Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

• the present invention relates to a method for producing a silicon network polymer.
• Silicone work polymers are attracting attention as optoelectronic materials and ceramic precursors.
• the present inventor has conducted intensive studies in view of the current state of the prior art as described above, and as a result, uses trihalosilanes in an electrode reaction using a specific metal as an anode and switching the polarity of both electrodes at regular intervals. This substantially eliminates the significant problems associated with known synthetic methods using alkali metals. Or significantly reduced.
• the present invention provides the following method for producing a silicon network polymer:
• a method for producing a silicon network polymer comprising:
• R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group:
• X represents a halogen atom.
• Perchlorate is used as the supporting electrolyte with the trihalosilane represented by, and a non-protonic solvent is used as the solvent.Mg, Cu, or A1 is used as one of the electrodes.
• R is the same as above corresponding to the starting material; n is 10 to: L 00000) is formed.
• a method for producing a silicone network polymer comprising:
• .R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group:
• X represents a halogen atom.
• a method comprising forming a silicon network polymer represented by the following formula:
• trihalosilane used as a starting material is represented by the general formula
• R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group:
• X represents a halogen atom.
• the reaction product of the present invention has a general formula
• examples of the alkyl group include those having about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable.
• examples of the aryl group include a phenyl group, a phenyl group having at least one alkyl group having 1 to 6 carbon atoms as a substituent, a p-alkoxyphenyl group, and a naphthyl group.
• examples of the alkoxy group include those having about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable.
• R is an amino group or an organic substituent as described above, at least one of its hydrogen atoms is replaced with another alkyl group, aryl group, or alcohol group. It may be substituted by a functional group such as a xy group.
• X represents a halogen atom (C I, F, B r, I).
• C 1 is more preferred.
• one of the trihalosilanes represented by the general formula (1) may be used alone, or two or more may be used in combination.
• Trihalosilane is preferably as pure as possible, for example, it is preferable to distill it before use.
• trihalosilane is used after dissolving in a solvent.
• a non-protonic medium can be widely used, and more specifically, propylene carbonate, acetonitril, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,2-dimethyl Solvents such as toxetane, bis (2-methoxethyl) ether, p-dioxane, and methylene chloride are exemplified. These solvents can be used alone or as a mixture of two or more.
• an ether-based solvent such as tetrahydrofuran, 1,2-dimethoxetane, bis (2-methoxethyl) ether, p-dioxane, or a mixture of other solvents is used. It is better to do it.
• Particularly preferred solvents are tetrahydrofuran and 1,2-dimethyl It is Kishetan. If the concentration of trinodolosilane in the solvent is too low, the current efficiency will be reduced, while if it is too high, the supporting electrolyte may not be dissolved.
• the concentration of trihalosilane in the solvent is usually about 0.05 to 20 mol / 1, more preferably about 0.2 to 15 mol / 1, and particularly preferably about 0 to 15 mol / 1. It is about 3 to 13 mol / l.
• the supporting electrolyte used in the present invention includes sodium perchlorate and metal perchlorate such as lithium perchlorate and lithium perchlorate; and perchlorate such as sodium perchlorate and n-butylammonium. Use perchlorates such as traalkylammonium.
• These supporting electrolytes may be used alone or in combination of two or more. Among these supporting electrolytes, lithium perchlorate and tetra-n-butylammonium perchlorate are more preferable, and lithium perchlorate is most preferable.
• the concentration of the supporting electrolyte in the solvent is usually about 0.05 to 5 mol / 1, more preferably about 0.1 to 3 mol / 1, particularly preferably about 0.15 mol / 1. It is about 1.2 mol / l.
• Mg, Cu or A1 or an alloy mainly composed of these metals is used as one of the poles, and the same or different conductive materials (Ni, C, Pt) are used. ) Is used as the other pole.
• metal ions for example, Mg 2x
• Mg, A1, and alloys based on these metals as the bipolar electrode, and most preferably to use Mg as the bipolar electrode.
• the shape of the electrode is not particularly limited as long as current can be supplied stably, but is preferably a rod-shaped, square-shaped, cylindrical-shaped, or a coil-shaped coil. It is preferable that the oxide film be removed from the surface of the electrode in advance as much as possible.
• the oxide film may be removed from the electrode by any method.For example, the electrode may be washed with an acid, then washed with ethanol and ether, and dried under a low pressure, or the electrode may be polished under a nitrogen atmosphere. Or a combination of these methods.
• trihalosilane represented by the general formula (1) and a supporting electrolyte are accommodated together with a solvent in a hermetically sealable reaction vessel provided with both electrodes, and preferably a Alternatively, a predetermined amount of current is applied while switching the polarity of the electrode while stirring magnetically to cause an electrode reaction.
• the polarity switching may be performed at a time interval of about 1 second to 20 seconds in order to realize a strong reduction system.
• the inside of the reaction vessel may be a dry atmosphere, but more preferably a dry nitrogen or inert gas atmosphere, and most preferably a deoxygenated and dry nitrogen or inert gas atmosphere. I like it.
• the amount of electricity is usually 1 unit based on the halogen atom in trihalosilane.
• the molecular weight can be controlled by adjusting the amount of current. It is also possible to take out the silicon network polymer produced with a current of about 0.1 F / m 01 or more out of the system, collect the remaining raw material halosilane, and reuse it.
• the reaction time may vary depending on the amount of the raw material trihalosilane, the resistance of the electrolyte related to the amount of the supporting electrolyte, the molecular weight of the desired silicone network polymer, and the like. good.
• the temperature during the reaction may be within a temperature range not higher than the boiling point of the solvent used. In the first invention of the present application, it is not necessary to use a diaphragm which is indispensable for ordinary electrode reduction reaction, and the operation is simplified and advantageous.
• the second invention of the present application is substantially the same as the first invention of the present application except that ultrasonic waves are applied to the reaction vessel or the reaction solution during the electrode reaction.
• the method of irradiating ultrasonic waves during the electrode reaction is not particularly limited, but the method of irradiating with the reactor housed in an ultrasonic bath, and irradiating with an ultrasonic oscillator inserted in the reactor The method is exemplified. It is preferable that the frequency of the ultrasonic waves be about 10 to 70 kHz.
• the output of the ultrasonic wave may be appropriately determined according to the reaction conditions such as the type of raw materials, the amount of the reaction solution, the shape and size of the reaction vessel and the electrode, the material and the surface area of the electrode, etc. It is in the range of about 0.01 to 24 kW. By such ultrasonic irradiation, the reaction time is greatly shortened, and 1 Z 3 ⁇
• the stirring is suitably performed by ultrasonic irradiation, but if necessary, mechanical stirring may be further used.
• water in the solvent and the supporting electrolyte is removed in advance. It is desirable to keep it.
• water in the solvent and the supporting electrolyte is removed in advance. It is desirable to keep it.
• tetrahydrofuran or 1,2-dimethoxetane is used as a solvent, it is preferable to previously dry with sodium-benzophenenoketyl or the like.
• a supporting electrolyte drying by heating under reduced pressure or removal of water by addition of a substance which reacts easily with water and can be easily removed (for example, trimethyl chlorosilane) is performed. I like it.
• the molecular weight of the resulting silicon network polymer can be controlled by adjusting the amount of electricity.
• phenyltrichlorosilane which has been dried and distilled with calcium hydride in advance, is added by syringe, and the reactor is kept at room temperature by a water bath. Was turned on. At this time, using a commutator, the polarity of the two electrodes is changed every 15 seconds, and the amount of electricity of 2.0 F / mo1 based on chlorine in phenyltrichlorosilane is used. The battery was energized for 28 hours.
• a silicone network polymer having a weight average molecular weight of 9860 was obtained in a yield of 65%.
• the oxygen content in the main chain of this silicone network polymer was 0.1% or less, and it was confirmed that the oxygen content was extremely low.
• An electrode reaction was performed in the same manner as in Example 1 except that the reactor was immersed in an ultrasonic cleaner having an output of 60 W and a frequency of 45 KHz to perform the reaction.
• the energization time was 15 hours.
• the electrode reaction was performed in the same manner as in Example 2 except that the amount of tetrahydrofuran was changed to 7.5 mi.
• the energization time was 21 hours.
• the electrode reaction was carried out in the same manner as in Example 2 except that 1,2-dimethoxetane (15 ml) previously dried with sodium benzophenone ketyl was used as a solvent.
• An electrode reaction of pheninoletrichlorosilane was carried out in the same manner as in Example 2, except that 3.0 g of chlorate tetra-n-butylammonium was used as a supporting electrolyte.
• An electrode reaction of phenyltrichlorosilane was carried out in the same manner as in Example 2 except that aluminum (lcmxO.1cmX5cm) was used as both electrodes.
• the electrode reaction of phenyl tricyclosilane was carried out in the same manner as in Example 2 except that copper (lcmxO.Icmx5cm) was used as both electrodes.
• the electrode reaction was carried out in the same manner as in Example 2 except that 1.98 ml of ⁇ -hexyltrichlorosilane was used as the raw material represented by the general formula (1).
• the electrode reaction was carried out in the same manner as in Example 2 except that / S-phenethyltrichlorosilane was used as the raw material represented by the general formula (1).
• the polarity of the electrode is changed every 15 seconds until the current reaches 1.0 FZmo 1, and then the polarity of the electrode continues until the current reaches 2.OFZmol.
• the electrode reaction was performed in the same manner as in Example 2 except that the reaction was performed at 10-second intervals. As a result, a silicone network polymer having a weight average molecular weight of 1,480,000 was obtained at a yield of 70%.
• the electrode reaction was performed in the same manner as in Example 2 except that the polarity of the electrode was changed at irregular intervals of 1 to 20 seconds.
• Example 2 The same procedure as in Example 2 was repeated except that 0.8 ml of phenyltrichlorosilane and 1.0 ml of n-hexyltrichlorosilane were used as the raw materials represented by the general formula (1). Electrode reaction.

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• Organic Chemistry (AREA)
• Silicon Polymers (AREA)

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• 1992
  • 1992-09-18 WO PCT/JP1992/001191 patent/WO1993006152A1/ja not_active Ceased
  • 1992-09-18 EP EP92920057A patent/EP0558760B1/en not_active Expired - Lifetime
  • 1992-09-18 DE DE69221467T patent/DE69221467T2/de not_active Expired - Fee Related
  • 1992-09-18 US US08/064,063 patent/US5416182A/en not_active Expired - Fee Related
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