WO2012111594A1 - Composition de polystyrène bromé à fluidité élevée et procédé pour la produire - Google Patents

Composition de polystyrène bromé à fluidité élevée et procédé pour la produire 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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English (en)
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 CN2012800087945A priority Critical patent/CN103370370A/zh
Priority to JP2012557942A priority patent/JP5829630B2/ja
Publication of WO2012111594A1 publication Critical patent/WO2012111594A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de polystyrène bromé qui, utile comme ignifugeant pour divers plastiques industriels, présente une fluidité élevée et une ininflammabilité élevée et qui ne perd pas sa résistance à la chaleur ; elle concerne également un procédé pour la produire. Cette composition de polystyrène bromé comprend un polystyrène bromé de haut poids moléculaire obtenu par bromation de polystyrène de poids moléculaire moyen en poids de 10k-70k, et un polystyrène bromé de faible poids moléculaire obtenu par bromation d'un polystyrène de poids moléculaire moyen en poids de 500-5000, ladite composition de polystyrène bromé se caractérisant en ce que le polystyrène de poids moléculaire moyen en poids de 10k-70k représente 70-99 % en poids du polystyrène brut et le polystyrène de poids moléculaire moyen en poids de 500-5000 représente 1-30 % en poids du polystyrène brut. Ce procédé de production de la composition de polystyrène bromé implique une étape de bromation du matériau brut de polystyrène de ladite composition en présence d'un catalyseur et d'un agent bromant.
PCT/JP2012/053235 2011-02-17 2012-02-13 Composition de polystyrène bromé à fluidité élevée et procédé pour la produire WO2012111594A1 (fr)

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CN2012800087945A CN103370370A (zh) 2011-02-17 2012-02-13 高流动性溴化聚苯乙烯组合物及其制造方法
JP2012557942A JP5829630B2 (ja) 2011-02-17 2012-02-13 高流動性臭素化ポリスチレン組成物及びその製造方法

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CN109694419A (zh) * 2018-12-27 2019-04-30 山东旭锐新材有限公司 一种bps产品及其全溴法的制备方法
CN109762082A (zh) * 2018-12-27 2019-05-17 山东旭锐新材有限公司 一种小分子量bps产品及其制备方法
CN117106109A (zh) * 2023-10-25 2023-11-24 山东海化集团有限公司 一种连续化制备溴化聚苯乙烯的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694419A (zh) * 2018-12-27 2019-04-30 山东旭锐新材有限公司 一种bps产品及其全溴法的制备方法
CN109762082A (zh) * 2018-12-27 2019-05-17 山东旭锐新材有限公司 一种小分子量bps产品及其制备方法
CN109694419B (zh) * 2018-12-27 2021-07-30 山东旭锐新材有限公司 一种bps产品及其全溴法的制备方法
CN109762082B (zh) * 2018-12-27 2021-07-30 山东旭锐新材有限公司 一种小分子量bps产品及其制备方法
CN117106109A (zh) * 2023-10-25 2023-11-24 山东海化集团有限公司 一种连续化制备溴化聚苯乙烯的方法
CN117106109B (zh) * 2023-10-25 2024-06-04 山东海化集团有限公司 一种连续化制备溴化聚苯乙烯的方法

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