JPH0912709A - Production of siloxane-modified polyoxyalkylne compound, its production and room temperature curing composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having a high curing grate and a low degree of greasiness useful as a sealing material, etc., by using a specific vinyl group-containing polyoxyalkylene compound as a raw material compound. SOLUTION: This siloxane-modified polyoxyalkylene compound of formula I (R<1> is a 1-9 bifunctional hydrocarbon; R<2> is a 1-4C bifunctional hydrocarbon; R3 is an alkyl or phenyl; X is an alkoxy or an aryl; Me is methyl; (a) is 0-2; (n) is 1-100; (m) is 20-500) is obtained by hydrosilylating (A) a vinyl group- containing polyoxyalkylene compound of formula II with (B) a reactive silylethylene group-containing polyorganopolysiloxane of formula III in (C) an inactive organic solvent (e.g. toluene, etc.,) in the presence of (D) a platinum metal catalyst (e.g. rhodium-olefin complex, etc.).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a siloxane-modified polyoxyalkylene compound capable of obtaining, for example, a sealing material or an adhesive, a method for producing the same, and a room temperature curable composition containing the same.

[0002]

2. Description of the Related Art Conventionally, as a polyoxyalkylene polymer used as a raw material for a sealing material or an adhesive, one having a reactive silyl group at both ends of a molecular chain is known (Japanese Patent Laid-Open No. 156599/1975). Gazette, JP-A-54-60
96, JP-A-50-18767, JP-B-4
6-12154, etc.). However, room-temperature curable compositions using these polymers have the drawbacks that the curing speed is slower than that of silicone-based room-temperature curable compositions, and the surface of the cured product obtained is sticky. Therefore, for the purpose of improving the curing speed, a polyoxyalkylene polymer in which a hydrolyzable group which the reactive silyl group has as a reactive group is substituted with an alkenyloxy group has been proposed (JP-A-55-131022). reference). However, this polymer
The disadvantage that the surface of the cured product is sticky has not been solved, and there is also the disadvantage that the cured product becomes colored.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a siloxane-modified polyoxyalkylene compound, a method of producing the same, and a method for producing a cured product which has a faster curing rate and which is less sticky on the surface than conventional ones. The present invention is to provide a room temperature curable composition containing.

[0004]

The first aspect of the present invention is to provide the following general formula (1):

Embedded image (In the formula, R ¹ is independently a divalent hydrocarbon group having 1 to 9 carbon atoms, R ² is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ³ is independently an alkyl group. Group or a phenyl group, X is an alkoxy group or an acyloxy group, M
e is a methyl group, a is an integer of 0 to 2, and n is 1
Is an integer of -100 and m is an integer of 20-500).

The second aspect of the present invention is to provide the following general formula (2): CH ₂ ═CH—R ¹ — (OR ² ) _m OR ¹ —CH═CH ₂ (2) at the molecular chain end (wherein R ¹ Is independently a divalent hydrocarbon group having 1 to 9 carbon atoms, R ² is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, and m is an integer of 20 to 500). A vinyl group-containing polyoxyalkylene compound and the following general formula (3):

[0006]

Embedded image [Wherein R ³ is independently an alkyl group or a phenyl group, X is an alkoxy group or an acyloxy group (provided that when there are a plurality of X, they may be the same or different), and Me is a methyl group. , N is an integer of 1 to 100, and a is an integer of 0 to 2] with a reactive silethylene group-containing organopolysiloxane represented by the formula (1) in the presence of a platinum group metal catalyst in an inert organic solvent. It is a method for producing the above-mentioned siloxane-modified polyoxyalkylene compound which undergoes a hydrosilylation reaction.

The third aspect of the present invention is a room temperature curable composition containing the siloxane-modified polyoxyalkylene compound and a curing catalyst. Hereinafter, the present invention will be described in detail.

Siloxane modified polyoxyalkylene compound
The siloxane-modified polyoxyalkylene compound of the present invention is represented by the above general formula (1), and in the formula, examples of the divalent hydrocarbon group having 1 to 9 carbon atoms represented by R ¹ include
Alkylene groups such as methylene group, ethylene group, propylene group, methylethylene group, butylene group and hexamethylene group, especially alkylene groups having 1 to 3 carbon atoms such as methylene group, ethylene group, propylene group; cyclohexylene group, etc. A cycloalkylene group having 3 to 7 carbon atoms; an arylene group such as a phenylene group, a tolylene group and a xylylene group, particularly an arylene group having a carbon number of 6 to 9 such as a phenylene group and a tolylene group; or a hydrogen atom of these groups Examples include groups in which a part or all of them are substituted with a halogen atom or the like, or combinations of these substituted or unsubstituted alkylene groups and arylene groups. Of these, a methylene group and an ethylene group are preferable from the viewpoints of easiness of synthesis and stability of the compound.

In the general formula (1), examples of the divalent hydrocarbon group having 1 to 4 carbon atoms represented by R ² include carbon atoms such as methylene group, ethylene group, propylene group, methylethylene group and butylene group. Examples thereof include an alkylene group having 1 to 4 atoms; or a group obtained by substituting a part or all of hydrogen atoms of these groups with a halogen atom or the like, a combination of these substituted or unsubstituted alkylene groups, and the like. Among them, a methylene group, from the viewpoint of ease of synthesis, stability of the compound, etc.
Ethylene group, propylene group, methylethylene group and butylene group are preferred.

R ^{3 in the} general formula (1) is an alkyl group or a phenyl group. Typical examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Group, pentyl group, neopentyl group, hexyl group and the like. Among them, a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group is preferable from the viewpoints of easiness of synthesis and stability of the compound.

X in the general formula (1) is an alkoxy group or an acyloxy group. Typical examples of the alkoxy group include an alkoxy group having 1 to 5 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like. Of these, a lower alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group is preferable from the viewpoint of ease of synthesis and reactivity. Typical examples of the acyloxy group include an acyloxy group having 1 to 5 carbon atoms, and specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group and a valeryloxy group. Above all, from the viewpoint of ease of synthesis, reactivity, etc., an acetoxy group,
It is an acyloxy group having 1 to 3 carbon atoms of a propionyloxy group.

A in the general formula (1) is an integer of 0 to 2,
n is an integer of 1 to 100, preferably 1 to 10. M in the general formula (1) is an integer of 20 to 500,
Considering the availability of raw materials, the range of m is preferably such that the polyoxyalkylene chain of the general formula (1) has a molecular weight of 1,000 to 15,000, and particularly preferably 20 to 250. Representative examples of the siloxane-modified polyoxyalkylene compound of the present invention include, but are not limited to, those represented by the following formula.

[0013]

Embedded image (In the formula, X is a methoxy group or an acetoxy group, and R ²
Is a methylethylene group or a butylene group, Me is a methyl group, n is an integer of 1 to 6, j is an integer of 3 to 11, and m is an integer of 20 to 250).

[0014]

[Chemical 6] (In the formula, X is a methoxy group or an acetoxy group, and R ⁴
Is a methylethylene group, R ⁵ is a butylene group,
Me is a methyl group, n is an integer of 1 to 6, j is an integer of 3 to 11, L is an integer of 1 to 249,
M is an integer from 1 to 249, and L + M is 20 to 25
0)

[0015]

Embedded image (In the formula, X is a methoxy group or an acetoxy group, and R ²
Is a methylethylene group or a butylene group, Me is a methyl group, n is an integer of 1 to 6, j is an integer of 3 to 11, and m is an integer of 20 to 250).

[0016]

Embedded image (In the formula, X is a methoxy group or an acetoxy group, and R ⁴
Is a methylethylene group, R ⁵ is a butylene group,
Me is a methyl group, n is an integer of 1 to 6, j is an integer of 3 to 11, L is an integer of 1 to 249,
M is an integer from 1 to 249, and L + M is 20 to 25
0)

Siloxane modified polyoxyalkylene compound
Manufacturing method of thing The manufacturing method of this invention is a vinyl group containing polyoxyalkylene compound represented by the said General formula (2), and a reactive silethylene group containing organopolysiloxane represented by the said General formula (3). Is a hydrosilylation reaction in the presence of a platinum group metal catalyst in an inert organic solvent to produce a siloxane-modified polyoxyalkylene compound represented by the general formula (1).

Vinyl Group-Containing Polyoxyalkylene Compound The vinyl group-containing polyoxyalkylene compound used in the production method of the present invention is represented by the above general formula (2), in which R is
^1, R ² and m are the same as R ^1, R ² and m in the general formula (1). Representative examples of the vinyl group-containing polyoxyalkylene compound include, but are not limited to, for example, Vi—CH ₂ [OCH (CH ₃ ) C.
H _{2] m} OCH ₂ -Vi (wherein, Vi is a vinyl radical, m is 20 to 250), in particular Vi-CH ₂ [O
_{CH (CH 3) CH 2]} 100 OCH 2 -Vi, Vi-C
_{H 2 [OCH (CH 3)} CH 2] 170 OCH 2 -Vi;
_{Vi-CH 2 [OCH (CH} 3) CH 2] L (OC 4 H
₈ ) _M OCH ₂ -Vi (wherein Vi is a vinyl group,
L is an integer of 1 to 249, M is an integer of 1 to 249, and L + M is 20 to 250), particularly Vi-
CH ₂ [OCH (CH ₃ ) CH ₂ ] ₂₀ (OC ₄ H ₈ ) _{20
OCH 2 -Vi; Vi-CH 2} (OC 4 H 8) m OCH
_2- Vi (wherein Vi is a vinyl group, m is 20 to 2)
50 is a), in particular _{Vi-CH 2 (OC 4 H} 8) 20 OC
H ₂ -Vi; and the like, and particularly preferable one is one type of oxyalkylene chain, and particularly representative one is polyoxypropylene glycol diallyl ether having an average molecular weight of 1,000 to 15,000.

The vinyl group-containing polyoxyalkylene compound represented by the general formula (2) can be prepared by a known method, for example, JP-A-50-156599 and JP-A-53-.
It can be produced by the method described in JP-A-12927, JP-A-53-134095, or the like. For example, polyoxypropylene glycol having an average molecular weight of 3,000 is reacted with dibromomethane in the presence of caustic soda, and the end of the molecular chain is further allylated with allyl chloride to give a polyoxypropylene glycol diallyl ether having an average molecular weight of 9000. Can be manufactured.

Reactive silethylene group-containing organopolysiloxane The reactive silethylene group-containing organopolysiloxane used in the production method of the present invention is represented by the above general formula (3),
In the formula, R ³ , X, Me, a and n are represented by the general formula (1).
Of R ³ , X, a and n. Representative examples of the reactive silethylene group-containing organopolysiloxane include, but are not limited to, H
[(Me) ₂ SiO] _n -Si (Me) ₂ C ₂ H ₄ Si (Me) X ₂
(In the formula, X is a methoxy group or an acetoxy group, and Me is
Is a methyl group and n is 1 to 6), especially H [(Me)
₂ SiO] -Si (Me) ₂ C ₂ H ₄ Si (Me) (OMe) ₂ , H
[(Me) ₂ SiO] ₄ -Si (Me) ₂ C ₂ H ₄ Si (Me) (OCO
Me) ₂ ; H [(Me) ₂ SiO] _n -Si (Me) ₂ C ₂ H ₄ Si
X ₃ (In the formula, X is a methoxy group or an acetoxy group,
Me is a methyl group and n is 1 to 6), especially H
[(Me) ₂ SiO] ₆ -Si (Me) ₂ C ₂ H ₄ Si (OMe) ₃ ,
H [(Me) ₂ SiO] ₆ -Si (Me) ₂ C ₂ H ₄ Si (OCOM
e) ₃ ; and the like. Particularly, those having a molecular weight of 1000 or less are preferable from the viewpoint of easy purification.

The reactivity represented by the general formula (3)
Organopolysiloxanes containing silethylene groups are known
For example, the following general formula: H [(R^Three)_TwoSiO]_n− (R^Three )_TwoSiH (In the formula, R^ThreeAnd n are the same as above).
Idrogen polysiloxane and the following general formula: CH_Two= CH-Si (Me)_aX_3-a (Wherein X, Me and a are the same as above)
Vinyl group-containing silane in the presence of a platinum group metal catalyst.
It can be obtained by a dorosilylation reaction.

Inert organic solvent and platinum group metal catalyst Examples of the inert organic solvent used in the production method of the present invention include toluene, xylene, hexane, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, etc. Toluene is preferable because it can azeotropically dehydrate the water contained therein.

Examples of the platinum group metal catalyst used in the production method of the present invention include chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972),
Complex of chloroplatinic acid and olefin (US Pat. Nos. 3,159,601 and 3,159,66)
No. 2, the same No. 3,775,452 reference),
Examples include platinum black, palladium, etc. supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. Of these, those of the complex type are preferably used by dissolving them in an organic solvent of alcohol type, ketone type, ether type or the like.

Production of siloxane-modified polyoxyalkylene compound In carrying out hydrosilylation reaction of the above-mentioned vinyl group-containing polyoxyalkylene compound and reactive silethylene group-containing organopolysiloxane, the compounding ratio of both is vinyl group-containing polyoxyalkylene compound. The amount of the reactive silethylene group-containing polysiloxane is usually 2 moles or more per mole of the compound, and it is preferable to use the reactive silethylene group-containing polysiloxane in an amount of 2 to 8 times by mole from the viewpoint of completing the addition reaction.

The amount of the platinum group metal catalyst used may be a so-called catalytic amount.
100 ppm is sufficient, and it is particularly preferable to use 1 to 30 ppm. The amount of the inert organic solvent used may be about 10 to 80% by weight based on the total amount. The reaction temperature is usually about 50 to 180 ° C., but particularly 80 to 150 ° C.
It is desirable to set the range to. The siloxane-modified polyoxyalkylene compound of the present invention thus obtained has a high curing rate and serves as a raw material for a room temperature curable composition which can give a cured product having a non-sticky surface.

Room Temperature Curable Composition The room temperature curable composition of the present invention contains a siloxane-modified polyoxyalkylene compound represented by the general formula (1) and a curing catalyst. As the curing catalyst, for example,
Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimethoxide, butyltin tri-2-
Tin compounds such as ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butyrate;
Titanium compounds such as titanium naphthenate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) titanate, organosiloxy titanium and β-carbonyl titanium; lead. 2-ethyl octoate, iron-2-ethyl hexoate, cobalt-2-ethyl hexoate, manganese-2-ethyl hexoate, zinc-
Metal compounds such as 2-ethylhexoate, zinc naphthenate, cobalt naphthenate, zinc stearate and alkoxyaluminum compounds; substitution of aminoalkyl groups such as 3-aminopropyltriethoxysilane and N- (trimethoxysilylpropyl) ethylenediamine Alkoxysilanes; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acids of alkali metals such as potassium acetate, sodium acetate, lithium oxalate; dimethylhydroxyamine , A dialkylhydroxylamine such as diethylhydroxylamine; a guanidyl compound such as tetramethylguanidine, and the like. Particularly representative ones are tin compounds and titanium compounds. Ones, dibutyltin dilaurate, dibutyltin dimethoxide, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate. These may be used alone or in combination of two or more.

The amount of the curing catalyst used may be 0.01 to 10 parts by weight, and particularly preferably 0.05 to 1 part by weight, per 100 parts by weight of the siloxane-modified polyoxyalkylene compound. In addition to the siloxane-modified polyoxyalkylene compound and the curing catalyst, the room temperature curable composition of the present invention includes, for example, inorganic fillers such as calcium carbonate, magnesium carbonate, fused silica, titanium oxide; pigments;
You may mix | blend antioxidants; ultraviolet absorbers; flame retardants.

The room temperature curable composition of the present invention, when cured at room temperature, is compared to a curable composition containing a conventional polyoxyalkylene compound having the same reactive silyl group as the polyoxyalkylene compound of the present invention. However, the curing speed is more than twice as fast, and the surface of the cured product is not sticky. Therefore, it is useful as a sealing material or an adhesive.

[0029]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, in this example, Me represents a methyl group. Example 1 Preparation of Reactive Silethylene Group-Containing Organopolysiloxane
In concrete flask tetramethyldisiloxane 284 g (2.12 mol), toluene 424 g, 0.5% chloroplatinic acid isopropanol solution 0.83g of (4.2 mg of platinum) were charged, and heating the flask contents to 80 ° C.. Then, 140 g (1.06 mol) of vinyl monomethyldimethoxysilane was dropped into the flask to carry out the reaction. Then, the contents of the flask were analyzed by gas chromatography, and after confirming that most of the SiH groups had disappeared, the contents of the flask were vacuum stripped to obtain 189 g of a reaction product (yield 67%). . The boiling point and ¹ H-NMR of this reaction product were measured. The results are shown below.

Boiling point: 69 to 71 ° C./5 mmHg, ¹ H-NMR: δ: 0.0 to 0.1 ppm (15 H, m, SiCH ₃ ), 3.7
_{ppm (6H, s, OCH 3} ), 4.7 ~5.0 ppm (1
H, m, SiH) From these results, the obtained reaction product has the following formula: H [(Me) ₂ SiO] -Si (Me) ₂ C ₂ H ₄ Si (Me) (OM
it was confirmed that the reactive silethylene group-containing polysiloxane represented by e) _2.

Siloxane modified polyoxyalkylene compound
The following formula having an average molecular weight of 10,000 in the production flask _{things: Vi-CH 2 [OCH (} CH 3) CH 2] m OCH 2 -
136 g of polyoxypropylene glycol diallyl ether represented by Vi (wherein Vi is a vinyl group, m≈170)
(14 mmol), toluene (85 g) and 0.5% chloroplatinic acid isopropanol solution (0.9 g, 4.7 mg of platinum) were added. Next, the flask was heated and 28 g (0.11 mol) of the reactive silethylene group-containing polysiloxane was dropped into the flask while refluxing toluene, and the reaction was carried out for 12 hours. Next, the low boiling point components such as the solvent in the flask contents were distilled off under reduced pressure to obtain 133 g of a reaction product. Next, ¹ H-NMR measurement of this reaction product and molecular weight measurement by gel permeation chromatography (GPC) were performed. The results are shown below. Number average molecular weight: 11000, weight average molecular weight: 30,000 ¹ H-NMR: δ: 0.0 to 0.1 ppm (m, SiCH ₃ ), 1.6 pp
m (d, CH ₃ ), 3.7 ppm (s, OCH ₃ ),
3.6-4.6 ppm (m, OCH ₂ CH)

From these results, the obtained reaction product has the following formula:

Embedded image It was confirmed to be a siloxane-modified polyoxyalkylene compound represented by (in the formula, m≈170).

Preparation of Room Temperature Curable Composition and Hardening of the Composition
Chemical conversion test The above-mentioned siloxane-modified polyoxyalkylene compound 99
After 1 part by weight and 1 part by weight of dibutyltin dilaurate were enclosed in a vinyl bag, they were mixed by hand for 1 hour to prepare a room temperature curable composition. Next, the room temperature curable composition thus obtained was filled in a cylindrical container having a diameter of 3 cm and a depth of 1 cm, and
The composition was cured by leaving it in an atmosphere of 5 ° C. and 60% RH. The curing time (hours) at this time is shown in Table 1. Then, the degree of stickiness of the surface of the obtained cured product was evaluated by the feel of a finger in the following four grades A to D in order from weak to strong stickiness. Table 1 shows the results. (Evaluation Criteria for Stickiness) A ... Stickiness is extremely weak. B: There is some stickiness. C: It is very sticky. D: Very sticky.

Example 2 Preparation of Reactive Silethylene Group-Containing Organopolysiloxane
In concrete flask tetramethyldisiloxane 134 g (2.0 mol), toluene 416 g, 0.5% chloroplatinic acid isopropanol solution 0.78g of (3.9 mg of platinum) were charged, and heating the flask contents to 80 ° C.. Then, 148 g (1.0 mol) of vinyltrimethoxysilane was dropped into the flask to carry out the reaction. Then, the contents of the flask are analyzed by gas chromatographic analysis, and after confirming that the SiH groups have almost disappeared, the contents of the flask are vacuum stripped,
The reaction product (197 g, yield 70%) was obtained. The boiling point and ¹ H-NMR of this reaction product were measured. The results are shown below. Boiling point: 84 to 86 ° C./7 mmHg, ¹ H-NMR: δ: 0.0 to 0.1 ppm (15 H, m, SiCH ₃ ), 3.6
_{ppm (6H, s, OCH 3} ), 4.6 ~4.9 ppm (1
H, m, SiH) From these results, the obtained reaction product is a reactive sil of the following formula: H [(Me) ₂ SiO] -Si (Me) ₂ C ₂ H ₄ Si (OMe) _3. It was confirmed to be an ethylene group-containing polysiloxane.

Siloxane modified polyoxyalkylene compound
Manufacture of the product Example except that 28 g (0.09 mol) of the reactive silethylene group-containing organopolysiloxane prepared in this example was dropped in place of the reactive silethylene group-containing organopolysiloxane used in Example 1. Reaction product similar to 1
Obtained 134 g. Next, ¹ H-NMR measurement of the reaction product and gel permeation chromatography (GP
The molecular weight was measured according to C). The results are shown below. Number average molecular weight: 16000, weight average molecular weight: 35000 ¹ H-NMR: δ: 0.0 to 0.1 ppm (m, SiCH ₃ ), 1.6 pp
m (d, CH ₃ ), 3.7 ppm (s, OCH ₃ ),
3.6-4.6 ppm (m, OCH ₂ CH)

From these results, the obtained reaction product has the following formula:

Embedded image It was confirmed to be a siloxane-modified polyoxyalkylene compound represented by (in the formula, m≈170).

Then, using the obtained siloxane-modified polyoxyalkylene compound, a room temperature curable composition was prepared in the same manner as in Example 1, and the curing time of the composition and the degree of stickiness of the surface of the cured product were determined by the examples. It evaluated similarly to 1. Table 1 shows the results.

Comparative Example 1 The same polyoxypropylene glycol diallyl ether 13 as in Example 1 was placed in the flask.
6 g (14 mmol), toluene 85 g, 0.5% isopropanol chloroplatinate solution 0.12 g (0.6 mg as platinum)
Was introduced. Next, the flask is heated, and while refluxing toluene, 3.3 g of dimethoxymethylsilane is placed in the flask.
(31 mmol) was added dropwise and reacted for 3 hours. next,
The low boiling point components such as the solvent in the flask contents were distilled off under reduced pressure to obtain 128 g of a reaction product.

Next, ¹ H-NMR measurement of this reaction product and gel permeation chromatography (GP
The molecular weight was measured according to C). The results are shown below. Number average molecular weight: 9300, weight average molecular weight: 32000 ¹ H-NMR: δ: 0.0 to 0.1 ppm (s, SiCH ₃ ) 1.6 ppm (d, CH ₃ ) 3.7 ppm (s, OCH ₃ ) 3.5 to 4.5 ppm (m , OCH ₂ CH)

The reaction products obtained from these results are:
The following formula:

Embedded image It was confirmed to be a silyl group-containing polyoxyalkylene compound represented by (in the formula, m≈170).

Next, a room temperature curable composition was prepared in the same manner as in Example 1, except that the silyl group-containing polyoxyalkylene compound was used in place of the siloxane-modified polyoxyalkylene compound. Then, the curing time of the composition and the degree of stickiness of the cured product surface were evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 The same polyoxypropylene glycol diallyl ether 13 as in Example 1 was placed in the flask.
6 g (14 mmol), toluene 85 g, 0.5% isopropanol chloroplatinate solution 0.12 g (0.6 mg as platinum)
Was introduced. Next, the flask is heated, and while refluxing toluene, 3.8 g (31 g) of trimethoxysilane is placed in the flask.
(Mmol) was added dropwise and reacted for 3 hours. Next, the low boiling point components such as the solvent of the contents of the flask were distilled off under reduced pressure to obtain the reaction product
129 g was obtained.

Next, ¹ H-NMR measurement and gel permeation chromatography (GPC) of this reaction product were carried out.
The molecular weight was measured by. The results are shown below. Number average molecular weight: 9800, weight average molecular weight: 3200 ¹ H-NMR: δ: 1.6 ppm (d, CH ₃ ) 3.7 ppm (s, OCH ₃ ) 3.6 to 4.6 ppm (m, OCH ₂ CH)

The reaction products obtained from these results are:
The following formula:

Embedded image It was confirmed to be a silyl group-containing polyoxyalkylene compound represented by (in the formula, m≈170).

Then, a room temperature curable composition was prepared in the same manner as in Example 1 except that the silyl group-containing polyoxyalkylene compound was used in place of the siloxane-modified polyoxyalkylene compound. Then, the curing time of the composition and the degree of stickiness of the cured product surface were evaluated in the same manner as in Example 1. Table 1 shows the results.

[0046]

[Table 1]

[0047]

The room temperature curable composition containing the siloxane-modified polyoxyalkylene compound of the present invention is a room temperature curable composition containing a conventional silyl group-containing polyoxyalkylene polymer having the same reactive silyl group at the terminal of the molecular chain. Compared to the composition
The curing speed is twice or more faster, and the degree of stickiness on the surface of the cured product is small. Therefore, the compound of the present invention and the room temperature curable composition containing the same are extremely useful as a sealant and an adhesive.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 83/12 LRR C08L 83/12 LRR

Claims (3)

[Claims] 1. The following general formula (1): (In the formula, R ¹ is independently a divalent hydrocarbon group having 1 to 9 carbon atoms, R ² is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ³ is independently an alkyl group. Group or a phenyl group, X is an alkoxy group or an acyloxy group, M
e is a methyl group, a is an integer of 0 to 2, and n is 1
To an integer of 100, and m is an integer of 20 to 500). 2. The following general formula (2): CH ₂ ═CH—R ¹ — (OR ² ) _m OR ¹ —CH═CH ₂ (2) at the end of the molecular chain (wherein R ¹ is independently a carbon atom). A vinyl group represented by formula (1) to (9), R ² is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, and m is an integer of 20 to 500). A polyoxyalkylene compound and the following general formula (3): [Wherein R ³ is independently an alkyl group or a phenyl group, X is an alkoxy group or an acyloxy group (provided that when there are a plurality of X, they may be the same or different), and Me is a methyl group. , N is an integer of 1 to 100, and a is an integer of 0 to 2] with a reactive silethylene group-containing organopolysiloxane represented by the formula (1) in the presence of a platinum group metal catalyst in an inert organic solvent. The method for producing a siloxane-modified polyoxyalkylene compound according to claim 1, wherein a hydrosilylation reaction is carried out. 3. A room temperature curable composition containing the siloxane-modified polyoxyalkylene compound according to claim 1 and a curing catalyst.