JPH11100430A - Polysulfide polyether-modified epoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin, good in storage stability, curability or the like, having a low viscosity, excellent in operating efficiency and useful in a sealing material for building, an adhesive or the like by reacting a polyether having a specific structure with a polysulfide polyether polymer containing a polysulfide having a specified structure and an epoxy resin having a specific structure. SOLUTION: This resin is obtained by reacting a polyether represented by he formula (R<1> O)n [R<1> is an alkylene; (n) is an integer of 6-200] with a polysulfide polyether polymer containing a polysulfide represented by the formula (R<2> Sx )m [R<2> is especially C2 H4 OCH2 OC2 H4 or the like; (x) is an integer of 1-5; (m) is an integer of 1-50] and an epoxy resin having a terminal structure represented by the formula (R<3> is an organic group containing the bisphenol skeleton), e.g. a bisphenol A type epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysulfide-polyether-modified epoxy resin, and more particularly to a resin having good storage stability, curability and adhesion between materials of the same or different types, and having low viscosity and excellent workability. The present invention relates to a polysulfide polyether-modified epoxy resin which has excellent flexibility for a long time.

[0002]

2. Description of the Related Art Mercaptan-terminated polysulfide polymers having a polysulfide bond in the molecule have been used in a wide variety of fields such as architectural sealing materials, civil engineering sealing materials, industrial sealing materials and adhesives.

[0003] When these mercaptan-terminated polysulfide polymers are cured with a peroxide such as lead dioxide or manganese dioxide, they become rubbery elastic bodies. The cured product of the mercaptan-terminated polysulfide compound has excellent adhesion to concrete and metal, and has good workability on site, dimensional stability, durability, oil resistance, and solvent resistance.
It has features such as high barrier properties against gases such as carbon dioxide and chlorofluorocarbon.

[0004] For this reason, these mercaptan-terminated polysulfide polymers have been used for many years as modifiers for imparting adhesiveness and other properties to epoxy resins.

However, there has been a problem that the mercaptan-terminated polysulfide polymer has an odor due to the terminal mercaptan group. In recent years, epoxy group-terminated polysulfide polymers that solve this problem have been developed.
Due to its excellent adhesion, chemical resistance, durability, impact resistance, gas barrier properties, etc., it has been widely used.

However, the epoxy group-terminated polysulfide polymer has a problem that the viscosity of the epoxy group-terminated polysulfide polymer is also high because the viscosity of the mercaptan-terminated polysulfide compound is high.

On the other hand, in recent years, mercaptan-terminated polysulfide polyether polymers having a polysulfide bond and a polyether bond in the molecule have been developed. These mercaptan-terminated polysulfide polyether polymers have a lower viscosity than conventional mercaptan-terminated polysulfide polymers, and become a rubbery elastic body when cured with a peroxide such as an isocyanate compound or lead dioxide or manganese dioxide. BACKGROUND ART Mercaptan-terminated polysulfide polyether polymers are expected to be used in a wide range of fields such as sealing materials for buildings, sealing materials for civil engineering, industrial sealing materials, and adhesives.

[0008]

SUMMARY OF THE INVENTION Based on these prior arts, an object of the present invention is to provide excellent adhesiveness, chemical resistance, durability, impact resistance, thermal shock resistance and gas barrier properties of polysulfide bonds. An object of the present invention is to provide a polysulfide polyether-modified epoxy resin having a reduced viscosity and improved workability while maintaining the same.

[0009]

Means for Solving the Problems In view of the above object, as a result of intensive studies on polysulfide polyether-modified epoxy resin, the present inventors have found that (A) polyether having a specific structure and (A) specific structure In the polysulfide polyether polymer containing a polysulfide having and a polysulfide polyether-modified epoxy resin obtained by reacting an epoxy resin having a specific structure, it has been found that the viscosity is low and the workability is good, and the present invention I arrived. That is, the polysulfide polyether-modified epoxy resin of the present invention comprises (a)-
(R ¹ O) n- (where R ¹ is an alkylene group, and n is 6 to 2)
Indicates an integer of 00. ) And a polyether represented by
_{^{(B) - (R 2 Sx) m}} - (. Here, x is an integer from 1 to 5, m is an integer of 1 to 50) vital containing a polysulfide represented by the terminal epoxy groups It is characterized by being.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The above polyether is represented by the following general formula (A).

-(R ¹ O) n-... (A) In the general formula (A), R ¹ is an alkylene group, preferably —C ₃ H ₆ — and / or —C ₂ H ₄ —. And
n is an integer of 6 to 200. The polysulfide is represented by the following general formula (A).

[0013] _{^{- (R 2 Sx) m -}} ......... ( b) ^{R 2} in the general formula (A) is an alkylene group containing an oxygen preferably _{-C 2 H 4 OCH 2 OC 2} H 4 -, and / or _{-CH 2 CH (OH) CH 2} -, a, x is an integer from 1 to 5, m is an integer of 1 to 50. The polysulfide polyether polymer used for synthesizing the polysulfide polyether-modified epoxy resin of the present invention contains the polyether represented by the general formula (A) and the polysulfide represented by the general formula (A). One example is described in Japanese Patent Publication No. 8-32784.

The terminal structure is represented by the following general formula:

[0015]

Embedded image R ³ is an organic group containing a bisphenol skeleton.

The above organic group R ³ containing a bisphenol skeleton
As, for example, bisphenol A type epoxy resin,
Bisphenol AD epoxy resin, Bisphenol S
Molecules similar to epoxy resin, halogenated bisphenol A epoxy resin, halogenated bisphenol AD epoxy resin, bisphenol F epoxy resin, halogenated bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, etc. And those containing structures.

The polysulfide polyether-modified epoxy resin of the present invention can be prepared by using a conventional epoxy resin (for example, a bisphenol-type epoxy resin or a novolak-type epoxy resin) or a polysulfide polyether polymer in the presence of a catalyst such as a tertiary amine or an alkali. It can be obtained by reacting under or without a catalyst.

The content of the polysulfide polyether skeleton of the polysulfide polyether-modified epoxy resin of the present invention can be controlled by appropriately selecting the molecular weight of the raw material polysulfide polyether polymer. Furthermore, the content of the polysulfide polyether skeleton can also be controlled by adjusting the reaction ratio of the polysulfide polyether polymer and the bisphenol-type epoxy resin (the ratio of the two components to be reacted).

In the present invention, a solvent or the like can be blended with the above-mentioned compound in order to obtain a compound having better workability.

Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, tetrahydrofuran,
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate,
Pentyl acetate, cellosolve, methyl cellosolve, butyl cellosolve, sorbite, n-propanol, isopropanol, n-butanol, isobutanol and the like.

The polysulfide polyether-modified epoxy resin of the present invention has excellent adhesiveness, chemical resistance, durability, impact resistance, thermal shock resistance, gas barrier properties, etc., which are the characteristics of the polysulfide skeleton. Compared with the epoxy group-terminated polysulfide compound, it has a low viscosity and excellent workability.

[0022]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 100 g of a mercaptan-terminated polysulfide polyether polymer ("LP-282" manufactured by Toray Thiokol Co., Ltd.) was added to a glass three-necked flask (with a stirrer, a thermometer, and a nitrogen inlet tube). As a compound having an epoxy group, bisphenol F type epoxy resin ("Epicoat 80" manufactured by Yuka Shell Epoxy Co., Ltd.)
7 ″) 200 g and 0.005 g of 2,4,6-tris (dimethylaminomethylphenol) were charged and mixed at 90 ° C. It was confirmed that the mercaptan group concentration in the mixture had disappeared by the standard analysis procedure, and room temperature was confirmed. After cooling, a polysulfide polyether-modified epoxy resin was obtained, and the properties of the product are shown in Table 1.

Example 2 100 g of a mercaptan-terminated polysulfide polyether polymer ("LP-282" manufactured by Toray Thiokol Co., Ltd.) was placed in a glass three-necked flask (with a stirrer, thermometer, condenser, and nitrogen inlet tube). And 300 g of bisphenol A type epoxy resin (“Epicoat 1001X-75” manufactured by Yuka Shell Epoxy Co., Ltd.), 100 g of xylene, and 2,4,6-tris (dimethylaminomethylphenol) as a compound having an epoxy group at the terminal. 0.005 g and mixed at 90 ° C. After confirming that the mercaptan group concentration in the mixture had disappeared by the standard analysis procedure, the mixture was cooled to room temperature to obtain a polysulfide polyether-modified epoxy resin. The properties of the product are shown in Table 1.

Comparative Example 1 100 g of a mercaptan-terminated polysulfide polymer ("LP-56" manufactured by Toray Thiokol Co., Ltd.) and a terminal epoxy group were placed in a glass three-necked flask (with a stirrer, a thermometer, and a nitrogen inlet tube). 200 g of bisphenol F type epoxy resin (“Epicoat 807” manufactured by Yuka Shell Epoxy Co., Ltd.) and 0.005 g of 2,4,6-tris (dimethylaminomethylphenol) were charged as a compound having the above, and mixed at 90 ° C. After confirming that the mercaptan group concentration in the mixture had disappeared by the standard analysis procedure, the mixture was cooled to room temperature to obtain a polysulfide-modified epoxy resin. The properties of the product are shown in Table 1.

Comparative Example 2 100 g of a mercaptan-terminated polysulfide polymer ("LP-3" manufactured by Toraythiol Co., Ltd.) and an epoxy group at the end were placed in a glass three-necked flask (with a stirrer, a thermometer, and a nitrogen inlet tube). 200 g of bisphenol F type epoxy resin (“Epicoat 807” manufactured by Yuka Shell Epoxy Co., Ltd.) and 0.005 g of 2,4,6-tris (dimethylaminomethylphenol) were charged as a compound having the above, and mixed at 90 ° C. After confirming that the mercaptan group concentration in the mixture had disappeared by the standard analysis procedure, the mixture was cooled to room temperature to obtain a polysulfide-modified epoxy resin. The properties of the product are shown in Table 1.

Comparative Example 3 100 g of a mercaptan-terminated polysulfide polymer (“LP-55” manufactured by Toray Thiokol Co., Ltd.) was placed in a glass three-necked flask (with a stirrer, a thermometer, a cooling tube, and a nitrogen inlet tube). Bisphenol A type epoxy resin (Epicoat 1001X manufactured by Yuka Shell Epoxy Co., Ltd.) as a compound having an epoxy group
-75 ") 300 g, xylene 100 g and 2,4,6-
Tris (dimethylaminomethylphenol) 0.00
5 g was charged and mixed at 90 ° C. After confirming that the mercaptan group concentration in the mixture had disappeared by the standard analysis procedure, the mixture was cooled to room temperature to obtain a polysulfide-modified epoxy resin. The properties of the product are shown in Table 1.

[0028]

[Table 1] As is clear from Table 1, the polysulfide polyether-modified epoxy resin of the present invention has a lower viscosity and better workability than the conventional polysulfide-modified epoxy resin.

[0029]

As described in detail above, since the polysulfide polyether-modified epoxy resin of the present invention contains polysulfide polyether as a main component, excellent adhesiveness, chemical resistance, durability, and the like characteristic of the polysulfide skeleton are obtained. It has impact resistance, thermal shock resistance and gas barrier properties. Further, the polysulfide-polyether-modified epoxy resin of the present invention has a lower viscosity and is superior in workability as compared with the conventional polysulfide-modified epoxy resin.

Claims (3)

[Claims] 1. A (A) ^- (R 1 O) n-(where ^{R 1} is an alkylene radical, n is an integer of 6 to 200.) And a polyether represented by the (i) - ^{(R 2} Sx) _m- (where x
Is an integer of 1 to 5, and m is an integer of 1 to 50. )
And a polysulfide polyether-modified epoxy resin containing a polysulfide represented by the formula: 2. The method according to claim 1, wherein R ^{1 in} the general formula (A) is -C ₃
H ₆ -, and / or _-C 2 _{H 4} - a and claim 1 of the general formula ^{R 2} in (b) is _{-C 2 H 4 OCH 2 OC 2} H 4
- and / or _{-CH 2 CH (OH) CH 2} -, polysulfide polyether-modified epoxy resin which is a. 3. The method according to claim 1, wherein the terminal structure is represented by the following general formula (wherein R ³ is an organic group containing a bisphenol skeleton). A polysulfide polyether-modified epoxy resin characterized by the following.