JPH1192562A - Curable composition and preparation of molded item therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable compsn. which gives a molded item excellent in mechanical properties by compounding a silicon compd. having Si-H groups and a mol.wt. of a specified value or lower, a compd. having propargyl ether groups, and a hydrosilylation catalyst. SOLUTION: This compsn. contains a silicon compd. represented by formula I, etc., and having at least two Si-H groups and a mol.wt. of 1,000 or lower, a compd. represented by formula III, etc., (e.g. a compd. represented by formula II) and having propargyl ether groups in such an amt. of this compd. that the molar ratio of the Si-H group of the foregoing compd. to the carbon-carbon triple bond of this compd. is 0.5-5, and a hydrosilylation catalyst (e.g. chloroplatinic acid) in a molar ratio to Si-vinyl group of 101<-1> -10<-8> . 100 pts.wt. this compsn. is dissolved in 0-1.000 pts.vol. org. solvent (e.g. tetrahydrofuran), then is kept at the b.p. of the solvent or lower for at least 8 hr, and is raised to 20-250 deg.C, thus giving a molded item having a thickness of 1.0 mm or higher. In formula III, R<1> is a group represented by formula IV, etc.; and R and R' are each a 0-20C monovalent hydrocarbon group. In formula I, R is a 1-20C monovalent hydrocarbon group; and X is a divalent group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition using a compound having a SiH group and a compound having a propargyl ether group.

[0002]

2. Description of the Related Art As a curable composition curable by a hydrosilylation reaction, a rubber-based (straight-chain) / resin-based (high crosslinking density type) siloxane-based curable composition having a main chain consisting of only a siloxane unit Things are known. However, since the main chain consists only of a siloxane unit, there is a problem that the mechanical properties required for use as a structural material are low. Also, Japanese Patent Application Laid-Open No. 08-1576
03 shows a method for synthesizing a curable composition curable by a hydrosilylation reaction. However, their flexural modulus was 1.36 to 1.79 GPa, which was a small value for use as a structural material.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an
An object of the present invention is to provide a silicon-based curable composition curable by a one-pot reaction using a compound having an H group and a compound having a propargyl ether group. According to the present invention, a silicon-based cured product having excellent mechanical properties can be obtained.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies and as a result,
The present inventors have found that a curable composition curable by a hydrosilylation reaction gives a cured product having excellent mechanical properties, and have accomplished the present invention. That is, as the component (A), a molecular weight of 100 having at least two or more SiH groups in one molecule.
0 or less silicon compound, the following formula (1) as component (B):
A compound containing a propargyl ether group represented by

[0005]

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In the formula, R ¹ is a group independently selected from the following.

[0007]

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[0008]

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(R and R ′ are monovalent hydrocarbon groups having 0 to 20 carbon atoms and may be the same or different.
Ar is an aromatic group. A) a curable composition containing a hydrosilylation catalyst as a component (C) (claim 1);
2. The molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.5-5.
2. The curable composition according to claim 1, wherein the molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.6-3. A curable composition (Claim 3), wherein the molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.8 to 1.
5. The curable composition according to claim 1 (claim 4), wherein the curable composition is uniformly dispersed in 0 to 1000 parts by volume of an organic solvent with respect to 100 parts by weight of (A) to (C). The cured curable composition according to any one of claims 1 to 4 is kept at a temperature lower than the boiling point of the organic solvent used for 8 hours or more, and then 20 to
A method for producing a molded body having a thickness of 1.0 mm or more, characterized in that the temperature is raised stepwise or continuously at a temperature of 250 ° C (Claim 5).

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a component (A) having a molecular weight of at least 2 having at least two SiH groups per molecule.
000 or less silicon compound, a compound containing a propargyl ether group represented by the following formula (1) as a component (B),

[0011]

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In the formula, R ¹ is a group independently selected from the following.

[0013]

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[0014]

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(R and R ′ are monovalent hydrocarbon groups having 0 to 20 carbon atoms, and may be the same or different.
Ar is an aromatic group. A) a curable composition containing a hydrosilylation catalyst as a component (C); Component (A) used in the present invention contains at least two or more S
Any silicon compound having an iH group and having a molecular weight of 1,000 or less can be used without particular limitation. _{Formula: HSiR 2 -X-SiR 2 H} (2) HSiR 2 H (3) H a SiR (4-a) (4) H (a-1) SiR (4-a) - (X) m (SiRH) _n SiR _(4-a) H _(a-1) (5) R '-(X) _m (SiRH) _{(n + 2)} -R' (6) [X-SiR _(4-a) H _{(a- 2)} ] _{(n + 2)} (7) (wherein, R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ′ represents hydrogen or a monovalent hydrocarbon group, and X represents 2
A represents an integer of 3 to 4, a represents an integer of 0 to 30, and m represents an integer of 1 to 31. ) Or three or more hydrogens on the aromatic ring are SiR ₂ H,
An aromatic ring substituted with SiRH ₂ or SiH ₃ (R represents a monovalent organic group having 1 to 20 carbon atoms) and a hydrosilane comprising the substituent can be preferably used. One or two or more of these compounds may be used. Examples of the monovalent organic group in the formulas (2) to (7) include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, isoamyl, n-octyl, n-nonyl, Examples include a phenyl group, a chloro group, and a trimethylsiloxy group, and a methyl group and a phenyl group are preferable. A divalent group in the formulas (2), (5), (6) and (7): X is
Specifically, the following structures are exemplified.

[0016]

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(In the formula, n represents an integer of 1 to 4.)

[0018]

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(Wherein Me represents a methyl group and n is the same as described above). Furthermore,

[0020]

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(Wherein n is as defined above) is particularly preferred. The hydrogen or the monovalent organic group R ′ in the formula (7) is specifically hydrogen, methyl, ethyl, phenyl, trimethylsiloxy, or the like, and hydrogen is particularly preferable.
As a preferred specific example of the component (A),

[0022]

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(Wherein Me is the same as above, Ph is a phenyl group, and n is an integer of 3 to 5). The molecular weight of the component (A) of the present invention is 1000
Or less, more preferably 500 or less. As the component (B) used in the present invention, any compound having a propargyl ether group represented by the following formula (1) can be used without particular limitation.

[0024]

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Specific examples of R ¹ include the following structures.

[0026]

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[0027]

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(R and R ′ are monovalent hydrocarbon groups having 0 to 20 carbon atoms, and may be the same or different.
Ar is an aromatic group. ) Of these,

[0029]

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Is preferred. Furthermore,

[0031]

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Is particularly preferred. As preferred specific examples of the component (B),

[0033]

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The following structure can be given. All compounds involved in the addition reaction in the curable composition of the present invention
The ratio of iH group / carbon-carbon triple bond is preferably from 0.5 to 5, more preferably from 0.6 to 3, and particularly preferably from 0.8 to 1.5 from the mechanical properties of the obtained cured product. The hydrosilylation catalyst which is the component (C) of the first invention is a complex of platinum, alumina, silica, carbon black or the like, on which solid platinum is supported, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Complexes such as ketones, platinum-olefin complexes (for example, Pt (CH ₂ ＣＨCH ₂ ) ₂ (PP
_{h 3) 2 Pt (CH 2} = CH 2) 2 Cl 2); platinum-vinyl siloxane complex (e.g., Ptn (ViMe ₂ SiOSiM
e ₂ Vi) _m , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , P (PB
u) ₄ ), a platinum-phosphite complex (eg, Pt [P
(OPh) ₃ ] ₄ ) (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, m,
n represents an integer), dicarbonyldichloroplatinum,
Ashby U.S. Pat. No. 3,159,601.
And the platinum-hydrocarbon complex described in US Pat. No. 3,159,662, and the platinum alcoholate catalyst described in Lamoreaus US Pat. No. 3,220,972. In addition, Modik (M
Odic) in U.S. Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include:
RhCl (PPh_Three)_Three, RhCl _Three, RhAl_TwoO_Three, R
uCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, PdCl
_Two・ _TwoH_TwoO, NiCl_Two, TiCl_Four, Etc.
You. These catalysts may be used alone or in combination of two or more.
You can use it. From the viewpoint of catalytic activity, chloroplatinic acid, white
Gold-olefin complex, platinum-vinylsiloxane complex, white
Gold acetylacetonate is preferred. As the amount of catalyst
Although there is no particular limitation, with respect to 1 mol of a Si-vinyl group,
10^{ー 1}-10^-8It is good to use in the range of mol. further
Is 10^{ー 3}-10^-6mol is preferred.

In the present invention, a storage stability improving agent can be used in combination for the purpose of enhancing the storage stability of the curable composition. As the storage stability improver, a storage stability improver such as a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide may be used in combination. . Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohol, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphone, and triorganophosphite. Examples of the organic sulfur compound include organomercaptan, diorganosulfide, hydrogen sulfide, benzothiazole, benzothiazole disulfite, and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. As organic peroxides, di-t
-Butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like. The storage stability improver is preferably used in a range of 0 to 1000 mol, more preferably in a range of 10 to 500 mol, and particularly preferably in a range of 30 to 300 mol, based on 1 mol of the platinum catalyst used. .

Specific examples of the solvent that can be used at the time of curing include hydrocarbon solvents such as benzene, toluene, hexane and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether, acetone and methyl ethyl ketone. And a halogen-based solvent such as chloroform, methylene chloride, and 1,2-dichloroethane. The solvent can be used as a mixed solvent of two or more kinds. As the solvent, tetrahydrofuran and chloroform are preferred. The amount of the solvent used is preferably in the range of 0 to 10 ml with respect to 1 g of the silicon compound to be used.
More preferably, it is used in the range of 5 to 5 ml.
It is particularly preferred to use in the range of l.

Next, a method of manufacturing a molded article according to the second aspect of the present invention will be described. The present invention relates to 100 to 100 parts by weight of the components (A) to (C) described in claims 1 to 2, and 0 to 100 parts by weight.
The curable composition uniformly dissolved in 0 parts by volume of an organic solvent is kept at a temperature lower than the boiling point of the used organic solvent for 8 hours or more, and then the temperature is raised stepwise or continuously at a temperature of 20 to 250 ° C. The present invention relates to a method for producing a molded body having a thickness of 1.0 mm or more, characterized in that it is performed.

When the curable composition of the present invention is cured by heating, the rate of curing of the system, the rate of volatilization of the solvent from the system, the rate of diffusion of the solvent remaining in the system, and the like are controlled by controlling the heating temperature. A well-balanced product can be produced without causing significant cracks in the formed cured product. To raise the temperature of the curable composition, first, the temperature is kept at a temperature lower than the boiling point of the organic solvent used for 8 hours or more, and then the temperature is raised stepwise or continuously at a temperature of 20 to 250 ° C. Thick molded body, for example, pour this curable composition into a mold with a polyimide film stuck with double-sided tape, cover and place it horizontally in a hot air drier, heat curing while gradually increasing the temperature It can be produced by performing Or 2 with cellophane
It can be produced by sandwiching a silicone tube between two glass plates, pouring the curable composition between them, allowing the curable composition to stand vertically in a hot-air drier, and heating and curing while gradually increasing the temperature. In the heat curing, the temperature is preferably increased stepwise or continuously in the range of 20 to 400 ° C. When the temperature is continuously increased, 5 ° C./hr. Preferably, the temperature is gradually increased at the following rate. For example, preferred stepwise heating conditions are as follows: 50 ° C. for 8 to 24 hours, 80 ° C. for 8 to 24 hours,
Conditions for heating and curing at 100 ° C. for 5 to 20 hours and at 150 ° C. for 12 to 70 hours are listed. The heat curing can be performed in air, in an inert gas such as nitrogen or argon, or under reduced pressure.

After the heat curing, a heat treatment may be further performed according to the improvement of physical properties or the purpose of use. The condition is 15
The reaction can be performed in a temperature range of 0 to 450 ° C. in air, in an inert gas such as nitrogen or argon, or under reduced pressure.

[0041]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the contents of the present invention are not limited thereto. -Synthesis of bisphenol A dipropargyl ether It was synthesized according to the following reaction scheme.

[0042]

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In a 1 L four-necked flask, 114.15 g (0.5 mol) of bisphenol A and tetrabutylammonium bromide (TBAB, manufactured by Koei Chemical) 11
8.95 g (1.0 mol) and sodium hydroxide 4
300 ml of an aqueous solution of 0.0 g (1.0 mol) was added. The solution was stirred at room temperature for about 10 minutes. There, 118.95 g (1.0 mol) of propargyl bromide
Was dropped in about 30 minutes. After heating and stirring at 80 ° C. for 13 hours, a solid was deposited. After chloroform was added to dissolve the solid, the organic layer was separated and recrystallized to obtain the desired product. Yield: 134.6 g. Example 1 In a 30 ml sample tube, 3.59 g (11.8 mmol) of bisphenol A dipropargyl ether was weighed and dissolved using 6 ml of tetrahydrofuran.
1.41 g (5.9 mmol) of 1,3,5,7-tetramethylcyclotetrasiloxane was added to the above solution and mixed by light shaking (SiH group / carbon-carbon triple bond = 1 /
1). Then, the Pt-vinylsiloxane complex (9.71)
(× 10 ⁻⁵ mmol / mg) (1 × 10 ⁻⁴ equivalent to SiH group). Φ6.7 in which a polyimide film having a thickness of 25 μm was previously spread using a double-sided tape.
cm ointment cans were prepared. Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. Then, 50 ° C / 16h → 80 ° C / 9.5h → 10
The mixture was cured by heating at 0 ° C./14 h → 150 ° C./8 h to obtain a cured product (a). Gel fraction: 93%. Approximately 40mm long and 5m wide from the cured product using a diamond cutter
The sample for the bending test of m was cut out. Example 2 In a 30 ml sample tube, 2.79 g (9.2 mmol) of bisphenol A dipropargyl ether was weighed and dissolved using 5 ml of tetrahydrofuran. 2.21 g (9.2 mmol) of 1,3,5,7-tetramethylcyclotetrasiloxane was added to the above solution and mixed gently by shaking (SiH group / carbon-carbon triple bond = 2/1).
Thereafter, a Pt-vinylsiloxane complex (9.71 × 10
^-5 mmol / mg) (1 × 10 −4 equivalents based on SiH groups). An ointment can having a diameter of 6.7 cm, in which a polyimide film having a thickness of 25 μm was spread using a double-sided tape, was prepared in advance. Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. Then, 50 ° C / 16h → 80 ° C / 9.5h → 100 ° C /
The mixture was cured by heating for 14 hours → 150 ° C./24 hours to obtain a cured product (b). Gel fraction: 100%. Approximately 40mm long and 5mm wide from the cured product using a diamond cutter
A sample for bending test was cut out. Example 3 3.59 g (11.8 mmol) of bisphenol A dipropargyl ether was weighed and placed in a 30 ml sample tube, and dissolved using 6 ml of tetrahydrofuran.
1.41 g (5.9 mmol) of 1,3,5,7-tetramethylcyclotetrasiloxane was added to the above solution and mixed by light shaking (SiH group / carbon-carbon triple bond = 1 /
1). Then, the Pt-vinylsiloxane complex (9.71)
(× 10 ⁻⁵ mmol / mg) (1 × 10 ⁻⁴ equivalent to SiH group). Φ6.7 in which a polyimide film having a thickness of 25 μm was previously spread using a double-sided tape.
cm ointment cans were prepared. Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. After heating in air at 50 ° C / 18h → 80 ° C / 21h, it was cooled to room temperature. Then, under a nitrogen stream (flow rate: 5
0 L / min) at 35 ° C. for 30 minutes, and then 100 under a nitrogen stream (flow rate: 10 L / min) for 30 minutes.
° C and held for 1 hour, then 15 minutes over 30 minutes
The temperature was raised to 0 ° C., and the composition was cured by heating for 25 hours to obtain a cured product (c). A bending test sample having a length of about 40 mm and a width of about 5 mm was cut out from the cured product using a diamond cutter. Comparative Example 1 3.50 g (14.2 mmol) of 1,4-bis (dimethylvinylsilyl) benzene was placed in a 30 ml sample tube,
1.71, g (7.1 mmol) of 1,3,5,7-tetramethylcyclotetrasiloxane was weighed, 40 mg of a 10 wt% THF solution of dimethyl malate as a storage stabilizer was added thereto, and the mixture was shaken gently and mixed (platinum catalyst). 1 for
00 equivalents). Then, the Pt-vinylsiloxane complex
29 mg (9.71 × 10 ⁻⁶ mmol / mg) was added (1 × 10 ⁻⁵ equivalent to Si-vinyl group). In advance,
An ointment can having a diameter of 6.7 cm, in which a polyimide film having a thickness of 25 μm was spread using a double-sided tape, was prepared.
Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. Then, 50 ℃ / 23h → 8
The composition was heated and cured at 0 ° C / 7h → 100 ° C / 16h → 150 ° C / 25h to obtain a cured product (d). Gel fraction: 10
0%. A bending test sample having a length of about 40 mm and a width of about 5 mm was cut out from the cured product using a diamond cutter. Method of bending test The test was performed using a Shimadzu precision universal testing machine. The measurement conditions are
The test was performed in accordance with the “Bending test method using a small test piece” specified in JIS (K7203). (Span: 15m
m, indenter: 5R, fulcrum: 2R, test speed: 0.
5 mm / min).

Table 1 shows the results of bending tests of the cured products of the present invention obtained in Examples 1, 2, and 3, and the cured product obtained in Comparative Example 1.

[0045]

[Table 1]

[0046]

The heat-resistant lightweight structural material can be manufactured using the cured product provided by the present invention.

Claims (5)

[Claims] (1) at least two components per molecule as component (A);
A silicon compound having a molecular weight of 1000 or less having at least two SiH groups, a compound containing a propargyl ether group represented by the following formula (1) as a component (B): In the formula, R1 is a group independently selected from the following. Embedded image Embedded image (R and R ′ are monovalent hydrocarbon groups having 0 to 20 carbon atoms and may be the same or different. Ar is an aromatic group.) As the component (C), a hydrosilylation catalyst is used. Curable composition containing. 2. The curable composition according to claim 1, wherein the molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.5 to 5. 3. The curable composition according to claim 1, wherein the molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.6 to 3. 4. The curable composition according to claim 1, wherein the molar ratio of all SiH groups / carbon-carbon triple bonds involved in the addition reaction is 0.8 to 1.5. 5. A method according to claim 1, wherein 100 parts by weight of (A) to (C)
The curable composition according to any one of claims 1 to 4, which is uniformly dissolved in ~ 1000 volume parts of an organic solvent, is kept at a temperature lower than the boiling point of the organic solvent used for 8 hours or more, and thereafter 20 to 250 ° C
A method for producing a molded body having a thickness of 1.0 mm or more, characterized in that the temperature is increased stepwise or continuously at a temperature of 1.0 mm.