JP5603711B2 - Diethyl zinc composition, method for thermal stabilization of diethyl zinc, compound for improving thermal stability of diethyl zinc - Google Patents

Description

The present invention relates to a diethylzinc composition excellent in thermal stability, a method for thermal stabilization of diethylzinc, and a compound that improves the thermal stability of diethylzinc.

  Diethyl zinc is conventionally used as a reaction reagent for organic synthesis in polymerization catalyst applications such as polyethylene oxide and polypropylene oxide, and in the production of intermediates such as pharmaceuticals and functional materials, and is known as an extremely useful industrial material. ing.

In recent years, a method of forming a zinc oxide thin film by a technique called MOCVD (Metal Organic Chemical Vapor Deposition) method using diethyl zinc as raw materials and water vapor as an oxidizing agent has been studied. The zinc oxide thin film obtained by this MOCVD method has various functions in solar cells such as CIGS solar cell buffer layer, transparent conductive film, dye-sensitized solar cell electrode film, thin-film Si solar cell intermediate layer, and transparent conductive film. It is used in various functional films such as films, photocatalytic films, ultraviolet cut films, infrared reflective films, and antistatic films, compound semiconductor light emitting devices, electronic devices such as thin film transistors, etc., and has a wide range of uses.

  It is known that diethyl zinc is gradually decomposed and metal zinc particles are deposited when heat is applied (for example, see Non-Patent Document 1). Therefore, handling of diethyl zinc has problems such as a decrease in product purity due to precipitation of metal zinc particles generated by pyrolysis, contamination of storage containers, and blockage of manufacturing equipment piping.

  As a method for solving the above-mentioned problems related to the precipitation of metal zinc particles generated by pyrolysis, for example, a method of adding a compound such as anthracene, acenaphthene, or acenaphthylene to obtain a composition in which diethyl zinc is stabilized is known. (For example, refer to Patent Documents 1 to 3).

U.S. Pat. No. 4,385,003 U.S. Pat. No. 4,402,880 U.S. Pat. No. 4,407,758

Yasuo Kuniya et al. , Applied Organometallic Chemistry, 5, 337-347, published in 1991

As disclosed in Patent Documents 1 to 3, even if anthracene, acenaphthene, and acenaphthylene are added, diethylzinc cannot be sufficiently stabilized, and diethylzinc having higher thermal stability is required.

  In addition, anthracene, acenaphthene, and acenaphthylene are compounds that are solid at room temperature, and there is a problem that operations such as charging powder are required in the preparation of the diethylzinc composition.

In other words, the present invention improves the thermal stability of diethyl zinc used for a raw material for producing a zinc oxide thin film by a polymerization catalyst, an organic synthesis reagent, MOCVD method, etc., and does not precipitate metallic zinc particles even when handled for a long time. It aims at providing the diethyl zinc composition excellent in property.

As a result of diligent research and development to solve the above-mentioned problems, the present inventor made a composition in which an aromatic compound having an isopropenyl group in the side chain coexists in diethyl zinc (CAS No. 557-20-0). As a result, it was found that the thermal stability was remarkably improved, and the present invention was completed.

  The diethyl zinc composition according to the present invention is a diethyl zinc composition obtained by adding an aromatic compound having an isopropenyl group in the side chain as an additive to diethyl zinc.

  The diethylzinc composition according to the present invention is selected from the group consisting of aromatic compounds having an isopropenyl group represented by the following general formula (1), general formula (2), and general formula (3) in the side chain. Contains one or more compounds.

In formula (1), formula (2), and formula (3), each R is independently hydrogen, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched group having 1 to 8 carbon atoms. An alkenyl group (an alkenyl group includes an isopropenyl group) and an allyl group having 6 to 14 carbon atoms.

R, which is a substituent bonded to the side chain of the aromatic compound having the isopropenyl group represented by the above general formula (1), general formula (2), or general formula (3) in the side chain, Independently, not only the isopropenyl group characterized in the present invention, but also a linear or branched alkyl group having 1 to 8 carbon atoms such as hydrogen, a methyl group, and an isopropyl group, or a carbon number of 1 such as a vinyl group and a propenyl group. -8 linear or branched alkenyl groups (the alkenyl group includes an isopropenyl group characterized in the present invention as described above) and an allyl group having 6 to 14 carbon atoms such as a phenyl group and a toluyl group, etc. It may have a substituent different from the isopropenyl group. The number of isopropenyl groups present in the side chain may be one or a plurality of two or more. For example, in the case of benzene as an aromatic compound, 1,3-diisopropenyl having two isopropenyl groups Benzene and 1,4-diisopropenylbenzene have a high thermal stability effect.

  Examples of the aromatic compound having the aforementioned isopropenyl group in the side chain include, for example, mono-substituted products of isopropenyl groups such as α-methylstyrene, 4-isopropenyltoluene, 1-isopropenylnaphthalene, 2-isopropenylnaphthalene, and the like. , 3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3,5-triisopropenylbenzene, 2,4-diisopropenylnaphthalene, etc. I can do it.

  Among these aromatic compounds, α-methylstyrene, 4-isopropenyltoluene, 1,3-dithiol is an additive which has a simple structure and can be easily obtained industrially and has a high effect. Isopropenylbenzene, 1,4-diisopropenylbenzene, and 2-isopropenylnaphthalene can be preferably used.

  In particular, α-methylstyrene, 4-isopropenyltoluene, and 1,3-diisopropenylbenzene are liquid at a temperature of about 20 ° C., and the diethylzinc composition can be easily adjusted.

  The additive used in the present invention can provide a sufficient effect when added alone, but a plurality of additives may be used in combination.

  Here, the amount of the aromatic compound having an isopropenyl group in the side chain is not particularly limited as long as the performance of diethyl zinc is maintained and a thermal stabilization effect can be obtained. On the other hand, if it is 100 ppm to 20 wt%, preferably 200 ppm to 10 wt%, more preferably 500 ppm to 5 wt%, a diethylzinc composition having excellent thermal stability can be obtained.

When the amount of the aromatic compound having an isopropenyl group in the side chain is too small, the sufficient effect of improving the thermal stability may not be obtained, or when the amount is too large, the effect of increasing the added amount may not be obtained. Therefore, it is desirable to add an appropriate amount for obtaining the desired effect of thermal stability.

The diethylzinc composition of the present invention has excellent thermal stability at a low temperature of 180 ° C. or lower from the measured value of the ARC measurement (Accelerating Rate Calorimetry) result that is generally used as an accelerated test of thermal stability. doing. From the temperature dependency of the measured value of the ARC test, the effect of the thermal stability of the diethylzinc composition is more manifested as the temperature decreases.

  Diethyl zinc used in the present invention is generally known as an industrial material used as a reaction reagent for organic synthesis in polymerization catalyst applications such as polyethylene oxide and polypropylene oxide, and in the production of intermediates such as pharmaceuticals and functional materials. What is being used can be used.

  In the present invention, it is used in a method of forming a zinc oxide thin film by MOCVD or the like, and includes a buffer layer for CIGS solar cells, a transparent conductive film, an electrode film for dye-sensitized solar cells, an intermediate layer for thin-film Si solar cells, Various functional films in solar cells such as transparent conductive films, photocatalytic films, ultraviolet cut films, infrared reflective films, various functional films such as antistatic films, compound semiconductor light emitting devices, electronic devices such as thin film transistors, etc. Diethyl zinc having a purity higher than that of industrial materials can also be used.

In the preparation of the diethylzinc composition of the present invention, diethylzinc and an additive which is an aromatic compound having an isopropenyl group in the side chain may be mixed. For example, the aforementioned additive is added to diethylzinc, etc. The addition method is not particularly limited.
For example, in order to improve storage stability, a method of adding an additive to diethyl zinc in advance can be used.

Further, for example, when used for a reaction or the like, an additive can be added to diethyl zinc immediately before use.

  In addition, the temperature for preparing the diethylzinc composition of the present invention is preferably 70 ° C. or less, which is less affected by the thermal decomposition of diethylzinc. Usually, the composition of the present invention can be prepared at -20 ° C to 35 ° C. Also, the pressure is not particularly limited. Except for special cases such as reaction, diethylzinc and the composition of the present invention can be usually prepared near atmospheric pressure, such as 0.1013 MPa.

  The equipment used and the atmosphere used in equipment such as storage / transport containers, storage tanks, and piping for the diethyl zinc composition of the present invention can be used as they are. For example, the material of the above-mentioned equipment can be a metal such as SUS, carbon steel, titanium, or Hastelloy, or a resin such as Teflon (registered trademark) or fluorine rubber. In addition, an inert gas such as nitrogen, helium, or argon can be used in the same manner as diethyl zinc.

  The diethyl zinc composition of the present invention can be used by dissolving in a known solvent that can be used when diethyl zinc is used. Examples of the solvent include, for example, saturated hydrocarbons such as pentane, hexane, heptane and octane, hydrocarbon compounds such as aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and diglyme. And ether compounds such as

  Examples of the use of the diethylzinc composition of the present invention include use as a polymerization catalyst such as polyethylene oxide and polypropylene oxide, use as a reaction reagent for organic synthesis in the production of intermediates such as pharmaceuticals and functional materials, , Used in a method of forming a zinc oxide thin film by MOCVD method, etc., and CIGS solar cell buffer layer, transparent conductive film, dye-sensitized solar cell electrode film, thin film Si solar cell intermediate layer, transparent conductive film, etc. Various functional films such as various functional films, photocatalytic films, ultraviolet cut films, infrared reflective films, antistatic films, etc. in batteries, oxide forming applications such as compound semiconductor light emitting devices, electronic devices such as thin film transistors, etc., ZnS List the same applications where diethyl zinc has been used so far, such as thin film formation applications for II-VI electronic devices. Can.

  The diethylzinc composition to which an aromatic compound having an isopropenyl group in the side chain of the present invention is excellent in thermal stability, and precipitation of metallic zinc particles generated when diethylzinc is thermally decomposed is extremely small. As a result, it is possible to prevent problems such as a decrease in product purity, contamination of storage containers, and blockage of manufacturing equipment piping.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the present invention.

[measuring equipment]
DSC measurement was performed using DSC6200 (manufactured by Seiko Instruments Inc.).
ARC measurement was performed using ARC2000 (manufactured by ADL (Authur D Little)).

[Preparation of diethyl zinc composition]
Diethyl zinc (manufactured by Tosoh Finechem Co., Ltd.) and aromatic compounds having various isopropenyl groups in the side chain (commercial reagents) were weighed in glass containers at a predetermined concentration at room temperature in a nitrogen atmosphere. The additive was dissolved in diethyl zinc to prepare a diethyl zinc composition.

The addition rate (wt%) of the additive to diethyl zinc was defined by the following formula.
Addition rate (% by weight) of additive = (additive weight / (additive weight + diethyl zinc weight)) × 100

  DSC measurement (Differential Scanning Calorimetry), ARC measurement (Accelerating Rate Calorimetry) and long-term thermal stability test were performed on the diethylzinc composition prepared by the method described above, and the heat of the additive The stability effect was evaluated.

[Reference Example 1]
[Thermal stability test by DSC measurement of diethyl zinc]
Diethyl zinc was weighed and sealed in a SUS DSC cell under a nitrogen atmosphere. The obtained sample was subjected to DSC measurement, and thermal analysis measurement was performed at a temperature increase rate of 10 ° C./min with a temperature range of 30 to 450 ° C. The decomposition temperature of each sample is observed at the initial exothermic temperature of DSC measurement. Table 1 shows the initial exothermic temperature of a sample containing only diethyl zinc with no additive added.

[Examples 1 to 5]
[Thermal stability test of diethyl zinc composition by DSC measurement]
In the same manner as in Reference Example 1, in a nitrogen atmosphere, a diethylzinc composition to which various aromatic compounds having an isopropenyl group of the present invention in the side chain were added was weighed in a SUS DSC cell and sealed. The obtained sample was subjected to DSC measurement, and the same thermal analysis measurement as in Reference Example 1 was carried out at a rate of temperature increase of 10 ° C./min with a temperature range of 30 to 450 ° C. Table 1 shows the initial heat generation temperature of each sample.
The initial exothermic temperature of the sample of the diethylzinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention is added is higher than the initial exothermic temperature of the sample of only diethylzinc obtained in the reference example. This composition has a higher decomposition onset temperature than the diethylzinc-only sample. From this result, the high thermal stability of the diethyl zinc composition to which the additive was added was confirmed.

[Comparative Examples 1-2]
In the same manner as in Examples 1 to 5, as an aromatic compound having no isopropenyl group in the side chain, benzene in which the isopropenyl group was replaced with hydrogen from the compounds in Examples 1 to 5 and diethyl zinc to which toluene was added A similar study was conducted on the composition. Table 1 shows the initial heat generation temperature of each sample.
From the results of Comparative Examples 1 and 2, all of these samples were lower than the initial exothermic temperature of the sample of the diethylzinc composition to which the aromatic compound having an isopropenyl group of the present invention in the side chain was added. The thermal stability was inferior to the composition. From this result, it was confirmed that having an isopropenyl group in the side chain has an extremely high effect on thermal stability.

[Comparative Examples 3 to 5]
In the same manner as in Examples 1 to 5, the same study was performed on a diethyl zinc composition to which anthracene, acenaphthene, and acenaphthylene, which are compounds described in Patent Documents 1 to 3, were added. Table 1 shows the initial heat generation temperature of each sample.
These samples are lower than the initial exothermic temperature of the sample of the diethyl zinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention is added, and the composition to which the existing additive is added is the composition of the present invention. The thermal stability was inferior to the product.

[Comparative Examples 6 to 11]
About the diethyl zinc composition which added the anthracene, acenaphthene, and acenaphthylene which are the compounds of patent documents 1-3, the addition rate of the additive was changed and the thermal analysis measurement similar to Examples 1-5 was performed. Table 2 shows the initial heat generation temperature of each sample.
These samples are lower than the initial exothermic temperature of the sample of the diethyl zinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention is added, and the composition to which the existing additive is added It was confirmed that the thermal stability was inferior to the composition of the present invention even when the addition rate was low.

[Examples 6 to 20]
The thermal analysis measurement similar to Examples 1-5 was performed by changing the addition rate of the additive. Table 3 shows the initial heat generation temperature of each sample.
The initial exothermic temperature of the sample of the diethylzinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention is added is only that of diethylzinc obtained in the reference example, even if the addition rate of the additive is changed. Beyond the initial exothermic temperature of the sample, the composition of the present invention has a higher decomposition initiation temperature than the sample of diethyl zinc alone.
From the results of Examples 6 to 19, high thermal stability of the diethylzinc composition to which the additive of the present invention was added was confirmed even when the additive addition rate was changed.

In addition, the initial exothermic temperature of the sample of the diethylzinc composition obtained by adding an oxygen compound such as a methoxy group to the side chain R of the aromatic compound is higher than the initial exothermic temperature of the sample of only diethylzinc obtained in the reference example. The decomposition start temperature of the composition of the present invention is higher than that of the diethylzinc-only sample. From the results of Example 20, an additive containing oxygen such as a methoxy group in the side chain of the aromatic compound is added. Even in this case, high thermal stability of the diethylzinc composition to which the additive of the present invention was added was confirmed.

[Reference Example 2]
[Thermal stability test of diethyl zinc by ARC measurement]
Under a nitrogen atmosphere, diethyl zinc was weighed into an ARC cylinder made of Hastelloy C and sealed. For the obtained sample, ARC measurement was performed at a measurement start temperature of 50 ° C., a measurement end temperature of 350 ° C., a temperature increase step temperature of 5 ° C., a waiting time of 10 minutes, a search detection sensitivity of 0.02 ° C./min, and a data output interval of 0.2 ° C. The measurement was performed at a maximum pressure of 170 bar and a nitrogen atmosphere. In the obtained ARC measurement data, the initial heat generation temperature of the sample is shown in Reference Example 2 of Table 3.

[Examples 21 to 23]
[Thermal stability test by ARC measurement of diethyl zinc composition]
In the same manner as in Reference Example 2, a diethyl zinc composition to which an aromatic compound having an isopropenyl group in the side chain of the present invention was added was examined in the same manner as in Reference Example 2. In the obtained ARC measurement data, the initial heat generation temperature of the sample is shown in Examples 21 to 23 in Table 4.
The initial exothermic temperature of the diethylzinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention is added is higher than the initial exothermic temperature of the sample of only diethylzinc, and the diethylzinc composition of the present invention is thermally stable. It was confirmed that the properties were excellent.

[Examples 24 to 50 and Reference Examples 3 to 11]
Using the ARC measurement data obtained in Examples 21 to 23 and Reference Example 2, the maximum exothermic rate arrival time (TMR) at each temperature was calculated for diethyl zinc and various diethyl zinc compositions. In calculating TMR, J. E. Using the Huff method, an equation for extrapolating the self-heating rate and TMR to the low temperature side was obtained, and the method for calculating the self-heating rate and TMR obtained after (Φ) correction at each temperature was used.
For the value outside the range of the ARC measurement temperature (less than 50 ° C.), TMR was calculated using an approximate expression obtained from each of the four data of 50 ° C., 60 ° C., 70 ° C., and 80 ° C.

The TMR value of the diethylzinc composition to which the aromatic compound having an isopropenyl group in the side chain of the present invention was added was compared with that of the diethylzinc composition to which the additive was not added and the TMR value was set to 1. It calculated in each temperature as a relative value with respect to a value. That is, the higher the relative value of TMR of the diethyl zinc composition to which the additive is added, the longer it takes to reach the maximum heat generation rate, and the diethyl zinc composition is more stable against diethyl zinc to which no additive is added. It shows having sex.

[Examples 24-26 and Reference Example 3]
The relative value of the maximum heat release rate arrival time (TMR) at 120 ° C. of each diethyl zinc composition when the TMR value of diethyl zinc at 120 ° C. with no additive added is 1 (Reference Example 3). Table 5 shows.
From Examples 24 to 26 in Table 5, each diethyl zinc composition had a relative value of maximum exothermic rate arrival time (TMR) larger than 1, and thus diethyl zinc obtained by adding the additive of the present invention. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 27 to 29 and Reference Example 4]
The relative value of the maximum heat generation rate arrival time (TMR) at 100 ° C of each diethylzinc composition when the TMR value of diethylzinc with no additive at 100 ° C is set to 1 (Reference Example 4). Table 6 shows.
From Examples 27 to 29 in Table 6, each diethyl zinc composition had a relative value of maximum exothermic rate arrival time (TMR) greater than 1, and thus diethyl zinc obtained by adding the additive of the present invention. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 30 to 32 and Reference Example 5]
The relative value of the maximum heat release rate arrival time (TMR) of each diethyl zinc composition at 80 ° C. when the TMR value of diethyl zinc at 80 ° C. with no additive added is 1 (Reference Example 5). It is shown in Table 7.
From Examples 30 to 32 in Table 7, each diethyl zinc composition has a relative value of maximum exothermic rate arrival time (TMR) greater than 1, and thus diethyl zinc obtained by adding the additive of the present invention. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 33 to 35 and Reference Example 6]
The relative value of the maximum heat release rate arrival time (TMR) at 60 ° C of each diethylzinc composition when the TMR value of diethylzinc with no additive at 60 ° C is 1 (Reference Example 6). Table 8 shows.
From Examples 33 to 35 in Table 8, each diethyl zinc composition had a relative value of maximum exothermic rate arrival time (TMR) greater than 1, so that diethyl zinc obtained by adding the additive of the present invention was used. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 36 to 38 and Reference Example 7]
The relative value of the maximum heat release rate arrival time (TMR) at 40 ° C of each diethylzinc composition when the TMR value of diethylzinc with no additive at 40 ° C is 1 (Reference Example 7). It is shown in Table 9.
From Examples 36 to 38 in Table 9, each diethyl zinc composition has a relative value of maximum exothermic rate arrival time (TMR) larger than 1, and thus diethyl zinc obtained by adding the additive of the present invention. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 39 to 41 and Reference Example 8]
The relative value of the maximum heat release rate arrival time (TMR) at 30 ° C. of each diethyl zinc composition when the TMR value of diethyl zinc at 30 ° C. with no additive added is 1 (Reference Example 8). Table 10 shows.
From Examples 39 to 41 in Table 10, the diethyl zinc obtained by adding the additive of the present invention has a relative value of the maximum exothermic rate arrival time (TMR) greater than 1 in each diethyl zinc composition. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 42 to 44 and Reference Example 9]
The relative value of the maximum heat release rate arrival time (TMR) at 25 ° C. of each diethyl zinc composition when the TMR value of diethyl zinc not added at 25 ° C. was 1 (Reference Example 9). Table 11 shows.
From Examples 42 to 44 in Table 11, each zinc zinc composition had a relative value of maximum exothermic rate arrival time (TMR) greater than 1, and thus diethyl zinc obtained by adding the additive of the present invention. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 45 to 47 and Reference Example 10]
The relative value of the maximum heat release rate arrival time (TMR) at 20 ° C of each diethylzinc composition when the TMR value of diethylzinc with no additive at 20 ° C is 1 (Reference Example 10). It is shown in Table 12.
From Examples 45 to 47 in Table 12, each diethyl zinc composition has a relative value of maximum exothermic rate arrival time (TMR) larger than 1, and thus the diethyl zinc composition obtained by adding the additive of the present invention. The product was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 48 to 50 and Reference Example 11]
The relative value of the maximum heat release rate arrival time (TMR) at 10 ° C of each diethylzinc composition when the TMR value of diethylzinc with no additive at 10 ° C is 1 (Reference Example 11). Table 13 shows.
From Examples 48 to 50 in Table 13, the diethyl zinc obtained by adding the additive of the present invention has a relative value of maximum exothermic rate arrival time (TMR) greater than 1 in each diethyl zinc composition. The composition was confirmed to have high thermal stability.

* Relative value calculated by taking the maximum exothermic rate arrival time (TMR) value of diethyl zinc with no additive as 1.

[Examples 51 to 52 and Reference Example 12]
[Long-term thermal stability test of diethyl zinc composition]
About 200 g of the sample prepared by the method described in the preparation of the diethylzinc composition was charged in a 200 ml pressure-resistant autoclave equipped with a glass insertion container, and an accelerated test was performed by heating and storing at 70 ° C. for 32 days. As a reference example, diethyl zinc to which no additive was added was also subjected to the same accelerated test by charging a similar sample in a 200 ml pressure-resistant autoclave (Reference Example 12). After completion of the test, the sample was opened in a nitrogen atmosphere, and the precipitation state of the precipitate produced in each sample was visually confirmed. Furthermore, diethyl zinc was removed under a nitrogen atmosphere, the precipitate was washed with hexane, and the remaining precipitate was dried. The remaining precipitate was confirmed to be zinc metal by ICP analysis. When the deposited zinc could be recovered, the container was weighed, and when it was so small that it could not be recovered, the container was washed with a 10% nitric acid aqueous solution, and the absolute amount of zinc in the nitric acid solution was quantified.

  The amount of precipitates generated by pyrolysis of the diethylzinc composition to which the additive was added was compared with the amount of precipitates generated by pyrolysis of diethylzinc to which the additive was not added was set to 1. Calculated as a relative amount to the value. That is, the amount of precipitates generated by thermal decomposition of the diethylzinc composition to which the additive is added is smaller than 1 relative to the above-mentioned value, and the diethylzinc composition is less than diethylzinc to which no additive is added. It shows that it has thermal stability.

  Table 14 shows the relative amount of precipitated zinc in each sample. From Example 51-52 of Table 14, the quantity of the precipitate produced | generated by the thermal decomposition of the diethyl zinc composition which added the additive is the quantity of the precipitate produced | generated by the thermal decomposition of the diethyl zinc which does not add an additive. Of less than 1/50. From this result, it was confirmed that the diethyl zinc composition obtained by adding the additive of the present invention has high thermal stability over a long period of time.

* Relative amount calculated with 1 as the amount of precipitate from pyrolysis of only diethylzinc without additives

[Examples 53 to 55 and Comparative Examples 12 to 14]
[Examples 53 to 55]
As an aromatic compound having an isopropenyl group in the side chain of the present invention, a kind of hydrocarbon different from an additive that further improves the thermal stability of diethyl zinc to diethyl zinc added with 1,3-diisopropenylbenzene Samples in which hexane and aromatic hydrocarbon compound toluene coexisted were adjusted as shown in Table 15 and subjected to the same thermal analysis measurement as in Examples 1-5. Table 15 shows the initial heat generation temperature of each sample.

[Comparative Examples 12-14]
In Examples 53 to 55, samples similar to those in Examples 53 to 55 were prepared as shown in Table 15 except that 1,3-diisopropenylbenzene of the present invention was not added, and Examples 1 to 5 were prepared. The same thermal analysis measurement was performed. Table 15 shows the initial heat generation temperature of each sample.

From the results of Examples 53 to 55 and Comparative Examples 12 to 14, the aromatic compound having an isopropenyl group in the side chain of the present invention is a different kind of hydrocarbon from the additive that improves the thermal stability of diethyl zinc. It is effective as an additive to improve the thermal stability of diethyl zinc even when certain hexane or aromatic hydrocarbon compound toluene coexists, and the high thermal stability of the diethyl zinc composition to which the additive of the present invention is added It was confirmed even when hexane, which is a different kind of hydrocarbon from the additive that improves the thermal stability of diethyl zinc, and toluene, which is an aromatic hydrocarbon compound, coexist.

Claims (7)

  A diethyl zinc composition in which an aromatic compound having an isopropenyl group in the side chain is added as an additive to diethyl zinc. The additive is one or more compounds selected from the group consisting of aromatic compounds having an isopropenyl group in the side chain represented by the following general formula (1), general formula (2), or general formula (3) The diethylzinc composition according to claim 1, wherein












(In formula (1), formula (2), and formula (3), each R is independently hydrogen, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched group having 1 to 8 carbon atoms. An alkenyl group (an alkenyl group includes an isopropenyl group) and an allyl group having 6 to 14 carbon atoms)   The additive is one or more selected from the group consisting of α-methylstyrene, 4-isopropenyltoluene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and 2-isopropenylnaphthalene The diethyl zinc composition of Claim 1 or Claim 2 which is a compound.   The diethyl zinc composition in any one of Claims 1-3 whose addition rate of the additive to diethyl zinc is 100 ppm-20 wt%. As a method of improving the thermal stability of diethylzinc, with claims 1-3 compound according as an additive, it is characterized by adding at addition rate of claims 4, the thermal stabilization of diethylzinc Method.   The diethylzinc composition according to claims 1 to 4, wherein the saturated and / or unsaturated hydrocarbon having 5 to 25 carbon atoms and an aromatic having 6 to 30 carbon atoms are different from the additive constituting the diethylzinc composition. The diethyl zinc composition according to claim 1, wherein a hydrocarbon compound or an ether compound coexists.   6. The method of stabilizing diethylzinc according to claim 5, wherein the saturated and / or unsaturated hydrocarbons having 5 to 25 carbon atoms and the carbon atoms having 6 to 30 carbon atoms are different from the additive having an effect on the thermal stability of diethyl zinc. The method for thermal stabilization of diethylzinc according to claim 5, wherein said aromatic hydrocarbon compound or ether compound coexists in diethylzinc.