JPH04210694A - Cyclopentadienyl group-containing silane compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R<1> to R<4> are monofunctional hydrocarbon; m is 0-3; n is 1-3 and n is 2 or 3 when m is 0). EXAMPLE:gamma-Cyclopentadienylpropyltris(trimethylsilyloxy)silane. USE:A synthetic resin modifier. The compound is obtained by a simple process by using readily obtainable raw materials. PREPARATION:A halogen-containing silane compound shown by formula II (R<1> to R<4> are methyl) is reacted with cyclopentadienylsodium under an anhydrous condition in a neutral polar solvent.

Description

[Detailed description of the invention]

[00011

[Industrial Application Field] The present invention is useful as a modifier for various synthetic resins, especially ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EPM), and as a modifier for various functional groups. The present invention relates to a cyclopentadienyl group-containing silane compound, which is a new substance useful as a raw material for the synthesis of a silane compound, and a method for producing the same. [0002] [Prior Art] Among various synthetic resins, olefin rubber ethylene-propylene-diene copolymer (EPDM
) and ethylene-propylene copolymer (EPM) have much better heat resistance, weather resistance, and ozone resistance than diene rubbers. Therefore, it is particularly useful for automobile parts and industrial products, such as tires, belts, weather strips, various sealants, tubes, hoses, gaskets, and electric wires.
Ethylene-propylene-diene copolymer (EP
DM) and ethylene-propylene copolymer (EPM) are preferably used, and the demand for them has increased significantly in recent years. [0003] However, ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EPM) have further improved heat resistance, weather resistance, cold resistance, and Improved oil resistance is required. As a modifier for further improving the above-mentioned physical properties, cyclopentadienyl group-containing silane compounds are known, and ethylene-propylene-diene copolymers (EP
DM) or ethylene-propylene copolymer (EPM)
Methods for introducing the compound into the compound include blending the copolymer and the compound, or copolymerizing the compound with ethylene and propylene as a third component diene monomer for crosslinking. . [0004] Conventionally, cyclopentadienyl group-containing silane compounds used for the above-mentioned purposes include cyclopentadienyl group-containing alkoxysilanes, JP-A-61-47
ω-cyclopentagenyl alkyl group-containing alkoxysilanes described in Publication No. 493, and J, Org, C
The following silane compounds (a), (b) and (C) described in Hew, 25.1986-90 (1960) are known, but [0005]

embedded image (a) (b) (C) [0006] These compounds do not have sufficient compatibility with resins and are difficult to blend with resins. Furthermore, the modification of the flexibility of the resin by the compound was not at a satisfactory level. Therefore, there has been a need for a novel cyclopentadienyl group-containing silane compound that can solve the above problems. [0007]

OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made to solve the above-mentioned problems. The object of the present invention is to provide a cyclopentadienyl group-containing silane compound that is useful as a modifier for the invention and as a raw material for synthesizing silane compounds having various functional groups, and a simple method for producing the same. [0008]

[Means for Solving the Problems] As a result of intensive studies in order to meet the above-mentioned needs, the present inventors have found that chemical formula (2) % formula %]

[5] A halogen-containing silane compound represented by [00101],
By reacting cyclopentadienyl sodium under anhydrous conditions in a neutral polar organic solvent, the chemical formula

[Formula 6] A cyclopentadienyl group-containing silane compound represented by [0012] [X in the formulas (1) and (2) above is a halogen atom, and R1, R2, R3 and R4 are monovalent monovalent atoms of the same or different types. A hydrocarbon group, m is an integer of O to 3, n is an integer of 1 to 3, and when m is 0, n is 2 or 3] is reliably and easily obtained, and
The compound of chemical formula (1), in which more preferably two or more triorganosilyloxy groups are bonded to the silicon atom to which the cyclopentadienyl group or ω-cyclopentagenyl alkyl group is bonded, solves the above problem. Various synthetic resins, especially ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EP
It can be used more effectively as a modifier for M), and also because it can introduce different types of functional groups into the cyclopentadienyl group contained in the molecule through the Diels-Alder reaction. The present inventors have discovered that the present invention is also useful as a raw material for the synthesis of novel silane compounds, and have completed the present invention. [00131 The novel substance of the present invention has the chemical formula (1)% formula%
[7] [0015] (R1, R2, R3 and R4 are the same or different monovalent hydrocarbon groups, m is an integer of 0 to 3, n is 1
is an integer of ~3, and when m is O, n is 2 or 3) A cyclopentadienyl group-containing silane compound. [0016] The cyclopentadienyl group-containing silanized compound has R1, R2, R
Those in which 3 and R4 are methyl groups are preferred, and examples include the following. [0017]

embedded image [0018] Further, a method for producing the cyclopentadienyl group-containing silane compound represented by the chemical formula (1) is as follows. Chemical formula (2), [0019]

[00201 (X is a halogen atom, R1, R2, R3 and R4 are mutually the same or different monovalent hydrocarbon groups, m is an integer of 0 to 3, n is an integer of 1 to 3, and when m is O, n is 2 or 3) and cyclopentagenyl sodium under anhydrous conditions. The reaction is carried out in a neutral polar organic solvent. This reaction involves dropping a halogen-containing silane compound into a solution of cyclopentadienyl sodium synthesized by reacting sodium metal with a cyclopentadiene monomer in a neutral polar organic solvent while stirring. This is done by following the steps below. [0022]

[0023] R1, R2, R3 and R4 of the halogen-containing silane compound represented by the chemical formula (2) are lower alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, or aryl group, For example, a phenyl group is preferred, and a methyl group is particularly preferred from an industrial standpoint. Further, the halogen atom X in the chemical formula (2) is preferably, for example, a chlorine atom, a bromine atom, an iodine atom, or the like. Examples of the halogen-containing silane compound of the chemical formula (2) include the following. [0024] Cl5i(O5i(CH:+)3)3,
C1cH2S i (O5i (CH3)3 )3CI
CH2CH2CHzSi(O5!(CHa):+)3,
IS! (O5i(CH3)3)3. ICH2S i
(O5i (CH3)3 )3ICH2CH2CH2S
i (O8! (CH3)3 )3, ClSi CCH
3) (O3i (CH3)3 )2CICH2Si(C
H3)(O5i(CH3)3)2, C1cH2CH2C
H2S 1(CH3) (O5! (CH3)3)2 IS 1(CH3) (O5i (CH3)3)2,
lCH2S! (CH3) (O5i (CH3)3
)2ICH2CH2CH2S i (CH3) (O
3i (CH3)3)2 The neutral polar organic solvent used in the reaction of the above production method is preferably an ether solvent such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, dibutyl ether, or ethylene glycol dimethyl ether. . Further, a mixed solvent of the above-mentioned ether solvent and a saturated hydrocarbon solvent or an aromatic solvent may be used. Examples of the saturated hydrocarbon solvent include n-pentane, n-hexane, n-hebutane, isooctane, and cyclohexane. Examples of aromatic solvents include benzene, toluene, xylene, and mesitylene. Among the neutral polar organic solvents, tetrahydrofuran is particularly preferred because it can be removed by washing with water, is inexpensive, and is easy to handle. [0025] Since the reaction in the above production method is carried out under anhydrous conditions, the reaction operation is preferably carried out under an atmosphere of an inert gas, such as nitrogen, helium, or argon. When the reaction is carried out in the presence of water, side reactions such as loss of cyclopentadienyl sodium due to hydrolysis and hydrolytic condensation of chlorosilanes occur, resulting in a decrease in yield. [0026] After the reaction of the production method is completed, the chemical reaction formula (
The sodium halide produced by the reaction shown in 3) and some unreacted cyclopentadienyl sodium are removed by washing with water, then the solvent is removed by washing with water or distillation, and finally the cyclopentadienyl group-containing silane of the product is removed. The compound is isolated and purified, for example, by distillation under reduced pressure. [0027] In the reaction of the production method, various conditions may be set as follows. As for the amounts of the halogen-containing silane compound and cyclopentagenyl sodium used as raw materials, it is sufficient to use equivalent amounts since the reaction proceeds almost quantitatively as shown in the chemical reaction formula (3). [0028] The reaction temperature may be set as follows. When dropping the halogen-containing silane compound, the temperature is usually -50°C to the boiling point of the solvent, preferably 0°C to room temperature. From the end of the dropwise addition to the completion of the reaction, the temperature is usually -5
0°C to the boiling point of the solvent, preferably 0°C to the boiling point of the solvent. [0029] Further, the reaction time can be freely selected usually within the range of 1 to 80 hours. Since the reaction proceeds satisfactorily under atmospheric pressure, it is usually sufficient to carry out the reaction at normal pressure, but it can also be carried out under increased pressure if necessary. [00301 Note that in the halogen-containing silane compound of the chemical formula (2), when m = 1 to 3, the chemical reaction formula (3
) When X=chlorine atom, several days are required for the reaction to be completed, and when X=iodine, several hours may be sufficient. Therefore, in order to obtain the desired product in high yield in a short time, it is preferable to use an iodine-substituted halogen-containing silane compound. m=1
The method for producing the iodine-substituted halogen-containing silane compound of ~3 is as follows. Iodine-substituted halogen-containing silane compounds can be easily prepared by reacting the corresponding chlorine-substituted halogen-containing silane compounds with sodium iodide in a ketone solvent such as acetone, methyl ethyl ketone, or methyl isobutyl ketone at the reflux temperature of the solvent. can be obtained quantitatively. [00311

[Action] The action of the compound of the present invention when applied to a raw material for the synthesis of a novel functional silane compound is as follows. [003-2] The cyclopentadienyl group contained in the molecule of the cyclopentadienyl group-containing silane compound of the present invention is a compound in which at least one electron-withdrawing group is bonded to the carbon atom of the double bond. (Genophile) can be easily added by Diels-Alder reaction. Therefore, the cyclopentadienyl group-containing silane compound of the present invention represented by the chemical formula (1) can serve as a raw material for the synthesis of a novel functional silane compound. Diels Alder
Genophiles that can be added to the cyclopentadienyl group by reaction include, for example, thiophene, benzoquinone, acrylic acid, methacrylic acid, maleic anhydride, and acrylonitrile. By adding the Genophile, novel functional silane compounds having respective functional properties can be obtained. [0033] [0033] Examples of the present invention will be described below, but the present invention is not limited to the following examples. [0034] Example 1 Synthesis of γ-cyclopentadienylprobyltris(trimethylsilyloxy)silane 500 m equipped with a thermometer, a stirring device, and a Dimroth condenser
The interior of the Shiro glass reactor No. 1 was sufficiently purged with nitrogen in advance. Thereafter, 108.5 g of a 2.0 mol/I tetrahydrofuran (THF) solution of cyclopentadienyl sodium (containing 0.23 mol of cyclopentadienyl sodium) was added to the reactor, and the mixture was cooled with water and stirred for 27 to 30 minutes. γ-Iodopropyltris(trimethylsilyloxy)silane 10 while maintaining a temperature range of 28°C.
8.3 g (0.22 mo I) was added dropwise over 2 hours. As the mixture was added, heat generation occurred, and at the same time, a large amount of fine, reddish-colored crystals precipitated. Next, after further stirring at room temperature for 1 hour, the internal composition was measured by GC (gas chromatography), and it was found that the raw material γ-iodopropyltris(trimethylsilyloxy)silane was completely consumed. Next, 100 ml of water was added to the solution to crush unreacted cyclopentadienyl sodium, and the solution was further washed with water until the aqueous layer became neutral. Next, THF was distilled off from this liquid using an evaporator, and then distilled under reduced pressure.
57.9 g of a compound with a boiling point of mmHg were obtained. Mass spectrum (MS), nuclear magnetic resonance spectrum (IHNMR), infrared absorption spectrum (IR) of this compound
), the following results were obtained, and it was confirmed that it was the target product, γ-cyclopentadienylpropyltris(trimethylsilyloxy)silane. Yield is 6
It was 5%. [0035] Measurement results/Mass spectrum (MS): l/
Z (spectral intensity ratio, attribution) 402 (38, M”), 387 (72, M-CH3)
, 295 (100,5i (O5i (OL) 3) 3, 279 (24). 265 (14), 249 (6), 233 (4),
208 (98), 193 (56), 179 (12
), 165(66), 137(26). 121(8), 106(12), 91(12),
73(98,5i(CH3)3"), 59(40). Nuclear magnetic resonance spectrum (IHNMR): δ(pp
m) [0036]

[0037] a: 0.10 (27H, s)
b: 0.28-0.63 (2H, m) c: 1.20-1.85 (2H, m) d: 2
．． 10-2.55 (2H, m) e: 2.68-3.
00(LH,m) f:5.77~6.45(4H
, In) ・Infrared absorption spectrum (IR): (cr 1) 30
50, 2950.2900.1450.1415.13
70.1347.1256.1185.1060(S
its i), 840°757, 715.680 Example 2 Cyclopentadienyltris(trimethylsilyloxy)
Synthesis of silane The interior of a 500 ml four-glass reactor equipped with a thermometer, a stirring device, and a Dimroth condenser was sufficiently purged with nitrogen in advance. Thereafter, 132.5 g of a 2.0 mol/l tetrahydrofuran (THF) solution of cyclopentadienyl sodium (containing 0.28 mol of cyclopentadienyl sodium) was added to the reactor, and the mixture was cooled with water and stirred for 13 to 30 minutes. While maintaining a temperature range of 25°C, chlorotris(trimethylsilyloxy)silane 9
2.7 g (0.28 m○1) was added dropwise over 3.3 hours. As the mixture was added, heat was generated, and at the same time, fine azuki-colored crystals were precipitated. Next, the temperature of the solution was raised and the solution was aged at 74° C. for 24 hours under reflux of THF, and then 100 ml of water was added to crush unreacted cyclopentadienyl sodium, and the solution was washed with water one more time. Next, it was dehydrated with sodium sulfate, and THF was distilled off from this liquid using an evaporator.
A compound having a boiling point of 68-b was obtained by distillation under reduced pressure. Mass spectrum (MS), nuclear magnetic resonance spectrum (IHNMR) of this compound
When the infrared absorption spectrum (IR) was measured, the following results were obtained, and it was confirmed that it was the target product, cyclopentadienyltris(trimethylsilyloxy)silane. The measurement results are shown below. [0038] Measurement results/Mass spectrum (MS): m/
z (spectral intensity ratio, attribution) 360 (5, M”), 345 (5, M C1h), 2
95(24,5i(O3i(CH3)3)+”), 2
57(8), 241(4). 207 (100), 191 (5), 123 (55)
, 95(5), 73(70), 59(5), 4
5(5).・Nuclear magnetic resonance spectrum (IHNMR): δ(p
pm) [0039]

[00401a:0.10(27H,s) b:
2.90-3.15 (LH. m) c: 6.20-7.00 (4H, m) Infrared absorption spectrum (IR): (cr') 3060
, 2955.2890.1500.1460.1420
．． 1380.1350.1256.1070 (SiO5
i), 955,841°759,700 [00411 Effects of the Invention] As explained in detail above, the cyclopentadienyl group-containing silane compound of the present invention can be used with various synthetic resins, especially ethylene-propylene-diene. Polymer (
EPDM) and ethylene-propylene copolymer (EPM)
It is useful as a modifier. Furthermore, the compound of the present invention can be used as a raw material for the synthesis of various novel functional silane compounds, since it is possible to introduce a different type of functional group into the cyclopentadienyl group contained in the molecule by a Diels-Alder reaction. Further, according to the production method of the present invention, by using readily available raw materials, a novel cyclopentadienyl group-containing silane compound can be reliably produced in a simple process. Continuing from the front page (72) Inventor Mikio Endo 28-1 Nishi-Fukushima, Oaza Nishi-Fukushima, Kubiki-mura, Nakakushi-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthesis Technology Laboratory (72) Inventor Jinketsu 1) Toru Niigata Prefecture, Nakakushi-gun, Kubiki-mura, Oaza Nishi Fukushima 28-1 Shin-Etsu Chemical Co., Ltd. Synthesis Technology Laboratory

Claims (4)

[Claims] [Claim 1] General formula (1) [Chemical formula 1] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (R1, R2, R3 and R4 are mutually the same or different monovalent hydrocarbon groups, m is 0 -3, n is an integer of 1 to 3, and when m is 0, n is 2 or 3) A cyclopentadienyl group-containing silane compound. 2. The cyclopentadienyl group-containing silane compound according to claim 1, wherein R1, R2, R3 and R4 are methyl groups. [Claim 3] A halogen-containing silane compound represented by general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) A halogen-containing silane compound represented by the formula (2) and cyclopentadienyl sodium are mixed in a neutral polar organic solvent under anhydrous conditions. The general formula (1
) [Chemical formula 3] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) Method for producing a cyclopentadienyl group-containing silane compound [X in the above formulas (1) and (2) is a halogen atom, R1 , R2, R3 and R4 are the same or different monovalent hydrocarbon groups, m is an integer of 0 to 3, n is an integer of 1 to 3, and when m is 0, n is 2 or 3]. 4. The method for producing a cyclopentadienyl group-containing silane compound according to claim 3, wherein R1, R2, R3 and R4 are methyl groups.