CN101643388B - Preparation method of decabromo-diphehylethane - Google Patents

Preparation method of decabromo-diphehylethane Download PDF

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CN101643388B
CN101643388B CN 200910031666 CN200910031666A CN101643388B CN 101643388 B CN101643388 B CN 101643388B CN 200910031666 CN200910031666 CN 200910031666 CN 200910031666 A CN200910031666 A CN 200910031666A CN 101643388 B CN101643388 B CN 101643388B
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CN101643388A (en
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印熀宏
杨爱华
潘兵波
缪金凤
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泰州百力化学股份有限公司
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Abstract

The invention relates to a preparation method of decabromo-diphehylethane (DBDPE) prepared by the reaction between diphenylethane and excessive bromine under catalysts. The reaction is carried out in three stages, and Al powder, anhydrous AlCl3 and anhydrous TiCl4 are adopted as the catalysts, wherein the Al powder and the anhydrous AlCl3 form a first catalyst which is added at the first stage of the reaction; the anhydrous TiCl4 solely forms a second catalyst which is added at the second stage of the reaction; the anhydrous AlCl3 solely forms a third catalyst which is added at the third stage of the reaction. The total input mass of the first catalyst, the second catalyst and the third catalyst accounts for 0.08-0.15% of the theoretical yield of the DBDPE of a finished product; the molar ratio of the first catalyst to the second catalyst to the third catalyzer is (1-3):(1-4):(0.6-0.9), the reaction at the first stage is controlled at 12-26 DEG C for 2-4 hours; the reaction at the second stage is controlled at 26-40 DEG C for 3-5 hours or 40-60 DEG C for 4-6 hours; and after the three reaction stages are ended, the temperature is continuously increased to 60-65 DEC C and kept for 3 hours. The preparation method can effectively improve the whiteness and the thermal stability performance of the DBDPE under low-cost operation.

Description

十溴二苯乙烷的制备方法 Preparing decabromodiphenyl ethane

(-)技术领域 (-) FIELD

[0001] 本发明涉及一种十溴二苯乙烷的制备方法。 [0001] The present invention relates to a method for preparing decabromodiphenyl oxide. 属工程材料的阻燃剂技术领域。 Flame retardant technology belongs to the field of engineering materials.

(二)背景技术 (B) Background Art

[0002] 十溴二苯乙烷,又名1,2_ 二(五溴苯基)乙烷,白色粉末,熔点358-360°C,理论含溴量82.观%。 [0002] decabromodiphenyl oxide, also known as 1,2_ di (pentabromophenyl) ethane as a white powder, m.p. 358-360 ° C, the theoretical bromine content 82. View%. 它是美国乙基公司上世纪九十年代开发并商品化的一种芳基溴化阻燃剂(其商品名MytexSOlO)。 It is the US Ethyl Corporation to develop and commercialize the nineties of the last century and an aryl group of brominated flame retardants (its trade name MytexSOlO). 其阻燃性、热稳定性、抗紫外能力等几方面性能都优于阻燃剂十溴二苯醚,更为重要的特征是再热分解时,不产生二噁英致癌物质。 Flame retardancy, thermal stability, UV resistance properties are superior to other aspects decabromodiphenyl oxide flame retardant, is even more important feature when thermally decomposed again, do not produce carcinogenic dioxins.

[0003] 十溴二苯乙烷,大多采用过量溴素法生产,以Al粉、! [0003] decabromodiphenyl ethane, they use an excess of bromine production process, powders of Al,! ^e粉、无水AlCl3、无水AlBr3 或狗(:13或它们的组合物为催化剂,产品较成熟的运用于聚烯烃类工程材料,但在较高温度的环境如PA66玻璃纤维增强技术,运用不是很理想。现在的美国雅宝公司(前身乙基公司)的产品在这方面运用较成熟,但也采用了部分添加剂改善其使用性能。 ^ E powder, anhydrous AlCl3, AlBr3 or dry dog ​​(: 13 or a composition thereof as catalyst, the product more mature polyolefin engineering materials used, but in the higher temperature environments, such as glass fiber reinforced PA66 technology, use is not very satisfactory. now the United States Albemarle Corporation (formerly ethyl Corporation) products use more mature in this regard, but also contains some additives to improve its performance.

[0004] 上述方法生产的十溴二苯乙烷均不同程度含有游离溴、残余催化剂及低溴代衍生物等杂质,产品颗粒直径大,白度和热稳定性也没有较高突破。 [0004] The above-described method of producing decabromodiphenyl ethane are different levels of free bromine containing impurities, catalyst residues and low-bromo derivatives, the product particles of large diameter, whiteness and high thermal stability and no break. 众所周知,十溴二苯乙烷中带有游离溴,在塑料加工中会对加工设备腐蚀,同样,也很大程度影响阻燃塑料的色度。 Known, decabromodiphenyl ethane with free bromine, corrosion of equipment would be processed in plastic processing, the same, but also greatly influence the chromaticity flame retardant plastic. 而热稳定性能则影响塑料高温时的色度。 Thermal stability while the influence of chromatic when the temperature of the plastic. 为解决十溴二苯乙烷产品质量问题,国内外均作了不同程度的纯化研究。 To solve decabromodiphenyl ethane product quality problems, and purification of varying degrees were made at home and abroad. 对于固体化合物来说,重结晶是去除杂质、纯化产品的有效途径。 For solid compound, the recrystallization is an effective way to remove impurities, the purified product. 美国专利US. 5457248以高沸点芳烃为溶剂,175°C下重结晶。 U.S. Patent No. US. 5457248 high boiling point aromatic solvent, recrystallized at 175 ° C. 美国大湖化工公司用二苯醚和乙醇为双溶剂重结晶。 Great Lakes Chemical Company with ether and recrystallized from ethanol-bis solvent. 以上发明对十溴二苯乙烷产品质量有很大的提高,但这类方法成本极高,在工业化生产中很难实施。 Foregoing invention has for decabromodiphenyl ethane product quality greatly improved, but the high cost of such methods, difficult to implement in industrial production.

(三)发明内容 (Iii) Disclosure of the Invention

[0005] 本发明的目的在于克服上述不足,提供一种在低成本运行下能有效提高十溴二苯乙烷的白度和热稳定性能的十溴二苯乙烷的制备方法。 [0005] The object of the present invention is to overcome the above disadvantages, to provide a low cost method for preparation run in decabromodiphenyl oxide, decabromodiphenyl ethane whiteness and thermal stability can be effectively improved.

[0006] 本发明的目的是这样实现的:一种十溴二苯乙烷的制备方法,采用二苯乙烷与过量溴素在催化剂下反应制得,其特征在于所述反应分三个阶段进行,所述催化剂采用Al粉、无水AlCl3和无水TiCl4,其中Al粉与无水AlCl3形成第一催化剂,在反应的第一阶段加入,无水TiCl4单独形成第二催化剂,在反应的第二阶段加入,无水AlCl3单独形成第三催化剂,在反应的第三阶段加入,第一、第二和第三催化剂的总投料质量占成品十溴二苯乙烷理论产量的0. 08-0. 15%,第一、第二和第三催化剂的投料摩尔比为: (1-3) : (1-4) : (0.6-0.9),控制第一阶段12-261:,时间2-4小时,第二阶段沈-401:,时间3-5小时,第三阶段反应温度40-60°C,时间4-6小时,在以上三个反应阶段完成后,继续提高温度至60-65°C保温1〜3小时。 [0006] The object of the present invention is implemented as follows: A method for preparing decabromodiphenyl oxide, diphenyl oxide with use of an excess of bromine over a catalyst prepared by the reaction, characterized in that the reaction in three stages for the catalyst employed Al powder, dry over anhydrous AlCl3 and TiCl4, wherein the Al powder is formed with a first catalyst of AlCl3 was added in the first stage of the reaction, the second catalyst is formed separately in anhydrous TiCl4, in the reaction of stage two was added anhydrous AlCl3 third catalyst is formed separately, added in the third stage of the reaction, first, the total mass of the second and third feeding catalyst accounted theoretical yield finished decabromodiphenylethane 0. 08-0 15% in the first, second, and third feed molar ratio of catalyst: (1-3): (1-4): (0.6-0.9), a first phase control time :, 12-261 2-4 hours, the second stage time :, Shen -401 3-5 hours, the third stage reaction temperature 40-60 ° C, for 4-6 hours, after the completion of the above three reaction stages, continue to increase the temperature to 60-65 ° C ~ 3 h incubation.

[0007] 十溴二苯乙烷分子结构式: [0007] decabromodiphenyl oxide molecules of the formula:

[0008][0009] [0008] [0009]

[0010] [0010]

反应方程式为 Reaction equation is

Br Br

+ IOBr2 + IOBr2

催化剂 catalyst

HH HH

Br + IOHBr Br + IOHBr

[0011] 在没有催化剂存在下,苯环与溴素并不发生反应,催化剂的作用是使溴素变成强亲电试剂,促进溴素与苯环发生亲电取代反应。 [0011] In the absence of a catalyst, the phenyl ring does not react with the bromine, it is that the catalyst becomes strong bromine electrophilic reagent, bromine and phenyl promote electrophilic substitution reaction. 在催化性能上,Al粉的催化活性最强,反应速度极快;无水AlCl3的催化活性次之,反应速度较快;无水TiCl4活性中平,催化反应速度平稳。 On the catalytic performance, the catalytic activity of Al powder most, fast response; of AlCl3, followed by catalytic activity, faster response; stable activity over anhydrous TiCl4 Zhongping, the catalytic reaction rate.

[0012] 在整个反应过程中,十个溴取代苯环上的十个氢并不是一起进行的,有快有慢。 [0012] Throughout the course of the reaction, ten ten bromine for hydrogen on the benzene ring are not together, fast or slow. 根据定位效应(含有取代基的苯衍生物,在进行芳香族亲电取代反应时,原有的取代基,对新进入的取代基主要进入位置,存有一定指向性的效应),二苯乙烷显示邻、对位定位效应,实际上是一个反应速率问题,溴上邻、对位反应快而上间位反应慢。 The orientation effect (substituted benzene derivative-containing group, while the aromatic electrophilic substitution reaction is performed, the original substituents, substituents on the newly entered into the primary position, there is a certain directional effect), diphenylethyl alkoxy display ortho, para directing effect, in fact, the reaction rate is a problem, the ortho-bromo, para fast response and slow response on the meta position. 我们可以将反应分为: 阶段: The reaction we can be divided into: Stage:

[0013] 阶段一:两个苯环上主要进行1-6个溴的邻、对位取代反应,反应方程式如下 [0013] Stage a: 6-bromo-o mainly on the two benzene rings, for the substitution reactions, the reaction equation is as follows

[0014] [0014]

Figure CN101643388BD00041

[0015] 这个反应发生在原料二苯乙烷的滴加过程中,此时溴素大量过量,在催化剂的作用下根据邻、对位定位效应,溴取代反应的位置多为邻位和对位,且比较容易发生。 Position [0015] This reaction occurs during the addition of diphenylethane material, in which case a large excess of bromine, according to ortho, para directing effect, bromine substitution reaction under the action of catalyst mostly ortho and para and it is more likely to occur. 为了防止反应太快不易控制,此时添加的催化剂为Al粉与无水AlCl3的混合物,因为Al粉活性太强,单独加入会使反应更加快速难控制,而无水AlCl3的活性度则达不到反应速率要求,因此使用它们的混合物第一催化剂,二者的投量质量比为:A1粉:无水AlCl3 = 1 : (0.7-1.5)。 The reaction is difficult to control in order to prevent too fast, this time the catalyst is a mixture of Al powder was added with anhydrous AlCl3, because the activity of Al powder is too strong, will join the more quickly the reaction difficult to control separately, and the degree of activity of AlCl3 was not the reaction rate requirement, thus the use of a first catalyst mixtures thereof, the amount administered in a ratio of mass: powder A1: anhydrous AlCl3 = 1: (0.7-1.5). 在此反应过程中,反应产物均呈液态。 During this reaction, the reaction product showed a liquid state.

[0016] 阶段二:两个苯环上主要进行6-8个溴的间位取代反应,反应方程式如下: [0016] Phase II: mainly on two benzene rings meta to 6-8 bromine substitution reaction, the reaction equation is as follows:

[0017] [0017]

Figure CN101643388BD00042

[0018] 相对第一阶段来讲,这个阶段的反应速率已经减慢。 [0018] relative to the first stage is concerned, the reaction rate has slowed at this stage. 在此过程中,反应产物由六溴二苯乙烷向八溴二苯乙烷转变,是由液态转变为固态的过程。 In this process, the reaction product was converted to the hexabromodiphenylethane octabromodiphenyl diphenyl ethane, the process is converted from liquid to solid. 在这个过程中若使用Al粉或无水AlCl3作催化剂,反应产物在由液态转化为固态的过程中会产生一种分子团聚包裹现象,即产生的六溴二苯乙烷至八溴二苯乙烷由液态转变为固态分子时团聚在一起,包裹成球状物,且较稳定不易分散。 In this process, when used as a powder or Al of AlCl3 catalyst, the reaction product into a solid by a liquid process will produce an agglomerated molecular Encapsulation, i.e. produced hexabromodiphenylethane eight-bromo-diphenylethyl an alkoxy agglomerates from liquid to solid transition elements together, wrapped into a ball, and is easily dispersed stable. 这样一来,球状物仅有外层可以继续反应,而被包裹住的未反应完全的物料处于球中间,被外层物隔绝,不能继续与溴素进行反应,导致最终产品因含有不完全溴化的杂质而影响白度及热稳定性。 Thus, only outer ball can continue to react, is wrapped completely unreacted material in the middle of the ball, the outer layer was isolated, can not continue to react with bromine, resulting in the final product due to incomplete bromine containing Effects of impurities whiteness and thermal stability. 而此阶段采用无水TiCl4作为催化剂,因其高度对称的正四面体结构及催化活性的平稳性,可以有效阻止反应过程中的分子成团现象。 This phase uses the anhydrous TiCl4 as a catalyst, because of its highly symmetric tetrahedral structure and stability of the catalytic activity, the molecule can effectively prevent agglomeration phenomena during the reaction. 从而提高最终产品的白度及热稳定性。 Thereby improve the whiteness and thermal stability of the final product.

[0019] 阶段三:两个苯环上主要进行8-10个溴的间位取代反应,反应方程式如下: [0019] Stage III: mainly on two benzene rings meta 8-10 bromine substitution reaction, the reaction equation is as follows:

[0020] [0020]

Figure CN101643388BD00051

[0021] 相对于阶段二来说,这个阶段的反应更加困难。 [0021] with respect to Phase II, this stage of the reaction more difficult. 此时反应温度升高,物料已全部为固态,没有了成团的现象,为了提高反应速率,选择活性较高AlCl3S第三催化剂。 At this time, the reaction temperature increases, all the material is solid, there is no phenomenon into groups, in order to enhance the reaction rate, higher activity of selected AlCl3S third catalyst.

[0022] 在以上三个反应阶段完成后,为了强化反应效果,会继续提高温度至60_65°C保温1-3小时。 [0022] After completion of the above three reaction stages, in order to enhance the effect of the reaction, the temperature will continue to increase to 60_65 ° C incubated for 1-3 hours.

[0023] 本发明的有益效果是: [0023] Advantageous effects of the present invention are:

[0024] 研究表明,Ti元素的存在并不影响十溴二苯乙烷的最终产品质量,相反,它能够提高十溴二苯乙烷的白度及分散性能,在塑料中应用时分散效果更好。 [0024] Studies have shown that the presence of Ti does not affect the quality of the final decabromodiphenylethane product, on the contrary, it is possible to improve the whiteness and dispersion properties decabromodiphenylethane dispersed in plastics applications when the effect is more it is good.

[0025] 使用本发明的催化剂及工艺控制方法,工业化生产的十溴二苯乙烷白度> 92,在250°C高温下持续2-5小时热稳定性> 88,在高温PA66玻纤增强白色工程材料应用相当成功,其阻燃性能、材料色泽、PA66强度都超过普通十溴二苯乙烷的使用性能。 [0025] The catalyst and process control using the method of the present invention, industrial production decabromodiphenylethane whiteness> 92, at 250 ° C for 2-5 hours duration high temperature thermal stability of> 88, at a high temperature glass fiber reinforced PA66 white very successful applications of engineering materials, their flame-retardant properties, color and material, PA66 strength of more than ordinary performance decabromodiphenyl oxide.

[0026] 以上反应过程中,物料由液态转变为固态,物料粘度也随各反应阶段发生变化,从粘度值的变化很容易推测反应进行到哪一个阶段。 [0026] The above reaction process, the material changes from a liquid to a solid state, the material viscosity also varies with each stage of the reaction, the change in viscosity of the reaction is easily carried out where a phase estimation. 但是由于溴素的强腐蚀性及强刺激性, 反应过程中很难取样,也很难使用哪一种材质的粘度检测仪或传感仪,所以我们不能十分明确的得到物料粘度的变化数据情况。 However, since the highly corrosive bromine and strong irritant, sampling during the reaction is difficult, it is difficult to use the material of which the viscosity detector or sensing device, so we can not give a very clear change in the case of mass viscosity data .

[0027] 众所周知,十溴二苯乙烷的过量溴素法反应是在搅拌下进行的。 [0027] is well known, excess bromine reaction decabromodiphenylethane method is carried out with stirring. 在反应阶段一, 物料呈液态,粘度不大,搅拌负荷轻松;在反应阶段二,反应产物由液态向固态转变,物料粘度增大,搅拌受到的阻力增大,搅拌负荷相应增大;在反应阶段三,反应产物已完全转化为固态,搅拌阻力有所缓解,搅拌负荷也相应缓解。 In a reaction stage, the material is liquid, the viscosity is not, easily stirred load; two, the solid reaction product from the liquid reaction phase transitions, the viscosity of the material increases, the resistance increases by stirring, stirring load corresponding increase; in the reaction phase III, the reaction product was completely converted to a solid, stirring resistance eased stirred load mitigation accordingly. 为了有效的识别各反应阶段,严格控制各催化剂加入的时机,根据这一现象,在稳压电源前提下,为搅拌电机加装变频控制器及电流表,搅拌负荷的变化可以通过电流的大小直观体现出来,在这里,变频器的使用可以避免动力资源的浪费。 To effectively identify each reaction stage, controlling the timing of each catalyst was added, according to the phenomenon, under the premise power supply for installation of the stirring motor and the inverter controller ammeter stirred load changes visually embodied magnitude of the current out here, drive usage to avoid waste of power resources. 经过大量研究实践,发现十溴二苯乙烷反应在5000L反应釜内,电源电压220V,搅拌转速固定,并加装变频器和电流表前提下进行时有如下规律: After extensive research practice, we found that the reaction decabromodiphenyl ethane in the 5000L reactor, the power source voltage 220V, the fixed speed stirring, and the installation have the following rules when down-converter and ammeter premise:

[0028] 1、从滴加二苯乙烷开始,搅拌电机电流在12A左右电流下会持续一段时间,为2-4小时,这个阶段为反应阶段一; [0028] 1, starting diphenylethane dropwise addition, stirring motor current at a current of about 12A will continue for some time, a reaction stage is from 2 to 4 hours, at this stage;

[0029] 2、搅拌电机电流从12A缓慢上升至18A,这个阶段为反应阶段二,因为此时反应产物由液态转变为固态,粘度增大,搅拌受到阻力负荷增加,因此电流会有所增加; [0029] 2, the motor current rises from stirring slowly to 12A. 18A, the phase two stage reaction, because the reaction product is converted from a liquid to a solid state, an increase in viscosity was stirred by the load resistance increases, the current will increase;

[0030] 3、搅拌电机电流从18A缓慢下降至15A,这个阶段为反应阶段三,此时反应产物已完全转化为固态,搅拌负荷有所缓解,所以电流有所下降。 [0030] 3, stirred gradually decreased from the motor current. 15A to 18A, the three stage reaction stage, the reaction product at this time has been completely converted to a solid, stirred load eased, so that the current decline.

[0031] 4、而在最后一个保温阶段,电流从15A缓慢下降至13A,至此反应完全结束。 [0031] 4, in the final stage of a holding current decreases from 15A to slow. 13A, the end point the reaction was complete.

[0032] 经实践摸索出的电流指标值能够直观地反映十溴二苯乙烷溴化反应的具体情况, 使得操作人员能够直观的了解反应程度,确定加入催化剂的种类及时机,对反应的控制更加有效,从而避免了杂质的产生,对于工业化生产中提高十溴二苯乙烷的质量起到了很大的作用。 [0032] The current value of the index can be worked out by the practice directly reflects decabromodiphenyl ethane bromination reaction circumstances, enable the operator to intuitively understand the extent of the reaction, to determine the type and timing of addition of the catalyst, control of the reaction more efficient, thus avoiding the generation of impurities, for improving the quality of industrial production decabromodiphenylethane played a significant role.

(四)具体实施方式 (IV) DETAILED DESCRIPTION

[0033]实例 1 : [0033] Example 1:

[0034] 在带有变频控制、固定转速并加电流表的搅拌机并有加热装置的5000L搪玻璃反应釜中加入过量溴素,开启搅拌,向其中加入第一催化剂共0. (含Al粉0. Ikg, AlCl3O. 45kg),温度在1246°C滴加二苯乙烷共364. ^g,观察电流表读数。 [0034] with the frequency control, fixed speed mixer and add the ammeter and has a heating apparatus 5000L glass-lined reaction vessel was added an excess of bromine, open stirring, to which a first co-catalyst 0.5 (including 0 Al powder. Ikg, AlCl3O. 45kg), at a temperature of 1246 ° C were added dropwise diphenyl oxide 364. ^ g, observe the meter reading. 当电流开始从12A增大时,向反应釜中加入第二催化剂无水TiCl4L Ukg,继续反应并观察电流表,当电流上升至18A左右不再继续升高时,向反应釜内加入第三催化剂无水AlCl3O. 63kg,缓慢升温至60°C,升温过程持续1-2小时,保温3-4小时,在此过程中电流值缓慢下降。 When the current starts to increase. 12A, was added to the kettle over anhydrous second catalyst TiCl4L Ukg, and the reaction was continued to observe the ammeter, when the current rises to approximately 18A no longer continues to rise, the third catalyst was added to the reaction kettle no water AlCl3O. 63kg, was slowly warmed to 60 ° C, the heating process for 1-2 hours, 3-4 hours of incubation, during which the current value gradually decreased. 当电流值半小时内不再变化时,反应结束。 When the current value does not change within half an hour, the reaction was complete. 将反应物料进行后处理,得到成品十溴二苯乙烷1900kg。 The reaction mass was treated to give the finished decabromodiphenylethane 1900kg. 白度92. 3,250°C持续3小时后白度88. 6,含量(液相色谱)99. 87%,颗粒平均直径为3. 2 μ m。 Whiteness 92. 3,250 ° C for 3 hours after the whiteness of 88.6, content (HPLC) 99.87%, an average particle diameter of 3. 2 μ m.

[0035]实例 2 : [0035] Example 2:

[0036] 将所得产品应用于PA66玻纤增强白色材料。 [0036] The resultant product was applied to glass fiber reinforced PA66 white material. 添加比例为:11%十溴二苯乙烷、4% 三氧化二锑PA66、30%玻纤。 Adding ratio: 11% decabromodiphenyl ethane, 4% antimony trioxide PA66,30% glass fiber. 将一定量的PA 66和十溴二苯乙烷、三氧化二锑用高速混合机混合均勻后,从主进料口加人双螺杆挤出机中,并将适量GF从挤出机第8段进料口加入,控制挤出机温度为MO-^KTC,使四种物料在挤出机中熔融、塑化,挤出物经冷却造粒,即制得PA 66玻纤增强共混物,将粒料在80°C下干燥24h后用注塑机注塑成标准试样。 After a certain amount of PA 66 and decabromodiphenyl ethane, antimony trioxide were uniformly mixed using a high speed mixer, a main feed port from the addition of a twin-screw extruder, and the amount GF from the extruder 8 Add feed port section, the control temperature of the extruder MO- ^ KTC, four types of material melted in an extruder, plasticized, pelletized extrudate was cooled, i.e., to obtain a blend of glass fiber reinforced PA 66 , the pellets were dried 80 ° C for 24h after injection molding machine is used as a standard sample. 阻燃性能达到了UL94V-0,其拉伸强度为^8J/m、冲击强度130MPa和弯曲强度未变,冲击强度、弯曲模量减少只有10%。 Fire-retardant properties of UL94V-0, a tensile strength of ^ 8J / m, bending strength and impact strength of 130MPa unchanged, impact strength, flexural modulus reducing only 10%. 明显好于普通市场十溴二苯乙烷产品的力学性能。 Mechanical properties significantly better than the general market decabromodiphenyl ethane product.

[0037]实例 3 : [0037] Example 3:

[0038] 在带有变频控制、固定转速并加电流表的搅拌机并有加热装置的5000L搪玻璃反应釜中加入过量溴素,开启搅拌,向其中加入第一催化剂共0. 76kg(含Al粉0. 13kg, AlCl3O. 63kg),温度在1246°C滴加二苯乙烷共500kg,观察电流表读数。 [0038] In the heating apparatus 5000L glass lined reactor was added an excess of bromine, open stirring, to which a first co-catalyst 0. 76kg (including 0 Al powder with a frequency control, and fixed speed mixer, and there added ammeter . 13kg, AlCl3O. 63kg), at a temperature of 1246 ° C were added dropwise diphenylethane 500kg, observe the meter reading. 当电流开始从12A 增大时,向反应釜中加入第二催化剂无水TiCl4L 5Ag,继续反应并观察电流表,当电流上升至18A左右不再继续升高时,向反应釜内加入第三催化剂无水AlCl3O. 87kg,缓慢升温至60°C,升温过程持续1-2小时,保温3-4小时,在此过程中电流值缓慢下降。 When the current starts to increase. 12A, was added to the kettle over anhydrous second catalyst TiCl4L 5Ag, and the reaction was continued to observe the ammeter, when the current rises to approximately 18A no longer continues to rise, the third catalyst was added to the reaction kettle no water AlCl3O. 87kg, was slowly warmed to 60 ° C, the heating process for 1-2 hours, 3-4 hours of incubation, during which the current value gradually decreased. 当电流值半小时内不再变化时,反应结束。 When the current value does not change within half an hour, the reaction was complete. 将反应物料进行后处理,得到成品十溴二苯乙烷2615kg。 The reaction mass was treated to give the finished decabromodiphenylethane 2615kg. 白度92.0,250°C持续3小时后白度88. 4,含量(液相色谱)99. 85%,颗粒平均直径为4. 1 μ m。 Whiteness 92.0,250 ° C for 3 hours after 88.4 whiteness, content (HPLC) 99.85%, an average particle diameter of 4. 1 μ m.

[0039]实例 3 : [0039] Example 3:

6[0040] 在带有变频控制、固定转速并加电流表的搅拌机并有加热装置的5000L搪玻璃反应釜中加入过量溴素,开启搅拌,向其中加入第一催化剂共0. 85kg(含Al粉0. 2kg, AlCl3O. 65kg),温度在1246°C滴加二苯乙烷共500kg,观察电流表读数。 6 [0040] In the heating apparatus 5000L glass lined reactor was added an excess of bromine, open stirring, to which a first co-catalyst 0. 85kg (containing Al powder with a frequency control, and fixed speed mixer, and there added ammeter 0. 2kg, AlCl3O. 65kg), at a temperature of 1246 ° C were added dropwise diphenylethane 500kg, observe the meter reading. 当电流开始从12A 增大时,向反应釜中加入第二催化剂无水TiCl4L 3¾¾,继续反应并观察电流表,当电流上升至18A左右不再继续升高时,向反应釜内加入第三催化剂无水AlCl3O. 95kg,缓慢升温至60°C,升温过程持续1-2小时,保温3-4小时,在此过程中电流值缓慢下降。 When the current starts to increase. 12A, was added to the kettle over anhydrous second catalyst TiCl4L 3¾¾, and the reaction was continued to observe the ammeter, when the current rises to approximately 18A no longer continues to rise, the third catalyst was added to the reaction kettle no water AlCl3O. 95kg, was slowly warmed to 60 ° C, the heating process for 1-2 hours, 3-4 hours of incubation, during which the current value gradually decreased. 当电流值半小时内不再变化时,反应结束。 When the current value does not change within half an hour, the reaction was complete. 将反应物料进行后处理,得到成品十溴二苯乙烷2630kg。 The reaction mass was treated to give the finished decabromodiphenylethane 2630kg. 白度92. 1,250°C持续3小时后白度88. 7,含量(液相色谱)99. 88%,颗粒平均直径为3. 0 μ m。 Whiteness 92. 1,250 ° C for 3 hours after the whiteness of 88.7, content (HPLC) 99.88%, an average particle diameter of 3. 0 μ m.

Claims (1)

1. 一种十溴二苯乙烷的制备方法,采用二苯乙烷与过量溴素在催化剂下反应制得,其特征在于所述反应分三个阶段进行,所述催化剂采用Al粉、无水AlCl3和无水TiCl4,其中Al粉与无水AlCl3形成第一催化剂,在反应的第一阶段加入,无水TiCl4单独形成第二催化剂,在反应的第二阶段加入,无水AlCl3单独形成第三催化剂,在反应的第三阶段加入,第一、第二和第三催化剂的总投料质量占成品十溴二苯乙烷理论产量的0. 08-0. 15%,第一、 第二和第三催化剂的投料摩尔比为:(1-3) : (1-4) : (0.6-0. 9),控制第一阶段反应温度1246°C,时间2-4小时,第二阶段反应温度^-40°C,时间3_5小时,第三阶段反应温度40-60°C,时间4-6小时,在以上三个反应阶段完成后,继续提高温度至60-65°C保温1〜3 小时。 1. A method for preparing decabromodiphenyl oxide, using an excess of bromine with diphenyl oxide prepared by the reaction in the catalyst, wherein the reaction is carried out in three stages, the catalyst employed Al powder, no of anhydrous AlCl3 and TiCl4 water, wherein the Al powder is formed with a first catalyst of AlCl3 was added in the first stage of the reaction, the second catalyst is formed separately in anhydrous TiCl4, is added in the second stage of the reaction, anhydrous AlCl3 are formed of separate three catalyst, was added at the third stage of the reaction, the total mass of feeding first, second and third catalyst accounted 0. 08-0. 15% of the theoretical yield decabromodiphenylethane finished, the first, second, and third catalyst feed molar ratio: (1-3): (1-4): (. 0.6-0 9), controls the first stage reaction temperature of 1246 ° C, time of 2-4 hours, the second stage reaction temperature ^ -40 ° C, the time 3_5 hours, the third stage reaction temperature 40-60 ° C, for 4-6 hours, after the completion of the above three reaction stages, the temperature continues to increase to 60-65 ° C 1~3 hours incubation .
CN 200910031666 2009-06-22 2009-06-22 Preparation method of decabromo-diphehylethane CN101643388B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030778A (en) 1990-06-04 1991-07-09 Ethyl Corporation Decabromodiphenyl alkane process
US5055235A (en) 1990-12-12 1991-10-08 Ethyl Corporation Bromination process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030778A (en) 1990-06-04 1991-07-09 Ethyl Corporation Decabromodiphenyl alkane process
US5055235A (en) 1990-12-12 1991-10-08 Ethyl Corporation Bromination process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王德花.新型阻燃剂十溴二苯乙烷的合成与应用进展.《塑料助剂》.2007,(第6期),9-12,28.

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