JPH05230078A - New reactive silicone compound - Google Patents

Abstract

PURPOSE:To obtain a new reactive silicone compound combinable with a different kind of material, having thermal stability. CONSTITUTION:A terminal carboxyl group-containing reactive silicone compound of formula I (Z is direct bond, 1-20C bifunctional hydrocarbon or bifunctional aromatic group; X is 1 or 2; (n) is 1-200) such as a compound of formula II. The compound of formula I, for example, is obtained by reacting 1mol equivalent of a silicone compound of formula III having a butadiene monomer unit with 2mol equivalent of an aromatic carboxylic acid of formula VI having a double bond in the end or an aromatic carboxylic acid (e.g. acrylic acid or o-styrenecarboxylic acid) having a double bond in the end in the presence of preferably a catalyst of chloroplatinic acid in a solvent such as THF.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reactive silicone compound containing a terminal carboxyl group.

[0002]

2. Description of the Related Art Polysilicone is one of useful materials used in various forms such as silicone rubber, silicone oil, surface modifiers and sealing agents. Polybutadiene is also one of the materials widely used in various fields as tires and general-purpose materials as butadiene rubber (solid rubber, liquid rubber, etc.). In terms of thermal properties, polysilicone has a relatively high thermal decomposition onset temperature,
Although it can be used in a temperature range of up to 250 ° C, once pyrolysis begins, the rate of weight loss (that is, the rate of pyrolysis) tends to be fast, and polybutadiene cannot be crosslinked in a high temperature range. Is unsuitable for use in
It is used in the temperature range of 70 to 100 ° C. A material having both properties is known as a silicone having a linear oligobutadiene unit and can be synthesized by a known method (Polym.Prep.Jap.vo140, No.6,1836), but it is combined with a different material. Only the method of polymer blending can be adopted as a means for matching.

[0003]

SUMMARY OF THE INVENTION Therefore, the present invention is intended to solve the above-mentioned problems in the prior art, and the objective is to be able to combine different kinds of materials, It is intended to provide a novel thermally stable silicone compound containing a reactive carboxyl group.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted research to solve the above-mentioned problems in the prior art, and as a result, the end portion of silicone having a butadiene monomer unit, which is a known compound, has been investigated. Of Si is used as a hydrosilane having a hydrogen atom, and this is reacted with an aliphatic carboxylic acid having a double bond at the terminal or an aromatic carboxylic acid having a terminal double bond-containing group by a known method in the presence of a platinum catalyst. As a result, it was found that a silicone having a linear oligobutadiene unit having a carboxyl group which is a reactive functional group can be easily synthesized, and the present invention has been completed.

That is, the present invention resides in a terminal carboxyl group-containing reactive silicone compound represented by the following general formula (I).

[Chemical 2] (In the formula, Z represents a direct bond, a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic group, and x represents an integer of 1 or 2, n is 1 to 20
Represents an integer of 0. )

The present invention will be described in more detail below. The terminal carboxyl group-containing reactive silicone compound represented by the general formula (I) is a novel compound which has not been described in any literature, and is a silicone compound 1 containing a butadiene monomer unit represented by the following general formula (II). The molar equivalent and the following general formula (II
I) an aliphatic carboxylic acid having a double bond at the terminal or 2 molar equivalents of an aromatic carboxylic acid having a terminal double bond-containing group at a room temperature in the presence of a platinum catalyst in a reaction solvent. It can be obtained by reacting.

[Chemical 3] (In the formula, Z, n and x have the same meanings as described above.)

The aliphatic carboxylic acid having a double bond at the terminal or the aromatic carboxylic acid having a terminal double bond-containing group represented by the general formula (III) is not particularly limited, Is an aliphatic carboxylic acid containing a double bond at the linear end such as acrylic acid, vinyl acetic acid, 4-pentenoic acid, 10-undecenoic acid, 17-octadecenoic acid, o-styrenecarboxylic acid, m-styrene. Examples thereof include aromatic carboxylic acids having an aromatic ring and a terminal double bond-containing group such as carboxylic acid and p-styrenecarboxylic acid.

As the platinum-based catalyst, chloroplatinic acid (H ₂ P
tCl ₆ ) is preferably used. In addition, the reaction solvent must be one that does not react with the reaction components during the reaction and that sufficiently dissolves the reaction product. Specific examples include diethyl ether, tetrahydrofuran, diglyme, 1,4-dioxane, petroleum ether and the like. The reaction product can be purified by a conventional method.

The silicone compound containing the butadiene monomer unit represented by the general formula (II) can be synthesized by a known reaction route shown below.

[Chemical 4] (In the formula, n and x have the same meaning as described above.)

The catalysts and reducing agents used in the above reaction route are as follows. Examples of the alkali metal include metal Li, metal Na, and metal Ka. An acetyl chloride-aluminum chloride catalyst is preferably used as the chlorinating agent. LiAlH ₄ is preferably used as the reducing agent. As the Pt-based catalyst, dichlorobis (benzonitrile) palladium (II) [PtCl ₂ (C ₆ H
₅ CN) ₂ (II)], tetrakis (triphenylphosphine) palladium (0) [Pt (PPh ₃ ) ₄ (0)]
Can be used. As the Ni-based catalyst, dichlorobis (triethylphosphine) nickel (II) [NiCl ₂ (P
Et ₃ ) ₂ (II)] is preferably used.

In the above reaction route, a reaction solvent is optionally used, but the reaction solvent must be one that does not react with the reaction components during the reaction and that sufficiently dissolves the reaction product. Specific examples include diethyl ether, tetrahydrofuran, diglyme, 1,4-dioxane, petroleum ether and the like. In the reaction, it is necessary to thoroughly dehydrate and purify.

[0012]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 1) Synthesis of hexamethyldisilane 500 m equipped with a dry nitrogen introducing tube and a Dimroth cooling tube
In a four-neck round bottom flask, 1.1 mol (7.63 g) of granular metal lithium and 200 ml of dry tetrahydrofuran.
, And after cooling to 0 ° C, trimethylchlorosilane 1
250 ml of a dry tetrahydrofuran solution containing mol (99.62 g) was added dropwise over 2 hours so as not to generate heat, and reacted for 1 hour as it was. Then, the temperature was raised to 55 ° C., and the reaction was continued for further 60 hours. Then, the lithium chloride produced by the glass filter and the excess metallic lithium were separated by filtration and washed thoroughly with tetrahydrofuran. The filtrate was distilled off under normal pressure to remove tetrahydrofuran and unreacted trimethylchlorosilane to obtain hexamethyldisilane. The yield was 74%.

2) Synthesis of dichlorotetramethyldisilane In a 300 ml three-necked round bottom flask, 98.66 g (740 mmol) of anhydrous aluminum chloride was placed, and 58.12 g (740 mmol) of acetyl chloride was gradually added thereto so as not to generate heat, and reacted. The vessel was transferred to an ice bath, and 54.1 g (369 mmol) of hexamethyldisilane obtained in 1) was added dropwise over 1 hour. The mixture was stirred for 30 minutes as it was, heated to 50 ° C., and reacted for 16 hours. After the reaction, the mixture was filtered in a nitrogen stream, the solid matter was washed with dry hexane, the filtrates were collected and distilled to obtain the desired product, dichlorotetramethyldisilane, in a yield of 85%. ¹ H-NMR (ppm): 0.4 (Si-Me: solvent C
₂ H ₂ Cl ₄ ), ¹³ C-NMR (ppm): 18.0
(Si-Me) IR (cm ^-1 ): 2960, 2900, 1460, 14
00 (Si-Me), 1290, 760, 630 (Si
-C), 470 (-Cl)

3) Synthesis of α, ω-bis (dimethylchlorosilyl) -2-butenes (a) Synthesis of x = 1 Dichlorotetramethyldisilane 1 obtained in 2) above
8.73 g (100 mmol) and dry tetrahydrofuran 30ml and tetrakis (triphenylphosphine) palladium _{(0) [Pd (PPh 3} ) 4 (0)] 0.53
8 g (1 mmol) of the content of 100 m under dry nitrogen
After being placed in a glass autoclave (1), the autoclave was placed in liquid nitrogen for cooling, and deaeration was repeated 3 times under vacuum. After the temperature was raised to room temperature, butadiene gas was pressured up to 2 atm and reacted with stirring. As the reaction progressed, the pressure gauge decreased, and when the pressure became 1 atm, butadiene gas was further charged, and the operation was repeated until the pressure gauge did not decrease. After the reaction was completed, butadiene gas was released, the content was filtered through Celite, the Celite was thoroughly washed with dry tetrahydrofuran, and the filtrate was concentrated to obtain a crude product. The crude product was distilled under reduced pressure to give 83-84
A fraction of ° C / 40 mmHg was obtained with a yield of 48% (cis form only). result of analysis

[Chemical 5] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
(S) 12H (Si- Me : α), 1.30 (d)
_{4H (Si- CH 2 -CH =:} β), 5.3 (q) 2
H (C H = C H : γ) ¹³ C-NMR (solvent CDCl ₃ ) (ppm): 18.
1 (Si- Me: α), 34.3 (-Si- C H 2 -C
H =: β), 123.1 (= C H-CH ₂ : γ) IR (cm ⁻¹ ): 2965, 2910, 2880 (-C
_{H 3, -CH 2 -, =} CH- telescopic), 1461,14
09,1293,765,637 (Si-C bending angle),
1640 (-CH = CH-in-plane bending angle), 962, 694
(-CH = CH-out-of-plane bending angle), 472 (-Cl)

(B) Synthesis in the case of x = 2 Tetrakis (triphenylphosphine) palladium (0) [Pd of the palladium catalyst in the case of x = 1 above
(PPh ₃ ) ₄ (0)] 0.538 g (1 mmol)
Dichlorobis (benzonitrile) palladium (II)
[PdCl ₂ (PhCN) ₂ (II)] 0.383 g (1
Except that it was replaced with
A fraction of 100 ° C./0.38 mmHg was obtained with a yield of 57%. result of analysis

[Chemical 6] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
(S) 12H (Si- Me : α), 5.3 (q) 2
H (C H = CH: γ ), 5.0 (q) 2H (C = C
H: γ ′), 1.30 (d) 4H (Si— CH ₂ —C
H =: β), 1.60 (q) 4H (Si- CH ₂ -C
H =: β ′) (cis / trans = 15/8) ¹³ C-NMR (solvent CDCl ₃ ) (ppm): 18.
3 (Si- Me: α), 34.2 (-Si- C H 2 -C
H =: β), 37.2 ( -CH 2 - C H 2 -CH =:
β '), 123.1 (C H = CH 2: γ), 128.1
_{(C H = CH 2: γ} ') IR (cm -1): 2962,2905,2879 (-C
_{H 3, -CH 2 -, =} CH- telescopic), 1464,14
05, 1297, 763, 636 (Si-C bending angle),
1642 (-CH = CH-in-plane bending angle), 965,692
(-CH = CH-out-of-plane bending angle), 468 (-Cl)

4) Synthesis of reductant (a) In the case of x = 1 2.50 g (10.3 mmol) of α, ω-bis (dimethylchlorosilyl) -2-butene obtained in 3) above and dry tetrahydrofuran 40 ml was placed in a 100 ml three-necked flask equipped with a dry nitrogen line, a Dimroth reflux condenser, and a dropping funnel with a parallel tube of 30 ml, immersed in an ice bath adjusted to -10 ° C, and lithium aluminum hydride (LiAlH ₄ ) 0 was added from the dropping funnel. .39 g
40 ml of a tetrahydrofuran solution (1 mmol) was added dropwise for 40 minutes so as not to generate heat and reacted at -10 ° C for 1 hour. Then, the temperature was raised to room temperature and the reaction was continued for 24 hours. After the reaction, the excess lithium aluminum hydride was neutralized with ammonium chloride, the solid matter and the solution were filtered off under dry nitrogen, concentrated and then distilled under reduced pressure to obtain a fraction of 83-84 ° C./40 mmHg in a yield of 70. Earned in%. result of analysis

[Chemical 7] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
(S) 12H (Si- Me : α), 0.20 (s)
2H (Si- H :?), 1.30 (d) 4H (Si-
_{CH 2 -CH =: β),} 5.3 (q) 2H (C H = C
H : γ) ¹³ C-NMR (solvent CDCl ₃ ) (ppm): 18.
1 (Si- Me: α), 34.3 (-Si- C H 2 -C
H =: β), 123.1 (= C H-CH ₂ : γ), 12
_{8.1 (C H = CH 2:} γ ') IR (cm -1): 2965,2910,2880 (-C
_{H 3, -CH 2 -, =} CH- telescopic), 1461,14
09,1293,765,637 (Si-C bending angle),
1640 (-CH = CH-in-plane bending angle), 962, 694
(-CH = CH-out-of-plane bending angle)

(B) When x = 2 In the above synthesis method, 2.50 g (10.3 mmol) of α, ω-bis (dichlorosilyl) -2-butene was added to α, ω-bis (dimethylchlorosilyl). Except that 2.95 g (10 mmol) of -2,6-octadiene was used.
Perform the same reaction treatment, 89-90 ℃ / 0.45mmH
A fraction of g was obtained with a yield of 72%. result of analysis

[Chemical 8] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
1 (s) 12H (Si- Me : α), 5.25 (q)
2H (C H = CH: γ ), 5.10 (q) 2H (C
H = CH: γ ′), 1.36 (d) 4H (Si— CH
_2- CH =: β), 1.64 (q) 4H (Si- CH
_2- CH =: β ') (cis / trans = 15 /
8), 0.20 (s) 4H (Si- H: δ) 13 C-NMR ( solvent _{CDCl 3) (ppm): 18} .
1 (Si- Me: α), 34.4 (-Si- C H 2 -C
H =: β), 37.0 ( -CH 2 - C H 2 -CH =:
β '), 123.7 (C H = CH 2: γ), 128.0
_{(C H = CH 2: γ} ') IR (cm -1): 2964,2902,2878 (-C
_{H 3, -CH 2 -, =} CH- telescopic), 1461,14
08, 1294, 765, 632 (Variation of Si-C),
1640 (-CH = CH-in-plane bending angle), 967, 693
(-CH = CH-out-of-plane bending angle), 465 (-Cl)

5) Chain Length Extension of Siloxane Moiety J. F. Hyde “J. Am. Chem. Soc.” 7
5, p. 2166 (1953), and E. N. Tin
yskova et al., "J. Polym. Sci." 52 vol. 1
According to the polycondensation method involving dehydrogenation between oligosilanols described on page 59 (1961) and the like, the chain length was extended to quantitatively obtain oligomers having a predetermined chain length and different compositions.

[Chemical 9]

6) Coupling reaction with a carboxylic acid having a double bond at the terminal Among the silicone oligomers containing a linear butadiene monomer unit in which the chain length of the siloxane moiety obtained in 5) above is extended, x 2.16g (2 mmol) of the compound of n = 1 and n = 8 was placed in a 100 ml three-necked round bottom flask equipped with a Dimroth type reflux condenser, a dropping funnel and a dry nitrogen introducing tube, and 50 ml of dry tetrahydrofuran was added thereto, and platinum chloride was added thereto. Two drops of acid were added from a 5 ml syringe and stirred at room temperature for 15 minutes.
Then, a tetrahydrofuran solution (10 ml) of 0.189 g (2.2 mmol) of vinyl acetic acid was added dropwise over 20 minutes, and the mixture was stirred for 24 hours at room temperature. After the reaction,
A 0.1N aqueous sodium hydroxide solution was added, and the mixture was transferred to a separating funnel and shaken vigorously to separate the aqueous phase and the tetrohydrofuran layer, and excess vinyl acetic acid and chloroplatinic acid were removed. The tetrahydrofuran layer was dried over anhydrous magnesium sulfate, concentrated and dried under reduced pressure to obtain a carboxyl group-terminated silicone containing a butadiene monomer unit with a yield of 95%.

[Chemical 10] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
1-0.45 108H (Si- Me : α, α '),
5.20 (q) 2H (C H = CH: γ), 1.34
_{(D) 4H (Si- CH 2} -CH =: β), 0.90
(T) 4H (δ), 1.62 (m) 4H (ε),
2.40 (t) 4H (ζ) IR (cm ⁻¹ ): 3100-3400 (—CO OH ),
2960,2900,2875 (-CH _3, -CH
₂ -, = CH- telescopic), 1720 (- CO OH) , 1
462, 1410, 1290, 768, 635 (Si-
Deflection of C), 1643 (-CH = CH-in-plane variation), 9
67,693 (-CH = CH-out-of-plane bending angle)

Example 2 The silicone oligomer containing a butadiene monomer unit (x = 1, n = 8) of Example 1 was replaced with a silicone oligomer containing a butadiene monomer unit (x = 2, n = 2). A terminal carboxyl group-containing silicone containing oligobutadiene units was obtained in a yield of 91% by the same method except for the above.

[Chemical 11] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
1-0.45 36H (Si- Me : α, α '), 5.
20 (q) 2H (C H = CH: γ), 5.05 (q)
2H (C H = CH: γ ′), 1.34 (d) 4H
_{(Si- CH 2 -CH =: β} ), 1.64 (q) 4H
_{(CH 2 - CH 2 -CH =} : β '), 0.90 (t)
4H (δ), 1.62 (m) 4H (ε), 2.40
(T) 4H (ζ) IR (cm ⁻¹ ): 3100-3400 (—CO OH ),
2960,2900,2875 (-CH _3, -CH
₂ -, = CH- telescopic), 1720 (- CO OH) , 1
462, 1410, 1290, 768, 635 (Si-
Deflection of C), 1643 (-CH = CH-in-plane variation), 9
67,693 (-CH = CH-out-of-plane bending angle)

Example 3 0.189 g (2.2 mmol) of the vinyl acetic acid of Example 1
0.405 g (2.2 mmol) of 10-undecenoic acid
The reaction was performed in the same manner except that the above was replaced with to obtain a terminal carboxyl group-containing silicone containing a butadiene monomer unit in a yield of 89%.

[Chemical 12] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
1-0.45 108H (Si- Me : α, α '),
5.20 (q) 2H (C H = CH: γ), 1.34
_{(D) 4H (Si- CH 2} -CH =: β), 0.90
~2.40 (c) 40H (δ) IR (cm -1): 3100-3400 (-CO OH),
2964,2910,2872 (-CH _3, -CH
₂ -, = CH- telescopic), 1719 (- CO OH) , 1
468, 1414, 1289, 765, 633 (Si-
Deflection of C), 1648 (-CH = CH-in-plane deflection), 9
64,690 (-CH = CH-out-of-plane bending angle)

Example 4 0.189 g (2.2 mmol) of vinyl acetic acid of Example 2
0.343 g (2.2 mmol) of 10-undecenoic acid
The reaction was performed in the same manner except that the above was replaced with, to obtain a terminal carboxyl group-containing silicone containing a linear oligobutadiene unit with a yield of 87%.

[Chemical 13] ¹ H-NMR (solvent CDCl ₃ ) (ppm): 0.4
1-0.45 36H (Si- Me : α, α '), 5.
20 (q) 2H (C H = CH: γ), 5.05 (q)
2H (C H = CH: γ ′), 1.34 (d) 4H
_{(Si- CH 2 -CH =: β} ), 1.64 (q) 4H
_{(CH 2 - CH 2 -CH =} : β '), 0.90~1.6
2 (m) 40H (δ) IR (cm ⁻¹ ): 3100-3400 (—CO OH ),
2962,2905,2874 (-CH _3, -CH
₂ -, = CH- telescopic), 1722 (- CO OH) , 1
464, 1413, 1294, 765, 631 (Si-
Deflection of C), 1640 (-CH = CH-in-plane variation), 9
65,694 (-CH = CH-out-of-plane bending angle)

The thermal decomposition initiation temperature and the 50% by weight decomposition temperature of the silicone containing terminal carboxyl group and the known silicone rubber and butadiene rubber obtained in the above examples were investigated. The test was performed using a thermogravimetric analyzer TGA-30 manufactured by Shimadzu Corporation, using a sample of 100 mg, at a temperature rising temperature of 10 ° C./min. The results are as shown in Table 1 below.

[Table 1]

[0024]

INDUSTRIAL APPLICABILITY The reactive silicone compound containing a terminal carboxyl group of the present invention is a novel compound, which is very stable thermally and, as is clear from the above comparison, silicone rubber and butadiene. It retains both properties of rubber. Further, since it has good compatibility with other resins, it can be used for modifying other resins. Further, it is also useful as a resin raw material such as polyimide or polyamide.

Claims (1)

[Claims] 1. A reactive silicone compound containing a terminal carboxyl group represented by the following general formula (I). [Chemical 1] (In the formula, Z represents a direct bond, a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic group, and x represents an integer of 1 or 2, n is 1 to 20
Represents an integer of 0. )