JPH0262574B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a hydrolyzable silyl group useful as a base polymer for a room-temperature curable composition capable of forming a rubber-like elastic body having adhesive properties and high elongation and high flexibility. This invention relates to a method for producing a polyether whose ends are blocked. [Prior art and its problems] Regarding compositions using a polymer having a hydrolyzable silicon functional group and whose main chain is essentially a polyether as a base polymer, JP-A-52-7398 et al. In recent years, this type of composition has begun to be used as a sealant for joints in buildings. However, since this type of polymer does not inherently have adhesive properties, it is necessary to pre-treat the surface to be coated with a primer or add a silane coupling agent to the composition to impart adhesive properties. It is necessary. However, the addition of a silane coupling agent causes a problem in that the elongation rate of the cured rubber-like elastic body decreases in exchange for the acquisition of adhesive properties, making it brittle and unsuitable for use as a sealing material. The present invention was devised in view of such problems, and its purpose is to provide a base polymer suitable for a room-temperature curable composition capable of forming a rubber-like elastic body with adhesive properties and high elongation. , to provide a polyether end-capped with hydrolyzable silyl groups. [Means for solving the problem] The present inventors first developed (A) general formula; (In the formula, R ¹ , R ² and n are as described above) A polyoxyalkylene whose molecular chain terminal is blocked with an epoxy group, and (C) general formula;

^{A polyether (} It has been found that the following general formula []) cures at room temperature to provide an elastic body and has adhesive properties. K0076 Furthermore, with the aim of obtaining a highly flexible elastic body with a high elongation rate, the present inventors used the polyoxyalkylene shown above (A) in which the molecular chain end is blocked with an epoxy group, and (B ) general formula; a monovalent primary amine represented by R ³ −NH ₂ (in the formula, R ³ is as described above) or

A divalent secondary amine represented by the formula (in which R ⁴ , R ⁵ , and R ⁶ are as described above) and the organosilicon compound (C) shown above are reacted to [ An attempt was made to obtain a polyether having a hydrolyzable silyl group at the end of the molecular chain represented by the formula ] or [ ]. However, an unexpected increase in viscosity or gelation occurs during the reaction, making it difficult to obtain a polymer with a high degree of polymerization that yields a rubber-like cured product with high elongation and high flexibility. It was hot. As a result of further studies on how to solve these problems, the present inventors found that (A) the polyoxyalkylene whose molecular chain terminals are blocked with an epoxy group, and (B) a monovalent primary amine or a divalent primary amine. and (C) an organosilicon compound, (D) general formula; R ¹¹ -OH (in the formula,
By reacting in the presence ^of a monohydric primary alcohol represented by The present invention was completed based on the discovery that it is possible to obtain a polyether terminal-capped with a hydrolyzable silyl group, represented by the formulas [] and [], which provides an elastic body with adhesive properties. That is, the present invention provides (A) general formula; K0078 (in the formula, R ¹ and R ² are divalent hydrocarbon groups, n is 10
(B) general formula; R ³ -NH ₂ (in the formula, R ³ is a substituted or unsubstituted monovalent A monovalent primary amine ^represented by the general formula ( ^hydrocarbon group); or a ^monovalent primary amine represented by the general formula valent secondary amine and (C) general formula; K0080 (in the formula, R ⁷ is a monovalent hydrocarbon group, R ⁶ is a divalent hydrocarbon group, R ⁹ is a monovalent hydrocarbon group, R ¹⁰ is (D) General formula; R ¹¹ -OH (in the formula, R ¹¹ is a carbon number of 1 to
6) represents a monovalent hydrocarbon group
K0081 or K0082 (wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
R ¹⁰ , a and n are as described above, m is the molecular weight
The present invention relates to a method for producing a polyether terminal-capped with a hydrolyzable silyl group, represented by a number selected from 1,000 to 50,000. The first raw material component (A) used in the present invention is:
It is a polyoxyalkylene whose molecular chain end is blocked with an epoxy group, represented by the general formula K0083 (wherein R ¹ , R ² and n are as described above), and the oxyalkylene unit R ¹ O of (A) is It is preferable to use oxyethylene units, oxypropylene units, or a combination of oxyethylene units and oxypropylene units, and oxypropylene units are particularly preferable because raw materials are easy to obtain and polymerize, and liquid state is easily maintained even at a high degree of polymerization. (A)
The degree of polymerization n of the R ¹ O unit is preferably 10 or more because it is easy to obtain a polyether terminal-capped with a hydrolyzable silyl group, which gives a rubber-like cured product with high elongation. For the purpose of obtaining a composition with good quality, it is preferably 250 or less. Also R ²
The divalent hydrocarbon groups include methylene group, ethylene group, trimethylene group, tetramethylene group, phenylene group, cyclohexylene group and

Examples include groups represented by [Formula]. Typical examples of these (A) include those obtained by adding epichlorohydrin to polyoxyethylene or polyoxypropylene, both ends of which are blocked with hydroxyl groups, in the presence of a basic catalyst. The second raw material component (B) used in the present invention is:
General formula: A monovalent primary amine represented by R ³ -NH ₂ (wherein R ³ is as described above) or general formula;

It is a divalent secondary amine represented by [Formula] (in which R ⁴ , R ⁵ , and R ⁶ are as described above), and monovalent carbonization of R ³ , R ⁴ , and R ⁶ in (B). Examples of hydrogen groups include alkyl groups such as ethyl, propyl, butyl, and hexyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; benzyl group, β-phenylethyl group, etc. Examples include aralkyl groups. In addition,
In addition to the above, substituted hydrocarbon groups for R ³ include 2-
Hydroxyethyl group, 2-methoxyethyl group, p
-Hydroxyphenyl group, p-chlorophenyl group, etc. can also be used. Further, the divalent organic group of R ⁵ is preferably a divalent hydrocarbon group from the viewpoint of availability of raw materials and precursors and ease of synthesis. Examples of these divalent hydrocarbon groups include ethylene group, butylene group,
Examples include hexamethylene group, phenylene group, and cyclohexylene group. The third raw material component (C) used in the present invention is:
General formula;

〔Effect of the invention〕

The polyether end-capped with hydrolyzable silyl groups obtained in the present invention has tin carboxylates such as tin octylate; dibutyltin dilaurate;
Organic tin carboxylates such as dibutyltin dimaleate and dibutyltin phthalate; Reactants with organic tin oxides and their esters; Organic titanate esters such as tetrabutyl titanate; Amines, amine salts, quaternary ammonium salts, guanidine compounds, etc. curing catalyst; fillers such as calcium carbonate, talc, clay, ground silica, fumed silica, precipitated silica, titanium oxide; and other thixotropic agents, plasticizers, ultraviolet absorbers, etc. as necessary. In addition, it is possible to obtain a room-temperature-curable composition that can form a rubber-like elastic body that has adhesive properties, has high elongation, and is highly flexible, suitable as a sealing material for buildings. [Examples] The invention will be described below using Examples. In addition, % in an example shows weight %. Example 1 Polyoxypropylene with an average degree of polymerization of 15, a molecular weight of about 1000, and a viscosity of 270 cSt at 25° C. Both ends of the glycidyl group are blocked. For 10 epoxy equivalents, 10% of the polyoxypropylene is methanol and 4 moles of n- Add butylamine and 60 min under nitrogen atmosphere.
Heating and stirring was started at ℃. Incidentally, every hour after the start of heating and stirring, a small amount was taken out and the viscosity at 25°C was measured. The viscosity was 90 cSt before heating and stirring, but reached 1200 cSt 8 hours after heating and stirring started.
After that, the increase in viscosity stopped, so 12 hours after the start of heating and stirring,

Two moles of an organosilicon compound (silane compound) represented by the formula was added, and heating and stirring were continued under the same conditions. After adding the silane compound, a small amount was taken out every hour and the epoxy group was titrated using the hydrochloric acid dimethylformamide method. As a result, the disappearance of the epoxy group was observed 6 hours after the addition of the silane compound, so heating and stirring was performed. When finished, methanol is distilled off,
A pale yellow viscous liquid (polymer represented by the following formula) with a viscosity of 11000 cSt at 25°C and a specific gravity of 1.01 at the same temperature was obtained. K0088 Example 2 Polyoxypropylene with an average degree of polymerization of 32, a molecular weight of about 2000, and a viscosity of 550 cSt at 25°C, with glycidyl groups end-blocked. For 10 epoxy equivalents, methanol in an amount of 10% of the polyoxypropylene and 4 mol of n - Add amylamine and 60 minutes under nitrogen atmosphere.
Heating and stirring was started at ℃. Incidentally, every hour after the start of heating and stirring, a small amount was taken out and the viscosity at 25°C was measured. The viscosity was 210 cSt before heating and stirring, but reached 3700 cSt 8 hours after heating and stirring started.
After that, the increase in viscosity stopped, so 14 hours after the start of heating and stirring, Organosilicon compound (silane compound) represented by
2 mol of was added, and heating and stirring was continued under the same conditions.
After adding the silane compound, a small amount was taken out every hour and the epoxy group was titrated using the hydrochloric acid dimethylformamide method. As a result, the disappearance of the epoxy group was observed 6 hours after the addition of the silane compound, so methanol was distilled off. As a result, a viscous liquid (polymer represented by the following formula) with a viscosity of 24,000 cSt at 25°C and a specific gravity of 1.01 at the same temperature was obtained. K0090 Example 3 To 6 epoxy equivalents of glycidyl group-end-blocked polyoxypropylene with an average degree of polymerization of 50, a molecular weight of about 3000, and a viscosity of 970 cSt at 25°C, ethanol in an amount of 10% of the polyoxypropylene and 2 moles of allylamine were added. In addition, heating and stirring were started at 60°C under a nitrogen atmosphere. A small amount was taken out every hour from the start of heating and stirring, and the viscosity at 25°C was measured. The viscosity, which was 370 cSt before heating and stirring, reached 3900 cSt 8 hours after heating and stirring, and the viscosity increase stopped after that, so 10 hours after heating and stirring started, the organosilicon compound (silane compound) represented by K0091.
2 mol of was added, and heating and stirring was continued under the same conditions.
After adding the silane compound, a small amount was taken out every hour and the epoxy group was titrated using the hydrochloric acid dimethylformamide method. As a result, the disappearance of the epoxy group was observed 6 hours after the addition of the silane compound, so heating and stirring was stopped. , ethanol was distilled off to obtain a pale yellow viscous liquid (polymer shown below) with a viscosity of 31,000 cSt at 25°C and a specific gravity of 1.01 at the same temperature. K0092 Example 4 Glycidyl group-terminated polyoxypropylene with the same average weight of 15, molecular weight of about 1000, and viscosity at 25°C of 270 cSt as used in Example 1 10% of polyoxypropylene for 10 epoxy equivalents of methanol and 4 mol of n-hexylamine were added thereto, and heating and stirring at 60°C under nitrogen atmosphere was started. Incidentally, every hour after the start of heating and stirring, a small amount was taken out and the viscosity at 25°C was measured. The viscosity, which was 90 cSt before heating and stirring, reached 1100 cSt 8 hours after heating and stirring, and the increase in viscosity stopped after that, so 12 hours after heating and stirring started.

Organosilicon compound (silane compound) represented by [Formula] 1
moles and

One mole of an organosilicon compound (silane compound) represented by the formula was added, and heating and stirring were continued under the same conditions. After adding the silane compound, a small amount was taken out every hour and the epoxy group was titrated using the hydrochloric acid dimethylformamide method. As a result, the disappearance of the epoxy group was observed 6 hours after the addition of the silane compound, so heating and stirring was stopped. methanol was distilled off at 25
A pale yellow viscous liquid with a viscosity of 12,000 cSt at °C and a specific gravity of 1.01 at the same temperature was obtained. Example 5 For 6 epoxy equivalents of glycidyl group-end-capped polyoxypropylene having the same average polymerization degree of 50 and molecular weight of about 3000 as used in Example 3, methanol in an amount of 10% of the polyoxypropylene and 2 mol of

[Formula] was added, and heating and stirring was started at 90°C under pressure in a nitrogen atmosphere. A small amount was taken out every 6 hours from the start of heating and stirring and the viscosity at 25°C was measured.The viscosity was 390cSt before heating and stirring, but it reached 2900cSt 24 hours after heating and stirring and the increase in viscosity stopped. , cooled to 60°C 30 hours after the start of heating and stirring,

Organosilicon compound (silane compound) represented by [Formula] 2.4
mol was added, and heating and stirring were continued under the same conditions. After the addition of the silane compound, a small amount was taken out every hour and the epoxy group was titrated using the hydrochloric acid dimethylformamide method. As a result, the disappearance of the epoxy group was observed 6 hours after the addition of the silane compound, so heating and stirring was stopped. distill off methanol
A pale yellow viscous liquid (polymer shown below) with a viscosity of 28000 cSt at 25°C and a specific gravity of 1.01 at the same temperature was obtained. K0097 Application example 1 For 100 parts by weight of the polymer obtained in Example 1,
30 parts by weight of fatty acid-treated colloidal calcium carbonate, 15 parts by weight of rutile titanium oxide, 65 parts by weight of fatty acid-treated light calcium carbonate, 15 parts by weight of dioctyl phthalate,
3 parts by weight of hydrogenated castor oil, 2 parts by weight of antioxidant [2,2'-methylenebis(4-methyl-6-t-butylphenol)], ultraviolet absorber [2(2'-hydroxy-3,5') -di-t-butylphenyl)-5-
After adding 2 parts by weight of chlorobenzotriazole and 0.5 parts by weight of carbon black and uniformly mixing them using three rolls, kneading was carried out for 2 hours at 60 to 70°C and a degree of vacuum of 5 mmHg. After cooling, 1 part by weight of dibutyltin dilaurate was added and mixed under reduced pressure to obtain Sample 1. Using Sample 1 thus obtained, a specimen for the tensile test shown in FIG. 1 was prepared. After curing and curing the prepared specimens at 25°C for 14 days, a tensile test was conducted to measure the rubber physical properties and adhesive strength. The results are shown in Table 1. Application example 2 For 100 parts by weight of the polymer obtained in Example 2,
50 parts by weight of fatty acid-treated colloidal calcium carbonate, 50 parts by weight of ground calcium carbonate, 30 parts by weight of dioctyl phthalate, 4 parts by weight of hydrogenated castor oil, 20 parts by weight of rutile titanium oxide, antioxidant [4,4'-butyldenvis] (3-methyl-6-t-butylphenol)]
2 parts by weight, ultraviolet absorber [2(2'-hydroxy-
Add 2 parts by weight of 3',5'-di-t-butylphenyl)-5-chlorobenzotriazole and mix uniformly using three rolls, then heat at 60 to 70°C and vacuum 5mmHg.
Kneading was carried out for 2 hours. Next, after cooling, 1 part by weight of dibutyltin dilaurate was added,
Sample 2 was obtained by mixing under reduced pressure. Using Sample 2, the same measurements as in Application Example 1 were performed. The results are also shown in Table 1. Application example 3 For 100 parts by weight of the polymer obtained in Example 3, 30 parts by weight of fatty acid-treated colloidal calcium carbonate, 30 parts by weight of light calcium carbonate, 15 parts by weight of rutile titanium oxide, 6 parts by weight of hydrogenated castor oil, and antioxidant. agent [2,6
-bis(2-hydroxy-5-methylbenzyl)
-4-methylphenol] 2 parts by weight, ultraviolet absorber [2(2'-hydroxy-5-methylphenyl)
Add 2 parts by weight of benzotriazole and mix uniformly using three rolls, then heat at 60 to 70℃ and vacuum 5mmHg.
Kneading was carried out for 2 hours. After cooling, 1 part by weight of dibutyltin oxide was added and mixed under reduced pressure to obtain Sample 3. The same measurements as in Application Example 1 were performed using Sample 3. The results are also shown in Table 1. Application example 4 For 100 parts by weight of the polymer obtained in Example 4,
30 parts by weight of fatty acid-treated colloidal calcium, 15 parts by weight of rutile titanium oxide, 65 parts by weight of fatty acid-treated light calcium carbonate, 15 parts by weight of dioctyl phthalate, 3 parts by weight of hydrogenated castor oil, antioxidant [1,3,5- Trimethyl-2,4,6-tris(3,5-di-t
-butyl-4-hydroxybenzyl)benzene]
5 parts by weight, ultraviolet absorber [2(2'-hydroxy-
Add 2 parts by weight of 5-methylphenyl)benzotriazole and 0.5 part by weight of carbon black, mix uniformly with three rolls, and then heat at 60 to 70°C and vacuum 5mm.
Kneading was performed with Hg for 2 hours. Then, after cooling, 1 part by weight of dibutyltin dilaurate was added,
Sample 4 was obtained by mixing under reduced pressure. The same measurements as in Application Example 1 were performed using Sample 4. The result is also the first
Shown in the table. Application example 5 For 100 parts by weight of the polymer obtained in Example 5, 30 parts by weight of fatty acid-treated colloidal calcium carbonate, 30 parts by weight of light calcium carbonate, 15 parts by weight of rutile titanium oxide, 6 parts by weight of hydrogenated castor oil, and antioxidant. agent [2,6
-bis(2-hydroxy-5-methylbenzyl)
-4-methylphenol] and an ultraviolet absorber [2(2'-hydroxy-5-methylphenyl)benzotriazole] were added, and 3 parts by weight were added.
After uniformly mixing with this roll, kneading was performed for 2 hours at 60 to 70°C and a degree of vacuum of 5 mmHg. After cooling, 1 part by weight of dibutyltin oxide was added and mixed under reduced pressure to obtain Sample 5. The same measurements as in Application Example 1 using Sample 5 were performed. The results are also shown in Table 1.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a perspective view of a test specimen for a tensile test. In addition, numerical values other than those shown below indicate dimensions, and the unit is mm. 1: sample, 2: adherend.

Claims (1)

[Claims] 1 (A) General formula; K0069 (In the formula, R ¹ and R ² are divalent hydrocarbon groups, and n is 10
-250), the molecular chain end is blocked with an epoxy group, and (B) the general formula; R ³ -NH ₂ (wherein R ³ is a substituted or unsubstituted monovalent A monovalent ^primary amine represented by ^{the general} formula (a hydrocarbon group of valent secondary amine and (C) general formula; K0071 (in the formula, R ⁷ is a monovalent hydrocarbon group, R ⁸ is a divalent hydrocarbon group, R ⁹ is a monovalent hydrocarbon group, R ¹⁰ is An organosilicon compound having an amino group and a hydrolyzable group represented by a monovalent hydrocarbon group having 1 to 6 carbon atoms (a represents a number of 1 to 3), (D) general formula; ¹¹ -OH (in the formula, R ¹¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms)
K0072 or K0073 (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
R ¹⁰ , a and n are as described above, m is the molecular weight
A method for producing a polyether terminal-capped with a hydrolyzable silyl group, represented by a number selected from 1,000 to 50,000. 2. The manufacturing method according to claim 1, wherein R ¹ is an ethylene group and/or a propylene group. 3. The manufacturing method according to claim 1, wherein R ⁵ is a divalent hydrocarbon group. 4. The manufacturing method according to claim 1, wherein R ¹⁰ and R ¹¹ are a methyl group or an ethyl group. 5. The manufacturing method according to claim 4, wherein R ¹⁰ and R ¹¹ are methyl groups.