CN1631919A - Method for preparing flame retardant brominated polystyrene by using composite catalyst - Google Patents
Method for preparing flame retardant brominated polystyrene by using composite catalyst Download PDFInfo
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- CN1631919A CN1631919A CN 200410067961 CN200410067961A CN1631919A CN 1631919 A CN1631919 A CN 1631919A CN 200410067961 CN200410067961 CN 200410067961 CN 200410067961 A CN200410067961 A CN 200410067961A CN 1631919 A CN1631919 A CN 1631919A
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Abstract
The invention relates to a method to prepare polystyrene bromide with compound catalyst system. Use polystyrene as the raw material, alkyl halide as solvent, with the existence of catalyst and dehydrating agent, the polystyrene bromide is made by bromination of brominating agent. Its characteristics include: the catalyst is composed of VIII family metal, IIB family metal, tin or stibium and lewis acid, and the polystyrene bromide has large content of bromine (the largest-one can be 60%), high melt point (30-50% higher) and productivity (larger than 95%). It can be applied for antiflaming of resin such as PET, PBT and nyloen nylon.
Description
Technical field
The present invention relates to a kind of preparation method of bromide fire retardant, specifically, relate to a kind of method of utilizing composite catalyst to prepare brominated Polystyrene.
Technical background
Brominated Polystyrene (BPS) since have Heat stability is good, toxicity low, be difficult for advantages such as migration and flame retardant properties be good, be widely used in PET, PBT, polyphenylene oxide, nylon 66, nylon 6, polyimide and thermosetting resines such as syndiotactic polystyrene, unsaturated polyester and Resins, epoxy as fire retardant.
The preparation method of brominated polystyrene of having reported is summarized as follows:
(1) people such as Barda, Gray (U.S.Pat 4 at United States Patent (USP), 352, a kind of preparation method of tribromide polystyrene fire retardant has been described 909), it as catalyzer, makes brominated Polystyrene with high molecular weight polystyrene resin and bromizating agent (bromine chloride) reaction with single Lewis acid (butter of antimony) in halogenated hydrocarbon solvent.The bromine content of final product is greater than 65%, yet does not mention the fusing point and the thermal weight loss of brominated Polystyrene in this patent;
(2) Shimosada, Takeshi are catalyzer with the aluminum chloride in Japanese Patent (JP 02215807) " brominated Polystyrene is as the manufacturing of fire retardant ", and methylene dichloride is that solvent has been made brominated Polystyrene, and bromine content is 66%;
(3) people such as Kadono, Mishima (U.S.Pat 5 at United States Patent (USP), 532,322) told about the Preparation of Brominated Polystyrene process in, described in the patent under the condition that dewatering agent exists, with single antimony oxygen compound is catalyzer, with the halohydrocarbon is solvent, polystyrene and bromizating agent prepared in reaction brominated Polystyrene, bromine content 64～67%;
(4) people such as Dadgar, Balhoff has reported a kind of Preparation of Brominated Polystyrene process in United States Patent (USP) (U.S.Pat 5,852,132).Being catalyzer with single aluminum chloride or iron trichloride in the patent, is solvent with the bromochloromethane, and the brominated Polystyrene fire retardant yield of preparation surpasses 95%, and bromine content is 68%;
(5) Huang Yanmei, model May Day etc., the people was in " the synthetic and performance study of brominated Polystyrene " (fine chemistry industry, Vol.17, No.3,159～161,2000) reported a kind of Preparation of Brominated Polystyrene method in, it is to be solvent with the methylene dichloride, and polystyrene and bromine prepared in reaction form under reflux temperature.The bromine content that makes brominated Polystyrene is 60%;
(6) people such as Xiao Weidong, He Peixin is at " research of Brominated Polystyrene " (Hubei University's journal, Vol.17, No.3,298～301,1995) having mentioned a kind of in is solvent with the tetracol phenixin, and bromine is a bromizating agent, and reduced iron powder is the method for Preparation of Catalyst brominated Polystyrene, the bromine content of wherein having mentioned fire retardant surpasses 68%, but fusing point has only 220 ℃.
It is fusing point (200～220 ℃) on the low side that there is topmost defective in the brominated Polystyrene that adopts prior art to make, and therefore developing a kind of preparation method of brominated polystyrene with higher melt becomes purpose of the present invention.
Summary of the invention
The said preparation method of brominated polystyrene of the present invention, it is raw material with the polystyrene, haloalkane is a solvent, in the presence of catalyzer and dewatering agent, make through the bromizating agent bromination, it is characterized in that: said catalyzer is made up of VIII family metal, IIB family metal, metallic tin or antimony and Louis (lewis) acid, and wherein metal and lewis acidic weight ratio are 1: 1～100.
In the present invention, the solvent of recommendation is: monochloro methane, methylene dichloride, chloroform, tetracol phenixin, monochloroethane, 1,2-ethylene dichloride, 1,1-ethylene dichloride, 1,1,1-trichloroethane, vinyl trichloride, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, monobromethane, bromofom, monobromethane, 1,2-ethylene dibromide, 1,1,2,2-tetrabromoethane, methyl chlorobromide are or/and 1-bromo-2-monochloroethane, and especially with methylene dichloride, 1, the 2-ethylene dichloride is or/and methyl chlorobromide is good;
The Lewis acid of recommending is: antimony, titanium, aluminium, iron, tin, boron, zinc, bismuth, zirconium or chromium halogenide, preferred butter of antimony, antimony tribro-, antimony pentachloride, titanium tetrachloride, titanium tetrabromide, aluminum chloride, alchlor, iron trichloride, ferric bromide, tindichloride, tin tetrachloride, boron trichloride, boron tribromide, zinc chloride, Trichlorobismuthine, zirconium tetrachloride or four chromium chlorides;
The metal of recommending is iron, cobalt, nickel, palladium, zinc or tin, preferred iron or nickel;
The dewatering agent of recommending is: calcium chloride, Vanadium Pentoxide in FLAKES are or/and sal epsom, preferably Vanadium Pentoxide in FLAKES;
The bromizating agent of recommending is that bromine is or/and bromine chloride.
Embodiment
The said preparation method of brominated polystyrene of the present invention comprises the steps:
With polystyrene (molecular weight 500～1,500,000) dissolves in the polystyrene solution of making 5～20wt% (the best is 5～10%) in the haloalkane solvent, adding weight is that the dewatering agent and the weight of polystyrene weight 0.1～30% (the best is 0.2～5%) are the composite catalyst of polystyrene weight 0.01～20% (the best is 0.1～5%) in this solution, under-20～80 ℃ of (the best is 0～20 ℃) conditions, drip bromizating agent, the mol ratio of bromizating agent and polystyrene is 1: 1～3.5 (the best is 1: 2～3.3), react 1～20 hour (being advisable) back and add sodium hydroxide or sodium sulfite solution termination reaction with 3～5 hours, water or alkaline solution washing are to neutral, then organic phase is added drop-wise to and separates out brominated Polystyrene in the alcohol, after filtration, drying obtains target compound.
The present invention is a kind of method for preparing flame retardant brominated polystyrene in the presence of complex catalyst system, its biggest advantage is, prepared brominated Polystyrene has bromine content height (reaching as high as 69%), high-melting-point (than 30～50 ℃ of existing raisings) and high yield (yield is greater than 95%), can be used for the fire-retardant of various kinds of resin such as PET, PBT, nylon.
The present invention is further elaborated below by embodiment, its objective is better to understand content of the present invention.Therefore the cited case does not limit protection scope of the present invention:
Embodiment 1
Take by weighing the adding of 10.4g (in 0.1 mole of vinylbenzene repeating unit) polystyrene mechanical stirrer is housed, thermometer, in the 250ml four-hole bottle of dropping funnel and prolong, add solvent 100ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.4g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds 0.1g butter of antimony and 0.025g zinc powder, after temperature reduced to 0 ℃, slowly drop to 43.6g liquid bromine in the reaction solution, dropwise the back temperature is risen to 10 ℃, be incubated 3h then, after question response finished, catalyzer and dewatering agent were removed in washing, after treating that water oil separates fully, organic phase added separate out product in the ethanol, after filtration, drying obtains the 30.5g brominated Polystyrene, product yield 95%, bromine content 68%, 250 ℃ of fusing points.
Embodiment 2
Agitator is equipped with in the adding of 15.6g (in 0.15 mole of styrene units) polystyrene, thermometer, in the 500ml four-hole bottle of funnel and prolong, add solvent 200ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.5g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds 0.2g aluminum chloride and 0.04g nickel powder, after temperature transferred to 10 ℃, slowly drop to 65g liquid bromine in the reaction solution, dropwise the back and continue 2h, after question response finishes, catalyzer and dewatering agent are removed in washing, treat that water oil separates fully after, organic phase added separates out product in the methyl alcohol, after filtration, drying obtains the 47g brominated Polystyrene, product yield 98%, bromine content 68.5%, 255 ℃ of fusing points.
Embodiment 3
Take by weighing the adding of 10.4g (in 0.1 mole of styrene units) polystyrene mechanical stirrer is housed, thermometer, in the 250ml flask of funnel and prolong, add solvent 150ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.2g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds 0.15g iron trichloride and 0.02g iron powder, after temperature reduced to 0 ℃, slowly drop to 43.6g liquid bromine in the reaction solution, dropwise the back temperature is risen to 10 ℃, continue reaction 1h then, after question response finished, catalyzer and dewatering agent were removed in washing, after treating that water oil separates fully, organic phase added separate out product in the ethanol, after filtration, drying obtains the 31g brominated Polystyrene, product yield 96%, bromine content 68%, 252 ℃ of fusing points.
Embodiment 4
Take by weighing the adding of 10.4g (in 0.1 mole of styrene units) polystyrene mechanical stirrer is housed, thermometer, in the 250ml flask of funnel and prolong, add solvent 120ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.4g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds 0.1g aluminum chloride and 0.02g iron powder, after temperature transferred to 10 ℃, slowly drop to 44g liquid bromine in the reaction solution, dropwise back insulation 3h, after question response finishes, catalyzer and dewatering agent are removed in washing, treat that water oil separates fully after, organic phase added separates out product in the ethanol, after filtration, drying obtains the 32g brominated Polystyrene, product yield 98%, bromine content 69%, 250 ℃ of fusing points.
Comparative Examples 1
Take by weighing the adding of 15.6g (in 0.15 mole of styrene units) polystyrene mechanical stirrer is housed, thermometer, in the 500ml flask of dropping funnel and prolong, add solvent 200ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.6g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds the 0.6g butter of antimony, temperature is transferred to 10 ℃, slowly drop to 65.6g liquid bromine in the reaction solution, dropwise back insulation 3h, after question response finishes, catalyzer and dewatering agent are removed in washing, treat that water oil separates fully after, organic phase added separates out product in the ethanol, after filtration, drying obtains the 28g brominated Polystyrene, product yield 60%, bromine content 45%, 208 ℃ of fusing points.
Comparative Examples 2
Take by weighing the adding of 10.4g (in 0.1 mole of styrene units) polystyrene agitator is housed, thermometer, in the 250ml flask of dropping funnel and prolong, add solvent 150ml1,2-ethylene dichloride (EDC) makes its dissolving, and adding 0.4g Vanadium Pentoxide in FLAKES dehydration, treat that polystyrene dissolves the back fully and adds the 0.4g aluminum chloride, temperature is transferred to 10 ℃, slowly drop to 43.6g liquid bromine in the reaction solution, dropwise back insulation 3h, after question response finishes, catalyzer and dewatering agent are removed in washing, treat that water oil separates fully after, organic phase added separates out product in the ethanol, after filtration, drying obtains the 30.1g brominated Polystyrene, product yield 93%, bromine content 65%, 220 ℃ of fusing points.
Claims (10)
1, a kind of Preparation of Brominated Polystyrene method, it is raw material with the polystyrene, haloalkane is a solvent, in the presence of catalyzer and dewatering agent, make through the bromizating agent bromination, it is characterized in that: said catalyzer is made up of VIII family metal, IIB family metal, metallic tin or antimony and Lewis acid, and wherein metal and lewis acidic weight ratio are 1: 1～100.
As the said preparation method of claim 1, it is characterized in that 2, said preparation method comprises the steps:
Polystyrene is dissolved in the polystyrene solution of making 5～20wt% in the haloalkane solvent, in this solution, add weight and be the dewatering agent of polystyrene weight 0.1～30% and weight and be polystyrene weight 0.01～20% by VIII family metal, IIB family metal, metallic tin or antimony and Lewis acid are formed catalyzer, under-20～80 ℃ of conditions, drip bromizating agent, the mol ratio of bromizating agent and polystyrene is 1: 1～3.5, react and add sodium hydroxide or sodium sulfite solution termination reaction after 1～20 hour, water or alkali liquid washing are to neutral, then organic phase is added drop-wise to and separates out brominated Polystyrene in the alcohol, after filtration, drying obtains target compound.
As the said preparation method of claim 2, it is characterized in that 3, wherein the concentration of polystyrene haloalkane solution is 5～10wt%, the add-on of dewatering agent is 0.2～5% of a polystyrene weight; The add-on of catalyzer is 0.1～5% of a polystyrene weight, and the mol ratio of bromizating agent and polystyrene is 1: 2～3.3.
As the said preparation method of claim 2, it is characterized in that 4, wherein temperature of reaction is 0～20 ℃, the reaction times is 3～5 hours.
As said any one preparation method of claim 1～4, it is characterized in that 5, wherein said haloalkane solvent is monochloro methane, methylene dichloride, chloroform, tetracol phenixin, monochloroethane, 1,2-ethylene dichloride, 1,1-ethylene dichloride, 1,1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, monobromethane, bromofom, monobromethane, glycol dibromide, 1,1,2,2-tetrabromoethane, methyl chlorobromide are or/and 1-bromo-2-monochloroethane.
As the said preparation method of claim 5, it is characterized in that 6, wherein said haloalkane solvent is a methylene dichloride, 1, the 2-ethylene dichloride is or/and methyl chlorobromide.
As said any one preparation method of claim 1～4, it is characterized in that 7, wherein said dewatering agent is that calcium chloride, Vanadium Pentoxide in FLAKES are or/and sal epsom.
As the said preparation method of claim 7, it is characterized in that 8, wherein said dewatering agent is a Vanadium Pentoxide in FLAKES.
As said any one preparation method of claim 1～4, it is characterized in that 9, wherein used metal is iron, cobalt, nickel, palladium, zinc, antimony or tin in the catalyzer; Used Lewis acid is the halogenide of antimony, titanium, aluminium, iron, tin, boron, zinc, bismuth, zirconium or chromium.
10, as the said preparation method of claim 9, it is characterized in that wherein said Lewis acid is butter of antimony, antimony tribro-, antimony pentachloride, titanium tetrachloride, titanium tetrabromide, aluminum chloride, alchlor, iron trichloride, ferric bromide, tindichloride, tin tetrachloride, boron trichloride, boron tribromide, zinc chloride, Trichlorobismuthine, zirconium tetrachloride or four chromium chlorides.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701047B (en) * | 2009-10-22 | 2011-09-07 | 国家海洋局天津海水淡化与综合利用研究所 | Preparation method of spray-dried brominated polystyrene |
| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
| CN112079803A (en) * | 2020-09-11 | 2020-12-15 | 山东润科化工股份有限公司 | Synthesis method of 4-halogenated phthalic anhydride and derivatives thereof |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN117106109A (en) * | 2023-10-25 | 2023-11-24 | 山东海化集团有限公司 | Method for continuously preparing brominated polystyrene |
-
2004
- 2004-11-09 CN CN 200410067961 patent/CN1275987C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701047B (en) * | 2009-10-22 | 2011-09-07 | 国家海洋局天津海水淡化与综合利用研究所 | Preparation method of spray-dried brominated polystyrene |
| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
| CN112079803A (en) * | 2020-09-11 | 2020-12-15 | 山东润科化工股份有限公司 | Synthesis method of 4-halogenated phthalic anhydride and derivatives thereof |
| CN112079803B (en) * | 2020-09-11 | 2023-01-31 | 山东润科化工股份有限公司 | Synthesis method of 4-halogenated phthalic anhydride and derivatives thereof |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114369024B (en) * | 2021-12-31 | 2024-01-30 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| 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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