CN1096504C - 液态的甲基锡卤化物组合物 - Google Patents
液态的甲基锡卤化物组合物 Download PDFInfo
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- CN1096504C CN1096504C CN96106649A CN96106649A CN1096504C CN 1096504 C CN1096504 C CN 1096504C CN 96106649 A CN96106649 A CN 96106649A CN 96106649 A CN96106649 A CN 96106649A CN 1096504 C CN1096504 C CN 1096504C
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- trichlorine
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- -1 methyltin halide Chemical class 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 43
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims description 26
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- 238000000034 method Methods 0.000 claims description 20
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 claims description 8
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
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- 239000011737 fluorine Substances 0.000 description 5
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- ZUOAYNYBICLREW-UHFFFAOYSA-N chloromethane;tin Chemical compound [Sn].ClC ZUOAYNYBICLREW-UHFFFAOYSA-N 0.000 description 4
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- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- RDUORFDQRFHYBF-UHFFFAOYSA-N 6-methoxy-1-methyl-2,3,4,9-tetrahydro-1h-pyrido[3,4-b]indole Chemical compound CC1NCCC2=C1NC1=CC=C(OC)C=C12 RDUORFDQRFHYBF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 2
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- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical compound [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 2
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- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
Abstract
本发明提示了液态的甲基锡齿化物及其作为化学合成中的中间体和作为在基材上形成氧化锡涂层的前体的用途。
Description
本发明背景
本发明涉及化学领域中的有机锡卤化物组合物，尤其是含卤化甲基锡的组合物及其制备方法和应用。如三氯一甲基锡和二氯二甲基锡等甲基锡卤化物在24℃时是固态物料。仅此特性就使它们对许多应用来说显得不适用或不经济。例如，当以甲基锡卤化物用作制备酯化催化剂或卤化聚合物的稳定剂的化学中间体时，首先必须将它们溶于合适的溶剂中，熔融或磨成细粉。所有这些工艺过程都将提高成本，降低生产效率。与此类似，当将甲基锡卤化物用作在玻璃等材料上生成氧化锡涂层的涂层前体时，最通常的是通过高温转化生成氧化锡，其固体、非液体特性需要将其溶于某种溶剂或将其汽化。汽化并不能完全解决与其固态特性有关的操作困难，尤其是在将甲基锡卤化物装入汽化设备时。蒸汽易使固体不仅在待涂物体上，而且还在邻近的设备壁上和涂敷设备的排气管上沉积，从而需要经常停机来清除固体。
引入酒精或水等溶剂可将甲基锡卤化物转化成液体组合物，从而使其更易处理，其缺点在于稀释了有效物质。
当欲将氯化甲基锡用作化学中间体时，这样的稀释提高了运输成本，降低了反应设备的体积效率，而且当以水为稀释剂时增加了腐蚀性。
当欲将氯化甲基锡通过热化学蒸汽沉积、喷涂或浸涂用于在玻璃或其它材料上产生氧化锡涂层时，为将固态的氯化甲基锡转化为易于处理的液态组份而引入溶剂，从而将产生诸多严重弊端。由于有效组份被稀释而需要使用更大量的原料，从而导致污染防治费用的提高。如果使用诸如酒精等有机溶剂，将增加火灾和爆炸的危险性，从而需要更多的安全防范措施，并安装特殊的防火防爆设备，或增加用于稀释氧气的气体，如氮气。而且，引入包括水在内的过量溶剂将损害氧化锡涂层的质量，常表现为浊雾、导电性降低或表面粗糙。在启动连续涂瓶流水线时，被溶剂稀释的组合物会降低涂覆效率。在获得满意的涂层前需要一段很长的时间来克服涂料袋中溶剂的冷却效应。由此导致起始生产能力的损失。
有许多美国专利描述了将有机锡氯化物用作制备卤化聚合物(特别是聚氯乙烯)热稳定剂的化学中间体；尿烷、酯化反应和缩合反应的催化剂，以及将其用作玻璃或其它材料上的氧化锡涂层的前体以提供导电和反射红外线的涂层，提高耐擦伤性，改善物理性能。如此涂覆过的玻璃被用于构造太阳能电池，汽车挡风玻璃，玻璃的冰箱门，“低-E”或IR反射玻璃，及用于电子设备，以下举几个例子。美国专利4,144,362-用三氯单烷基锡涂覆玻璃的方法
此专利论述了有机锡和无机锡作为在玻璃上产生氧化锡涂层的前体的用途。在此申请中对三氯单甲基锡的优越性进行了揭示并提出保护要求。美国专利4,130,673-用三氯丁基锡为前体在玻璃上涂覆氧化锡的工艺
该申请描述了通过在热处理过的玻璃表面涂以细粉状或可汽化的三氯丁基锡来用三氯丁基锡在玻璃上沉积一层氧化锡涂层。涂覆后的玻璃被涂以一层天然蜡或合成聚合物以降低摩擦系数。美国专利4,530,857-玻璃容器热端涂层制剂及其使用方法
此专利描述了用“掺杂剂”来避免用于在热的玻璃上沉积氧化锡涂层的液态有机锡前体中固体的形成。其中提到“掺杂剂”一般应理解为一种混合物且对涂覆过程和最终成品的质量没有任何积极作用。虽然提到将三氯甲基锡用作前体，但并未指出该原料是固体的，所以不因掺杂剂的加入而受益。美国专利4,566,346一导电成品及它们的生产方法
该专利描述了使用某种锡化合物和可电离的氟化物的水溶液来生产导电性玻璃制品。美国专利4,187,336一非闪光玻璃结构
该专利叙述了用于生产无闪光的红外线反射玻璃(窗)的具有特定组成和厚度的涂层结构。这些涂层中的一层或多层可以是氧化锡。美国专利4,254,017-含硫化基的有机锡巯基链烷醇酯
该专利描述了可用作PVC稳定剂的有机锡化合物，它可由包括作为中间体或起始物的三氯单甲基锡在内的有机锡卤化物衍生而来。美国专利4,731,462-可用于形成掺氟氧化锡涂料的含氟的有机锡化合物
该专利描述了可用于产生掺氟氧化锡涂料的含氟有机锡化合物。可以三氯单甲基锡和二氯二甲基为制造含氟有机锡化合物的原料。美国专利4,584,206-浮法玻璃带材的底表面上反射膜的化学汽相积淀法
该专利描述了一种将有机锡化合物用作氧化锡涂层前体的涂覆方法。美国专利4,547,400-反射红外线的玻璃板材的制造方法
该专利描述了对某种不形成氯化钠晶体的金属氧化物密封涂层的使用。该密封涂层和最后形成的涂层是衍生自作为前体的有机锡化合物的氧化锡。美国专利5,004,490-涂有氧化锡的玻璃基片的制造方法
该专利使用了有机锡醇盐作为氧化锡的前体来产生一层氧化锡厚涂层。美国专利4,293,594-在材料上形成导电性透明涂层的方法
其中的基材是具有给定大小的玻璃管件(如荧光灯管)。透明涂层是衍生自有机锡卤化物前体的氧化锡。本发明目的
本发明目的之一是提供可用作玻璃和其它材料上的氧化锡涂层化学中间体和前体的新的、稳定的液态氯化甲基锡涂料组合物。
本发明目的之二是提供可用于玻璃瓶涂敷生产线的新型含甲基锡的组合物，其在生产线的启动阶段表现出较高的效率。
本发明的目的之三是提供新型的液态氧化锡的前体组合物，其中含有的甲基锡氯化物比起其它有机锡组合物在化学汽相积淀过程中的沉积速度更快，效率更高，而且可利用已知技术以液态组合物的形式回收和再循环。
本发明的另一目的是提供新型的含甲基锡氯化物的组合物，其在室温下(一般为24℃)是易于处理的液体。
本发明概述
就组合物而言，本发明提供了一种在24℃为液态的组合物，它主要含有一种选自三氯单甲基锡、二氯二甲基锡及其混合物的甲基锡卤化物和一种液态三氯单烷基锡。
本发明组合物具有作为生产其它已知有机锡衍生物的易于处理的中间体的固有使用特性，这些有机锡衍生物可特别用作有机聚合物的稳定剂。
本发明的组合物也是易于处理的在玻璃和其它材料上沉积氧化锡涂层的的前体。
使用本发明组合物的优点还在于，可使由于组合物中甲基锡卤化物较低的分子量而成为液态的组合物具有较高的单位重量的锡含量比。
本发明组合物是易于处理的液体，其运输和使用都较经济。
就方法而言，本发明还提供了一种在材料上沉积氧化锡涂层的改进型方法，其中的改进包括在该方法中使用了本发明的组合物。
就另一组合物而言，本发明还提供了利用本发明方法制造的制品。
在本说明和后继的权利要求中，“主要由……组成”的含义并不排除从大气中吸收的痕量水份和在本发明范围内为避免沉淀、延长保存期、降低腐蚀性和提高氧化锡沉积膜的IR反射性而可少量(至多约占总重的10％)加入组合物的各种已知助剂。
但必须排除大量的溶剂，其中包括重量含量明显高于10％的常用于溶解甲基锡氯化物的水和混合水溶液。
虽然可用水或其它溶剂在需要时稀释本发明的组合物，但“主要由……组成”一词指本发明的组合物基本不含这些溶剂。
本发明的说明
简单地混合固态甲基锡卤化物和所需的液态烷基锡卤化物，并进行必要的加热以形成溶液，由此可方便地制得本发明的组合物。
三氯单甲基锡和二氯二甲基锡都可用作在玻璃和其它基材上沉积氧化锡涂层的涂料组合物的前体，以及用作制造晶体及聚合物稳定剂的前体或中间体，它们在通常为24℃的室温下是难于处理、分装和运输的固体。
如后文实施例1至20所述，将固态三氯单甲基锡和/或二氯二甲基锡与液态三氯单烷基锡混合后形成了在24℃为液态的甲基锡氯化物组合物。这样的液体组合物较易处理、运输和使用。而且，如实施例21所示，证实了与用于在玻璃材料上沉积氧化锡涂层的标准非甲基锡类有机锡前体相比，本发明有两项优良特性，即产物的沉积速度较快，且氧化锡涂层辐射率较低。
对使用三氯单甲基锡时的24℃的液体组合物而言，三氯单甲基锡的最大含量为70％(重量)，二氯二甲基锡单独含于三氯单丁基锡中时的最大含量为10％(重量)，而与三氯单甲基锡混合时的最大含量为15％(重量)。在其它液态烷基锡卤化物中的浓度具有相似的数量级并可如本文所述方便地加以确定。
以下实施例进一步说明了发明人设计的实施其发明的最佳方式。
实施例1至20
在实施例1至20中，所用的锡化合物都是商品级的，其纯度大于等于95％。每一种锡化合物在24℃时的物理特性如下。MMTC 三氯单甲基锡 固体，MP 46℃MBTC 三氯单丁基锡 液体M2TC2 二氯二甲基锡 固体，MP 108℃MOTC 三氯单辛基锡 液体MPTC 三氯单苯基锡 液体SNCl2 氯化亚锡 固体，248℃SnG 糖氧化亚锡 固体，＞100℃
(stannous glycoxide)SnCl4 四氯化锡 液体SnO 氧化亚锡 固体，＞100℃
实施例1至20的制备是将锡化合物按表1中的重量百分比加入玻璃管形瓶中，然后加盖并振荡约3分钟。如表1所示提高温度以使之完全溶解。
最优选的是在24℃至35℃表现为完全溶解的实施例1和12。在24℃表现出部分可溶性而在50℃全溶解的实施例2、3、4、5、10和13也属优选之列。实施例6、7、8、9和14表明即使二氯二甲基锡或三氯单辛基锡的含量很高，仍可在低于100℃时制得液体产物。
实施例15和16表明了由于三氯单甲基锡与芳基锡化合物，三氯单苯基锡反应或再分配而造成的本发明对烷基锡化合物的限制。
实施例17至20进一步表明由于在有机锡氯化物的液体混合物中被测无机锡化合物的不溶性，或者由于四氯化锡与有机锡氯化物的反应，而造成了对本发明的限制。
令每一种液体产物经受三次冻融循环来证实其稳定性。完全溶解指在冻融试验后液态产物完全是液体。部分溶解指甲基锡氯化物的大部分在溶液相中而余下部分分散在三氯单甲基锡中。
除了加速冻融试验外，还在室温下对优选组合物进行了保存稳定性试验，50/50(重量/重量百分比)的三氯单甲基锡/三氯单丁基锡保存24个月。在封存于玻璃容器中进行保存后，样品未发生变质。
表1
| 实施例 | 锡化合物，重量％ | 溶解度 | ||||||||||
| MMTC | MBTC | M2TC2 | MOTC | MPTC | SnCl2 | SnO | SnG | SnCl4 | 24℃ | 50℃ | 75℃ | |
| 1 | 50 | 50 | 完全 | |||||||||
| 2 | 70 | 30 | 部分 | 完全 | ||||||||
| 3 | 60 | 40 | 部分 | 完全 | ||||||||
| 4 | 37.5 | 50 | 12.5 | 部分 | 完全 | |||||||
| 5 | 45 | 40 | 15 | 部分 | 完全 | 完全 | ||||||
| 6 | 50 | 50 | 不溶 | 部分 | 完全 | |||||||
| 7 | 60 | 40 | 不溶 | 部分 | 完全 | |||||||
| 8 | 67 | 33 | 不溶 | 部分 | 完全 | |||||||
| 9 | 75 | 25 | 不溶 | 部分 | 完全 | |||||||
| 10 | 80 | 20 | 不溶 | 完全 | ||||||||
| 11 | 90 | 10 | 部分 | 完全 | ||||||||
| 12 | 50 | 50 | 部分 | 完全(35℃) | ||||||||
| 13 | 70 | 30 | 部分 | 完全 | ||||||||
| 14 | 40 | 60 | 部分 | 部分 | 完全 | |||||||
| 15 | 60 | 40 | 不溶 | 反应 | ||||||||
| 16 | 50 | 50 | 部分 | 反应 | ||||||||
| 17 | 50 | 25 | 25 | 不溶 | 不溶 | 不溶 | ||||||
| 18 | 25 | 50 | 25 | 不溶 | 不溶 | 不溶 | ||||||
| 19 | 25 | 50 | 25 | 不溶 | 不溶 | 不溶 | ||||||
| 20 | 25 | 50 | 25 | 反应 | - | - |
实施例21
加入5％(重量)三氟乙酸和5％(重量)甲基异丁酮以进一步改性优选实施例1的组合物(50％(重量)三氯单甲基锡/50％(重量)三氯单丁基锡)后，经鉴定为CFMB。如美国专利4,601,917所述，对该物质作为热化学汽相沉淀涂覆玻璃法中的氧化锡前体进行评价。在同一专利中描述了所用的设备和步骤。作为对照组合物，通过加入5％(重量)三氟乙酸和5％(重量)甲基异辛酮来改性三氯单甲基锡并标示为CFB。用美国专利4,601,917所揭示的方法测定沉积速度和涂覆后的玻璃的辐射率，结果如下。
沉积速度(埃/秒) 辐射率
CFMB 533 0.39
CFB 461 0.41
CFMB具有较高的沉积速度，约高出15％，这是较为理想的，因为这样可在给定的涂覆时间内产生较厚的涂层。
较低的辐射率也是较为理想的，其部分原因是涂层的厚度，涂有CFMB的试样的厚度为1951埃，涂有CFB的试样为1837埃。用CFMB和CFB涂覆的玻璃试样的外观相同。在热化学汽相积淀法中，较快的沉积速度还可以加快平衡态的获得，从而减少启动时的报废率。
实施例22
如由America Chemical Society出版的1960年10月的Chemi-cal Reviews中，Robert Ingham、Sanders Rosenberg和HenryGilman的“有机锡化合物”中所述，采用本发明的甲基锡氯化物/三氯单烷基锡混合溶液可制备聚氯乙烯的热稳定剂。在将50/50(重量/重量)的三氯甲基锡/三氯单丁基锡用作原料之一时，首先要用氢氧化铵将其中和成可纯化、分离和干燥的甲基锡酸和丁基锡酸的混合物。或者通过与化学计算当量的巯基乙酸异辛酯的反应将混合锡酸转化成巯基乙酸单甲基锡三异辛酯和巯基乙酸单丁基锡三异辛酯的混合物。通常在聚氯乙烯中加入1％的该稳定剂来防止热处理过程中的降解。
实施例23
纯化、分离和干燥后的实施例22中的甲基锡酸(酸酐)/丁基锡酸(酸酐)混合物是有效的酯化反应催化剂。使用0.2％化学计量的邻苯二甲酸酐/异辛醇的混合物，可在低温下快速生成邻苯二甲酸二辛酯。
Claims (9)
1.一种24℃的组合物液体，其特征在于，它主要由选自三氯单甲基锡、二氯二甲基锡及其混合物的甲基锡卤化物和在25℃为液态的三氯烷基锡组成。
2.根据权利要求1所述的组合物，其特征还在于，其中的三氯烷基锡选自三氯单丁基锡、三氯单辛基锡及其混合物。
3.根据权利要求1所述的组合物，其特征还在于，其中的三氯烷基锡是三氯单丁基锡。
4.根据权利要求1所述的组合物，其特征还在于，其中的甲基锡卤化物为三氯单甲基锡。
5.根据权利要求1所述的组合物，其特征还在于，其中的甲基锡卤化物是三氯单甲基锡，而其中的三氯烷基锡是三氯单丁基锡。
6.在某种基材上高温沉积氧化锡涂层的改良方法，其特征在于，其中的改进之处在于在这种方法中使用了如权利要求1所述的组合物。
7.根据权利要求6所述的方法，其特征在于，其中沉积上的涂层中含有可降低红外线辐射率的成份。
8.一种采用权利要求6所述的方法生产的产品。
9.一种采用权利要求7所述的方法生产的产品。
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| US6238734B1 (en) * | 1999-07-08 | 2001-05-29 | Air Products And Chemicals, Inc. | Liquid precursor mixtures for deposition of multicomponent metal containing materials |
| US6503561B1 (en) * | 1999-07-08 | 2003-01-07 | Air Products And Chemicals, Inc. | Liquid precursor mixtures for deposition of multicomponent metal containing materials |
| US20070194470A1 (en) * | 2006-02-17 | 2007-08-23 | Aviza Technology, Inc. | Direct liquid injector device |
| US20080026147A1 (en) * | 2006-07-28 | 2008-01-31 | Gulbrandsen Chemicals, Inc. | Method and formulation for depositing a metal-containing coating on a substrate |
| US20080152804A1 (en) * | 2006-07-28 | 2008-06-26 | Gulbrandsen Chemicals, Inc. | Method for depositing a metal-containing coating on a substrate |
| US7947374B2 (en) * | 2009-02-19 | 2011-05-24 | Guardian Industries Corp. | Coated article with sputter-deposited transparent conductive coating capable of surviving harsh environments, and method of making the same |
| US8097342B2 (en) | 2009-02-19 | 2012-01-17 | Guardian Industries Corp. | Coated article with sputter-deposited transparent conductive coating capable of surviving harsh environments, and method of making the same |
| US20100209730A1 (en) * | 2009-02-19 | 2010-08-19 | Guardian Industries Corp., | Coated article with sputter-deposited transparent conductive coating for refrigeration/freezer units, and method of making the same |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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Family Cites Families (16)
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| US2566346A (en) * | 1948-09-08 | 1951-09-04 | Pittsburgh Plate Glass Co | Electroconductive products and production thereof |
| GB1520124A (en) * | 1974-09-18 | 1978-08-02 | M & T Chemicals Inc | Process for applying stannic oxide coatings to glass |
| IT1024841B (it) * | 1974-11-18 | 1978-07-20 | Olivetti Ing C S P A | Cartuccia per un nastro inchiostra to senza fine di macchine per ufficio soriventi |
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| US4187336A (en) * | 1977-04-04 | 1980-02-05 | Gordon Roy G | Non-iridescent glass structures |
| US4254017A (en) * | 1978-11-13 | 1981-03-03 | M&T Chemicals Inc. | Organotin mercaptoalkanol esters and alkoxides containing sulfide groups |
| JPS5714594A (en) * | 1980-06-30 | 1982-01-25 | Adeka Argus Chem Co Ltd | Preparing process for mixture of dimethyltin dichloride with monomethyltin trichloride |
| US4530857A (en) * | 1983-05-13 | 1985-07-23 | M&T Chemicals Inc. | Glass container hot end coating formulation and method of use |
| US4731256A (en) * | 1984-04-10 | 1988-03-15 | M&T Chemicals Inc. | Liquid coating composition for producing high quality, high performance fluorine-doped tin oxide coatings |
| US4584206A (en) * | 1984-07-30 | 1986-04-22 | Ppg Industries, Inc. | Chemical vapor deposition of a reflective film on the bottom surface of a float glass ribbon |
| US4590096A (en) * | 1984-12-28 | 1986-05-20 | M&T Chemicals Inc. | Water vapor, reaction rate and deposition rate control of tin oxide film by CVD on glass |
| US4547400A (en) * | 1985-02-25 | 1985-10-15 | Ford Motor Company | Method of making infrared reflective glass sheet-I |
| US4731462A (en) * | 1986-07-18 | 1988-03-15 | M&T Chemicals Inc. | Organotin compounds containing fluorine useful for forming fluorine-doped tin oxide coating |
| US5004490A (en) * | 1987-08-10 | 1991-04-02 | Ford Motor Company | Method of making glass substrate coated with tin oxide |
| US5090985A (en) * | 1989-10-17 | 1992-02-25 | Libbey-Owens-Ford Co. | Method for preparing vaporized reactants for chemical vapor deposition |
| US5725904A (en) * | 1995-06-02 | 1998-03-10 | Elf Atochem North America, Inc. | Liquid methyltin halide compositions |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4293594A (en) * | 1980-08-22 | 1981-10-06 | Westinghouse Electric Corp. | Method for forming conductive, transparent coating on a substrate |
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| DK0745605T3 (da) | 2003-08-18 |
| BR9602525A (pt) | 1998-10-27 |
| CO4560462A1 (es) | 1998-02-10 |
| ES2191725T3 (es) | 2003-09-16 |
| CZ161096A3 (en) | 1996-12-11 |
| CN1147024A (zh) | 1997-04-09 |
| US5853799A (en) | 1998-12-29 |
| CA2175953A1 (en) | 1996-12-03 |
| IN187865B (zh) | 2002-07-13 |
| KR100407420B1 (ko) | 2004-04-09 |
| EP0745605A3 (en) | 1999-03-17 |
| EP0745605A2 (en) | 1996-12-04 |
| EP0745605B1 (en) | 2003-04-23 |
| JPH08333376A (ja) | 1996-12-17 |
| AU701688B2 (en) | 1999-02-04 |
| CZ292143B6 (cs) | 2003-08-13 |
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