CN101263085A - 标记的无机添加剂 - Google Patents

标记的无机添加剂 Download PDF

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CN101263085A
CN101263085A CNA2006800333164A CN200680033316A CN101263085A CN 101263085 A CN101263085 A CN 101263085A CN A2006800333164 A CNA2006800333164 A CN A2006800333164A CN 200680033316 A CN200680033316 A CN 200680033316A CN 101263085 A CN101263085 A CN 101263085A
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inorganic additives
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R·艾克申
J·霍肯
J·卡斯特纳
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Venator Germany GmbH
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Abstract

本发明涉及被重的稳定同位素标记的无机添加剂及其制造方法和应用。

Description

标记的无机添加剂
本发明涉及标记的无机添加剂及其制造方法和应用。
特别地，本发明涉及标记的无机颜料和填料、及其制造方法和应用。
对于食品、饲料、药品、以及许多工业产品，都需要具有清晰的产地证明。由此，例如出于投诉目的需要证明某种原料是由哪个厂商供应的。反之，供应商需要通过清晰的产地证明来免受错加在其头上的索赔要求的可能性。例如，在药品中特殊的合成硫酸钡被用于X光造影剂使用领域。在发展中国家，对于所述应用目的有时会出现劣质的硫酸钡产品(剽窃品)。当服用这些产品时，不可能排除对病人健康的成害。因此为了优质产品制造商的利益，需要能毫无疑义和以最小的量证明使用了它们自己的产品，以在必要时能够保护他们自己免受不当的追索权损害。
现有技术中已知可以通过向供应的物质中加入具有更高比例的重稳定同位素的物质来标记它们。在所有化合物中，构成各个化合物的化学元素是由不同的稳定同位素组成的。这些稳定同位素天然存在并由此以天然的分布宽度即所谓的″平均天然频度″存在于待标记的物质中(表1，Chiuz.2005，39，93页)，因此为实现显著的偏差必须添加、尤其是掺混非常高浓度的标记物质。
表1：所选同位素的″平均天然频度″
  元素   同位素符号F[原子-％]   名称(缩写)   标准R
  氢   1H    99.98552H    0.0145   标准平均海水(V-SMOW) 0.00015576
  碳   12C    98.89213C    1.1080   PEE Dee箭石(V-PDB) 0.0011237
  氮   14N    99.633715N    0.3663   空气氮(Air) 0.0036765
  氧   16O    99.758717O    0.037518O    0.2039   标准平均海水(V-SMOW) 0.0020052
  硫   32S    95.018033S    0.750034S    4.215035S    0.0200   迪亚布洛峡谷硫铁矿(CDT) 0.0450045
表中给出了对于标记颜料或填料有意义的元素和它们的稳定同位素、它们的相对平均频度F(F＝[同位素]/[∑同位素]、国际同位素标准名称及其最常见的两种稳定同位素的同位素比R(R＝[同位素a]/[同位素b])。但是，实际上对于化合物中各种元素与指定的所述频度有轻微的局部和瞬时偏差。这也是为什么所有样品的精确同位素浓度都以与国际标准的相对差用千分数的δ值来表示。即，首先对于不同颜料和填料的相应同位素测定了所述δ值(例如：对于BaSO4，与相应的标准V-SMOW相比同位素比为18O/16O，或对于ZnS，与相应的标准CDT相比同位素比为34S/32S)，其次它被确定为对于此化合物在所应用条件(所用原材料，制造条件)下的天然同位素比。
对于根据现有技术进行标记的情形，必须考虑到待标记物质中的标记同位素的比例可能例如被工艺步骤降低的问题。因此，来源有待鉴别的样品可能会已经被稀释。对于饲料和食品例如果汁尤其如此。在添加例如同位素标记的水时，它可能由于干燥等原因已被从待标记的物质中取出。即使在稀释或干燥之后，稳定同位素的浓度也必须一直处于明显超过或低于天然存在的浓度水平，以便有可能证明来源。结果就是必须采用相对较高浓度的标记物质。但是，这会造成标记物质的高消耗量以及与此相关的高成本。此外，特别是对于食品来说，由于不希望的高浓度的标记物质的结果，可能会产生不可接受的毒副作用。如果稀释度任意地高，则标记可能会不再可侦测到。
从测量技术的角度，此问题已经由DE-A-10200802的技术教导部分地解决。但是，该方法仅仅涉及用重水标记。因此该方法的缺陷在于只有所引入的水至少部分地永久保留在最终产品中时该方法才适用。所以该方法不能用于标记无机添加剂，特别是颜料和填料。在无机添加剂的制造和处理过程中，它们会被反复干燥或经受热处理，期间温度经常会超过100℃，例如在挤出聚合物材料时。
本发明的目的在于克服现有技术的上述缺陷。
本发明的目的特别是在于提供一种被一或多种重稳定同位素永久标记的无机添加剂及其制造方法。本发明的另一目的在于提供一种其用于标记的一或多种同位素的含量不会受热处理影响的无机添加剂。
根据本发明，此问题令人意外地被通过主权利要求的特征解决。从属权利要求中是其优选的变化。
为了在制造最终产品时标记不会被改变或丢失，标记必须以一种永久或牢固的方式结合到添加剂的化合物中。如果例如一种无机添加剂如TiO2(其例如可被用作白色颜料)在使用前仅用O18标记的水润湿，则可能在制造出最终产品时该标记只被部分引入最终产品中或完全未被引入最终产品中。在使用标记的水时，如果在添加剂或使用该添加剂的最终产品的生产过程中包括加热或除水步骤，则总会发生上述情况。
使用重稳定同位素标记时必须注意选择，以使即使只有几毫克的最终产品也可以确定无疑地证明在最终产品中的含量(例如借助于稳定同位素质谱分析法)。
在这一点上，该问题根据本发明通过一种具有与天然状态相比升高比例(Δδ具有正值)或降低比例(Δδ具有负值)的重稳定同位素例如2H、13C、15N、18O和/或34S的无机添加剂得到解决。所述无机添加剂优选地为颜料或填料。这种无机添加剂的例子有TiO2、ZnS或BaSO4。
所述标记被牢固地结合在所述添加剂中。牢固地结合在此是指对于具体的添加剂相应的Δδ具有恒定值。此外，重同位素的具体含量，即具体Δδ，可以针对具体目的设定。
在这种情况下，Δδ表示富集重同位素的化合物与并不富集的″天然″化合物的δ值之间的差值(例如用34S标记的ZnS的δ34S减去″天然″ZnS的δ34S)。
根据本发明，所述Δδ值在3-1000‰之间，优选地在5-300‰之间，特别优选地在10-200‰之间，和/或-3‰到-100‰之间，特别优选地在-5‰到-20‰之间。
由于重同位素例如2H、13C、15N、18O和/或34S的升高或降低的比例，这些物质可以被清楚并永久地标记以及探测。对于用两种或两种以上同位素标记的物质，用于标记的同位素可以全部富集或全部贫化或者一或多种同位素富集而其它一或多种同位素贫化。
可以通过不同的方法实现标记，例如：
-无机添加剂直接在制造时通过在化合物中引入适当的重稳定同位素被永久标记。
-无机添加剂，特别是颜料和填料，常被施以无机和/或有机后处理，特别是被涂覆。由于这些后处理，所述添加剂的特性被改变从而优化适合于预定目的(Jochen Winkler，Titandioxid，3.4章，Hanover Vicentz2003；Elizabeth Reck，Farbe&Lack，第102卷3/96，40-48页)。此无机和/或有机后处理也可用于以重稳定同位素进行的永久标记。
-填料和颜料例如TiO2、ZnS或BaSO4(经无机后处理过的或未后处理过的)可以通过具有不同13C、18O、15N和/或34S同位素含量的难溶耐高温无机物质的有目的沾染进行标记。例如，难溶的含氧无机Al、Ba、Si、Ti、Zr、Ca、Mg、Fe、Zn和/或B化合物适合于这些沾染。这些无机化合物不必一定是氧化性的，而是也可包含例如阴离子，如氢氧化物、磷酸盐、碳酸盐、硝酸盐、硫化物乃至硫酸盐。
也可采用上述方法的任意组合。通过这些方法，无机添加剂被重同位素永久标记。
通过上述方法标记的无机添加剂可应用于添加剂的所有应用领域，例如用作颜料和/或填料，再例如用于：
a)塑料/聚合物材料(例如PET瓶、膜/箔、合成和化学纤维)；
b)涂料和漆；
c)食品；
d)药品；
e)化妆品；
f)纸；
g)橡胶；
h)玻璃；
i)饲料。
本发明的主题详细地为：
-被重稳定同位素标记的无机添加剂；
-被重稳定同位素标记的无机添加剂，其中所述标记被牢固地结合在所述添加剂中；
-被重稳定同位素永久标记的无机添加剂；
-其用于标记的一或多种同位素的含量不会受热处理影响的无机添加剂；
-被重稳定同位素标记的无机添加剂，其中所述同位素为选自2H、13C、15N、18O和34S中的一或多种；
-被重稳定同位素标记的无机添加剂，其中所述同位素是富集的；
-被重稳定同位素标记的无机添加剂，其中所述同位素是贫化的；
-被重稳定添加剂标记的无机添加剂，其中所述添加剂本身被标记；
-被重稳定添加剂标记的无机添加剂，其中所述添加剂的涂层被标记；
-被包含在添加剂的针对性沾染物中的重稳定添加剂标记的无机添加剂；
-被重稳定同位素标记的无机添加剂，其中Δδ值在3-1000‰之间，优选地在5-300‰之间，特别优选地在10-200‰之间，和/或-3到-100‰之间，特别优选地在-5到-20‰之间；
-被重稳定添加剂标记的无机添加剂，其中所述添加剂为颜料和/或填料；
-被重稳定添加剂标记的无机添加剂，其中所述添加剂为TiO2、ZnS或BaSO4；
-制造标记的无机添加剂的方法；
-制造标记的无机添加剂的方法，其中所述标记被牢固地结合在所述添加剂中；
-制造标记的无机添加剂的方法，其中所述标记通过一或多种重稳定同位素和/或其化合物实现；
-制造标记的无机添加剂的方法，其中所述同位素为选自2H、13C、15N、18O和/或34S中的一或多种；
-制造标记的无机添加剂的方法，其中所述同位素是富集的；
-制造记的无机添加剂的方法，其中所述同位素是贫化的；
-制造标记的无机添加剂的方法，其中所述添加剂直接在制造时通过在添加剂的化合物中引入重稳定同位素而被标记；
-制造标记的无机添加剂的方法，其中所述添加剂在无机和/或有机后处理时被重稳定同位素标记；
-制造标记的无机添加剂的方法，其中所述添加剂通过用难溶性耐高温无机物质进行有目的的沾染而被标记；
-制造标记的无机添加剂的方法，其中所述添加剂为颜料和/或填料；
-制造标记的无机添加剂的方法，其中所述添加剂为TiO2、ZnS或BaSO4；
-制造标记的无机添加剂的方法，其中TiO2或BaSO4中的18O含量被升高；
-制造标记的无机添加剂的方法，其中ZnS或BaSO4中的34S含量被升高；
-制造标记的无机添加剂的方法，其中18O含量在TiO2、ZnS或BaSO4的无机和/或有机后处理中被18O标记的铝、硅、锆、锰和/或钛的氧化物或氢氧化物升高；
-制造标记的无机添加剂的方法，其中2H、13C、15N、18O和/或34S含量在有机后处理中通过用具有不同2H、13C、18O、15N和/或34S同位素含量的多元醇、氨基化合物和/或硅油进行表面处理而被升高或降低；
-制造标记的无机添加剂的方法，其中2H、13C、15N、18O和/或34S含量被用具有不同2H、13C、18O、15N和/或34S同位素含量的难溶耐高无机材料、特别是含氧的无机Al、Si、Ti、Zr、Ca、Mg、Fe、Zn和/或B化合物的有目的沾染升高或降低；
-本发明的添加剂作为填料和/或颜料的应用；
-本发明的添加剂在塑料/聚合物材料(PET瓶、膜/箔、合成和化学纤维)、涂料和漆、食品；药品、化妆品、纸；橡胶、玻璃、饲料的制造和处理中的应用，优选地作为颜料和/或填料。
通过以下实施例对本发明进行了更详细地说明，但本发明并不仅限于以下实施例：
实施例1：标记的无机添加剂的制造
a.TiO2或BaSO4中的18O含量的升高：
i.通过用18O标记的水水解含钛化合物如四氯化钛制造TiO2；所述反应产生δ(18O)值为+50‰的TiO2产品；相反，未标记的TiO2产品的δ(18O)值为-2.7‰；因此Δδ值等于+52.7‰；
ii.通过用18O标记的水水解含钛化合物如钛氧基硫酸盐溶液制造TiO2；
iii.通过用18O标记的硫酸从氯化钡水溶液中沉淀制造BaSO4；所述反应产生δ(18O)值为+33‰的BaSO4产品；相反，未标记的BaSO4产品的δ(18O)值为-3‰；因此Δδ值等于+36‰；
b.ZnS或BaSO4中的34S含量的升高：
i.通过ZnO与34S标记的硫酸反应形成硫酸锌和随后与Na2S反应形成ZnS来制造ZnS；
ii.通过用34S标记的硫酸从氯化钡水溶液中沉淀制造BaSO4；
实施例2：在涂层中标记的无机添加剂的制造
a.在TiO2、ZnS或BaSO4的无机和/或有机后处理中增大18O含量。在无机后处理过程中，难溶无色无机化合物被沉淀到各个颜料颗粒上。例如，使用铝、硅、锆、锰和/或钛的氧化物或氢氧化物来进行所述表面处理。这些沉淀反应可以借助于18O标记的原材料来进行；
b.在TiO2、ZnS或BaSO4的有机后处理中增大2H、13C、15N和/或18O含量。例如，使用诸如多元醇、氨基化合物乃至硅油等化合物来进行对填料和颜料的所述表面处理。这些化合物同样达到具有添加剂的最终产品并由此可用于标记。
实施例3：通过有目的的沾染制造标记的颜料或填料：
a.用18O标记的ZrO2沾染TiO2；
b.用13C标记的CaCO3沾染ZnS；
c.用15N和/或18O标记的MgNH4PO4沾染BaSO4；
d.用18O标记的BaSO4沾染TiO2；添加1％重量的18O标记的BaSO4到TiO2颜料中导致在沾染的最终产品中δ(18O)值为+162‰；相反，添加1％重量的未标记的BaSO4到TiO2颜料中导致在沾染的最终产品中δ(18O)值为-3‰；因此Δδ值等于+165‰；
也可采用实施例1-3的任意组合。

Claims (21)

1.被重稳定同位素标记的无机添加剂，特征在于所述标记被牢固地结合在所述添加剂中。
2.权利要求1的无机添加剂，特征在于其为填料和/或颜料。
3.权利要求1或2的无机添加剂，特征在于其为TiO2、ZnS或BaSO4。
4.权利要求1-3之一的无机添加剂，特征在于所述同位素选自2H、13C、15N、18O和/或34S中的一或多种。
5.权利要求1-4之一的无机添加剂，特征在于所述同位素是富集的。
6.权利要求1-5之一的无机添加剂，特征在于所述同位素是贫化的。
7.权利要求1-6之一的无机添加剂，特征在于所述添加剂本身被标记。
8.权利要求1-7之一的无机添加剂，特征在于所述添加剂的涂层被标记。
9.权利要求1-8之一的无机添加剂，特征在于其通过有目的的沾染被标记。
10.权利要求1-9之一的无机添加剂，特征在于Δδ值在3-1000‰之间，优选地在5-300‰之间，特别优选地在10-200‰之间，和/或-3到-100‰之间，特别优选地在-5到-20‰之间。
11.制造权利要求1-10之一的无机添加剂的方法，特征在于所述标记被牢固地结合在所述添加剂中。
12.权利要求11的方法，特征在于所述无机添加剂直接在制造时通过在化合物中引入适合的重稳定同位素而被永久标记；
13.权利要求11或12的方法，特征在于所述无机添加剂在无机和/或有机后处理中用重稳定同位素永久标记。
14.权利要求11-13之一的方法，特征在于所述无机添加剂通过用难溶性耐高温无机物质有目的地沾染而被永久标记。
15.权利要求11-14之一的方法，特征在于TiO2或BaSO4中的18O含量被升高。
16.权利要求11-15之一的方法，特征在于ZnS或BaSO4中的34S含量被升高。
17.权利要求11-16之一的方法，特征在于中18O含量在TiO2、ZnS或BaSO4的无机和/或有机后处理中被18O标记的铝、硅、锆、锰和/或钛的氧化物或氢氧化物升高。
18.权利要求11-17之一的方法，特征在于2H、13C、15N、18O和/或34S含量在有机后处理中通过用具有不同13C、18O、15N和/或34S同位素含量的多元醇、氨基化合物和/或硅油进行表面处理而被升高。
19.权利要求11-18之一的方法，特征在于2H、13C、15N、18O和/或34S含量通过用具有不同2H、13C、18O、15N和/或34S同位素含量的难溶性耐高温无机物质、特别是含氧的无机Al、Si、Ti、Zr、Ca、Mg、Fe、Zn和/或B化合物进行有目的的沾染而被升高。
20.权利要求1-10之一的无机添加剂作为颜料和/或颜料的应用。
21.权利要求1-10之一的无机添加剂在塑料/聚合物材料、涂料和漆、食品；药品、化妆品、纸；橡胶、玻璃、饲料的制造和加工中的应用，优选用作颜料和/或填料。
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