JPH02215807A - Preparation of brominated polystyrene - Google Patents
Preparation of brominated polystyreneInfo
- Publication number
- JPH02215807A JPH02215807A JP3621489A JP3621489A JPH02215807A JP H02215807 A JPH02215807 A JP H02215807A JP 3621489 A JP3621489 A JP 3621489A JP 3621489 A JP3621489 A JP 3621489A JP H02215807 A JPH02215807 A JP H02215807A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- polystyrene
- water
- halogenated hydrocarbon
- benzene ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004793 Polystyrene Substances 0.000 title claims description 37
- 229920002223 polystyrene Polymers 0.000 title claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 13
- -1 aliphatic halogenated hydrocarbon Chemical class 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000007664 blowing Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 150000008282 halocarbons Chemical class 0.000 abstract 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 15
- 229910052794 bromium Inorganic materials 0.000 description 15
- 125000001246 bromo group Chemical group Br* 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- XIIAPOBAFRAUGJ-UHFFFAOYSA-N 14-oxo-8-oxa-15-azatetracyclo[7.7.1.02,7.013,17]heptadeca-2(7),3,5,9,11,13(17)-hexaene-4-sulfonic acid Chemical compound O=C1NCC2C3=CC(S(=O)(=O)O)=CC=C3OC3=CC=CC1=C32 XIIAPOBAFRAUGJ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- JWFDXKOVBQLBBL-UHFFFAOYSA-N 1,1-dibromo-1,2-dichloroethane Chemical compound ClCC(Cl)(Br)Br JWFDXKOVBQLBBL-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
耐熱性の難燃剤として有用な、乳白色乃至淡色の高臭素
化ポリスチレンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing milky-white to light-colored highly brominated polystyrene useful as a heat-resistant flame retardant.
ポリスチレンのルイス酸触媒を用いた臭素化反応につい
ては公知であるが、ベンゼン環１個当り２個以上の臭素
原子が導入されると着色が大きいことが知られている。The bromination reaction of polystyrene using a Lewis acid catalyst is known, but it is known that the introduction of two or more bromine atoms per benzene ring causes significant coloration.
生成物の外観色の改良のために特公昭６１−３４７２３
ではルイス酸に対して塩基性物質を加えており、また特
公昭６２−５８６０４では触媒としてアルカリ金属ハロ
ゲン化物とハロゲン化鉄との複塩を用いることが提案さ
れている。Special Publication No. 61-34723 for improving the appearance color of products
In Japanese Patent Publication No. 62-58604, it is proposed to use a double salt of an alkali metal halide and an iron halide as a catalyst.
又、特開昭５７−５３５０５では実質的に無水の状態で
塩化臭素を使用して臭素化することにより着色の少ない
生成物を得るとしている。Furthermore, JP-A-57-53505 states that a less colored product can be obtained by bromination using bromine chloride in a substantially anhydrous state.
外観色の改良された臭素化ポリスチレンの製造方法とし
て開示された特公昭６１−３４７２３や特公昭６２−５
８６０４ではベンゼン環１個当り臭素原子は１〜２個し
か導入されない、又臭素化の際、反応系を無水状態にｉ
弛とができればベンゼン環１個当り臭素原子は３つ以上
導入することができるが、臭素を用いて行うと着色が避
けられず、塩化臭素を用いる必要があった。Japanese Patent Publication No. 61-34723 and Japanese Patent Publication No. 62-5 which were disclosed as a method for producing brominated polystyrene with improved appearance color.
In 8604, only 1 to 2 bromine atoms are introduced per benzene ring, and during bromination, the reaction system is brought into an anhydrous state.
If relaxation is possible, three or more bromine atoms can be introduced per benzene ring, but if this is done using bromine, coloration is unavoidable, so it is necessary to use bromine chloride.
即ち、臭素を用いてベンゼン環１個当り３個以上臭素原
子を導入し、かつ外観色の良好な臭素化ポリスチレンの
製造法については知られていなかった。それ放臭素化ポ
リスチレンを樹脂用難燃剤として使用する際に着色が障
害となっていた。That is, there is no known method for producing brominated polystyrene that uses bromine to introduce three or more bromine atoms per benzene ring and has a good external color. Coloration has been an obstacle when using brominated polystyrene as a flame retardant for resins.
本発明鬼はこれらの！ＩＩＩＢを解決するものである。The inventor of this invention is these! This solves IIIB.
前述の課題を解決するために、鋭意検討した結果、脱水
剤の共存下、脂肪族ハロゲン化炭化水素の溶媒として、
該ポリスチレンのベンゼン環１個当り０．００１〜０．
０３モル比のルイス酸触媒を使用して、臭素を用いて、
ポリスチレンを臭素化することにより、乳白色乃至淡色
の臭素化ポリスチレンを得る方法を見出した。さらに難
燃剤として使用するに適切な結晶化の方法として、１０
０℃以下の沸点を持つ脂肪族ハロゲン化炭化水素を溶媒
として使用し、反応混合液を沸騰水中に滴下することに
より晶析と同時に溶媒の回収を行って、粉末および／ま
たは顆粒状の臭素化ポリスチレンを得る方法を見出した
。In order to solve the above-mentioned problems, as a result of intensive studies, we found that as a solvent for aliphatic halogenated hydrocarbons in the coexistence of a dehydrating agent,
0.001 to 0.00% per benzene ring of the polystyrene.
With bromine using a Lewis acid catalyst with a molar ratio of
We have discovered a method to obtain milky white to light-colored brominated polystyrene by brominating polystyrene. Furthermore, as a method of crystallization suitable for use as a flame retardant, 10
Using an aliphatic halogenated hydrocarbon with a boiling point below 0°C as a solvent, the reaction mixture is dropped into boiling water to recover the solvent at the same time as crystallization, resulting in bromination of powder and/or granules. Found a way to obtain polystyrene.
反応溶媒としての脂肪族ハロゲン化炭化水素としては塩
化メチレン、クロロホルム、四塩化炭素、塩化エチレン
、トリクロロエタン、テトラクロロエタン、ジクロロジ
ブロモエタン、ジブロモエタン、テトラブロモエタン等
があげられる。これらは無１水状態の溶媒だけでなく、
工業的によ１行われる様に溶解度以下の水を含有する回
収された溶媒であってもよい、これらの溶媒のなかでは
塩化メチレン又は塩化エチレンが好ましい、脱水剤とし
ては、一般に使用されている酸性又は中性であって、触
媒として用いられるルイス酸の吸水力より強い脱水剤が
使用でき、例えば五酸化リン、無水の硫酸、塩化カルシ
ウムなどがあげられるが、五酸化リンが最も好ましい、
脱水剤の使用量はポリスチレンのベンゼン環１個当り通
常０．０１〜０．０５モル比が適当であるが、前述の回
収溶媒使用の際にはその含有する水を吸収するのに必要
な量の使用量増加が必要である。Examples of aliphatic halogenated hydrocarbons used as reaction solvents include methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane, tetrachloroethane, dichlorodibromoethane, dibromoethane, and tetrabromoethane. These are not only solvents in anhydrous state, but also
As a dehydrating agent, it may be a recovered solvent containing water below its solubility, as is practiced in industry, and among these solvents methylene chloride or ethylene chloride are preferred. A dehydrating agent that is acidic or neutral and stronger in water absorption than the Lewis acid used as a catalyst can be used, such as phosphorus pentoxide, anhydrous sulfuric acid, calcium chloride, etc., but phosphorus pentoxide is most preferred.
The appropriate amount of dehydrating agent to be used is normally 0.01 to 0.05 molar ratio per benzene ring of polystyrene, but when using the above-mentioned recovered solvent, the amount necessary to absorb the water contained in it is appropriate. It is necessary to increase the usage of
脱水剤の使用量が０．１モル比を超える場合は、反応熱
やコスト上昇の点から、溶媒中の水を２００ｐｐｍ以下
とし脱水剤の使用量を少なくする方がメリットが多い。When the amount of dehydrating agent used exceeds 0.1 molar ratio, it is more advantageous to reduce the amount of water in the solvent by setting the amount of water in the solvent to 200 ppm or less in terms of reaction heat and cost increase.
さらに臭素、ポリスチレン等の試剤よりの水の混入も同
様に考え脱水剤の使用量を増加させることが必要である
。Furthermore, considering the contamination of water from reagents such as bromine and polystyrene, it is necessary to increase the amount of dehydrating agent used.
チタン、鉄の塩化物または／および臭弯物があげられる
０本発明においては、無水塩化アルミニウム、無水臭化
アルミニウムが白皮の高い製品を得るために最も好まし
い触媒として挙げることができる。触媒の使用量はベン
ゼン環１個当り０．００１〜０．０３モル比であり、０
．００１より少ないと、反応時間が長くなり、０．０３
を超えると、製品の着色が大きくなる。さらに好ましく
はｏ、ｏｏｓ〜０．０１５モル比である。In the present invention, anhydrous aluminum chloride and anhydrous aluminum bromide can be mentioned as the most preferred catalysts to obtain a product with high whiteness. The amount of catalyst used is 0.001 to 0.03 molar ratio per benzene ring, and 0.
．． If it is less than 0.001, the reaction time becomes longer and 0.03
If it exceeds , the coloring of the product will increase. More preferably, the molar ratio is o, oos to 0.015.
使用する原料ポリスチレンの重合度により、臭素化ポリ
スチレンの着色度が異なり、重量平均分子量５万以下で
は淡黄色になる。一方高分子量程白皮は高くなるが、実
用的には５０万程度までは使用できる。The degree of coloring of brominated polystyrene varies depending on the degree of polymerization of the raw material polystyrene used, and when the weight average molecular weight is 50,000 or less, it becomes pale yellow. On the other hand, the higher the molecular weight, the higher the white peel, but in practical terms it can be used up to about 500,000 yen.
臭素は置換するに要するモル数の１０１〜１０３％を使
用する。Bromine is used in an amount of 101 to 103% of the number of moles required for substitution.
反応温度は０４〜４０℃であり、０゛Ｃ以下では反応速
度が遅く、４０℃以上で反応した場合は、生成物の着色
が大きくなる。The reaction temperature is 04 to 40°C. Below 0°C, the reaction rate is slow, and when the reaction is carried out above 40°C, the product becomes heavily colored.
本発明の様に触媒使用量が溶媒に対し１００〜３０００
ｐｐ論程度の量では、水の他に含酸素化合物のような阻
害物質、例えばアルコール類、ケトン類、エステル類、
テトラヒドロフラン、ジオキサンの様な複素環化合物に
よって反応が阻害されるので、脂肪族ハロゲン化炭化水
素中に用いられている安定剤に注意することが必要であ
る。As in the present invention, the amount of catalyst used is 100 to 3000 relative to the solvent.
In amounts on the order of pp theory, in addition to water, inhibitory substances such as oxygenated compounds, such as alcohols, ketones, esters, etc.
Since the reaction is inhibited by heterocyclic compounds such as tetrahydrofuran and dioxane, care must be taken with the stabilizers used in aliphatic halogenated hydrocarbons.
所定量で反応を開始した際、上記の阻害物質が溶媒に含
まれている場合には、所望する臭素含有率より低いもの
か、はとんど臭素が導入されていないものが得られる。When the reaction is started at a predetermined amount, if the above-mentioned inhibitory substance is contained in the solvent, a bromine content lower than the desired one or almost no bromine introduced can be obtained.
触媒量を阻害物質に見合う量まで増加させることは、反
応を進行させるために必要であるが、多量の増加は生成
物の着色を増す原因となるので、阻害物質は２００ｐｐ
ｍ程度に抑えた方がよい。Increasing the amount of catalyst to a level commensurate with the amount of inhibitor is necessary for the reaction to proceed, but increasing the amount by a large amount will cause increased coloration of the product, so the amount of inhibitor should be increased to 200 pp.
It is better to keep it to about m.
触媒量も多く使用する場合でも５００ｐｐ−以下が望ま
しい０反応混合液から、得られた臭素化ポリスチレンを
結晶化するには、メタノールなどの低級アルコール類に
反応混合液を注ぎ析出させてもよい。In order to crystallize the obtained brominated polystyrene from the reaction mixture, which is preferably 500 pp or less even when a large amount of catalyst is used, the reaction mixture may be poured into a lower alcohol such as methanol to cause precipitation.
その際にはあらかじめ反応液に水を加えて触媒及び脱水
剤を水層に抽出し、水層を分離してから行うのが通常で
ある。In this case, it is usual to add water to the reaction solution in advance to extract the catalyst and dehydrating agent into the aqueous layer, and then to separate the aqueous layer.
更に好ましくは、反応液のまま、沸騰水中に滴下し、晶
析と同時に溶媒の回収を行う方法により、難燃剤として
使用するに適切な結晶を得ることができる。もちろん前
述の樺に触媒を抽出してから行うこともできる。又沸騰
水中に反応液を滴下する前に反応混合液に空気、窒素な
どの不活性ガスを導入し臭化水素を回収することが望ま
しい、あるいは結晶化の際沸騰水中に塩基を入れて置く
か、滴下しながら水を中和することもできる。また該結
晶化を大気圧下のみならず減圧下で行うこともできる。More preferably, crystals suitable for use as a flame retardant can be obtained by dropping the reaction solution as it is into boiling water and recovering the solvent at the same time as crystallization. Of course, this can also be carried out after extracting the catalyst from the birch tree mentioned above. In addition, it is preferable to introduce an inert gas such as air or nitrogen into the reaction mixture before dropping the reaction mixture into boiling water to recover hydrogen bromide, or to add a base to the boiling water during crystallization. , it is also possible to neutralize water while dripping. Further, the crystallization can be carried out not only under atmospheric pressure but also under reduced pressure.
本発明の方法で得られる臭素化ポリスチレンは、本質的
にはベンゼン環１個当り３個以上の臭素原子を有するも
のであるが、臭素化ポリスチレンに着色などの悪影響を
与えない程度に、例えばベンゼン環１個当り２ケの臭素
原子を有するものが微量含まれていてもよい。Brominated polystyrene obtained by the method of the present invention essentially has three or more bromine atoms per benzene ring, but benzene may be A trace amount of bromine atoms having two bromine atoms per ring may be included.
実施態様の一例を記すと
■ポリスチレンを脂肪族ハロゲン化炭化水素に溶解し
■脱水剤を加え更にポリスチレンのベンゼン環１個当り
ｏ、ｏｏｔ〜０．０３モル比のルイス酸触媒を加える。An example of the embodiment is as follows: (1) Polystyrene is dissolved in an aliphatic halogenated hydrocarbon, (2) a dehydrating agent is added, and a Lewis acid catalyst is added in a molar ratio of o,oot to 0.03 per benzene ring of the polystyrene.
■０°〜４０″Ｃで臭素を加えて反応を完結させる。■ Add bromine at 0° to 40″C to complete the reaction.
■（空気を吹き込み臭化水素を追い出し）反応液を沸騰
水中に滴下し結晶を析出させる。(Blow out air to drive out hydrogen bromide) Drop the reaction solution into boiling water to precipitate crystals.
（■結晶をろ集し水洗乾燥させる。）
となるが、上記の方法により外観の改良された臭素化ポ
リスチレンを得ることができる。(■ The crystals are collected by filtration, washed with water and dried.) However, brominated polystyrene with improved appearance can be obtained by the above method.
但し製品の品質は■乃至■の条件で決定され等メリット
が多い。However, the quality of the product is determined by the conditions of ■ to ■, and there are many advantages.
これらに限定されるものではない。It is not limited to these.
実施例１
塩化メチレン１００ｄに溶解したポリスチレン（日立化
成工業（株）ＧＰ−Ｐ重量平均分子量２８〜２９万）
１０．４ｇの入った２００ＣＣ四ツロフラスコに五酸化
リン０．４ｇ、無水塩化アルミニウム０．４ｇを加えて
後５〜１０℃で４０ｇの臭素を滴下する０滴下後撒２ｈ
ｒ同温度で反応を続は反応を完結させた後に発熱に注意
して水を滴下し、触媒を失活させる（必要、があれば還
元剤と）水を加えて、水層を分離し更に塩化メチレン層
を水で洗浄する。 ２５０ｄのメタノール層に水洗し
た塩化メチレン層を注ぎ、析出した結晶をろ集し洗浄乾
燥して、白色の臭素化ポリスチレン（臭素含量６６％）
２９．７ｇを得た。Example 1 Polystyrene (Hitachi Chemical Co., Ltd. GP-P weight average molecular weight 280,000 to 290,000) dissolved in 100 d of methylene chloride
Add 0.4 g of phosphorus pentoxide and 0.4 g of anhydrous aluminum chloride to a 200CC four-touch flask containing 10.4 g, then drop 40 g of bromine at 5 to 10°C. Sprinkle for 2 hours after 0 drops.
Continuing the reaction at the same temperature, after completing the reaction, add water dropwise, being careful not to generate heat, add water to deactivate the catalyst (and a reducing agent if necessary), separate the aqueous layer, and then Wash the methylene chloride layer with water. Pour the methylene chloride layer washed with water into the methanol layer of 250d, collect the precipitated crystals by filtration, wash and dry to obtain white brominated polystyrene (bromine content 66%).
29.7g was obtained.
実施例２
塩化エチレン１５０ｄに溶解したポリスチレンＧＰ−Ｐ
ｌｏ、４ｇの入った３００ＣＣ四ツロフラスコに五酸化
リン０．４ｇ、無水塩化アルミニウム０．１３ｇを加え
１０℃で臭素４３．６ｇを滴下し、滴下終了後更に４時
間反応温度を保持した０反応液中に空気を吹き込んで臭
化水素を追い出した後、水を少量加えて触媒を失活させ
全反応液を９０℃以上に保った湯中に滴下して晶析する
。洗浄乾燥後←白色顆粒状の臭素化ポリスチレンが、３
２．０ｇ （臭素含有率６８％）得られた。Example 2 Polystyrene GP-P dissolved in 150 d of ethylene chloride
0.4 g of phosphorus pentoxide and 0.13 g of anhydrous aluminum chloride were added to a 300CC four-way flask containing 4 g of 100% bromine, and 43.6 g of bromine was added dropwise at 10°C, and after the completion of the dropwise addition, the reaction temperature was maintained for an additional 4 hours. After blowing air into the mixture to drive out the hydrogen bromide, a small amount of water is added to deactivate the catalyst, and the entire reaction solution is dropped into hot water kept at 90° C. or higher for crystallization. After washing and drying, 3 white granular brominated polystyrene
2.0 g (bromine content: 68%) was obtained.
実施例３
アルコール類を含まないクロロホルム１００ｄを用いて
反応温度を２０℃とした他は実施例１と同様に行い白色
の臭素化ポリスチレンを２９．５ｇ得た。Example 3 The same procedure as in Example 1 was conducted except that 100 d of chloroform containing no alcohol was used and the reaction temperature was changed to 20° C. to obtain 29.5 g of white brominated polystyrene.
実施例４
ポリスチレンＧＰ−Ｐ６９．４ｇを８００ ｊｄ塩化エ
チレンに溶解し五酸化リン２．８ｇ、無水塩化アルミニ
ウム０．９ｇを加えて１０℃で２８２ｇの臭素を加える
０反応を更に２時間続けた後触媒を水で失活し、更に水
を加えて分液し、次いで塩化エチレン層を水で洗浄した
後、２１の沸騰水中に滴下して臭素化ポリスチレンの白
い顆粒２０５ｇを得た。Example 4 69.4 g of polystyrene GP-P was dissolved in 800 jd ethylene chloride, 2.8 g of phosphorus pentoxide and 0.9 g of anhydrous aluminum chloride were added, and 282 g of bromine was added at 10° C. The reaction was continued for another 2 hours. The catalyst was deactivated with water, further water was added to separate the layers, and the ethylene chloride layer was washed with water, and then added dropwise into boiling water of 21 to obtain 205 g of white brominated polystyrene granules.
比較例
メチルエチルケトン１０００ｐｐ−を含む塩化エチレン
１５０ＩｄにポリスチレンＧＰ−Ｐ１０．４ｇを溶解し
五酸化リン１．０ｇ無水塩化アルミニウム０．２６ｇを
加え臭素を加えたが、得られた臭素化ポリスチレンは臭
素が１ケ導入されているのみであった。さらに無水塩化
アルミニウムを０．２７ｇ追加したところ、５〜１０”
Ｃ７時間で反応が終了したが、得られた臭素化ポリスチ
レンは黄色に着色していた。Comparative Example 10.4 g of polystyrene GP-P was dissolved in 150 Id of ethylene chloride containing 1000 pp of methyl ethyl ketone, 1.0 g of phosphorus pentoxide and 0.26 g of anhydrous aluminum chloride were added, and bromine was added to the resulting brominated polystyrene. However, only a few had been introduced. Furthermore, when 0.27g of anhydrous aluminum chloride was added, 5 to 10"
Although the reaction was completed in C7 hours, the obtained brominated polystyrene was colored yellow.
白皮測定例
均−に粉砕したサンプルを色差計により反射光のＬｌｌ
、ａｌｌ 、ｂ＊を測定しＷ−Ｌ”−３ｂ”として白
炭を求めた。White skin measurement example A uniformly ground sample was measured using a color difference meter to measure the amount of reflected light.
, all and b* were measured and white charcoal was determined as W-L"-3b".
実施例４のＷは７９．０であった。W in Example 4 was 79.0.
本発明の一般的な例としてＷは７０−８０の値で得られ
る。In a typical example of the present invention, W is obtained with a value of 70-80.
比較例では５０−６０の値であった。In the comparative example, the value was 50-60.
塩化臭素により臭素化を行ったと見られる入手サンプル
のＷは６２．１であった。The W of the obtained sample, which appears to have been brominated with bromine chloride, was 62.1.
発明の効果
脂肪族ハロゲン化炭化水素溶媒中央ない量のルイス酸触
媒を用いてポリスチレンを臭素化する際に脱水剤を併用
することにより、乳白色〜淡色の外観色の改良された臭
素化ポリスチレンが得られる。結晶化方法としては反応
混合液を沸騰水中に滴下する方法により良好な品質のも
のが期待できる。Effects of the Invention Brominated polystyrene with an improved milky-white to pale external color can be obtained by using a dehydrating agent when brominating polystyrene using an aliphatic halogenated hydrocarbon solvent and a moderate amount of a Lewis acid catalyst. It will be done. As for the crystallization method, good quality can be expected by dropping the reaction mixture into boiling water.
臭素化ポリスチレンは本発明の方法により外観色が改良
され難燃剤としてますまを用なものとなる。The appearance color of brominated polystyrene is improved by the method of the present invention, making it useful as a flame retardant.
特許出願人 日本化薬株式会社Patent applicant: Nippon Kayaku Co., Ltd.
Claims (8)
媒として、ポリスチレンのベンゼン環１個当り０．００
１〜０．０３モル比のルイス酸触媒を使用し、０゜〜４
０℃で臭素化することを特徴とする臭素化ポリスチレン
の製造方法。(1) In the presence of a dehydrating agent, using an aliphatic halogenated hydrocarbon as a solvent, 0.00% per benzene ring of polystyrene
Using a Lewis acid catalyst with a molar ratio of 1 to 0.03, 0° to 4
A method for producing brominated polystyrene, which comprises brominating at 0°C.
囲第１項に記載の方法。(2) The method according to claim 1, wherein phosphorus pentoxide is used as a dehydrating agent.
は塩化エチレンを溶媒とする、特許請求の範囲第１項に
記載の方法。(3) The method according to claim 1, wherein methylene chloride or ethylene chloride is used as the aliphatic halogenated hydrocarbon as a solvent.
用する特許請求の範囲第１項記載の方法。(4) The method according to claim 1, wherein polystyrene having a weight average molecular weight of 50,000 to 500,000 is used.
０．０１５モル比無水塩化アルミニウムを使用する特許
請求の範囲第１項に記載の方法。(5) 0.005~ per benzene ring of polystyrene
A method according to claim 1, using 0.015 molar ratio anhydrous aluminum chloride.
よび／または含酸素有機化合物が２００ｐｐｍを超えな
い溶媒を使用する特許請求の範囲第１項に記載の方法。(6) The method according to claim 1, wherein a solvent is used in which water and/or oxygen-containing organic compounds as impurities in the aliphatic halogenated hydrocarbon do not exceed 200 ppm.
溶媒を用い、特許請求の範囲第１項に記載された方法で
得た反応混合液を、沸騰水中に滴下し、溶媒の回収と同
時に結晶化を行う臭素化ポリスチレンの製造方法。(7) Using an aliphatic halogenated hydrocarbon solvent with a boiling point of 100°C or less, drop the reaction mixture obtained by the method described in claim 1 into boiling water, and simultaneously recover the solvent. A method for producing brominated polystyrene by crystallization.
に記載の方法。(8) The method according to claim 7, in which ethylene chloride is used as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3621489A JPH02215807A (en) | 1989-02-17 | 1989-02-17 | Preparation of brominated polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3621489A JPH02215807A (en) | 1989-02-17 | 1989-02-17 | Preparation of brominated polystyrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02215807A true JPH02215807A (en) | 1990-08-28 |
Family
ID=12463506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3621489A Pending JPH02215807A (en) | 1989-02-17 | 1989-02-17 | Preparation of brominated polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02215807A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07292026A (en) * | 1994-04-25 | 1995-11-07 | Manac Inc | Production of brominated polystyrene |
| EP0765887A1 (en) | 1995-09-26 | 1997-04-02 | Manac Incorporated | Process for preparing brominated polystyrene |
| US5677390A (en) * | 1996-09-26 | 1997-10-14 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5686538A (en) * | 1996-09-26 | 1997-11-11 | Albemarle Corporation | Process for brominating polystyrenic resins |
| WO1998013396A1 (en) * | 1996-09-26 | 1998-04-02 | Albemarle Corporation | Process for brominated styrenic polymers |
| US5767203A (en) * | 1996-09-26 | 1998-06-16 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6133381A (en) * | 1996-09-26 | 2000-10-17 | Albelmarle Corporation | Brominated polystyrenic flame retardants |
| US6232408B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Brominated polstyrenic resins |
| US6232393B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Polymers flame retarded with brominated polystyrenic resins |
| US6235844B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Brominated polystyrenic resins |
| US6235831B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Polymer compositions containing brominated polystyrenic resins |
| US6326439B1 (en) | 1996-09-26 | 2001-12-04 | Albemarle Corporation | Process for brominating polystyrenic resins |
| USRE37902E1 (en) | 1996-06-14 | 2002-11-05 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| US6518368B2 (en) | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| US6521714B2 (en) | 1996-09-26 | 2003-02-18 | Albemarle Corporation | Brominated polystyrenic resins |
| EP1293518A3 (en) * | 1997-05-07 | 2003-11-26 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US7202296B2 (en) | 2003-12-19 | 2007-04-10 | Albemarle Corporation | Flame retardant compositions and their use |
| US7632893B2 (en) | 2005-06-30 | 2009-12-15 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
| US7638583B2 (en) | 2005-12-21 | 2009-12-29 | Albemarle Corporation | Brominated anionic styrenic polymers and their preparation |
| JP2010501677A (en) * | 2006-08-22 | 2010-01-21 | アルベマール・コーポレーシヨン | Termination of bromination of styrenic polymers in bromination reaction mixtures. |
| US7666944B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7666943B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
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|---|---|---|---|---|
| JPS55151007A (en) * | 1979-05-07 | 1980-11-25 | Ciba Geigy Ag | Manufacture of polystyrene bromide |
| JPS5753505A (en) * | 1980-08-20 | 1982-03-30 | Ferro Corp | Bromination |
| JPS63193904A (en) * | 1987-01-28 | 1988-08-11 | グレート・レークス・ケミカル・コーポレーション | Bromination of polystyrene aromatic ring using bromine as reactive solvent |
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1989
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55151007A (en) * | 1979-05-07 | 1980-11-25 | Ciba Geigy Ag | Manufacture of polystyrene bromide |
| JPS5753505A (en) * | 1980-08-20 | 1982-03-30 | Ferro Corp | Bromination |
| JPS63193904A (en) * | 1987-01-28 | 1988-08-11 | グレート・レークス・ケミカル・コーポレーション | Bromination of polystyrene aromatic ring using bromine as reactive solvent |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07292026A (en) * | 1994-04-25 | 1995-11-07 | Manac Inc | Production of brominated polystyrene |
| EP0765887A1 (en) | 1995-09-26 | 1997-04-02 | Manac Incorporated | Process for preparing brominated polystyrene |
| US6518368B2 (en) | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| USRE37902E1 (en) | 1996-06-14 | 2002-11-05 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| US6235831B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Polymer compositions containing brominated polystyrenic resins |
| US5677390A (en) * | 1996-09-26 | 1997-10-14 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5852132A (en) * | 1996-09-26 | 1998-12-22 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5852131A (en) * | 1996-09-26 | 1998-12-22 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5916978A (en) * | 1996-09-26 | 1999-06-29 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6133381A (en) * | 1996-09-26 | 2000-10-17 | Albelmarle Corporation | Brominated polystyrenic flame retardants |
| US6207765B1 (en) | 1996-09-26 | 2001-03-27 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6232408B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Brominated polstyrenic resins |
| US6232393B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Polymers flame retarded with brominated polystyrenic resins |
| US6235844B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Brominated polystyrenic resins |
| WO1998013396A1 (en) * | 1996-09-26 | 1998-04-02 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6326439B1 (en) | 1996-09-26 | 2001-12-04 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5686538A (en) * | 1996-09-26 | 1997-11-11 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5767203A (en) * | 1996-09-26 | 1998-06-16 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6521714B2 (en) | 1996-09-26 | 2003-02-18 | Albemarle Corporation | Brominated polystyrenic resins |
| JP2009215561A (en) * | 1996-09-26 | 2009-09-24 | Albemarle Corp | Thermoplastic material provided with flame retardancy |
| EP1293517A3 (en) * | 1997-05-07 | 2003-11-26 | Albemarle Corporation | Process for brominating polystyrenic resins |
| EP1293518A3 (en) * | 1997-05-07 | 2003-11-26 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US7202296B2 (en) | 2003-12-19 | 2007-04-10 | Albemarle Corporation | Flame retardant compositions and their use |
| US7405254B2 (en) | 2003-12-19 | 2008-07-29 | Albemarle Corporation | Flame retardant compositions and their use |
| US7666944B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7666943B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7632893B2 (en) | 2005-06-30 | 2009-12-15 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
| US8168723B2 (en) | 2005-06-30 | 2012-05-01 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
| US7638583B2 (en) | 2005-12-21 | 2009-12-29 | Albemarle Corporation | Brominated anionic styrenic polymers and their preparation |
| US8071688B2 (en) | 2005-12-21 | 2011-12-06 | Albemarle Corporation | Brominated anionic styrenic polymers and their preparation |
| JP2010501677A (en) * | 2006-08-22 | 2010-01-21 | アルベマール・コーポレーシヨン | Termination of bromination of styrenic polymers in bromination reaction mixtures. |
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