剤が塩化臭素である、［７］～［１３］いずれかに記載の製造方法。 As a result of intensive studies to solve the above problems, the present inventors have found that a brominated polystyrene composition having a specific molecular weight distribution has both excellent fluidity and heat resistance that could not be achieved conventionally. Furthermore, the present inventors have completed the present invention by discovering an industrially inexpensive and usable production method for such brominated polystyrene compositions.
That is, the present invention is as follows.
[1] A high molecular weight brominated polystyrene obtained by bromination of polystyrene having a weight average molecular weight of 10,000 to 70,000, and a low molecular weight brominated polystyrene obtained by brominating polystyrene having a weight average molecular weight of 500 to 5,000. A brominated polystyrene composition, in which the polystyrene having a weight average molecular weight of 10,000 to 70,000 is 70 to 99% by weight, and the polystyrene having a weight average molecular weight of 500 to 5,000 is 1 to 30% by weight. The brominated polystyrene composition characterized by the above-mentioned.
[2] The brominated polystyrene composition according to [1], wherein the brominated polystyrene composition has a weight average molecular weight of 7,000 to 80,000.
[3] The brominated polystyrene composition according to [1] or [2], wherein the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight of the brominated polystyrene composition is 2.0 to 5.0. .
[4] The brominated polystyrene composition according to any one of [1] to [3], wherein the polystyrene having a weight average molecular weight of 10,000 to 70,000 has Mw / Mn of 1.5 to 4.0.
[5] The brominated polystyrene composition according to any one of [1] to [4], wherein Mw / Mn of polystyrene having a weight average molecular weight of 500 to 5,000 is 2.5 to 4.5.
[6] Any of [1] to [5], wherein polystyrene having a weight average molecular weight of 10,000 to 70,000 is 80 to 85% by weight and polystyrene having a weight average molecular weight of 500 to 5,000 is 15 to 20% by weight. The brominated polystyrene composition described in 1.
[7] (a1) A step of mixing 70 to 99% by weight of polystyrene having a weight average molecular weight of 10,000 to 70,000 and 1 to 30% by weight of polystyrene having a weight average molecular weight of 500 to 5,000 to obtain a polystyrene mixture; b1) A method for producing a brominated polystyrene composition, comprising a step of brominating the polystyrene mixture obtained in the step (a1) in the presence of a catalyst and a brominating agent.
[8] The production method according to [7], wherein the polystyrene having a weight average molecular weight of 10,000 to 70,000 is 80 to 85% by weight and the polystyrene having a weight average molecular weight of 500 to 5,000 is 15 to 20% by weight.
[9] (a2) a step of brominating a polystyrene having a weight average molecular weight of 10,000 to 70,000 in the presence of a catalyst and a brominating agent to obtain a high molecular weight brominated polystyrene; (b2) a weight average molecular weight of 500 to 5, 000 polystyrenes in the presence of a catalyst and a brominating agent to obtain low molecular weight brominated polystyrene, and (c2) 70-99% by weight of the high molecular weight brominated polystyrene obtained in step (a2) and A method for producing a brominated polystyrene composition, comprising a step of mixing 1 to 30% by weight of the low molecular weight brominated polystyrene obtained in the step (b2).
[10] The production method according to [9], wherein the high molecular weight brominated polystyrene is from 80 to 85% by weight, and the low molecular weight brominated polystyrene is from 15 to 20% by weight.
[11] The production method according to any one of [7] to [10], wherein Mw / Mn of polystyrene having a weight average molecular weight of 10,000 to 70,000 is 1.5 to 4.0.
[12] The production method according to any one of [7] to [11], wherein the polystyrene having a weight average molecular weight of 500 to 5,000 has Mw / Mn of 2.5 to 4.5.
[13] The production method according to any one of [7] to [12], wherein the catalyst is antimony oxide.
[14] The production method according to any one of [7] to [13], wherein the brominating agent is bromine chloride.
　本発明により、各種エンジニアリングプラスチック用難燃剤として有用な、高難燃性で、耐熱性を損なうことがない、高い流動性を有する臭素化ポリスチレン組成物が提供される。また、本発明の製造方法によれば、高い耐熱性を保持しつつ、かつ優れた流動性を有する臭素化ポリスチレン組成物を工業的に利用可能な方法で提供することが可能となる。 The present invention provides a brominated polystyrene composition having high fluidity and high flame retardancy that does not impair heat resistance, which is useful as a flame retardant for various engineering plastics. Moreover, according to the production method of the present invention, it is possible to provide a brominated polystyrene composition having excellent fluidity while maintaining high heat resistance by an industrially available method.
　以下に本発明の実施の形態について詳細に説明する。
　本発明の臭素化ポリスチレン組成物は、重量平均分子量１万～７万の高分子量ポリスチレンを臭素化して得られる高分子量臭素化ポリスチレンと、重量平均分子量５００～５，０００の低分子量ポリスチレンを臭素化して得られる低分子量臭素化ポリスチレンとからなる、臭素化ポリスチレン組成物であって、原料ポリスチレンにおいて、重量平均分子量１万～７万の高分子量ポリスチレンが７０～９９重量％であり、重量平均分子量５００～５，０００のポリスチレンが１～３０重量％であることを特徴とする。
　本発明において、臭素化ポリスチレン組成物の重量平均分子量は、７，０００～８０，０００であるのが好ましく、３０，０００～５０，０００であるのがより好ましい。
　また、本発明において、臭素化ポリスチレン組成物の分子量の分散度、すなわち臭素化ポリスチレン組成物の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が、２．０～５．０であることが好ましい。このような範囲であれば、耐熱性を維持しながら、高い流動性が得られる点で好ましい。
　本発明において、重量平均分子量及び数平均分子量は、ゲルパミエーションクロマトグラフィ（ＧＰＣ）の測定により求められた値である。 Hereinafter, embodiments of the present invention will be described in detail.
The brominated polystyrene composition of the present invention is a brominated high molecular weight brominated polystyrene obtained by brominating a high molecular weight polystyrene having a weight average molecular weight of 10,000 to 70,000 and a low molecular weight polystyrene having a weight average molecular weight of 500 to 5,000. A brominated polystyrene composition comprising a low molecular weight brominated polystyrene obtained in the above manner, wherein the high molecular weight polystyrene having a weight average molecular weight of 10,000 to 70,000 is 70 to 99% by weight and the weight average molecular weight is 500 It is characterized by 1 to 30% by weight of ˜5,000 polystyrene.
In the present invention, the weight average molecular weight of the brominated polystyrene composition is preferably 7,000 to 80,000, and more preferably 30,000 to 50,000.
In the present invention, the molecular weight dispersity of the brominated polystyrene composition, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the brominated polystyrene composition is 2.0 to 5.0 is preferable. If it is such a range, it is preferable at the point from which high fluidity | liquidity is obtained, maintaining heat resistance.
In the present invention, the weight average molecular weight and the number average molecular weight are values obtained by measurement by gel permeation chromatography (GPC).
　臭素化ポリスチレンが十分な難燃効果を発揮するために、臭素化ポリスチレン組成物の臭素含量が６０重量％以上であることが望ましく、６０～７５重量％が好ましく、６５重量％～７５重量％がより好ましい。 In order for the brominated polystyrene to exhibit a sufficient flame retardant effect, it is desirable that the bromine content of the brominated polystyrene composition is 60% by weight or more, preferably 60 to 75% by weight, and 65% to 75% by weight. More preferred.
　本願発明の高分子量臭素化ポリスチレンは、重量平均分子量が１万～７万のポリスチレン（高分子量ポリスチレン）を臭素化することにより得られる。
　重量平均分子量が７万を超える重量平均分子量のポリスチレンを用いた場合は、耐熱性は維持されるものの、流動性が改善されない。また、重量平均分子量が１万未満のポリスチレンを用いた場合は、流動性は改善されるものの、難燃剤としての耐熱性が著しく低下する。入手の容易さを考慮すると、重量平均分子量３万～７万のポリスチレンが好ましい。
　本発明の高分子量ポリスチレンは、重量平均分子量及び数平均分子量の比（Ｍｗ／Ｍｎ）が、１．５～４．０であり、１．５～３．５であるのが好ましい。このような範囲のポリスチレンは入手が容易であり、臭素化した後の耐熱性も保持される。
　このような高分子量ポリスチレンは、例えば、アルドリッチ社のポリスチレン及びＤＩＣ株式会社のエラスチレン２００など、供給業者からの市販品として容易に入手可能である。 The high molecular weight brominated polystyrene of the present invention can be obtained by brominating polystyrene (high molecular weight polystyrene) having a weight average molecular weight of 10,000 to 70,000.
When polystyrene having a weight average molecular weight exceeding 70,000 is used, heat resistance is maintained, but fluidity is not improved. When polystyrene having a weight average molecular weight of less than 10,000 is used, the fluidity is improved, but the heat resistance as a flame retardant is significantly reduced. In view of availability, polystyrene having a weight average molecular weight of 30,000 to 70,000 is preferable.
The high molecular weight polystyrene of the present invention has a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of 1.5 to 4.0, preferably 1.5 to 3.5. Polystyrene in such a range is easily available, and heat resistance after bromination is maintained.
Such high molecular weight polystyrenes are readily available as commercial products from suppliers such as, for example, polystyrene from Aldrich and elastyrene 200 from DIC Corporation.
　本発明の低分子量臭素化ポリスチレンは、重量平均分子量が５００～５，０００のポリスチレン（低分子量ポリスチレン）を臭素化することにより得られる。
　重量平均分子量が５，０００を超えるポリスチレンを用いた場合は、流動性を改善するために多量に混合する必要があり、これにより耐熱性の低下を招く。また、重量平均分子量が５００未満のポリスチレンを用いた場合は、難燃剤としての耐熱性が著しく低下する。組成物の耐熱性を維持したまま流動性を改善するためには、重量平均分子量１，０００～３，０００のポリスチレンが好ましい。
　本発明の低分子量ポリスチレンは、数平均分子量と重量平均分子量との比（Ｍｗ／Ｍｎ）が、２．５～４．５であるのが好ましく、３．０～４．０であるのがより好ましい。このような範囲のポリスチレンは入手が容易であり、臭素化した後の耐熱性も保持される。
　このような低分子量ポリスチレンは、例えば、三洋化成工業株式会社のレジットＳ－９４など、供給業者からの市販品として容易に入手可能である。 The low molecular weight brominated polystyrene of the present invention can be obtained by brominating polystyrene having a weight average molecular weight of 500 to 5,000 (low molecular weight polystyrene).
When polystyrene having a weight average molecular weight of more than 5,000 is used, it is necessary to mix a large amount in order to improve fluidity, thereby causing a decrease in heat resistance. Moreover, when the polystyrene whose weight average molecular weight is less than 500 is used, the heat resistance as a flame retardant falls remarkably. In order to improve fluidity while maintaining the heat resistance of the composition, polystyrene having a weight average molecular weight of 1,000 to 3,000 is preferred.
The low molecular weight polystyrene of the present invention preferably has a ratio of number average molecular weight to weight average molecular weight (Mw / Mn) of 2.5 to 4.5, more preferably 3.0 to 4.0. preferable. Polystyrene in such a range is easily available, and heat resistance after bromination is maintained.
Such low molecular weight polystyrene is readily available as a commercial product from a supplier, such as, for example, SYO94, Sanyo Chemical Co., Ltd.
　本発明において、臭素化反応のためのポリスチレンの原料である、高分子量ポリスチレン及び低分子量ポリスチレンの含有量は、使用する全ポリスチレン、つまり臭素化する前のポリスチレンの総量に対して、高分子量ポリスチレンが９９～７０重量％であり、低分子量ポリスチレンが１～３０重量％である。このような範囲とすることで、耐熱性を維持したままで、流動性に優れた臭素化ポリスチレン組成物が得られる。低分子量ポリスチレンの含有量が３０重量％を超えると耐熱性が著しく低下し、１重量％未満では流動性を改善することができない。特に、さらに流動性が改善されることから、高分子量ポリスチレンが８０～９５重量％であり、低分子量ポリスチレンが５～２０重量％であるのが好ましく、高分子量ポリスチレンが８０～８５重量％であり、低分子量ポリスチレンが１５～２０重量％であるのがさらに好ましい。 In the present invention, the content of high molecular weight polystyrene and low molecular weight polystyrene, which are raw materials of polystyrene for bromination reaction, is such that the high molecular weight polystyrene is based on the total polystyrene used, that is, the total amount of polystyrene before bromination. 99 to 70% by weight, and low molecular weight polystyrene is 1 to 30% by weight. By setting it as such a range, the brominated polystyrene composition excellent in fluidity | liquidity is obtained, maintaining heat resistance. When the content of the low molecular weight polystyrene exceeds 30% by weight, the heat resistance is remarkably lowered, and when it is less than 1% by weight, the fluidity cannot be improved. Particularly, since the fluidity is further improved, the high molecular weight polystyrene is preferably 80 to 95% by weight, the low molecular weight polystyrene is preferably 5 to 20% by weight, and the high molecular weight polystyrene is 80 to 85% by weight. More preferably, the low molecular weight polystyrene is 15 to 20% by weight.
　本発明は、かかる臭素化ポリスチレン組成物の安価で容易な製造方法を提供する。
　本発明の臭素化ポリスチレン組成物は、高分子量ポリスチレン及び低分子量ポリスチレンを予め所定の割合で混合した後、臭素化する方法によって得られるか、あるいは、高分子量ポリスチレン及び低分子量ポリスチレンをそれぞれ別々に臭素化した後、所定の割合で混合することによって得られる。いずれの方法によっても構わないが、高分子量ポリスチレン及び低分子量ポリスチレンを予め所定の割合で混合した後、臭素化する方法は、臭素化を一工程で済ませることができるため、工業的観点からより好ましい。 The present invention provides an inexpensive and easy method for producing such brominated polystyrene compositions.
The brominated polystyrene composition of the present invention can be obtained by a method in which high molecular weight polystyrene and low molecular weight polystyrene are mixed in advance at a predetermined ratio and then brominated, or high molecular weight polystyrene and low molecular weight polystyrene are separately brominated. And then mixed at a predetermined ratio. Any method may be used, but the method of bromination after mixing high molecular weight polystyrene and low molecular weight polystyrene in a predetermined ratio in advance is more preferable from an industrial viewpoint because bromination can be completed in one step. .
　本発明において、高分子量ポリスチレン及び低分子量ポリスチレンを予め所定の割合で混合した後、臭素化する方法によって得られる、臭素化ポリスチレン組成物の製造方法は、下記工程（ａ１）～（ｂ１）：
　（ａ１）重量平均分子量１万～７万のポリスチレン１～３０重量％及び重量平均分子量５００～５，０００のポリスチレン７０～９９重量％を混合して、ポリスチレン混合物を得る工程、及び
　（ｂ１）工程（ａ１）で得られたポリスチレン混合物を、触媒及び臭素化剤の存在下で臭素化する工程
を含む。 In the present invention, a method for producing a brominated polystyrene composition obtained by a method in which a high molecular weight polystyrene and a low molecular weight polystyrene are previously mixed at a predetermined ratio and then brominated is obtained by the following steps (a1) to (b1):
(A1) mixing 1 to 30% by weight of polystyrene having a weight average molecular weight of 10,000 to 70,000 and 70 to 99% by weight of polystyrene having a weight average molecular weight of 500 to 5,000 to obtain a polystyrene mixture, and (b1) And a step of brominating the polystyrene mixture obtained in (a1) in the presence of a catalyst and a brominating agent.
　工程（ａ１）は、原料である高分子量ポリスチレン及び低分子量ポリスチレンの混合物を得る工程である。
　重量平均分子量１万～７万のポリスチレン、すなわち高分子量ポリスチレンは、好ましいものも含め、前記のとおりである。重量平均分子量５００～５，０００のポリスチレン、すなわち低分子量ポリスチレンは、好ましいものも含め、前記のとおりである。
　工程（ａ１）における、重量平均分子量１万～７万のポリスチレン及び重量平均分子量５００～５，０００のポリスチレン、すなわち高分子量ポリスチレン及び低分子量ポリスチレンの含有量は、低分子量ポリスチレンが５～２０重量％であり、高分子量ポリスチレンが８０～９５重量％であるのが好ましく、低分子量ポリスチレンが１５～２０重量％であり、高分子量ポリスチレンが８０～８５重量％であるのがさらに好ましい。このような範囲とすることで、耐熱性を維持したまま流動性が改善された臭素化ポリスチレン組成物が得られる。 Step (a1) is a step of obtaining a mixture of high molecular weight polystyrene and low molecular weight polystyrene as raw materials.
The polystyrene having a weight average molecular weight of 10,000 to 70,000, that is, high molecular weight polystyrene is as described above, including preferable ones. The polystyrene having a weight average molecular weight of 500 to 5,000, that is, a low molecular weight polystyrene is as described above including preferable ones.
In the step (a1), the content of polystyrene having a weight average molecular weight of 10,000 to 70,000 and polystyrene having a weight average molecular weight of 500 to 5,000, that is, high molecular weight polystyrene and low molecular weight polystyrene is 5 to 20% by weight of low molecular weight polystyrene. The high molecular weight polystyrene is preferably 80 to 95% by weight, the low molecular weight polystyrene is 15 to 20% by weight, and the high molecular weight polystyrene is more preferably 80 to 85% by weight. By setting it as such a range, the brominated polystyrene composition by which fluidity | liquidity was improved, maintaining heat resistance is obtained.
　原料ポリスチレンの混合方法としては、公知の方法であれば特に限定されない。均一に混合できるため、反応溶媒中であらかじめ溶解／混合しておくことが好ましい。
　反応溶媒としては、反応に不活性な溶媒であれば特に限定されないが、ハロゲン化炭化水素溶媒が好ましい。ハロゲン化炭化水素溶媒としては、塩化メチレン、クロロホルム、四塩化炭素、エチレンジクロリド、１，１，１－トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、及びモノクロルベンゼンなどの塩素化炭化水素；臭化メチレン、及びエチレンジブロミドなどの臭素化炭化水素が挙げられ、塩化メチレンがより好ましい。これらは単独で、又は２種類以上の溶媒を任意の割合で混合して用いてもよい。
　反応溶媒の使用量は、全ポリスチレン（高分子量ポリスチレン及び低分子量ポリスチレン）に対して１００～１，０００重量％が好ましく、３５０～７５０重量％がより好ましい。 The method for mixing the raw material polystyrene is not particularly limited as long as it is a known method. Since it can mix uniformly, it is preferable to dissolve / mix in advance in the reaction solvent.
The reaction solvent is not particularly limited as long as it is inert to the reaction, but a halogenated hydrocarbon solvent is preferable. Examples of halogenated hydrocarbon solvents include chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and monochlorobenzene; methylene bromide and ethylene dibromide. Brominated hydrocarbons such as methylene chloride are preferred. These may be used alone or as a mixture of two or more kinds of solvents at an arbitrary ratio.
The amount of the reaction solvent used is preferably 100 to 1,000% by weight, more preferably 350 to 750% by weight, based on the total polystyrene (high molecular weight polystyrene and low molecular weight polystyrene).
　工程（ｂ１）は、ポリスチレン混合物の臭素化反応のための工程である。これにより、本発明の臭素化ポリスチレン組成物が得られる。
　本発明の臭素化反応は、触媒及び臭素化剤の存在下で行うことができる。
　触媒としては、一般的なルイス酸触媒や酸化アンチモン触媒を用いることができる。系中の水分が反応に影響しない点から、酸化アンチモン触媒、例えば三酸化二アンチモン、四酸化二アンチモン、及び五酸化二アンチモンが好ましい。これらの触媒は、単独で、又は２種類以上を任意の割合で混合して用いてもよい。
　触媒の使用量は、臭素化反応に使用される全ポリスチレンのスチレン単位に対して１～３０モル％、好ましくは３～１０モル％である。 Step (b1) is a step for bromination reaction of the polystyrene mixture. Thereby, the brominated polystyrene composition of this invention is obtained.
The bromination reaction of the present invention can be carried out in the presence of a catalyst and a brominating agent.
As the catalyst, a general Lewis acid catalyst or antimony oxide catalyst can be used. Antimony oxide catalysts such as antimony trioxide, diantimony tetroxide, and diantimony pentoxide are preferred because water in the system does not affect the reaction. These catalysts may be used alone or in admixture of two or more at any ratio.
The catalyst is used in an amount of 1 to 30 mol%, preferably 3 to 10 mol%, based on the styrene units of all polystyrene used in the bromination reaction.
　臭素化剤としては、具体的には、臭素（Ｂｒ２）、塩化臭素、Ｎ－ブロモスクシンイミド、１，３－ジブロモ－５，５－ジメチルヒダントイン、及び臭化スルフリルなどが挙げられる。ポリスチレンに対する反応性の観点から、塩化臭素が好ましい。臭素化剤の使用量は、所望の臭素化ポリスチレンの臭素含量により適宜調整できるが、臭素化反応に使用される全ポリスチレンのスチレン単位に対して１００～３５０モル％が好ましい。得られる臭素化ポリスチレンが十分な難燃効果を発揮するためには臭素含量が６０重量％以上であることが望ましい点を考慮して、臭素化剤の使用量は、使用される全ポリスチレンのスチレン単位に対して２００～３５０モル％がさらに好ましい。 Specific examples of the brominating agent include bromine (Br 2 ), bromine chloride, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and sulfuryl bromide. From the viewpoint of reactivity with polystyrene, bromine chloride is preferred. The amount of the brominating agent used can be appropriately adjusted depending on the bromine content of the desired brominated polystyrene, but is preferably 100 to 350 mol% based on the styrene units of all polystyrene used in the bromination reaction. Considering that it is desirable that the bromine content is 60% by weight or more in order for the resulting brominated polystyrene to exhibit a sufficient flame retardant effect, the amount of brominating agent used is the styrene of all polystyrene used. More preferably, it is 200 to 350 mol% based on the unit.
　本発明の臭素化反応には、溶媒を用いてもよい。溶媒は、好ましいものを含め工程（ａ１）において反応溶媒として例示されたものが挙げられる。溶媒の使用量は、工程（ａ１）で使用した反応溶媒と工程（ｂ１）で用いられる溶媒の合計量が、臭素化工程に使用される全ポリスチレン（高分子量ポリスチレン及び低分子量ポリスチレン）に対して１００～１，０００重量％となるのが好ましく、３５０～７５０重量％となるのがより好ましい。 In the bromination reaction of the present invention, a solvent may be used. Examples of the solvent include those exemplified as the reaction solvent in the step (a1) including preferable ones. The amount of the solvent used is the total amount of the reaction solvent used in step (a1) and the solvent used in step (b1) relative to the total polystyrene (high molecular weight polystyrene and low molecular weight polystyrene) used in the bromination step. The amount is preferably 100 to 1,000% by weight, and more preferably 350 to 750% by weight.
　臭素化のための反応温度は、選択する溶媒の種類により異なることができる。得られる臭素化ポリスチレン組成物の色相の点から、－１０～５０℃の範囲が好ましく、－１０～３０℃の範囲がより好ましい。 The reaction temperature for bromination can vary depending on the type of solvent selected. From the viewpoint of the hue of the resulting brominated polystyrene composition, a range of −10 to 50 ° C. is preferable, and a range of −10 to 30 ° C. is more preferable.
　臭素化のための反応時間は、選択する溶媒または触媒の種類や量により異なることができ、１～２４時間が好ましく、３～１２時間がより好ましい。 The reaction time for bromination can vary depending on the type and amount of the solvent or catalyst selected, and is preferably 1 to 24 hours, more preferably 3 to 12 hours.
　臭素化反応の終了後に、過剰の臭素化剤をヒドラジン等の一般的な還元剤を用いて還元し、さらに水洗した後、得られた臭素化ポリスチレン溶液から反応溶媒を濃縮留去するか、又は臭素化ポリスチレン溶液をメタノールなどの貧溶媒中に加えることにより、臭素化ポリスチレン組成物の固体又は粉体を得ることができる。 After completion of the bromination reaction, the excess brominating agent is reduced with a general reducing agent such as hydrazine and further washed with water, and then the reaction solvent is concentrated and distilled off from the resulting brominated polystyrene solution, or By adding the brominated polystyrene solution in a poor solvent such as methanol, a solid or powder of the brominated polystyrene composition can be obtained.
　本発明において、高分子量ポリスチレン及び低分子量ポリスチレンをそれぞれ別々に臭素化した後、所定の割合で混合することによって得られる、臭素化ポリスチレン組成物の製造方法は、具体的には、下記工程（ａ２）～（ｃ２）：
（ａ２）重量平均分子量１万～７万のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、高分子量臭素化ポリスチレンを得る工程、
（ｂ２）重量平均分子量５００～５，０００のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、低分子量臭素化ポリスチレンを得る工程、及び
（ｃ２）工程（ａ２）で得られた高分子量臭素化ポリスチレン７０～９９重量％及び工程（ｂ２）で得られた低分子量臭素化ポリスチレン１～３０重量％を混合する工程
を含む、臭素化ポリスチレン組成物の製造方法である。 In the present invention, a method for producing a brominated polystyrene composition obtained by separately brominating high molecular weight polystyrene and low molecular weight polystyrene and then mixing them at a predetermined ratio is specifically described in the following step (a2). ) To (c2):
(A2) a step of brominating a polystyrene having a weight average molecular weight of 10,000 to 70,000 in the presence of a catalyst and a brominating agent to obtain a high molecular weight brominated polystyrene;
(B2) a step of brominating a polystyrene having a weight average molecular weight of 500 to 5,000 in the presence of a catalyst and a brominating agent to obtain a low molecular weight brominated polystyrene, and (c2) a high molecular weight obtained in step (a2). A method for producing a brominated polystyrene composition comprising a step of mixing 70 to 99% by weight of a molecular weight brominated polystyrene and 1 to 30% by weight of a low molecular weight brominated polystyrene obtained in step (b2).
　工程（ａ２）及び工程（ｂ２）は、それぞれ別々に行ってよい。すなわち、高分子量ポリスチレンを臭素化した後で、低分子量ポリスチレンを臭素化してもよく、低分子量ポリスチレンを臭素化した後で、低分子量ポリスチレンを臭素化してもよい。
　工程（ａ２）及び工程（ｂ２）における、重量平均分子量１万～７万のポリスチレン（高分子量ポリスチレン）、重量平均分子量５００～５，０００のポリスチレン（低分子量ポリスチレン）は、好ましいものを含め工程（ａ１）において記載されたとおりであり、臭素化反応のための条件は、好ましいものを含め工程（ｂ１）において記載されたとおりである。 Step (a2) and step (b2) may be performed separately. That is, after brominating high molecular weight polystyrene, the low molecular weight polystyrene may be brominated, and after low molecular weight polystyrene is brominated, the low molecular weight polystyrene may be brominated.
In the step (a2) and the step (b2), polystyrene having a weight average molecular weight of 10,000 to 70,000 (high molecular weight polystyrene) and polystyrene having a weight average molecular weight of 500 to 5,000 (low molecular weight polystyrene) include those including preferable ones ( The conditions for the bromination reaction are as described in step (b1), including the preferred ones, as described in a1).
　工程（ｃ２）において、高分子量臭素化ポリスチレンは、重量平均分子量が１５，０００～９０，０００であり、重量平均分子量と数平均分子量との比（Ｍｗ／Ｍｎ）が、１．５～４．０であるのが好ましい。また、工程（ｃ２）において、低分子量臭素化ポリスチレンは、重量平均分子量が６００～７，０００であり、重量平均分子量と数平均分子量との比（Ｍｗ／Ｍｎ）が、３．０～４．０であるのが好ましい。 In the step (c2), the high molecular weight brominated polystyrene has a weight average molecular weight of 15,000 to 90,000, and a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.5 to 4. 0 is preferred. In the step (c2), the low molecular weight brominated polystyrene has a weight average molecular weight of 600 to 7,000, and a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 3.0 to 4. 0 is preferred.
　工程（ｃ２）における、高分子量臭素化ポリスチレン及び低分子量臭素化ポリスチレンの混合方法は、公知の方法であれば特に限定されない。
　高分子量臭素化ポリスチレン及び低分子量臭素化ポリスチレンの含有量は、高分子量臭素化ポリスチレンが７０～９９重量％、及び低分子量臭素化ポリスチレンが１～３０重量％であり、高分子量臭素化ポリスチレンが８０～９５重量％、及び低分子量臭素化ポリスチレンが５～２０重量％であるのが好ましく、高分子量臭素化ポリスチレンが８０～８５重量％、及び低分子量臭素化ポリスチレンが１５～２０重量％であるのがより好ましい。このような範囲とすることで、流動性が改善された臭素化ポリスチレン組成物が得られる。 The mixing method of the high molecular weight brominated polystyrene and the low molecular weight brominated polystyrene in the step (c2) is not particularly limited as long as it is a known method.
The contents of the high molecular weight brominated polystyrene and the low molecular weight brominated polystyrene are 70 to 99% by weight for the high molecular weight brominated polystyrene, 1 to 30% by weight for the low molecular weight brominated polystyrene, and 80% for the high molecular weight brominated polystyrene. Preferably 95% by weight and 5-20% by weight of low molecular weight brominated polystyrene, 80-85% by weight of high molecular weight brominated polystyrene and 15-20% by weight of low molecular weight brominated polystyrene. Is more preferable. By setting it as such a range, the brominated polystyrene composition by which fluidity | liquidity was improved is obtained.
　本発明の臭素化ポリスチレン組成物は、耐熱性を維持しながらも流動性が改善された臭素化ポリスチレン組成物である。よって、本発明の臭素化ポリスチレン組成物は、ポリスチレン、ABS、ポリアミド、ポリカーボネート、ポリアセタール、変性ポリフェニレンエーテル、及びポリエステル等の各種エンジニアリングプラスチック用難燃剤として有用である。 The brominated polystyrene composition of the present invention is a brominated polystyrene composition having improved fluidity while maintaining heat resistance. Therefore, the brominated polystyrene composition of the present invention is useful as a flame retardant for various engineering plastics such as polystyrene, ABS, polyamide, polycarbonate, polyacetal, modified polyphenylene ether, and polyester.
　以下に本発明の様態を明らかにするために、実施例と比較例とを示すが、本発明はここに示す実施例のみに限定されるわけではない。 In order to clarify aspects of the present invention, examples and comparative examples are shown below, but the present invention is not limited to the examples shown here.
　実施例及び比較例で得られた臭素化ポリスチレンの分子量、臭素含量、メルトフローレート（ＭＦＲ）及び加熱減量の測定方法は以下の通りである。
　重量平均分子量：ゲル浸透クロマトグラフ法により測定した。予め、東ソー製標準ポリスチレンを用い、分子量約１２０万までの検量線を作成し、次に試料０．０１ｇをテトラヒドロフラン１０ｍｌに溶解後、その１０μｌを東ソー製ＣＣＰＭシステムに注入し、得られたクロマトグラフによりデータ処理装置を用いて標準ポリスチレン換算の重量平均分子量を計算した。分析条件は以下の通りである。カラム（東ソー製ＴＳＫ－Ｇｅｌ　Ｇ４０００Ｈｘｌ×１、Ｇ３０００Ｈｘｌ×１、Ｇ２０００Ｈｘｌ×２４本連結）、移動相（テトラヒドロフラン）、流速（１．０ｍｌ／ｍｉｎ．）、カラム温度（４０℃）、検出波長（ＵＶ２５４ｎｍ）。
　臭素含量：ＪＩＳ　Ｋ　７２９９（フラスコ燃焼法）に準じる方法で測定した。
　メルトフローレート（ＭＦＲ）：ＪＩＳ　Ｋ　７２１０に準拠して、２４０℃、２．１６ｋｇ荷重、又は２５０℃、１．２ｋｇ荷重で測定した。
　加熱減量：試料５．０ｇを正確に秤量し、アルミ皿に入れ、２７０℃に温調された熱風乾燥機（いすゞ製作所社製；ＥＰＰＨ－２１０Ｓ）中、０．５時間処理した。乾燥機投入前の重量に対する処理後の減量分を加熱減量（重量％）とした。 The measurement methods of the molecular weight, bromine content, melt flow rate (MFR) and loss on heating of the brominated polystyrene obtained in Examples and Comparative Examples are as follows.
Weight average molecular weight: Measured by gel permeation chromatography. A calibration curve with a molecular weight of up to about 1.2 million was prepared in advance using Tosoh standard polystyrene. Next, 0.01 g of a sample was dissolved in 10 ml of tetrahydrofuran, and 10 μl thereof was injected into a Tosoh CCPM system. The weight average molecular weight in terms of standard polystyrene was calculated using a data processor. The analysis conditions are as follows. Column (Tosoh TSK-Gel G4000Hxl × 1, G3000Hxl × 1, G2000Hxl × 24 linked), mobile phase (tetrahydrofuran), flow rate (1.0 ml / min.), Column temperature (40 ° C.), detection wavelength (UV254 nm) .
Bromine content: Measured by a method according to JIS K 7299 (flask combustion method).
Melt flow rate (MFR): Measured in accordance with JIS K 7210 at 240 ° C., 2.16 kg load, or 250 ° C., 1.2 kg load.
Loss on heating: A sample of 5.0 g was accurately weighed, placed in an aluminum dish, and treated in a hot air dryer (Isuzu Seisakusho; EPPH-210S) adjusted to 270 ° C. for 0.5 hour. The weight loss after the treatment relative to the weight before the dryer was charged was defined as the weight loss by heating (% by weight).
　合成例１
　攪拌装置、コンデンサー、温度計及び塩素導入管を備えた１Ｌのガラス製四つ口フラスコに、塩化メチレン４５０ｍｌ及び臭素６１７．８ｇを加えて攪拌し、内温５℃以下まで冷却した。次いで、塩素導入管より１．０ｇ／ｍｉｎ．の速度で塩素を導入し、４．８時間かけて合計２８８．５ｇの塩素を加え、１４９７．３ｇの塩化臭素／塩化メチレン溶液を得た。塩素導入中の反応温度は０～５℃であった。 Synthesis example 1
To a 1 L glass four-necked flask equipped with a stirrer, a condenser, a thermometer and a chlorine inlet tube, 450 ml of methylene chloride and 617.8 g of bromine were added and stirred, and the internal temperature was cooled to 5 ° C. or lower. Next, 1.0 g / min. Chlorine was introduced at a rate of, and a total of 288.5 g of chlorine was added over 4.8 hours to obtain 1497.3 g of bromine chloride / methylene chloride solution. The reaction temperature during the introduction of chlorine was 0 to 5 ° C.
　実施例１
　攪拌装置、コンデンサー、温度計及び滴下ロートを備えた３Ｌのガラス製四つ口フラスコに、塩化メチレン８４０ｍｌ、ポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））２８５．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））１５．０ｇを加え、溶解／混合した後、三酸化二アンチモン３３．２ｇを加え、反応温度１０～２５℃にて、合成例１で得られた塩化臭素／塩化メチレン溶液１４９７．３ｇを滴下ロートより２時間かけて滴下した。滴下終了後、内温を２０～３０℃に保持してさらに１時間反応させた。水９００ｍｌを追加し反応を終了させた後、２０％ヒドラジン４０ｇを用いて過剰の塩化臭素を還元した。得られた反応液を静置後、有機層を分液し、９００ｍｌの水を加えて洗浄した。洗浄後の有機層はメタノール６Ｌ中に滴下して結晶を析出させた。この結晶を濾過乾燥することで、臭素化ポリスチレンの粉体８５９．６ｇを得た。得られた臭素化ポリスチレンの分析結果を表１に示す。 Example 1
In a 3 L glass four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 840 ml of methylene chloride, polystyrene (polystyrene made by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 ( 285.0 g of high molecular weight PS) and 15.0 g of polystyrene (Regit S-94 manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight: 2,530, Mw / Mn = 3.31 (low molecular weight PS)) were added and dissolved / After mixing, 33.2 g of diantimony trioxide was added, and 1497.3 g of the bromine chloride / methylene chloride solution obtained in Synthesis Example 1 was added dropwise from a dropping funnel over 2 hours at a reaction temperature of 10 to 25 ° C. After completion of the dropwise addition, the internal temperature was kept at 20-30 ° C., and the reaction was further continued for 1 hour. After the reaction was completed by adding 900 ml of water, excess bromine chloride was reduced using 40 g of 20% hydrazine. The resulting reaction solution was allowed to stand, then the organic layer was separated, and 900 ml of water was added for washing. The organic layer after washing was dropped into 6 L of methanol to precipitate crystals. The crystals were filtered and dried to obtain 859.6 g of brominated polystyrene powder. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　実施例２
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））２７０．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））３０．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表１に示す。 Example 2
Polystyrene (polystyrene by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)) 270.0 g and polystyrene (Sanyo Chemical Industries, Digit S-94, weight average molecular weight) were used. : 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was carried out except that the amount was changed to 30.0 g. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　実施例３
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））２５５．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））４５．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表１に示す。 Example 3
Polystyrene (polystyrene made by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)) 255.0 g and polystyrene (Sanyo Chemical Industries, Ltd., Digit S-94, weight average molecular weight) were used. : 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was carried out except that it was changed to 45.0 g. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　実施例４
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））２４０．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））６０．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表１に示す。 Example 4
Polystyrene (polystyrene made by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)) 240.0 g and polystyrene (Sanyo Chemical Industries, Ltd., Digit S-94, weight average molecular weight) were used. : 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was carried out except that the amount was changed to 60.0 g. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　実施例５
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））２１０．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））９０．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表１に示す。 Example 5
Polystyrene (polystyrene by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)) 210.0 g and polystyrene (Sanyo Chemical Industries, Ltd., Digit S-94, weight average molecular weight) were used. : 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was carried out except that it was changed to 90.0 g. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　比較例１
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））３００．０ｇのみに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレン（高分子量Ｂｒ－ＰＳ）の分析結果を表１に示す。 Comparative Example 1
The same operation as in Example 1 was performed except that the polystyrene used was changed to only 300.0 g of polystyrene (polystyrene made by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)). . Table 1 shows the analysis results of the resulting brominated polystyrene (high molecular weight Br—PS).
　比較例２
　用いるポリスチレンをポリスチレン（アルドリッチ社製ポリスチレン、重量平均分子量：３５，０００、Ｍｗ／Ｍｎ＝２．９８（高分子量ＰＳ））１８０．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））１２０．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表１に示す。 Comparative Example 2
Polystyrene (polystyrene by Aldrich, weight average molecular weight: 35,000, Mw / Mn = 2.98 (high molecular weight PS)) 180.0 g and polystyrene (Sanyo Chemical Industries, Ltd., Digit S-94, weight average molecular weight) were used. : 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was carried out except that it was changed to 120.0 g. The analysis results of the obtained brominated polystyrene are shown in Table 1.
　実施例６
　比較例１で得られた臭素化ポリスチレン（高分子量Ｂｒ－ＰＳ）と、用いるポリスチレンをポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））３００．０ｇのみに変更した以外は実施例１と同様の操作を行って得られた臭素化ポリスチレン（低分子量Ｂｒ－ＰＳ、臭素含量：６６．８％、重量平均分子量：３，８８８、Ｍｗ／Ｍｎ＝３．４４）とを、重量比で９０：１０となるように混合した。得られた混合物の分析結果を表２に示す。 Example 6
The brominated polystyrene (high molecular weight Br-PS) obtained in Comparative Example 1 and the polystyrene used were polystyrene (Regit S-94 manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight: 2,530, Mw / Mn = 3.31 ( Low molecular weight PS)) Brominated polystyrene obtained by performing the same operation as in Example 1 except that it was changed to 300.0 g (low molecular weight Br-PS, bromine content: 66.8%, weight average molecular weight: 3 888, Mw / Mn = 3.44) were mixed at a weight ratio of 90:10. Table 2 shows the analysis results of the obtained mixture.
　実施例７
　高分子量Ｂｒ－ＰＳと低分子量Ｂｒ－ＰＳとの混合比を重量比で８５：１５に変更した以外は実施例６と同様の操作を行い、臭素化ポリスチレンの混合物を得た。得られた混合物の分析結果を表２に示す。 Example 7
A mixture of brominated polystyrene was obtained in the same manner as in Example 6 except that the mixing ratio of the high molecular weight Br-PS and the low molecular weight Br-PS was changed to 85:15 by weight. Table 2 shows the analysis results of the obtained mixture.
　実施例８
　高分子量Ｂｒ－ＰＳと低分子量Ｂｒ－ＰＳの混合比を、重量比で８０：２０に変更した以外は実施例６と同様の操作を行い、臭素化ポリスチレンの混合物を得た。得られた混合物の分析結果を表２に示す。 Example 8
A mixture of brominated polystyrene was obtained in the same manner as in Example 6 except that the mixing ratio of the high molecular weight Br-PS and the low molecular weight Br-PS was changed to 80:20 by weight. Table 2 shows the analysis results of the obtained mixture.
　実施例９
　用いるポリスチレンをポリスチレン（ＤＩＣ社製エラスチレン２００、重量平均分子量：５９，５００、Ｍｗ／Ｍｎ＝１．８０（高分子量ＰＳ））２７６．０ｇ及びポリスチレン（三洋化成工業社製レジットＳ－９４、重量平均分子量：２，５３０、Ｍｗ／Ｍｎ＝３．３１（低分子量ＰＳ））２４．０ｇに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表３に示す。 Example 9
The polystyrene used was 276.0 g of polystyrene (Elastostyrene 200 manufactured by DIC, weight average molecular weight: 59,500, Mw / Mn = 1.80 (high molecular weight PS)) and polystyrene (Regit S-94 manufactured by Sanyo Chemical Industries, weight average). Molecular weight: 2,530, Mw / Mn = 3.31 (low molecular weight PS)) The same operation as in Example 1 was performed except that the molecular weight was changed to 24.0 g. Table 3 shows the analysis results of the obtained brominated polystyrene.
　比較例３
　用いるポリスチレンをポリスチレン（ＤＩＣ社製エラスチレン２００、重量平均分子量：５９，５００、Ｍｗ／Ｍｎ＝１．８０（高分子量ＰＳ））３００．０ｇのみに変更した以外は実施例１と同様の操作を行った。得られた臭素化ポリスチレンの分析結果を表３に示す。 Comparative Example 3
The same operation as in Example 1 was performed except that the polystyrene used was changed to only 300.0 g of polystyrene (Elastostyrene 200 manufactured by DIC, weight average molecular weight: 59,500, Mw / Mn = 1.80 (high molecular weight PS)). It was. Table 3 shows the analysis results of the obtained brominated polystyrene.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の臭素化ポリスチレンは、優れた流動性及び耐熱性を有する。よって、本発明の臭素化ポリスチレン組成物は、各種エンジニアリングプラスチック用難燃剤として有用である。また、本発明の製造方法によれば、優れた流動性及び耐熱性を有する臭素化ポリスチレン組成物を安価で工業的に利用可能な方法で提供することが可能となる。 The brominated polystyrene of the present invention has excellent fluidity and heat resistance. Therefore, the brominated polystyrene composition of the present invention is useful as a flame retardant for various engineering plastics. Moreover, according to the manufacturing method of this invention, it becomes possible to provide the brominated polystyrene composition which has the outstanding fluidity | liquidity and heat resistance by the method which can be utilized industrially cheaply.

Claims (14)

  1. 　重量平均分子量１万～７万のポリスチレンを臭素化して得られる高分子量臭素化ポリスチレンと、重量平均分子量５００～５，０００のポリスチレンを臭素化して得られる低分子量臭素化ポリスチレンとからなる臭素化ポリスチレン組成物であって、原料ポリスチレンにおいて、重量平均分子量１万～７万のポリスチレンが７０～９９重量％であり、重量平均分子量５００～５，０００のポリスチレンが１～３０重量％であることを特徴とする、臭素化ポリスチレン組成物。 Brominated polystyrene comprising high molecular weight brominated polystyrene obtained by brominating polystyrene having a weight average molecular weight of 10,000 to 70,000 and low molecular weight brominated polystyrene obtained by brominating polystyrene having a weight average molecular weight of 500 to 5,000. The composition is characterized in that in the raw material polystyrene, polystyrene having a weight average molecular weight of 10,000 to 70,000 is 70 to 99% by weight, and polystyrene having a weight average molecular weight of 500 to 5,000 is 1 to 30% by weight. A brominated polystyrene composition.
  2. 　臭素化ポリスチレン組成物の重量平均分子量が、７，０００～８０，０００である、請求項１記載の臭素化ポリスチレン組成物。 The brominated polystyrene composition according to claim 1, wherein the brominated polystyrene composition has a weight average molecular weight of 7,000 to 80,000.
  3. 　臭素化ポリスチレン組成物の重量平均分子量と数平均分子量との比（Ｍｗ／Ｍｎ）が、２．０～５．０である、請求項１又は２記載の臭素化ポリスチレン組成物。 The brominated polystyrene composition according to claim 1 or 2, wherein the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight of the brominated polystyrene composition is 2.0 to 5.0.
  4. 　重量平均分子量１万～７万のポリスチレンのＭｗ／Ｍｎが、１．５～４．０である、請求項１～３いずれか１項記載の臭素化ポリスチレン組成物。 The brominated polystyrene composition according to any one of claims 1 to 3, wherein Mw / Mn of polystyrene having a weight average molecular weight of 10,000 to 70,000 is 1.5 to 4.0.
  5. 　重量平均分子量５００～５，０００のポリスチレンのＭｗ／Ｍｎが、２．５～４．５である、請求項１～４いずれか１項記載の臭素化ポリスチレン組成物。 The brominated polystyrene composition according to any one of claims 1 to 4, wherein Mw / Mn of polystyrene having a weight average molecular weight of 500 to 5,000 is 2.5 to 4.5.
  6. 　重量平均分子量１万～７万のポリスチレンが８０～８５重量％であり、重量平均分子量５００～５，０００のポリスチレンが１５～２０重量％である、請求項１～５いずれか１項記載の臭素化ポリスチレン組成物。 The bromine according to any one of claims 1 to 5, wherein the polystyrene having a weight average molecular weight of 10,000 to 70,000 is 80 to 85% by weight and the polystyrene having a weight average molecular weight of 500 to 5,000 is 15 to 20% by weight. Polystyrene composition.
  7. 　（ａ１）重量平均分子量１万～７万のポリスチレン７０～９９重量％及び重量平均分子量５００～５，０００のポリスチレン１～３０重量％を混合して、ポリスチレン混合物を得る工程、及び
    　（ｂ１）工程（ａ１）で得られたポリスチレン混合物を、触媒及び臭素化剤の存在下で臭素化する工程
    を含む、臭素化ポリスチレン組成物の製造方法。     (A1) mixing 70 to 99% by weight of polystyrene having a weight average molecular weight of 10,000 to 70,000 and 1 to 30% by weight of polystyrene having a weight average molecular weight of 500 to 5,000 to obtain a polystyrene mixture, and (b1) A method for producing a brominated polystyrene composition, comprising a step of brominating the polystyrene mixture obtained in (a1) in the presence of a catalyst and a brominating agent.
  8. 　重量平均分子量１万～７万のポリスチレンが８０～８５重量％であり、重量平均分子量５００～５，０００のポリスチレンが１５～２０重量％である、請求項７記載の製造方法。 The production method according to claim 7, wherein the polystyrene having a weight average molecular weight of 10,000 to 70,000 is 80 to 85% by weight and the polystyrene having a weight average molecular weight of 500 to 5,000 is 15 to 20% by weight.
  9. （ａ２）重量平均分子量１万～７万のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、高分子量臭素化ポリスチレンを得る工程、
    （ｂ２）重量平均分子量５００～５，０００のポリスチレンを、触媒及び臭素化剤の存在下で臭素化して、低分子量臭素化ポリスチレンを得る工程、及び
    （ｃ２）工程（ａ２）で得られた高分子量臭素化ポリスチレン７０～９９重量％及び工程（ｂ２）で得られた低分子量臭素化ポリスチレン１～３０重量％を混合する工程
    を含む、臭素化ポリスチレン組成物の製造方法。     (A2) a step of brominating a polystyrene having a weight average molecular weight of 10,000 to 70,000 in the presence of a catalyst and a brominating agent to obtain a high molecular weight brominated polystyrene;
    (B2) a step of brominating a polystyrene having a weight average molecular weight of 500 to 5,000 in the presence of a catalyst and a brominating agent to obtain a low molecular weight brominated polystyrene, and (c2) a high molecular weight obtained in step (a2). A method for producing a brominated polystyrene composition, comprising a step of mixing 70 to 99% by weight of a molecular weight brominated polystyrene and 1 to 30% by weight of the low molecular weight brominated polystyrene obtained in the step (b2).
  10. 　高分子量臭素化ポリスチレンが８０～８５重量％であり、低分子量臭素化ポリスチレンが１５～２０重量％である、請求項９記載の製造方法。 The production method according to claim 9, wherein the high molecular weight brominated polystyrene is from 80 to 85% by weight and the low molecular weight brominated polystyrene is from 15 to 20% by weight.
  11. 　重量平均分子量１万～７万のポリスチレンのＭｗ／Ｍｎが、１．５～４．０である、請求項７～１０いずれか１項記載の製造方法。 The production method according to any one of claims 7 to 10, wherein Mw / Mn of polystyrene having a weight average molecular weight of 10,000 to 70,000 is 1.5 to 4.0.
  12. 　重量平均分子量５００～５，０００のポリスチレンのＭｗ／Ｍｎが、２．５～４．５である、請求項７～１１いずれか１項記載の製造方法。 The production method according to any one of claims 7 to 11, wherein Mw / Mn of polystyrene having a weight average molecular weight of 500 to 5,000 is 2.5 to 4.5.
  13. 　触媒が酸化アンチモンである、請求項７～１２いずれか１項記載の製造方法。 The production method according to any one of claims 7 to 12, wherein the catalyst is antimony oxide.
  14. 　臭素化剤が塩化臭素である、請求項７～１３いずれか１項記載の製造方法。 The process according to any one of claims 7 to 13, wherein the brominating agent is bromine chloride.
PCT/JP2012/053235 2011-02-17 2012-02-13 High fluidity brominated polystyrene composition and method of producing same WO2012111594A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694419A (en) * 2018-12-27 2019-04-30 山东旭锐新材有限公司 BPS product and preparation method thereof by full bromine method
CN109762082A (en) * 2018-12-27 2019-05-17 山东旭锐新材有限公司 A kind of small-molecular-weight BPS product and preparation method thereof
CN117106109A (en) * 2023-10-25 2023-11-24 山东海化集团有限公司 Method for continuously preparing brominated polystyrene
CN117106109B (en) * 2023-10-25 2024-06-04 山东海化集团有限公司 Method for continuously preparing brominated polystyrene

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0366755A (en) * 1989-07-27 1991-03-22 Basf Ag Flameproof, thermoplastic molding material
JPH0718165A (en) * 1993-06-30 1995-01-20 Du Pont Kk Flame-retardant polyester resin composition
JPH07126463A (en) * 1993-11-05 1995-05-16 Manac Inc Flame-retardant for styrenic resin
JPH07292026A (en) * 1994-04-25 1995-11-07 Manac Inc Production of brominated polystyrene
JPH10101946A (en) * 1996-08-08 1998-04-21 Toray Ind Inc Thermoplastic resin composition and molded product
JP2009500470A (en) * 2005-06-30 2009-01-08 アルベマール・コーポレーシヨン Brominated styrenic polymers and their production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0366755A (en) * 1989-07-27 1991-03-22 Basf Ag Flameproof, thermoplastic molding material
JPH0718165A (en) * 1993-06-30 1995-01-20 Du Pont Kk Flame-retardant polyester resin composition
JPH07126463A (en) * 1993-11-05 1995-05-16 Manac Inc Flame-retardant for styrenic resin
JPH07292026A (en) * 1994-04-25 1995-11-07 Manac Inc Production of brominated polystyrene
JPH10101946A (en) * 1996-08-08 1998-04-21 Toray Ind Inc Thermoplastic resin composition and molded product
JP2009500470A (en) * 2005-06-30 2009-01-08 アルベマール・コーポレーシヨン Brominated styrenic polymers and their production

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694419A (en) * 2018-12-27 2019-04-30 山东旭锐新材有限公司 BPS product and preparation method thereof by full bromine method
CN109762082A (en) * 2018-12-27 2019-05-17 山东旭锐新材有限公司 A kind of small-molecular-weight BPS product and preparation method thereof
CN109694419B (en) * 2018-12-27 2021-07-30 山东旭锐新材有限公司 BPS product and preparation method thereof by full bromine method
CN109762082B (en) * 2018-12-27 2021-07-30 山东旭锐新材有限公司 Low-molecular-weight BPS product and preparation method thereof
CN117106109A (en) * 2023-10-25 2023-11-24 山东海化集团有限公司 Method for continuously preparing brominated polystyrene
CN117106109B (en) * 2023-10-25 2024-06-04 山东海化集团有限公司 Method for continuously preparing brominated polystyrene

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