# US 9,040,009 B2 · Kinetically stable chlorinated polysilanes and production thereof

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- Number: US 9,040,009 B2
- Document ID: US9040009B2
- Status: Granted
- Kind: B2
- Application number: 13/513,018
- Filed: 2010-12-06
- Published: 2013-01-03
- Granted: 2015-05-26
- Earliest claimed: 2009-12-04
- Assignees: Spawnt Private S.à.r.1.
- Applicants: Norbert Auner; Christian Bauch; Sven Holl; Rumen Deltschew; Javad Mohsseni; Gerd Lippold; Thoralf Gebel
- Inventors: Norbert Auner; Christian Bauch; Sven Holl; Rumen Deltschew; Javad Mohsseni; Gerd Lippold; Thoralf Gebel
- Web page: https://patentgrep.com/patent/US9040009B2

## CPC

- C08G 77/60: in which all the silicon atoms are connected by linkages other than oxygen atoms
- C01B 33/04: Hydrides of silicon
- C01G 17/00: Compounds of germanium
- C08G 79/14: a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Kinetically stable halogenated polysilanes include mixture of compounds having respectively at least four silicon atoms bound together, the substituents thereof comprising chlorine, and chlorine and hydrogen, and in the composition thereof, the atomic ratio of substituent to silicon is at least 1:1, wherein a) the kinetically stable halogenated polysilanes have a kinetically high stability in relation to oxidative splitting by chlorine, and the degree of conversion at temperatures of 120° C. within 10 hours with an excess of chlorine gas at 1013 hPa does not exceed 30 mol %, and b) the kinetically stable halogenated polysilanes have a percentage of branching points in the polysilane molecules of more than 8 mol %.

## Claims

### Claim 1

Kinetically stable halogenated polysilanes comprising a mixture of compounds having more than three silicon atoms in the backbone with in each case at least four interconnected Si atoms whose substituents comprise chlorine or chlorine and hydrogen and in whose composition an atomic ratio of substituent to silicon is at least 1:1, where
a) the polysilanes have a kinetically high stability toward oxidative cleavage by chlorine, with there being no reaction of the polysilanes to an extent of more than 30 mol %, at a temperature of 120° C. over 10 hours under excess chlorine gas at 1013 hPa, and
b) the polysilanes have a fraction of branching sites in polysilane molecules of more than 8 mol %.

### Claim 2 (depends on 1)

The polysilanes according to claim 1, having a fraction of neo-Si5Cl12 of at least 10 mol %.

### Claim 3 (depends on 1)

The polysilanes according to claim 1, having an empirical formula SiClx with x=2.2 to 2.5.

### Claim 4 (depends on 1)

The polysilanes according to claim 1, having an average chain length of n equals 4 to 10.

### Claim 5 (depends on 1)

The polysilanes according to claim 1, wherein 29Si NMR spectra exhibits sharp significant product signals in a chemical shift range of 15 ppm to −10 ppm, and in chemical shift range of −28 to −35 ppm, and in a chemical shift range of −70 to −85 ppm.

### Claim 6 (depends on 5)

The polysilanes according to claim 5, where the sharp significant product signals in 29Si NMR spectra are present in a chemical shift range selected from the group consisting of 8.5 ppm to 3 ppm, 1 ppm to −1 ppm, −3 to −5 ppm, and −6 ppm to −8.3 ppm, or combinations thereof.

### Claim 7 (depends on 1)

The polysilanes according to claim 1, wherein 29Si NMR spectra possesses in each case at least a number of significant sharp product signals in the following chemical shift ranges: four signals of 7 to 3 ppm, one signal of 1 to −1 ppm, one signal of −29.5 to −33 ppm, two signals of −78 to −82 ppm.

### Claim 8 (depends on 1)

The polysilanes according to claim 1, further comprising hydrogen substituents.

### Claim 9 (depends on 8)

The polysilanes according to claim 8, wherein the hydrogen content is less than 2 atom %.

### Claim 10 (depends on 8)

The polysilanes according to claim 8, wherein 1H NMR spectra has product signals in the chemical shift range of 6.5 to 3.55 ppm.

### Claim 11 (depends on 1)

The polysilanes according to claim 1, wherein Raman spectra possesses significant product at below 650 wavenumbers and between 520 and 640 wavenumbers.

### Claim 12 (depends on 1)

The polysilanes according to claim 1, wherein Raman spectra possesses at least three significant product signals at 270 to 340 wavenumbers and at least two significant product signals at 540 to 640 wavenumbers.

### Claim 13 (depends on 1)

The polysilanes according to claim 1, which are colorless to pale yellow or ivory.

### Claim 14 (depends on 1)

The polysilanes according to claim 1, obtained in low-viscosity and/or crystalline form, the viscosity of a liquid fraction at RT being less than, 1000 mPa s.

### Claim 15 (depends on 1)

The polysilanes according to claim 1, which are predominantly soluble in inert solvents.

### Claim 16 (depends on 1)

The polysilanes according to claim 1, wherein the soluble fraction is distillable and/or volatile without decomposition to an extent of more than 80% under reduced pressure of 1 to 100 Pa.

### Claim 17 (depends on 1)

The polysilanes according to claim 1, wherein the substituents consist of chlorine.

### Claim 18 (depends on 1)

The polysilanes according to claim 1, further comprising a fraction of halogenated polysilanes having a chain length n=2 to 3 (Si2Cl6 and Si2Cl8, readily separable from the higher-chain polysilanes by distillation).

### Claim 19 (depends on 18)

The polysilanes according to claim 18, having a stoichiometric formula SiClx with x=2.2 to 2.5.

### Claim 20 (depends on 1)

The polysilanes according to claim 1, containing a fraction of less than 10 mol % of direct bonds between two secondary Si atoms.

### Claim 21

Kinetically stable halogenated polysilanes comprising a mixture of compounds having more than three silicon atoms in a backbone with in each case at least four interconnected Si atoms whose substituents comprise chlorine or chlorine and hydrogen and in whose composition an atomic ratio of substituent to silicon is at least 1:1, where
a) the polysilanes have a kinetically high stability toward oxidative cleavage by chlorine, with there being no reaction of the polysilanes to an extent of more than 30 mol %, up to temperatures of 120° C. over the course of 10 hours under excess chlorine gas at 1013 hPa,
b) the polysilanes are obtained by partial degradation of halogenated polysilanes which comprise either
1. thermally prepared chlorinated polysilanes, or
2. plasma-chemically prepared chlorinated polysilanes,
and the partial degradation includes a chlorination and is carried out over a period of 4 hours to 29 hours under a pressure of 200 to 2000 hPa.

### Claim 22 (depends on 21)

The polysilanes according to claim 21, where the thermally prepared polysilanes have in each case at least one direct Si—Si bond, and their substituents consist of halogen and in their composition an atomic ratio of substituent to silicon is at least 1:1, the polysilanes consisting of rings and chains having a high fraction of branching sites, the fraction, based on overall product mixture, being >1 mol %, and said polysilanes having a RAMAN molecular vibration spectrum of I100/I132<1, where I100 is the Raman intensity at 100 cm−1 and I132 is the Raman intensity at 132 cm−1, and in 29Si NMR spectra significant product signals are present in the chemical shift range of +23 ppm to −13 ppm, −18 ppm to −33 ppm and −73 ppm to −93 ppm, or the plasma-chemically prepared polysilanes have at least one direct Si—Si bond and their substituents consist of halogen or of halogen and hydrogen and in their composition an atomic ratio of substituent to silicon is at least 1:1, where a) the halogen is chlorine, b) the hydrogen content of the polysilane is less than 2 atom %, c) the polysilane contains substantially no short-chain branched chains and rings, with an amount of branching sites of a summed fraction of perhalogenated derivatives of neohexasilane, neopentasilane, isotetrasilane, isopentasilane, and isohexasilane, based on overall product mixture, being less than 1 mol %, d) it has a RAMAN molecular vibration spectrum of I100/I132>1, where I100 is the Raman intensity at 100 cm−1 and I132 is the Raman intensity at 132 cm−1, e) in 29Si NMR spectra it has its significant product signals in the chemical shift range of +15 ppm to −7 ppm.

### Claim 23 (depends on 21)

The polysilanes according to claim 21, where the partial degradation is carried out at temperatures of 60° C. to 140° C.

### Claim 24 (depends on 1)

A process for preparing a kinetically stable halogenated polysilane mixture according to claim 1, comprising partial degradation of halogenated polysilanes which have been prepared by a thermal and/or plasma-chemical process, where the partial degradation
a) includes a chlorination,
b) temperature during degradation is 60 to 140° C., and
c) takes place at a pressure of 200 to 2000 hPa.

### Claim 25 (depends on 24)

The process according to claim 24, wherein, after the partial degradation, further comprising distillation to remove a fraction of the kinetically stable halogenated polysilanes formed with chain lengths n=2 and 3.

### Claim 26 (depends on 24)

The process according to claim 24, where the halogenated polysilanes are diluted prior to the partial degradation with SiCl4, Si2Cl6 and/or Si3Cl8 as diluents.

### Claim 27 (depends on 24)

The process according to claim 24, wherein as polysilanes which have been prepared by a thermal process, polysilanes are used which in each case have at least one direct Si—Si bond, and whose substituents consist of halogen, and in whose composition an atomic ratio of substituent to silicon is at least 1:1, the polysilanes consisting of rings and chains having a high fraction of branching sites, the fraction, based on the overall product mixture, being >1 mol %, said polysilanes having a RAMAN molecular vibration spectrum of I100/I132<1, where I100 is the Raman intensity at 100 cm−1 and I132 is the Raman intensity at 132 cm−1, and in 29Si NMR spectra the significant product signals are present in the chemical shift range of +23 ppm to −13 ppm, −18 ppm to −33 ppm, and −73 ppm to −93 ppm.

### Claim 28 (depends on 24)

The process according to claim 24, wherein the polysilanes are prepared by a plasma-chemical process which have at least one direct Si—Si bond and whose substituents consist of halogen or of halogen and hydrogen and in whose composition an atomic ratio of substituent to silicon is at least 1:1, where a) the halogen is chlorine, b) hydrogen content of the polysilane is less than 2 atom %, c) the polysilane contains substantially no short-chain branched chains and rings, an amount of branching sites of a summed fraction of perhalogenated derivatives of neohexasilane, neopentasilane, isotetrasilane, isopentasilane, and isohexasilane, based on an overall product mixture, being less than 1 mol %, d) it has a RAMAN molecular vibration spectrum of I100/I132>1, where I100 is the Raman intensity at 100 cm-1 and I132 is the Raman intensity at 132 cm-1, e) in 29Si NMR spectra it has its significant product signals in the chemical shift range of +15 ppm to −7 ppm.