JPS5953280B2 - Magnesium Sactaino Seizouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel siloxy group-containing organomagnesium complex.

An organic magnesium compound obtained by reacting an organic halide and metallic magnesium in the presence of an ether is known as a so-called Grignard reagent, and is widely used as a raw material for organic synthesis or as a raw material for a catalyst.

This compound can also be synthesized by reacting in a hydrocarbon medium in the absence of ether, and further modified compounds can be synthesized depending on the purpose of use. For example, British Patent No. 1003551 discloses a complex of organomagnesium with a metal derivative of an organic compound having a hydroxyl group or an enolizable keto group, and states that it can be used in place of an organolithium catalyst. . As a result of research into organomagnesium compounds useful as catalyst raw materials for Ziegler process polyolefin production, the present inventors discovered a novel organomagnesium complex containing a siloxy group, leading to the present invention. That is, the present invention is based on the general formula RIaMgX2-a (wherein R'' has 1 to 1 carbon atoms)
20 hydrocarbon groups, X represents a halogen, and a is a number greater than 0 and less than or equal to 2);
General formula R2bMR3m-b (wherein, M is a beryllium, boron, zinc, or aluminum atom, R2 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R3 is a carbon atom number of 1
~10 hydrocarbon groups, m is the valence of M, b is O~
1), and an organometallic compound (B) having the general formula (wherein R4 and R5 are hydrogen atoms or carbon atoms 1 to 1), and
Compounds consisting of constitutional units (indicating 10 hydrocarbon groups) (
C) General formula MaM, βR characterized by reacting
l, R2, R3, (0S1R4R5R6)8 (wherein, M
, Rl, R2, R3, R4, R5 have the above meanings,
R6 is partially composed of Rl, R2, and R5 and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, α, β,
s is a number greater than 0, P, q, r are numbers greater than 0, β/
This is a method for producing a siloxy group-containing organomagnesium complex which is soluble in an inert hydrocarbon medium and has the relational expression α=0.5 to 20, mα+2β=p+q+r+s, where m has the above meaning.

The complex represented by the above general formula will be explained in detail below.

In the formula, the hydrocarbon groups represented by Rl, R2, R3, R4, R5, and R6 can be aliphatic, aromatic, or alicyclic hydrocarbon groups. These are, for example,
Methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, hexadecyl, benzyl, phenyl, and cyclohexyl groups.

As the hydrocarbon group R1, an alkyl group is particularly preferred. 0
As the siloxy group represented by S1R4R5R6, S
Also included are those in which R4, R5, and R6 bonded to i are all hydrocarbon groups, and hydrosoloxy groups in which one or two of these groups are hydrogen atoms.

β/α is important to obtain a soluble complex and is between 0.5 and
A range of 20 is preferable in order to obtain a stable complex. The content of siloxy groups can be varied in the range from 0 to 2.0 based on the sum of metal atoms. This complex is obtained in the form of a hydrocarbon solution, and is presumed to be a single complex or a mixture of multiple types of complexes.

The composition of the complex can be determined by analyzing the solution, and the average composition can be determined by measuring the molecular weight. It is recognized from the nuclear magnetic resonance spectrum that the siloxy group in the complex is distributed between the magnesium atom and the metal M. The complexes of the present invention are characterized firstly by being easy to handle since they are dissolved in an inert hydrocarbon medium and obtained in the form of a solution, making them extremely suitable for use on an industrial scale. Also, since it contains a siloxy group that is stable in water, oxygen, etc., it is safer to handle than products that do not contain this group. Furthermore, this complex is extremely useful as a catalyst for olefin polymerization, and has various desirable properties such as high activity and easy control of physical properties by changing the content of siloxy groups. The compound of the general formula RlaMgX,-a used in the above reaction is synthesized from a halogenated hydrocarbon and metallic magnesium according to the known Grignard reagent synthesis method.

As the synthesis solvent, either ether or inert hydrocarbon can be used, but ether lowers the yield of the desired hydroxyloxy group-containing complex and is not a preferred component when this complex is used as a catalyst component. isn't it. Therefore, when synthesized in an ether, it is desirable to remove the ether. Particularly preferred are organomagnesium compounds synthesized in a hydrocarbon medium. Furthermore, R2bMR3
The organometallic compound represented by m-b includes those in which all of the substituents are hydrocarbon groups and those in which some of the substituents are hydrogen.

These compounds include the following. Dimethyl beryllium, isopropyl beryllium hydride, diethyl beryllium, dibutyl beryllium, diphenyl beryllium, trimethyl boron, triethyl boron, tripropyl boron, tributyl boron, dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, diphenyl zinc, dimethyl aluminum hydride, trimethyl Aluminum, diethylaluminium hydride, triethylaluminum, diisobutylaluminum hydride, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum,
Trihexylaluminum, triphenylaluminum, etc. Among these compounds, alkyl metal compounds having 5 or less carbon atoms, especially hydride, are preferred.Compounds consisting of the structural unit of the general formula -ki-0- include 2 compounds consisting of one type or two or more types of the above-mentioned structural units. A linear or cyclic siloxane compound having more than one molecule is used.

Specific compounds include, for example, symmetric dihydrotetramethyldisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, hexamethyldisiloxane, polymethylhydrosiloxane, polyphenylhydrosiloxane, polydimethylsiloxane, etc. . In addition, polyethers in the form of (R1 hydrocarbon group), R4R5R6Sl (0H), R4R5SI (0H
) It is also possible to use silanols in the form 2.

Hydrosiloxane compounds are particularly preferred in terms of ease of reaction and high reaction yield. In the production method of the present invention, components (A), (B), and It is carried out by reacting.

The reaction ratio of (B) to (O) is 0.05 to 2.0 for component (B) to 1 for component (C) in molar ratio, and -Sl for component (C).
It is carried out at a ratio of -0- to 2.0. The reaction can be carried out by simultaneously adding three components (A), (B), and (0) to the reaction system;
This can be carried out by reacting the two components 0 in advance and then adding the remaining components, or by adding the components (B), 1, and 0 under the synthesis conditions of the captive components. In addition, by reacting the two components of (B) and 0 in advance, the general formula R2
bR3OM(0SiR4R5R6)m-(b+o) (However, B and c are numbers greater than or equal to O, b+c is less than or equal to m-1, and m is M
The target compound of the present invention can also be obtained by synthesizing a compound with a valence of .

This method is the most preferable since it can increase the yield (similar reactions of (B) and (C) are
As a result of research, we have confirmed that this method can be used in the same way as tenon. General formula R2bR3cM (0S
Examples of compounds of 1R3R4R5)n1-(b+C) include the following.

Al(0S1-H-CH3・C2H5)3,C2H,A
1 (0S1・H-CH3・C2H5) 2, (C2H5)
2A1(0SiH2・CH3), (C2H,)Al[0
S1(CH3)3]2,(C2H5)2AIC0S1(
CH3)2・C2H5], (C4H,)2A1(0SI
-H-C6H5・C4H9), (CH3)2A1[0S
i・H・(CH3)2], l−C4H, All(0S1
-H-CH3l-C4H,)2, (IC4H,)2A1
(0SiH2・CH3), (C6Hl3)1.5A1(
0Si-H-CH3C6Hl3),. 5, C8H17A
2(0Si-H-CH3・C8Hl7)2,C2H5Z
n(0S1-H-CH3・C2H5), C4H, Zn(
0Si-H-C6H, ・C4H9), C2H5Be(0
Si・H-CH3・C2H5), C3H7Be (0S1
-H-CH3・C3H7), C4H, Be(0S!・H
-CH3・C4H, ), (C2H5)2B(0S1-H
-CH3・C2H5), C4H, B(0S!・H-CH
3.C2H5)2 starting material, general formula RlaMgX2
The organomagnesium compound of -a is insoluble or poorly soluble in an inert hydrocarbon medium, but due to the above reaction, the organomagnesium component forms a complex with the siloxy group-containing component and the organometallic component and becomes soluble in the solvent. Become.

Partitioning of the siloxy group occurs between the organomagnesium component and the siloxy group-containing compound, and this is recognized from the nuclear magnetic resonance spectrum. In addition, the occurrence of cleavage of the siloxane compound and bonding of Sl-0- to Mg and metal M results in the disappearance of the Si-0-Sl bond in the infrared spectrum and the new Si-H This can be confirmed from the appearance of absorption. The present invention will be explained in more detail below with reference to Examples.

Example 1 A flask with a capacity of 500 ml was charged with 3.89 magnesium powder (0.16 gram atoms) under a nitrogen atmosphere, to which was added 30 ml of 200 ml of a dry heptane solution containing 0.15 mol of n-butyl chloride. Ta.

Heat the flask to the boiling point while stirring, and after the reaction has started, add the remaining n-butyl chloride over 30 minutes.
After the addition was complete, the mixture was heated under reflux for an additional hour and a half. To the resulting reaction mixture, 0.04 mol of triethylaluminum and 0.10 mol of symmetrical dihydrotetramethyldisiloxane were added together with 60111 heptane, and the mixture was reacted at 80° C. for 3 hours.

After the reaction, the precipitate was filtered off to obtain a solution with a magnesium concentration of 0.17 mol/l. As a result of the analysis, the composition of the complex in the liquid was AlMgOJO(C2H5)(n-C4H9)0
．． 20(0SiH゛CHlC,H5)0.98(0Si
HCH・3゜n-C4H9),. It was 60. Example 2 In the same manner as in Example 1, n-propyl bromide and magnesium were reacted.

0.05 mol of diethylaluminium hydride and 0.05 mol of methylhydrocyclic tetramer were added to the resulting reaction mixture, and the mixture was reacted at 100° C. for 3 hours to obtain a solution containing 0.19 mol/l of magnesium. As a result of analysis, the composition of the complex is AI! Mgl. 28(C,H5)2.0(n
-C4Hg)2.56(0SiH,CH,),. It was 00. Example 3 In the same manner as in Example 1, n-butyl bromide and magnesium powder were reacted.

Subsequently, 0.02 mol of diisobutylaluminum hydride was added to this together with 301 t1 of heptane, and 1
The reaction was carried out at 00°C for 1 hour. To the resulting reaction product, 0.3 mol of methylhydrotrisiloxane was added together with 30 mj of heptane, and the mixture was reacted at 80° C. for 3 hours to obtain a solution containing magnesium at a concentration of 0.20 mol/l. As a result of analysis, the composition of the obtained complex was AlMg3. O(n-C,H,
),. 90(1-C4H,)2.0(0Si・H,・C
H,)1,0(0Si-H-CH3・n-C,H9)0
．． It was 50.

Example 4 In a flask with a capacity of 500 ml, 3.89 ml of magnesium powder, 0.03 mol of triethylboron and 30 d(:
! ) n-heptane was added.

0.15 mol of ethyl bromide was added to this in the same manner as in Example 1, and the mixture was reacted at 80° C. for 4 hours. 0.06 mol of polyphenylhydrosiloxane (3
(viscosity of 100 centistokes at 0°C),
React at ℃ for 2 hours, add 0.16 mol/2 magnesium
A solution was obtained containing a concentration of . The composition of this complex is BMgl.
6O(C2H,)4.3. (0SiH.C2H,.C6
H,) was 2.01. Example 5 In the same manner as in Example 1, 3.89 magnesium powder and 0
．． 15 mol of n-octyl chloride were reacted in toluene.

0.2 mol of isobutylaluminum hydride and 0.3 mol of polyhydromethylsiloxane (viscosity of 1000 centistokes at 30°C) were added to the resulting reactant.
The reaction solution reacted at 00°C for 3 hours was added, and the reaction was further carried out at 100°C for 2 hours to obtain a solution containing magnesium at a concentration of 0.21 mol/l. As a result of analysis, the composition of the complex was AlMg3A3(i-C,H,)1. ,8(n-
C8H,,),. 42(0SiH2CH,)1.00(
0SiH・CH3. C8Hl,). It was A6. Examples 6 to 9 Organomagnesium compounds synthesized from magnesium powder and n-butyl chloride in exactly the same manner as in Example 1 were reacted with components (B) and (C) under the conditions shown in Table 1. Got the results.

Examples 10-12 As shown in Table 2, dialkylmagnesium, organometallic compound and siloxane were mixed in cyclohexane at 80°C.
The reaction was carried out for 3 hours, and the results shown in the table were obtained.

Example 13 Composition C was added to the reaction mixture obtained in the same manner as in Example 1.
0.08 mol of a siloxyaluminum compound of 2H5Al(0Si-H-CH3.C2H5)2 was added together with 30 ml of heptane and reacted under reflux for 1 hour.

After the reaction, the precipitate was filtered off and the bottom liquid was analyzed. Composition AlM
gO. 82 (C2H5) 1.01 (n-C4H9) 1.
A complex of 6,(0Si-H.CH3.C,H5)2.02 was obtained as a solution with a magnesium concentration of 0.27 mol/l. Example 14 3.809% of magnesium metal (0.16 mol) and 0.80% of magnesium metal (0.16 mol).
15 moles of n-butyl bromide in octane with 12
The reaction was carried out in the same manner as in Example 1 at 0° C. for 3 hours.

The resulting reaction mixture was added with the composition (1-C4H,)2A1(
0.04 mol of 0SiH2.CH3X:I) siloxyaluminum compound was added and reacted at 120°C for 30 minutes. Analysis of the reaction solution revealed that the composition was AlMg2. ,O(1-C
4]-19) 1.98 (n-C4H9)4. ! 7 (0S
iH7・CH3x). , 5 complex is 0.31 mol/l (
Mg concentration). Example 15 3.809, metallic magnesium (0.16 mol), and 0.05 mol of siloxyaluminum having the composition C8Nl7Al(0Si-H-CH3C8Hl7)2 were added together with 50 ml of cyclohexane in the same manner as in Example 1, 5001!1I!
into a flask.

Subsequently, 200 d of a cyclohexane solution containing 0.15 mol of ethyl bromide was reacted at 80° C. for 4 hours in the same manner as in Example 1. Analysis of the reaction solution revealed that the composition Al
Mgl. O5(C,H5)2.1, (C8Hl7)1.
01 (0SiH-a7・C8Hl7)1. , 4 was obtained as a solution with a concentration of 0.23 mol/l. Example 16 In the same manner as in Example 15, 3.809 of metallic magnesium, 0.15 mol of methyl iodide and composition C2H, Zn
0.075 mol of a siloxyzinc compound (0SiH-CH3.C2H,) was reacted in heptane at 100 DEG C. for 4 hours.

Composition ZnMgO. ,6(CH3)1. ,,(C2H5)
. ．． 03 (0S1H-CH3・C2). ．． , 8 was obtained as a 0.21 mol/l solution. Example 1
7 3.809 (0.16 gram atoms) of magnesium metal and 0.15 mol of n-octyl chloride in 1 ml of toluene
The reaction was carried out in the same manner as in Example 1 at 10° C. for 2 hours.

The resulting reaction mixture was added with the composition C2H,Be(0Si・H
-CH3・C2H5) siloxyberyllium compound 0.
03 mol was added to 30 d of toluene and \\, and the mixture was reacted at 110°C for 1 hour.

After the reaction, analysis of the liquid phase revealed that the composition was EMg, . ,O(C
,H5)1,(C,Hl?￥1(0Si-H-CH,・
C, H,). ．． . The complex was obtained in the form of a 0.30 mol/l solution. Example 18 To a reaction mixture obtained by reacting magnesium and n-butyl chloride under exactly the same conditions as in Example 1, 0.075 mol of siloxyaluminum having the composition (C, H,)2A11 (0SiH2・C8H5) was added. , reacted at 100° C. for 1 hour to obtain a composition AlMgO. 9O(C2H5)2.01(n-
C4H9)! ．． 85 (0SiH2IC6H5) 0.95
The complex was obtained in the form of a solution of O.26 mol/11.

Example 19 0.1 mol of di-n-butylmagnesium and composition (C,H
,)Al(0Si-H-CH3.C2H5)2 siloxyaluminum and hexane 2007n1 were placed in a pressure vessel with a capacity of 300Tn1 and reacted at 80°C for 2 hours to obtain a homogeneous and transparent solution.

The composition of the complex is AlMg6. O3(C2H5)(n-C4
12P5 (0Si゜H゜CH3・C,H,),. o
It was 1. Example 20 0.2 mol of n-butylmagnesium bromide and 0.05 mol of siloxyaluminum having the composition (CH3)2A1C0S1-H.(CH,),] were reacted in the same manner as in Example 9, and the composition AlMg,. ,l(CH8)2.0,(n
1C4H,)3. ,0(0S1H・(CH3)2)0.
, , was obtained in the form of a 0.38 mol/l solution.

Example 21 0.1 mol of diethylmagnesium and composition (C2H^A
j (0SiH, .CH,) of siloxyaluminum 0.
15 mol was reacted in the same manner as in Example 20 to obtain a homogeneous solution.

The composition of the complex is AjMgO. 66(C2H,),,1(0
SiH,・CH,),. . , it was. Example 22 Under exactly the same conditions as in Example 1, 3.89 magnesium powder (0.16 gram atom) and 0.9 g of n-dodecyl bromide were added.
Composition A was obtained by adding 0.04 mol of triethylaluminum and 0.10 mol of symmetrical dihydrotetramethyldisiloxane together with 50 d of heptane to the reaction mixture obtained by reacting 15 mol of triethylaluminum with 50 d of heptane, and reacting at 100°C for 2 hours.
lMgl. ,5(C2H5)2. ! 5(n-Cl2H2
5)! ．． 35(0SiH″CH33C2H,)0.85
A complex of (0SiHCH, .n-Cl2,) 1.6 was obtained in the form of a 0.31 mol/11 solution.

Example 23 A reaction was carried out under the same conditions as in Example 22, except that n-hexadecyl chloride was used instead of n-dodecyl bromide, and the composition was AIlMgl. ,6(C,H,),. .

, (n-Cl6H33),. 5, (0SiH-CH,・
C, H,). ．． ,,(0SiH-CH3・n-Cl6H
3,),. , , was obtained in the form of a 0.29 mol/j solution. Example 24 The reaction was carried out under exactly the same conditions as in Example 22, except that n-eicosyl chloride was used instead of n-dodecyl bromide, and the composition was AlMg2.25(C2H5)2.2, (
n-C2OH4! )2.76(0SiH'CHS'C2
H5) 0.76 (0SiH-CH3・n-C2OH4,
)1. , 4 was obtained in the form of a 0.35 mol/l solution.

Claims (1)

[Claims] 1 General formula R^1_aMgX_2_-_a (in the formula, R^
1 is a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and a is a number greater than 0 and less than or equal to 2), an organomagnesium compound (A) with the general formula R^2_bMR^3_m
＿−＿b(In the formula, M is beryllium, boron, zinc, aluminum atom, R^2 is hydrogen atom or carbon atom number 1~
10 hydrocarbon groups, R^3 represents a hydrocarbon group having 1 to 10 carbon atoms, m is the valence of M, and b is a number of 0 to 1), and general Reacting a compound (C) consisting of a constituent unit of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. The general formula MαM_gβR^1_pR^2_qR^3 is characterized by
_r(OSiR^4R^5R^6)_s (in the formula, M, R
^1, R^2, R^3, R^4, R^5 have the above meanings, R^6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and α, β, s is a number greater than 0, p, q
, r is a number greater than or equal to 0, β/α=0.5 to 20, mα+2
A method for producing a siloxy group-containing organomagnesium complex which is soluble in an inert hydrocarbon medium and has the relational expression β=p+q+r+s, where m has the above meaning.