CN1169816C - 一种制备含硫和磷的有机硅化合物的方法 - Google Patents
一种制备含硫和磷的有机硅化合物的方法 Download PDFInfo
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- CN1169816C CN1169816C CNB001326333A CN00132633A CN1169816C CN 1169816 C CN1169816 C CN 1169816C CN B001326333 A CNB001326333 A CN B001326333A CN 00132633 A CN00132633 A CN 00132633A CN 1169816 C CN1169816 C CN 1169816C
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- 238000000034 method Methods 0.000 title claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 9
- 239000011574 phosphorus Substances 0.000 title claims description 9
- 239000005864 Sulphur Substances 0.000 title 1
- 150000003961 organosilicon compounds Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 2
- 150000004756 silanes Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical class CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- ITRFOBBKTCNNFN-UHFFFAOYSA-N tris(sulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound SP(S)(S)=S ITRFOBBKTCNNFN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
本发明涉及一种制备下式所示的含硫和磷的化合物的方法：[Rn 1(R2O)3-n-Si-Alk-S-]3P＝S。它是用式为Rn 1(R2O)3-n-Si-Alk-Hal、含卤素的硅烷与五硫化二磷(P4S10)和金属硫化物反应制得。
Description
技术领域
本发明涉及一种制备含硫和磷的有机硅化合物的方法。
背景技术
DE 2658368C2公开了一种如下式所示的化合物：
[R1 n(R2O)3-n-Si-Alk-S-]3P＝S
式中，Alk表示具有2-4个碳原子的亚烷基，R1、R2表示具有1-5个碳原子的烷基、5-8个碳原子的环烷基、苯基、苄基或者2-甲氧基乙基，其中R1或R2在每种情况下可以相同，也可以不同，n＝0、1或2。制备这类化合物时，采用硫代磷酰氯或三溴硫化磷与化学式如下的巯基硅烷反应：
R1 n(R2O)3-n-Si-Alk-SH
式中，各基团所代表的意义与上面提到的各基团相同。
巯基硅烷是昂贵的起始化合物，因为一般来说，它们是由相应的氯代硅烷制得的(EP 471 164 B1、DE-AS 20 35 619、DE-PS 33 46 910、US-PS 3 849 471、GB-PS 1 102 251)。
这些已知方法的缺点是，在制备上面提到的含磷化合物时，采用昂贵的巯基硅烷作为离析物。
发明内容
本发明的目的就是提供制备含硫和磷的有机硅化合物的替代方法。
本发明提供了一种制备下式所示的含硫和磷的化合物的方法：
[R1 n(R2O)3-n-Si-Alk-S-]3P＝S
式中，Alk表示具有1-10个碳原子的亚烷基，R1、R2表示具有1-5个碳原子的烷基、5-8个碳原子的环烷基、苯基、苄基或者2-甲氧基乙基，其中R1或R2在每种情况下可以相同，也可以不同，n＝0、1或2，该方法的特征在于，采用下式所示的含卤素的硅烷
R1 n(R2O)3-n-Si-Alk-Hal
式中，Alk表示具有1-10个碳原子的亚烷基，R1、R2表示具有1-5个碳原子的烷基、5-8个碳原子的环烷基、苯基、苄基或者2-甲氧基乙基，其中R1或R2在每种情况下可以相同，也可以不同，Hal表示卤素，优选为氯或溴，n＝0、1或2，
与五硫化二磷(P4S10)和金属硫化物反应。
上述反应是按照下面的反应式进行的：
3 R1 n(R2O)3-n-Si-Alk-Hal+1.5 M2S+0.25 P4S10
↓-3 MCl
[R1 n(R2O)3-n-Si-Alk-S-]3P＝S
反应可以在溶剂中进行，优选的溶剂是己烷、乙腈、甲苯、庚烷或环己烷。由于五硫化二磷溶于R1 n(R2O)3-n-Si-Alk-Hal中，所以反应也可以在没有溶剂的存在下进行。进行反应时可以隔绝空气和水分。
反应可以在惰性气氛下进行，优选的惰性气体是氮气、氩气或氦气。反应的温度可以在20-300℃的范围内，优选的温度范围是150-250℃。所使用的金属硫化物可以为硫化钠(Na2S)、硫化钾(K2S)或硫化铵((NH4)2S)。
按照本发明制备的含硫和磷的化合物可以用于橡胶混合物中。
具体实施方式
实施例：
先将30.8克(69.2毫摩尔)P4S10、200.0克(830.3毫摩尔)氯丙基三乙氧基硅烷和32.4克(415.3毫摩尔)硫化钠(Na2S)的混合物引入到500毫升的三颈烧瓶中，该三颈烧瓶处于氩气氛中；然后加热到200℃。在200℃下搅拌2.5小时后，将不溶的组份滤出。在真空中除掉所有挥发性的组份，得到168.5克(收率79％)的四硫代磷酸S，S，S-三(三乙氧基甲硅烷基丙基)酯，它是一种淡黄色的透明液体。
1H-NMR(CDCl3)：δ0.75(m，2JH-Si＝111.4Hz，6H，Si-CH2-CH2-CH2-S-)，1.22(t，3JH-H＝7.4Hz，27H，CH3-CH2-O-Si)，1.85(dm，3JH-H＝7.5Hz，6H，Si-CH2-CH2-CH2-S-)，3.02(dt，3JH-H＝7.5Hz，3JH-P＝17.0Hz，6H，Si-CH2-CH2-CH2-S-)，3.82(q，3JH-H＝7.4Hz，18H，CH3-CH2-O-Si).
31P-NMR(CDCl3)：δ94.5(s).
Claims (3)
1、一种制备如下式所示的、含硫和磷的化合物的方法：
[R1 n(R2O)3-n-Si-Alk-S-]3P＝S
式中，Alk表示具有1-5个碳原子的亚烷基，R1、R2表示具有1-5个碳原子的烷基，其中R1或R2在每种情况下可以相同，也可以不同，n＝0、1或2；其特征在于，该化合物是由下式所示的、含卤素的硅烷
R1 n(R2O)3-n-Si-Alk-Hal
式中，Alk表示具有1-5个碳原子的亚烷基，R1、R2表示具有1-5个碳原子的烷基，其中R1或R2在每种情况下可以相同，也可以不同，Hal表示Cl、Br或I，n＝0、1或2，
与五硫化二磷(P4S10)和硫化钠(Na2S)、硫化钾(K2S)或硫化铵((NH4)2S)反应制得。
2、如权利要求1所述的制备含硫和磷的化合物的方法，其特征在于，卤素为氯或溴。
3、如权利要求1所述的制备含硫和磷的化合物的方法，其特征在于，反应是在没有溶剂的存在下进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19954815A DE19954815C1 (de) | 1999-11-13 | 1999-11-13 | Verfahren zur Herstellung von schwefel- und phosphorhaltigen Organosiliziumverbindungen |
| DE19954815.3 | 1999-11-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1298879A CN1298879A (zh) | 2001-06-13 |
| CN1169816C true CN1169816C (zh) | 2004-10-06 |
Family
ID=7929046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001326333A Expired - Fee Related CN1169816C (zh) | 1999-11-13 | 2000-11-10 | 一种制备含硫和磷的有机硅化合物的方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6274753B1 (zh) |
| EP (1) | EP1099704B1 (zh) |
| JP (1) | JP2001163891A (zh) |
| KR (1) | KR20010051569A (zh) |
| CN (1) | CN1169816C (zh) |
| DE (2) | DE19954815C1 (zh) |
| PL (1) | PL343815A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376585C (zh) | 1997-08-21 | 2008-03-26 | 通用电气公司 | 用于填充橡胶的封端巯基硅烷偶联剂 |
| JP4722482B2 (ja) * | 2002-07-09 | 2011-07-13 | モーメンティブ・パフォーマンス・マテリアルズ・インク | 硬度の向上したシリカ−ゴム混合物 |
| US7138537B2 (en) | 2003-04-02 | 2006-11-21 | General Electric Company | Coupling agents for mineral-filled elastomer compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2658368C2 (de) * | 1976-12-23 | 1982-09-23 | Degussa Ag, 6000 Frankfurt | Schwefel und Phosphor enthaltende Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung |
| DE3070645D1 (en) * | 1979-08-30 | 1985-06-20 | Biotechnolog Forschung Gmbh | Phosphoric acids and their derivatives |
-
1999
- 1999-11-13 DE DE19954815A patent/DE19954815C1/de not_active Expired - Fee Related
-
2000
- 2000-11-04 DE DE50003514T patent/DE50003514D1/de not_active Expired - Fee Related
- 2000-11-04 EP EP00124046A patent/EP1099704B1/de not_active Expired - Lifetime
- 2000-11-09 KR KR1020000066425A patent/KR20010051569A/ko not_active Application Discontinuation
- 2000-11-10 CN CNB001326333A patent/CN1169816C/zh not_active Expired - Fee Related
- 2000-11-10 JP JP2000344186A patent/JP2001163891A/ja active Pending
- 2000-11-13 PL PL00343815A patent/PL343815A1/xx not_active IP Right Cessation
- 2000-11-13 US US09/709,572 patent/US6274753B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1298879A (zh) | 2001-06-13 |
| EP1099704A1 (de) | 2001-05-16 |
| PL343815A1 (en) | 2001-05-21 |
| KR20010051569A (ko) | 2001-06-25 |
| DE50003514D1 (de) | 2003-10-09 |
| US6274753B1 (en) | 2001-08-14 |
| JP2001163891A (ja) | 2001-06-19 |
| EP1099704B1 (de) | 2003-09-03 |
| DE19954815C1 (de) | 2001-06-07 |
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