CN100345832C - 粒状吩噻嗪 - Google Patents
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- CN100345832C CN100345832C CNB008187363A CN00818736A CN100345832C CN 100345832 C CN100345832 C CN 100345832C CN B008187363 A CNB008187363 A CN B008187363A CN 00818736 A CN00818736 A CN 00818736A CN 100345832 C CN100345832 C CN 100345832C
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Abstract
本发明涉及(a)细碎物含量非常低的通常为球粒的粒状吩噻嗪或吩噻嗪类似物或衍生物(吩噻嗪物质),本发明还涉及(b)一种通常为球粒的粒状吩噻嗪物质的制备方法。成粒的吩噻嗪物质展现出改善的处理性、流动性和溶解时间,同时最大程度地减少了细碎物的形成以及由于暴露于这种细碎物下出现的刺激和过敏问题。
Description
发明背景
吩噻嗪是一种芳香胺基产品,广泛用于各种用途,包括作为各种用途如丙烯酸、酯和单体的稳定的抑制剂、抗氧化剂和速止剂或作为氯丁二烯单体、苯乙烯单体和其它乙烯基单体的稳定剂;作为在合成润滑剂和油、在聚氨酯和聚酯和乙烯基酯树脂用多元醇中的抗氧化剂;和作为药物中间体。
吩噻嗪通常以片状和粉状生产,并且具有亮黄色外观(表明缺乏氧化)。片状形式可通过将熔融吩噻嗪涂布在转鼓刨片机上,在其上冷却并结晶成薄层,以片和细碎物(粉末)的混合物刮下来制备。然后将产物传递到物理分离(分类)工序,通常通过使用分级筛来将细碎物(粉)与片分离。然后将片状吩噻嗪包装并送到用户手中,用户使用其拥有的加工设备传递或运输。经管经过分类,生产出的产品一般最多可含有约6%的细碎物。此外,在随后的运输和处理中吩噻嗪片易碎裂成细碎物。
在片状吩噻嗪中细碎物(粉末)的产生和存在会带来问题。含这种细碎物的片状产物会有粒径不均匀、结块、尘污和团集的缺点。作为呼吸道、皮肤、眼和消化道刺激剂和皮肤过敏剂的吩噻嗪在细碎形式时更易引起问题。在片状产物中的细碎物也增加了爆炸的可能性。含高水平细碎物(即含有约6%以上粒径小于500微米的颗粒)的片状吩噻嗪特别易于结块或团集。
在片状吩噻嗪中的不均匀粒径增加了产物结块和/或团集的倾向,并且增加了内部和用户设备中抗流动的程度。结块和/或团集使得难以将吩噻嗪从容器如存储斗、袋、货车、贮仓等卸出,并且难以传送。它也可引起容器中桥接物或块的形成。细碎物也带来安全、健康和环境方面的问题。从安全观点来看,细碎物由于增加了爆炸的危险以及增加危及雇员的健康(特别是如上所述的皮肤刺激和皮肤过敏等)而特别令人关注。
常规的造粒技术要求将熔融材料送过开孔并然后当其掉落时由空气冷却和固化成球粒。一般造粒塔有80-300英尺高并且需要大体积的空气。常规造粒技术的缺陷包括需要大塔和极大体积的空气。这需要高的基建费用和极大的操作成本。另外,吩噻嗪目前不能通过常规技术造粒,因为熔融态产物会起反应和氧化而改变化学组成和颜色。氧化形式的吩噻嗪为绿色到灰色。这种形式是改变了所需的纯吩噻嗪化学组成。未氧化形式的纯吩噻嗪为亮黄色。
吩噻嗪的熔点为184℃,因此其难以以熔融态处理和传送。没有大量热跟踪管线难以将熔融吩噻嗪泵送到常规造粒塔的顶部,80-300英尺高的地方。如果温度降到产物的熔点以下,其在传送管线快速固化,导致操作困难。
按照前面所述,本领域需要有一种减少最终吩噻嗪中出现高水平细碎物伴随的问题,并仍能产生高质量物质的制备方法。本领域也需要减少在运输、传送和存贮上伴随着吩噻嗪的结块和/或团集的问题。
对于质量来说,高度需要任何能制备出吩噻嗪含量≥99.6%的满足工业质量要求的产品的新方法。但是,颜色也是一个纯度的重要指示,高度需要产品具有从淡绿黄到亮黄色的颜色,尤其是没有任何灰色或完全绿色的产品,这种产品即使分析纯度为≥99.6%也能负面影响后续的使用。吩噻嗪颜色可方便地使用孟塞尔颜色图来评价,高度要求产品的外观在孟塞尔颜色图中由色相符号(Hue Symbol)5Y和颜色空间(Color Spaces):8/4-8/12,8.5/4-8.5/12和9/4-9/8定义的区域内,更尤其是由色相符号5Y和颜色空间:8.5/8-8.5/12和9/6-9/8定义的区域内。
发明简述
本发明包括含众多颗粒物的固体吩噻嗪或其类似物或衍生物(如后文所述),其中所述颗粒主要为球粒。
在下面的说明书和权利要求书中,吩噻嗪是指式(I)(见下文)的化合物,吩噻嗪物质一般是指式(I)的吩噻嗪和/或式(II)(见下文)的吩噻嗪的类似物或衍生物。
本发明还包括降低吩噻嗪物质中细碎物(粉末)水平的方法,包括将吩噻嗪物质形成颗粒,使得颗粒主要为球形。
本发明也包括含众多吩噻嗪物质颗粒的固体吩噻嗪物质,其中所述颗粒主要具有球形并且产物中的细碎物(即粒径<500μ的颗粒)不大于约6%重量。
本发明包括一种制备吩噻嗪物质颗粒的方法,包括将熔融吩噻嗪物质导入到至少一个具有多个孔的喷嘴中形成吩噻嗪物质的熔融细滴,冷却所述细滴形成固体颗粒,所有这些步骤均在惰性环境中进行。所述方法特别适用于制备绿黄色到黄色的的粒状吩噻嗪。本发明也包括通过该方法形成的固体吩噻嗪物质。
本发明涉及具有改良的性能和降低细碎物(粉末)水平的粒状吩噻嗪物质及其制备方法。本发明还涉及降低吩噻嗪物质中细碎物水平并同时保持产品质量的方法。在本发明的所有方面,优选所述吩噻嗪物质为吩噻嗪。
本发明的第一个方面提供了众多主要为球形粒状固体吩噻嗪物质。
在吩噻嗪的情况下,所述颗粒优选具有绿黄到黄色的颜色,更优选在孟塞尔颜色图中由色相符号5Y和颜色空间:8/4-8/12,8.5/4-8.5/12和9/4-9/8定义的区域内,更尤其是由色相符号5Y和颜色空间:8.5/8-8.5/12和9/6-9/8定义的区域内的颜色。特别优选粒状吩噻嗪具有亮黄色,更尤其是相当于片状吩噻嗪的亮黄色。
优选所述粒状吩噻嗪产品包含至少99.6%的吩噻嗪。
本发明的另一方面提供了一种制备粒状固体吩噻嗪物质的方法,包括将熔融吩噻嗪物质流碎裂成众多大小均一的细滴,并将细滴冷却形成粒状的固体吩噻嗪物质,吩噻嗪物质在熔融态下保持在惰性气体(优选氮气)环境内。还优选保持惰性气体环境直到将粒状的吩噻嗪物质冷却到约140℃以下。
本发明的详细说明
所述颗粒可通过将熔融吩噻嗪物质进料到至少一个具有多孔的喷嘴中而形成吩噻嗪物质熔融细滴,将细滴冷却而形成颗粒。所述熔融吩噻嗪物质可以是任何适合的吩噻嗪物质形式,如粉末状或片状。
吩噻嗪是一种目前可以片状和粉末状商品购置的固体物质。此中所用的吩噻嗪物质可包括任何吩噻嗪类似物或衍生物,条件是其为固体形式并且可例如通过加热制成熔融形式。
吩噻嗪具有199.26的分子量和C12H9NS的化学式。典型的商品吩噻嗪具有184℃的熔点和371℃的沸点。片状产品具有约0.85的堆积密度,粉状产品具有约0.75的堆积密度。吩噻嗪的化学式如下:
吩噻嗪物质包括吩噻嗪和其类似物和衍生物,包括(但不限于)式(II)的化合物:
式中R1、R2和R3可相同或不同并且可为氢;卤素,如氯和氟等;支链或直链和取代或未取代的烃基,如1到26个碳原子的烷基、链烯基或链炔基;取代和未取代的芳基和芳烷基;或官能基团,包括但不限于磺酰基、羧基、胺、烷基胺、羟基、羧基、甲硅烷基、甲硅烷氧基;和其它类似衍生物和其盐。前述烃、芳基和芳烷基的取代基可包括任何上述官能基以及链间元素如氧、硫、硅、氮等。最优选式(II)中的R1、R2和R3各自为氢。在式(II)中,优选m和n独立地为约1到约4。
为了形成颗粒,将熔融形式的吩噻嗪物质(可以是式(I)的吩噻嗪和/或式(II)的吩噻嗪衍生物或类似物)进料到能接收熔融吩噻嗪物质的喷粒装置的喷嘴室中并通过具有多孔的造粒喷嘴。
通过联系附图加以考虑可有助于理解前面本发明的简述和详细说明(包括其优选的实施方案)。为了说明本发明,图中显示了一优选的实施方案。但是,应该理解本发明并不限于图中所示的精确装备和工具。在图中,图1为适合于按照本发明制备吩噻嗪颗粒的喷粒装置和附属设备的示意图。参照图1来说明一种按照本发明形成吩噻嗪颗粒的方法。
吩噻嗪通过在由高压惰性气体贮器(2)提供的惰性气氛(优选氮气)下在进料罐(1)中加热到约190至约215℃并更优选约205至约215℃的温度而方便地转变成熔融态。然后通过惰性气体压力将熔融物传送到调节器(3),在其中将温度调节到约195-200℃。为了在氮气气氛下将熔融吩噻嗪经去除外来物质的过滤器(4)驱送到喷粒装置(6)的喷嘴室(5)中,保持调节器(3)的惰性气体(优选氮气)的压力在约1.5-3千克/平方厘米(1.5-3巴)。为了控制吩噻嗪通过造粒喷嘴(7)的流量,喷嘴室(5)中的惰性气体压力小心控制在0-1千克/平方厘米(0-1巴)、更优选0.035-0.80千克/平方厘米(0.035-0.80巴)的某一固定压力下。已经观察到将熔融吩噻嗪以约215℃以上的温度进料到喷嘴室和/或在喷嘴室(5)中以约1千克/平方厘米(1巴)以上的压力操作导致了熔融吩噻嗪以不那么受控的方式碎裂,形成更细的滴粒,并因此导致在最终产品中有更多的细碎物。
在熔融吩噻嗪通过造粒喷嘴(7)孔进入造粒塔(8)顶部的过程中,由在喷嘴室(5)壁上振动膜(9)的作用以受控的方式碎裂成约1至约2mm的细滴,振动膜通过在约100至约1500Hz、更优选约400至约1100Hz频率下操作的振动设备(10)振动。液化惰性气体(特别是液氮)同时从液化惰性气体贮器(11)进料到造粒塔(8)的侧面,液态或气态形式的冷惰性气体的混合物快速冷却所述熔融吩噻嗪的细滴而形成主要为球形的颗粒。使用冷惰性气体(特别是氮气)在保持产品质量以及获得绿黄色到黄色产品方面起重要作用。虽然也可使用其它惰性气体来按照本发明形成吩噻嗪颗粒,但是优选使用氮气,因为它能快速有效地冷却颗粒并因而防止了与氧化气体的接触,从而保持了优选的黄色,特别是在色相符号5Y和颜色空间:8/4-8/12,8.5/4-8.5/12和9/4-9/8区域内的颜色。
当细滴从造粒塔(8)掉落时最初被冷的气态和液态惰性气体(特别是氮气)冷却成部分结晶颗粒。在颗粒到达造粒塔(8)的底部时,它们通常处于约120至约170℃的温度,更优选处于约140℃的温度,由造粒塔(8)的底部将它们送入具有旋风分离器形式的螺旋冷却器(12),在其中使颗粒在冷的惰性气氛下进一步冷却,直到结晶完全,此时它们到达螺旋冷却器(12)的底部。在此将它们从喷粒设备(6)移出,经一气阻(13)以防止空气导入,同时将在通过喷嘴时偶然形成的细碎物的惰性气体通过侧管导出螺旋冷却器(12)。
已经发现吩噻嗪颗粒的质量对吩噻嗪和惰性气体的相对流速敏感。通过造粒塔(8)和螺旋冷却器(12)的氮气流速优选为每千克粒状吩噻嗪0.25-0.3千克。
离开螺旋冷却器的惰性气体通过风扇(15)送入到旋风分离器(14)以除去细碎物并经冷却器(16)循环到造粒塔(8)以补充新鲜液氮进料。
一种优选的喷粒装置为可购自荷兰Waddinzveen的GMF Gouda,Goudsche Machinefabriek,B.V的JP15型喷粒装置,可使用这种喷粒装置制备各种颗粒。
粒状的吩噻嗪可用于许多用途,特别是那些使用吩噻嗪粉末有问题的领域。按照本发明的吩噻嗪颗粒可用于宽范围的用途,包括作为各种化学用途中的稳定剂。所述产品也可用作各种用途如稳定丙烯酸、酯和单体中的抑制剂、抗氧化剂和速止剂或作为氯丁二烯单体、苯乙烯单体和其它乙烯基单体的稳定剂。所述颗粒产品也可作为在合成润滑剂和油、在聚氨酯和聚酯和乙烯基酯树脂用多元醇中的抗氧化剂。由于其高水平的活性,吩噻嗪在非常低的浓度就起作用并增强其它稳定剂的性能。其在强酸环境以及在空气或氮气环境下也良好地起作用。粒状的吩噻嗪物质也是一种有用的药物中间体。
优选本发明的粒状吩噻嗪物质具有低于约6%并更优选低于约1%重量的细碎物(粉末),即粒径小于约500微米的颗粒。此外,优选制成的粒状吩噻嗪物质具有约0.5至约2.3mm并更优选约1至约2mm的在最长方向测定的平均粒径。本发明的主要为球粒的吩噻嗪物质由于其均一的尺寸而具有显著改善的流动性能,并且在使用中比标准的片状或粉末形式吩噻嗪物质通常更为安全。
现在将参照下面的非限定性实施例更详细地说明本发明。
实施例1
在模拟实验室规模造粒装置中的小规模试验
使用一个1升的3-颈反应烧瓶模拟刨片机进料罐。其配有氮气进料管、搅拌器、温度探头和底部出口。将设备抽真空并在氮气气氛下装载产品前用氮气吹扫三次。然后向反应器装入吩噻嗪片,在氮气气氛下在约200℃加热到熔融态。接着将熔融吩噻嗪缓慢滴过底部出口阀(模拟喷嘴)进入在一个具有真空夹套的Dewar烧瓶中的约1升液氮(约-192℃)中。形成亮黄色颗粒并进行选择分析。所述亮黄色颗粒满足所有产品技术规格要求,没有沉淀物,并且以与标准吩噻嗪片相同的方式和效率运作。
实施例2
在工业喷粒装置中的大规模试验(参见图1)
将吩噻嗪片注入到进料罐(1)中。将吩噻嗪片在3.1千克/平方厘米(3.1巴)压力(氮气)及大约200℃下熔融并传送到调节罐(3)。然后在氮气压力下将产品送入到购自GMF Gouda的JP 15/1型闭环喷粒装置(6)的喷嘴室(5)中,所述装置具有一个含100个约0.5mm直径孔的喷嘴。通过在喷嘴室(5)中保持一恒定的氮气压力来控制通过喷嘴(7)的吩噻嗪流量。当产品通过喷嘴(7)时,借助于在喷嘴室(5)壁上的振动膜(9)碎裂成1-2mm的细滴,所述振动膜(9)通过1005-1007Hz频率下的频闪仪控制。通过将熔融细滴立即用液氮冷却成固体粒状来形成颗粒。熔融进料为约200℃(一般范围为约194.7-195.5℃),液氮温度为约-192℃。来自于液化惰性气体贮器(11)的液氮的流量为每千克颗粒0.25-0.30千克氮气。当产品在低温造粒塔(8)中掉落通过液态/气态氮环境时固化成颗粒。产品在螺旋冷却器(12)中进一步冷却,随后经气阻(13)从喷粒装置(6)排放。含有所形成细碎物的氮气通过风扇(15)送过旋风分离器(14)而去除细碎物并将氮气在通过冷却器(16)后再循环回造粒塔(8)。
所述试验生产出了绿黄色(孟塞尔颜色空间:5Y/8/6)到黄色(孟塞尔颜色空间:5Y/9/6)的吩噻嗪颗粒,其满足所有标准产品技术规格要求、没有沉淀物并且产生与标准吩噻嗪片类似的效力。所述颗粒也提供了改善的处理性和流动性。
所形成的颗粒主要为球形并且具有约1mm的平均直径。所述颗粒也具有低的静止角并且展现出非常窄的粒度分布。达到了低于1%的低细碎物(粉末)水平,并且产品不易结块。产品也显示出优于现有片状产品的流动、传送和处理性能。另外,由于其更均匀的形状和更小的平均粒径,所述颗粒与片状产品相比展现出较优的溶解时间。标准片剂和实施例2形成的颗粒的性能比较列于下表1中。
表1
性能 | 片剂 | 颗粒(实施例2) |
外观 | 黄色片状 | 黄色颗粒 |
熔点,℃ | 184(最低) | 184.9(最低) |
纯度(%) | 99.6 | 99.9 |
静止角 | 36 | 25 |
堆积密度 | 0.8 | 0.77 |
粉末的摇瓶试验 | 轻到重 | 无到非常轻微 |
厚度(mm) | 1.40 | 1.65 |
平均直径(mm) | N/A | 1 |
粒度分布 | ||
≥2360微米颗粒(%) | 75 | 0 |
<2360-500微米颗粒(%) | 19 | 99 |
<500微米颗粒(%) | 6 | 1 |
溶解时间 | ||
丙酮(最小) | 5 | 3 |
甲基丙烯酸甲酯(最小) | 12.5 | 11 |
丙烯酸丁酯(最小) | 8 | 5.5 |
产品效力(对于聚甲基丙烯酸甲酯的小时数) | 13 | 14 |
通过此中所述的适当控制和惰性环境(优选由液态或气态氮提供),可以制备出具有所需性质和颜色的粒状吩噻嗪。
基于前面所述,本发明方法制备出了性能至少可比于并且大多数情况下优于片状和粉末状吩噻嗪的吩噻嗪颗粒。所述颗粒也有利地展现出了基本均匀的平均直径和窄的粒度分布,以及只含非常低水平的细碎物。这种特征降低了结块和/或团集的出现并证实改善了运输和使用时的流动性能。通过使用这些颗粒获得的其它显著的优点包括改善了环境和车间的安全性以及由于细碎物的低水平而降低了生产费用。
本领域技术人员知道在没有背离本发明的广义概念下可对上述实施方案作出各种改变。所以,应理解本发明并不限于所公开的具体实施方案,而是覆盖所附权利要求书定义的本发明精神和范围内的各种修改。
Claims (14)
2.权利要求1的固体产品,其中所述球粒具有在孟塞尔颜色图中由色相符号5Y和颜色空间:8/4-8/12,8.5/4-8.5/12和9/4-9/8定义的区域内的黄色。
3.权利要求2的固体产品,其中所述黄色在孟塞尔颜色图中由色相符号5Y和颜色空间:8.5/8-8.5/12和9/6-9/8定义的区域内。
4.权利要求1或2的固体产品,其中所述球粒具有0.5至2.3mm的平均直径。
5.权利要求1或2的固体产品,所述固体产品包含不超过1%重量的细碎物。
7.权利要求1的固体产品,其中所述球粒通过在惰性气氛中冷却熔融的吩噻嗪物质细滴形成。
8.权利要求1的产品,其中所述球粒为绿黄色到黄色。
9.权利要求8的产品,其中所述颜色落在孟塞尔颜色图中由色相符号5Y和颜色空间:8/4-8/12,8.5/4-8.5/12和9/4-9/8定义的区域内。
10.权利要求8的产品,其中所述颜色落在孟塞尔颜色图中由色相符号5Y和颜色空间:8.5/8-8.5/12和9/6-9/8定义的区域内。
12.权利要求11的方法,其中所述惰性气体气氛由氮气提供。
13.权利要求11或12的方法,其中所述熔融吩噻嗪的温度不高于215℃。
14.权利要求11或12的方法,其中所述吩噻嗪物质为吩噻嗪。
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- 1999-12-03 US US09/453,685 patent/US6284279B1/en not_active Expired - Lifetime
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2000
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- 2000-12-01 WO PCT/GB2000/004600 patent/WO2001040209A1/en active Application Filing
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2001
- 2001-08-07 US US09/923,806 patent/US6485750B2/en not_active Expired - Lifetime
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2012
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