CN1051088C - 含氟有机锡化合物的制备方法 - Google Patents
含氟有机锡化合物的制备方法 Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 4
- 150000002894 organic compounds Chemical class 0.000 title description 2
- 150000002222 fluorine compounds Chemical group 0.000 title 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 12
- -1 fluorine ester Chemical class 0.000 claims description 11
- MQGQDVQLYCVWNW-UHFFFAOYSA-L C(CCC)[Sn](Cl)Cl.FC(C(=O)O)(F)F Chemical compound C(CCC)[Sn](Cl)Cl.FC(C(=O)O)(F)F MQGQDVQLYCVWNW-UHFFFAOYSA-L 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ORKZCBYLJXXOFZ-UHFFFAOYSA-N [Sn].C(CCC)(=O)Cl Chemical compound [Sn].C(CCC)(=O)Cl ORKZCBYLJXXOFZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005466 alkylenyl group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 12
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- GGBFOKTZTGOTFG-UHFFFAOYSA-K [butyl(dichloro)stannyl] 2,2,2-trifluoroacetate Chemical compound CCCC[Sn](Cl)(Cl)OC(=O)C(F)(F)F GGBFOKTZTGOTFG-UHFFFAOYSA-K 0.000 abstract 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QYFZCTDKWGVUIO-UHFFFAOYSA-N [Cl].[Sn] Chemical compound [Cl].[Sn] QYFZCTDKWGVUIO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FQDXJYBXPOMIBX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methylpropan-2-ol Chemical compound FC(F)(F)C(O)(C)C(F)(F)F FQDXJYBXPOMIBX-UHFFFAOYSA-N 0.000 description 1
- GILIYJDBJZWGBG-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-ol Chemical compound CC(O)C(F)(F)F GILIYJDBJZWGBG-UHFFFAOYSA-N 0.000 description 1
- KUQVFOOAIOMQOT-UHFFFAOYSA-N 2-methylpropyltin Chemical compound CC(C)C[Sn] KUQVFOOAIOMQOT-UHFFFAOYSA-N 0.000 description 1
- PLOURCGNBMFHHN-UHFFFAOYSA-N C(C)OC(=O)[Sn]CC Chemical compound C(C)OC(=O)[Sn]CC PLOURCGNBMFHHN-UHFFFAOYSA-N 0.000 description 1
- HCFQYBRLTOGLPO-UHFFFAOYSA-N C(CCC)[Sn]CCCC.[Cl] Chemical compound C(CCC)[Sn]CCCC.[Cl] HCFQYBRLTOGLPO-UHFFFAOYSA-N 0.000 description 1
- YAHXVBPQGLKXHK-UHFFFAOYSA-N CCCC(=O)Cl.[F] Chemical compound CCCC(=O)Cl.[F] YAHXVBPQGLKXHK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LGEOOMQHCBKWTM-UHFFFAOYSA-N FC(C(=O)OC(C(F)F)=O)F.[Cl] Chemical compound FC(C(=O)OC(C(F)F)=O)F.[Cl] LGEOOMQHCBKWTM-UHFFFAOYSA-N 0.000 description 1
- DXAOXPFFQPRUGW-UHFFFAOYSA-N FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl Chemical compound FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl DXAOXPFFQPRUGW-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical group FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- PZSXCNWLLFEOPM-UHFFFAOYSA-N [F].C(CC)(=O)O Chemical compound [F].C(CC)(=O)O PZSXCNWLLFEOPM-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AFOLZIVGFUUSMF-UHFFFAOYSA-K butyl(dichloro)stannanylium;acetate Chemical compound CCCC[Sn](Cl)(Cl)OC(C)=O AFOLZIVGFUUSMF-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- WBDIPKJFSYOAHL-UHFFFAOYSA-L dichloro(phenyl)tin Chemical compound Cl[Sn](Cl)C1=CC=CC=C1 WBDIPKJFSYOAHL-UHFFFAOYSA-L 0.000 description 1
- GXWLHTAAGCHDAV-UHFFFAOYSA-L dichloro-bis(2-methylpropyl)stannane Chemical compound CC(C)C[Sn](Cl)(Cl)CC(C)C GXWLHTAAGCHDAV-UHFFFAOYSA-L 0.000 description 1
- PEGCFRJASNUIPX-UHFFFAOYSA-L ditert-butyltin(2+);dichloride Chemical compound CC(C)(C)[Sn](Cl)(Cl)C(C)(C)C PEGCFRJASNUIPX-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UYCAUPASBSROMS-UHFFFAOYSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-]C(=O)C(F)(F)F UYCAUPASBSROMS-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
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- 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
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- A—HUMAN NECESSITIES
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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Abstract
本发明涉及特别适用于以化学蒸汽沉积法形成掺氟氧化锡涂层的含氟有机锡化合物。在优先实施的方案中使用的化合物是三氟乙酸一丁基二氯锡，它是由三氯化一丁基锡和三氯乙酸反应制得的。
Description
本发明涉及可用于形成掺氟氧化锡涂层的含氟有机锡化合物。
下面是些介绍与本发明中有机锡化合物有关的化合物的先有技术文献。但是文献中的化合物不具有用化学蒸汽沉积法形成液体涂料组合物所要求的性质。
门克(Menke)在美国专利3,759,743中介绍了非卤化三氟乙酸有机锡的制备，以及将组合物溶于诸如丁酮的有机溶剂中、用喷液法形成掺氟氧化锡涂层。但是这些化合物挥发性低并且不适用于不添加溶剂的、较便利的化学蒸汽沉积法。
在《化学通讯》(Chemical Communications)(1970年)第151页及《有机金属化学》杂志(Organomet.Chem.)38卷287页(1972年)作者王(Wang)和施里夫(Shreeve)介绍了三氟乙酸二烷基氯锡的制备。遗憾的是这类化合物都是不能适用于化学蒸汽沉积法的固体。
在美国专利4,093,636中，博斯特(Bost)等介绍了有关的非氟化有机锡化合物，这些化合物不能用来形成掺氟氧化锡涂层。
在美国专利4,374,778中，普卢姆(Plum)等透露了氟原子直接与锡原子键合的含氟有机锡化合物。
在美国专利4,254,046中，弗朗兹(Franz)等透露了用于粉末沉积法形成掺氟氧化锡涂层的二氟二烷基锡。
在法国专利1,400,314中汤普森(Thompson)介绍了三氟乙酸一、二和三烷基锡及其制备。
在《有机制备及方法》(Organic Preparation and Procedures)1卷3期第173～176页上(1969)利伯蒂(Liberte)，赖夫(Reiff)及戴维森(Davidsohn)介绍了多氟羧酸二烷基锡。
在《有机金属化学》(Organomet，Chem.)杂志第3期151页(1970)一篇论文中介绍了三氟乙酸甲酯二烷基氯锡。
在《有机金属化学》杂志3972(1972)上介绍了三烷基锡全氟烷基氧化物。
这些文献没有透露一种可适用于特别是由液体涂料组合物进行化学蒸汽沉积的有机锡前体，而且，文献中没有透露一种带有一烷基(或有关的取代基)以及至少带有一个直接与锡原子连接的氯原子、并至少带有一种含三氟甲基成分的有机锡化合物。
因此，本发明的一个目的是要提供改进型的新有机锡化合物，它们可以直接用来形成具有薄层电阻小的掺氟氧化锡涂层。
另一个目的是要提供这样一些化合物，它们可用于以化学蒸汽沉积法来制作掺氟氧化锡涂层。
再有一个目的是要制备三氟乙酸一烷基氯锡及有关化合物。这些物质能方便地在化学蒸汽沉积法形成掺氟氧化锡涂层所用的液体涂料中使用。
本发明中的含氟有机化合物一般分子式为：
式中R＝C1～C6烷基；芳基；或烷酯基烷基；
a＝0，1；b＝1，2，3；c＝0，1；d＝0，1；e＝0-2；f＝1，2和n＝1-6；a+b+c+d＝4。
下列表1概述了属于此一般分子式范围的a、b、c、f、d、e和n的每一种情况、本发明中用的各种化合物。在制备此类化合物中使用的反应剂在此也一并列出。
| 编号abcfden | 化合物 | 起始物 | |
| 有机锡化合物 | 氟化合物 | ||
| 1 11020022 11020043 11021014 11021025 11021046 11020247 11021148 11110029 111100410 111100111 111110212 111110413 111102414 1111114 | R-Sn(Cl)(OC2F5)2R-Sn(Cl)(OC4F9)2R-Sn(Cl)(OCOCF3)2R-Sn(Cl)(OCOC2F5)2R-Sn(Cl)(OCOC4F9)2R-Sn(Cl)(OCH2CH2C4F9)2R-Sn(Cl)(OCOCH2C4F9)2R-Sn(Cl)(OCOCH3)(OC2F5)R-Sn(Cl)(OCOCH3(OC4F9)R-Sn(Cl)(OCOCH3)(OCOCF3)R-Sn(Cl)(OCOCH3)(OCOC2F5)R-Sn(Cl)(OCOCH3)(OCOC4F9)R-Sn(Cl)(OCOCH3)(OCH2CH2C4F9R-Sn(Cl)(OCOCH3(OCOCH2C4F9) | 1 R-SNCl3+2-OC2F51 R-SnCl3+2-OC2F91 R-SnCl3+2-OCOCF31 R-SnCl3+2-OCOC2F51 R-SnCl3+2-OCOC4F91 R-SnCl3+2-OCH2CH2C4F91 R-SnCl3+2-OCOCH2C4F91 R-SnCl3+1-OC2F51 R-SnCl3+1-OC4F91 R-SnCl3+1-OCOCF31 R-SnCl3+1-OCOC2F51 R-SnCl3+1-OCOC4F91 R-SnCl3+1-OCH2CH2C4F91 R-SnCl3+1-OCOCH2C4F9+1-OCOCH3 | +1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3 |
| 编号abcfden | 化合物 | 起始物 | |
| 有机锡化合物 | 氟化合物 | ||
| 15 120100216 120100417 120100118 120100219 120100420 120102421 120101422 030100223 030100424 030110125 030110226 030110427 030102428 0301114 | R-Sn(Cl)2(OC2F5)R-Sn(Cl)2(OC4F9)R-Sn(Cl)2(OCOCF3)R-Sn(Cl)2(OCOC2F5)R-Sn(Cl)2(OCOC4F9)R-Sn(Cl)2(OCH2CH2C4F9)R-Sn(Cl)2(OCOCH2C4F9)(Cl)3-Sn(OC2F5)(Cl)3-Sn(OC4F9)(Cl)3-Sn(OCOCF3)(Cl)3-Sn(OCOC2F5)(Cl)3-Sn(OCOC4F9)(Cl)3-Sn(OCH2CH2C4F9)(Cl)3-Sn(OCOCH2C4F9) | 1 R-SnCl3+1-OC2F51 R-SnCl3+1-OC4F91 R-SnCl3+1-OCOCF31 R-SnCl3+1-OCOC2F51 R-SnCl3+1-OCOC4F91 R-SnCl3+1-OCH2CH2C4F91 R-SnCl3+1-OCOCH2C4F91 SnCl4+1-OC2F51 SnCl4+1-OC4F91 SnCl4+1-OCOCF51 SnCl4+1-OCOC2F51 SnCl4+1-OCOC4F91 SnCl4+1-OCH2CH2C4F91 SnCl4+1-OCOCH2C4F9 | |
| 编号abcfden | 化合物 | 起始物 | |
| 有机锡化合物 | 氟化合物 | ||
| 29 020200230 020200431 020210132 020210233 020210434 020202435 020211436 021100237 021100438 021110139 021110240 021110441 0211024 | (Cl)2-Sn(OC2F5)2(Cl)2-Sn(OC2F5)2)(Cl)2-Sn(OCOCF3)2(Cl)2-Sn(OCOC2F5)2(Cl)2-Sn(OCOC4F9)2(Cl)2-Sn(OCH2CH2C4F9)2(Cl)2-Sn(OCOCH2C4F9)2(Cl)2-Sn(OCOCH3)(OC2F5)(Cl)2-Sn(OCOCH3)(OC4F9)(Cl)2-Sn(OCOCH3)(OCOCF3)(Cl)2-Sn(OCOCH3)(OCOC2F5)(Cl)2-Sn(OCOCH3)(OCOC4F9)(Cl)2-Sn(OCOCH3)(OCH2CH2C4F9) | 1 SnCl4+l-OC2F51 SnCl4+1-OC4F91 SnCl4+2-OCOCF31 SnCl4+2-OCOC2F51 SnCl4+2-OCOC4F91 SnCl4+2-OCH2CH2C4F91 SnCl4+2-OCOCH2C4F91 SnCl4+1-OC2F51 SnCl4+1-OC4F91 SnCl4+1-OCOCF31 SnCl4+1-OCOC2F51 SnCl4+1-OCOC4F91 SnCl4+1-OCH2CH2C4F9 | +1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3 |
| 编号abcfden | 化合物 | 起始物 | |
| 有机锡化合物 | 氟化合物 | ||
| 42 021111443 011200244 011200445 011200146 011200247 011200448 011202449 0112014 | (Cl)2-Sn(OCOCH3)(OCOCH2C4F9)Cl-Sn(OCOCH3)(OC2F5)2Cl-Sn(OCOCH3)(OC4F9)2Cl-Sn(OCOCH3)(OCOCF3)2Cl-Sn(OCOCH3)(OCOC2F5)2Cl-Sn(OCOCH3)(OCOC4F9)2Cl-Sn(OCOCH3)(OCH2CH2C4F9)2Cl-Sn(OCOCH3)(OCOCH2C4F9)2 | 1 SnCl4+1-OCOCH2C4F91 SnCl4+2-OC2F51 SnCl4+2-OC4F91 SnCl4+2-OCOCF31 SnCl4+2-OCOC2F51 SnCl4+2-OCOC4F91 SnCl4+2-OCH2CH2C4F91 SnCl4+2-OCOCH2C4F9 | +1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3+1-OCOCH3 |
所以，本发明优先选用的化合物有：
化合物 分子式1.三氟乙酸丁基二氯锡 C4H9Cl2SnOCOCF32.二-三氟乙酸丁基氯锡 C4H9ClSn(OCOCF3)23.乙酸基三氟乙酸丁基氯锡C4H9ClSn(OCOCH3)(OCOCF3)4.三氟乙酸乙酯基次乙基二CH3CH2OCOCH2CH2Cl2Sn(OCOCF3)氯锡5.三氟乙醇丁基二氯锡 C4H9Cl2SnOCH2CF36.三氟乙酸三氯锡 SnCl3OCOCF3本发明中的化合物可按下述制备。一般反应过程RaSnClb+1(OCOCH3)c+〔O(CO)d(CH2)e(CnF2n+1〕fM+回流加热------→RaSnClb(OCOCH3)c〔O(CO)d(CH2)e(CnF2n+1)〕f+M+Cl-
式中M+是阳离子。
这里所用术语“烷基”包括1到6个碳原子的直链和支链烷基。
这里所用术语“有机锡”包括四氯化锡。
因此，本发明中制备此类化合物所用的代表性有机反应剂有：三氯化一丁基锡，三氯化异丁基锡，三氯化甲基锡，二氯化二丁基锡，二氯化二异丁基锡，二氯化二叔丁基锡，乙酸丁基二氯锡和三氯化乙酯基乙基锡，以及四氯化锡。
含氟反应剂带有三氟甲基团，该基团位于碳与氧键合的官能团之α或β位置上。此类反应剂选自羧酸、酸酐、酰基囟或醇。因此，合适的含氟反应剂包括如下几种：羧酸 酸酐三氟乙酸 三氟醋酐氯二氟乙酸 七氟丁酐二氟乙酸 五氟丙酐七氟丁酸 氯二氟醋酐五氟丙酸 全氟戊二酐3-三氟甲基丁烯酸 全氟丁二酐九氟戊酸酰鹵七氟丁酰氯全氟戊二酰氟全氟辛酰氯全氟丁二酰氯醇2，2，2-三氟乙醇1H，1H-七氟丁醇-13，3，4，4，5，5，5-七氟戊醇-2七氟异丙醇六氟-2-甲基异丙醇1H，1H，5H-八氟-1-戊醇
全氟叔丁醇
2-三氟甲基丙醇-2
1，1，1-三氟丙醇-2
全氟乙醇
在本发明的优先具体实施方案中，将三氯化一丁基锡与三氟乙酸盐反应形成三氟乙酸丁基二氯锡。
本发明通过下列实例加以说明。
实例1
三氯化一丁基锡与三氟乙酸反应制备三氟乙酸一丁基二氯锡
A.将氢氧化钾(2.08g，0.03摩尔)溶于水(15毫升)中并加入三氟乙酸〔3.42g，0.03摩尔，28.8％(重量百分数)〕；另外单独将三氯化一丁基锡〔8.46g，0.03摩尔，71.2％(重量)〕，醚(50毫升)和丁酮(50毫升)混在一起并加入转相催化剂C16H33(CH3)3N+Br-(0.1g)；然后将第二种溶液加到第一种溶液中，加热回流同时在氮气层下搅拌。在48℃下回流加热2小时。
静置一夜以后生成水相和有机相，水相清澈无色在下层，上层是清澈黄色的有机相。将此有机相浓缩，残余物在真空干燥器内放置一夜，得到9.60克棕色、粘性液体产品-三氟乙酸一氯二丁基锡(89％产率)。分析：Sn 33％，实际为36％； Cl 20％，实际为21％。
B.将三氯化一丁基锡(200g，0.7摩尔)与三氟乙酸钠盐(10g，0.07摩尔)的混合物在70℃加热3小时，并在室温下静置一夜。将副产物氯化钠和未反应的钠盐过滤掉。所得液体涂料组合物中含有大约12％(重量)的三氟乙酸一丁基二氯锡及88％(重量)的三氯化一丁基锡。
实例2
一苯基二氯氢氧化锡与三氟乙酸反应制备三氟乙酸一苯基二氯锡
按实例1 将一苯基三氯氢氧化锡(9.0g，0.03摩尔)与三氟乙酸(3.42g，0.03摩尔)混合并回流加热2小时。所希望的产品产率为81％。
实例3
使用三氟乙酸的铵盐重复实例2实验，得到类似结果。
实例4
制作掺氟氧化锡涂层
用实例1B的液体涂料组合物以化学蒸汽沉积法在玻璃上制作掺氟氧化锡涂层，在650℃含水大气气氛中经2秒钟沉积便获得200纳米厚的透明无混浊的涂层。薄层电阻大约为每平方40欧姆；红外线反射率大于70％(在10微米)；可见光透射率大于70％。
Claims (4)
1.一种制备下式含氟酯的方法其中R是C4-6的烷基或苯基，
a＝1，
b＝1，2
c＝1.2
其中当b是1时，c是2或b是2时，c是1；所述的方法包括在热回流下将下式化合物
其中R，a，b，c定义同上，d是0或1且d是1时，R为苯基与下式化合物反应：
其中M+是阳离子。
2.根据权利要求1的制备方法，其中化合物为三氟乙酸丁基二氯锡。
3.根据权利要求1的制备方法，其中化合物为三氟乙酸苯基二氯锡。
4.根据权利要求1的制备方法，其中化合物为双-三氟乙酸丁基氯锡。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US888,298 | 1986-07-18 | ||
| US06/888,298 US4731462A (en) | 1986-07-18 | 1986-07-18 | Organotin compounds containing fluorine useful for forming fluorine-doped tin oxide coating |
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| Publication Number | Publication Date |
|---|---|
| CN87104911A CN87104911A (zh) | 1988-05-11 |
| CN1051088C true CN1051088C (zh) | 2000-04-05 |
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| CN87104911A Expired - Fee Related CN1051088C (zh) | 1986-07-18 | 1987-07-17 | 含氟有机锡化合物的制备方法 |
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| Country | Link |
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| US (1) | US4731462A (zh) |
| EP (1) | EP0318486B1 (zh) |
| JP (1) | JPH02500974A (zh) |
| KR (1) | KR900003453B1 (zh) |
| CN (1) | CN1051088C (zh) |
| AT (1) | ATE63918T1 (zh) |
| AU (1) | AU609734B2 (zh) |
| BR (1) | BR8707749A (zh) |
| CA (1) | CA1276160C (zh) |
| DE (1) | DE3770472D1 (zh) |
| DK (1) | DK167875B1 (zh) |
| EG (1) | EG19792A (zh) |
| ES (1) | ES2007080A6 (zh) |
| IL (1) | IL83178A (zh) |
| IN (1) | IN168762B (zh) |
| NO (1) | NO171068C (zh) |
| TR (1) | TR24843A (zh) |
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| DE4325648C1 (de) * | 1993-07-30 | 1994-09-08 | Goldschmidt Ag Th | Alkylzinnverbindungen, deren Herstellung und diese enthaltende Mittel zur Bildung elektrisch leitfähiger und IR-reflektierender Schichten auf Oberflächen von Glas, Glaskeramik oder Email |
| DE4433206A1 (de) * | 1994-09-17 | 1996-03-21 | Goldschmidt Ag Th | Verfahren zur pyrolytischen Beschichtung von Glas-, Glaskeramik- und Emailprodukten |
| US5725904A (en) * | 1995-06-02 | 1998-03-10 | Elf Atochem North America, Inc. | Liquid methyltin halide compositions |
| US5698262A (en) * | 1996-05-06 | 1997-12-16 | Libbey-Owens-Ford Co. | Method for forming tin oxide coating on glass |
| FR2795745B1 (fr) * | 1999-06-30 | 2001-08-03 | Saint Gobain Vitrage | Procede de depot d'une couche a base de tungstene et/ou de molybdene sur un substrat verrier, ceramique ou vitroceramique, et substrat ainsi revetu |
| EP1555696B1 (en) | 2002-10-25 | 2010-12-15 | Nakajima Glass Co., Inc. | Solar battery module manufacturing method |
| WO2005104242A1 (ja) * | 2004-04-27 | 2005-11-03 | Nakajima Glass Co., Inc. | 太陽電池モジュールの製造方法 |
| 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 |
| 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 |
| 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 |
| US9625723B2 (en) * | 2013-06-25 | 2017-04-18 | Microsoft Technology Licensing, Llc | Eye-tracking system using a freeform prism |
| US10228561B2 (en) * | 2013-06-25 | 2019-03-12 | Microsoft Technology Licensing, Llc | Eye-tracking system using a freeform prism and gaze-detection light |
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| DE1495783A1 (de) * | 1964-03-07 | 1969-04-03 | Hoechst Ag | Verfahren zur Herstellung von Polyaethylenterephthalat |
| US3836444A (en) * | 1968-10-01 | 1974-09-17 | Inst Francais Du Petrole | Process for polymerizing conjugated diolefins using organic compounds of the transition metals as catalysts |
| US3781315A (en) * | 1971-07-09 | 1973-12-25 | Prod Res & Chem Corp | Halo alkoxy metal compounds |
| US3775453A (en) * | 1972-03-14 | 1973-11-27 | Schaper | Preparation of hexafluoroisopropoxides of aluminum and group iv elements |
| DE3010077C2 (de) * | 1980-03-15 | 1981-07-30 | Vereinigte Glaswerke Gmbh, 5100 Aachen | Verfahren zum Aufbringen von mit einem Halogen, vorzugsweise mit Fluor dotierten Zinnoxidschichten auf Glasoberflächen durch Pyrolyse |
-
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Also Published As
| Publication number | Publication date |
|---|---|
| DK167875B1 (da) | 1993-12-27 |
| JPH0575756B2 (zh) | 1993-10-21 |
| KR880701724A (ko) | 1988-11-04 |
| CN87104911A (zh) | 1988-05-11 |
| EP0318486B1 (en) | 1991-05-29 |
| US4731462A (en) | 1988-03-15 |
| AU7783787A (en) | 1988-02-10 |
| DK137088D0 (da) | 1988-03-11 |
| WO1988000588A1 (en) | 1988-01-28 |
| EG19792A (en) | 1996-02-29 |
| CA1276160C (en) | 1990-11-13 |
| DK137088A (da) | 1988-03-11 |
| NO881186L (no) | 1988-03-17 |
| NO171068C (no) | 1993-01-20 |
| BR8707749A (pt) | 1989-08-15 |
| ES2007080A6 (es) | 1989-06-01 |
| IL83178A (en) | 1992-02-16 |
| TR24843A (tr) | 1992-06-19 |
| KR900003453B1 (ko) | 1990-05-19 |
| IN168762B (zh) | 1991-06-01 |
| JPH02500974A (ja) | 1990-04-05 |
| IL83178A0 (en) | 1987-12-31 |
| ZA875095B (en) | 1988-01-13 |
| NO171068B (no) | 1992-10-12 |
| EP0318486A1 (en) | 1989-06-07 |
| AU609734B2 (en) | 1991-05-09 |
| DE3770472D1 (de) | 1991-07-04 |
| NO881186D0 (no) | 1988-03-17 |
| ATE63918T1 (de) | 1991-06-15 |
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