WO2004033402A1

WO2004033402A1 - Novel clathrate compounds

Info

Publication number: WO2004033402A1
Application number: PCT/JP2003/012871
Authority: WO
Inventors: Natsuki Amanokura; Tetsuya Sahara
Original assignee: Nippon Soda Co., Ltd.
Priority date: 2002-10-09
Filing date: 2003-10-08
Publication date: 2004-04-22
Also published as: JP2004131412A; JP4234971B2

Abstract

The problems of the invention are facilitating the storage and handling in the air of silane compounds serving as highly reactive silane coupling agents, inhibiting the compounds from evaporating, and protecting the compounds from reactions with other compounds. The above problems are solved by converting silane coupling agents such as silane compounds represented by the general formula (II): (II) [wherein R5 is C1-C8 alkoxy; R6 is C1-C8 alkyl or C1-C8 alkoxy; t is an integer of 1 to 6; and Y is a group having at least one member selected from the group consisting of nitrogen, oxygen and sulfur] into clathrate compounds with tetrakis(hydroxyphenyl) compounds represented by the general formula (I): (I) [wherein X is (CH2)a or p-phenylene; a is 0, 1, 2, or 3; R1, R2, R3, and R4 are each independently halogeno, C1-C6 alkyl, C1-C6 alkoxy, or optionally substituted phenyl; and m, n, p, and q are each independently 0, 1, or 2].

Description

Specification

New clathrate compound

Technical field:

The present invention relates to a novel clathrate compound, and more particularly, to a novel clathrate compound using a silane compound as a silane coupling agent as a guest compound and a tetrax (hydroxyphenyl) compound as a host compound.

Background technology:

An inclusion compound is a compound having a structure in which a guest molecule is embedded in a cavity of a host molecule, and is expected to be used in technical fields such as selective separation, chemical stabilization, non-volatilization, and powdering.

As a conventional clathrate compound, for example, Japanese Patent Application Laid-Open No. Sho 61-53201 discloses 1,1,6,6-tetraphenyl 2,4_hexadione-1,6-diol or 1,1-di (2,4-dimethylphenyl) 1-2-propyn-1-ol is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 622-2701, and 1,1-bis-1-naphthol is disclosed in It is known that each host has 5-chloro-2-methyl-14-isothiazolin-3-one as a guest.

Further, as an inclusion compound using a tetrakis (hydroxyphenyl) compound as a host, for example, an inclusion compound using an industrial bactericide as a guest compound is disclosed in Japanese Patent Application Laid-Open No. 07-010791. Have been.

On the other hand, a silane compound is frequently used as a silane coupling agent as an adhesive layer for forming a composite of an organic material and an inorganic material, and the silane coupling agent is a semiconductor sealing agent, It is widely used in the fields of glass cloth reinforced epoxy resin, coated sand, paints, adhesives, sealants, elastomers and tires.

As described above, the silane coupling agent has the effect of curing the epoxy resin and improving the adhesiveness with the inorganic substance, and is often used together with the epoxy resin. However, they are generally unstable to moisture, and form water upon contact with moisture in the air to form oligosilanes and the like. For this reason, silane coupling agents are not suitable for long-term storage, and it is not preferable to expose them to the air even during use.

In addition, some silane coupling agents are volatile, and these volatilize during handling, causing not only loss of the silane coupling agent but also diffusion into the air, which may affect the environment. I don't.

Their volatility depends strongly on heat, and the tendency of volatilization becomes significant with heating or high ambient temperatures.

In addition, silane coupling agents are used as adhesives between epoxy resins and inorganic materials.However, these silane coupling agents have high reactivity, making it difficult to control the reaction, and also have high carohydrate decomposability. Problems have arisen in terms of handling and control of the reaction.

There has been a technique in which an alcohol is added to stabilize the silane coupling agent, and hydrolysis is suppressed by an equilibrium reaction with an alkoxy group of the silane coupling agent. However, this method uses a solvent, so when mixing it with the shelf, if the solvent is insoluble in the resin, or if there is a volatile substance in the system even if it is dissolved in the scale, the subsequent heat treatment Etc. caused a problem. Furthermore, since alcohol has P and water, it absorbs moisture during long-term storage, which in turn causes water to exist in the system, causing a serious problem.

As another means, Japanese Patent Application Laid-Open No. 2001-54583 discloses that a silane coupling agent is micro-forced with an acryl-based polymer to improve the storage stability and to improve the storage stability of the silane coupling agent. A technique for controlling the reactivity to a resin is described. However, microcapsules are prepared by emulsion polymerization / suspension polymerization methods, causing problems such as the need for microencapsulation.

It is an object of the present invention to facilitate storage and handling of a silane compound, which is a highly reactive silane coupling agent, in air, to suppress volatility, and to control the reaction with other components. DISCLOSURE OF THE INVENTION:

The present inventors have conducted intensive studies to solve the above problems, and as a result, found that the above problems can be solved by enclosing the silane coupling agent with a specific host compound, and solved the present invention. I came to.

That is, the present invention

(1) Equation (I)

(Wherein, X represents (CH ₂ ) a or p-phenylene group, a represents 0, 1, 2 or 3; Ri, R ₂ , R ₃ and R ₄ are each independently Represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group or a phenyl group which may have a substituent, m, n, p, and q each independently represent 0 , 1 or 2). An inclusion compound comprising a tetrakis (hydroxyphenyl) compound represented by the formula (1) and a silane coupling agent,

(2) The silane coupling agent has the formula (II)

(R ₅ represents a C 1 to C 8 alkoxy group, R ₆ represents (: 1 to 8 alkyl group or 〇 1 to 8 alkoxy group, t represents an integer of 1 to 6, Y represents , A nitrogen atom, an oxygen atom, and a sulfur atom, which represent a group containing at least one selected from the group consisting of: a) a silane compound represented by the formula (1).

In the compound represented by the formula (I) used in the present invention, X is a direct bond; an alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, and propylene; even if substituted with 1 to 4 methyl groups. Represents a good p-phenylene group, and R ₂ , R ₃ , and R ₄ are each independently a nitro group, an amino group, a carbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ; Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl A C 1 -C 6 alkyl group such as an isohexyl group, a 1-methylpentyl group, or a 2-methylpentyl group; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, C1-C6 alkoxy group such as n-butoxy group, t-butoxy group; C1-C6 alkoxy group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxy group, or It represents a phenyl group which may have a substituent. Further, as the substituent of the phenyl group which may have a substituent, a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, an n-propyl group and an isopropyl group , N-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentylene, n-hexyl, isohexyl, 1-methylpentyl, 2 —C 1 to C 6 alkyl group such as methylpentyl group; C 1 to C 6 alkoxy group such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, etc. can do.

Examples of the tetrakis (hydroxyphenyl) compound represented by the formula (I) include, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane,, a, ', α'-tetrakis (4-hydroxyphenyl) -p-xylene, a, a ,,'-tetrakis (3-methyl-4-hydroxyphenyl) -p- Xylene,, a, a, 1-tetrax (3,5-dimethyl-14-hydroxyphenyl) 1-p-xylene,, a,, α '1-tetrax (3 Enil) i ρ-xylene,, a,, '-tetrakis

(3,5-dichloro-4-hydroxyphenyl) -p-xylene, a, a, a, '-tetrakis (3-promo-4-hydroxyphenyl) -p-xylene, a,,, -tetrakis (3,5-Jib mouth 4-hydroxyphenyl) 1-p-xylene, a ,,,,-tetrakis (3-t-butyl_4-hydroxyphenyl) 1-p-xylene,, a ,,-tetrakis ( 3,5-di-t-butyl-1-hydroxyphenyl) -P-xylene,, a, a, α'tetrax (3-fluoro-4-hydroxyphenyl) -p-xylene,, a, ', α-Tetrakis (3,5-difluoro-4-hydroxyphenyl) -p-xylene, a, a,, —tetrakis (3-methoxy-4-hydroxyphenyl) p-xylene, a, a,, 'One tetrakis (3,5-dimethoxy-14-hydroxyphenyle) One p-xylene, α, a, a, '-tetrax (3-phenyl-1-hydroxyphenyl) -p-xylene, a ,,', '-tetrakis (3,5-diphenyl ^ /-1-4-hydroxyphenyl) -p —Xylene,,,, α'-tetrakis (3-fluoro-5-methyl-14-hydroxyphenyl) -p-xylene, α,,, α-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) -p-xylene , A, a, ', α -tetrakis (3-bromo-5-methyl-14-hydroxyphenylene) -p-xylene, hi, a,, 1-tetrakis (3-methoxy-5-methyl 4-Hydroxyphenyl) p-xylene, a,,, -tetrakis (3-t-butyl-15-methyl-14-hydroxyphenyl) p-xylene, a,, a, -tetrakis (3 —Phenyl-5-methyl-14-hydroxyphenyl) -ρ-xylene, a,,, α-tetrakis (3-chloro-5-bromo_4-hydroxyphenyl) -p-xylene, 《, a, ' , '—Tetrakis (3-chloro-1-5-phenyl 4-hydroxyphenyl) p-xylene, a, a, α ', -tetrakis (3-chloro-1-5-phenyl-1-hydroxyphenyl) -p-xylene, 1,1,2,2-tetrakis (3-chloro-5- Phenyl-1,4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-cloth 1,4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrax (3-promo-4-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3,5-dibromo-1-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-1-hydroxyphenyl) ) Ethane, 1,1,2,2-tetrakis (3,5-di-t-butyl-1-hydroxyphenyl) ethane, 1, 1,2,2-tetrakis (3-fluoro-1-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis (3-methoxy-l-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-phenyl 4-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3,5-diphenyl 4-hydroxyphenyl) ethane, 1,1,2 2-tetrakis (3-fluoro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-1-hydroxyphenyl) ethane, 1,1,2 , 2-Tetrakis (3-bromo-5-methyl-14-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-methoxy-5-methyl-1-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3- t-Butyl-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrax (3-phenyl-15-methyl-4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-chloro-mouth _ 5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl ^ /-1-4-hydroxyphenyl ^! Le) ethane, 1, 1,2,2-tetrakis (3-chloro-1-5-phenyl-14-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane, 1,1,3,3 —Tetrakis (3-methyl-1-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3: 5-dimethyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3 — 4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-1-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-te Trakis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl J-propane) 1,1,3,3- Tetrakis (3,5-di-1-butyl-1-4-hydroxyphenyl) propane, 1,1,3,3-Tetrakis (3-fluoro-4-hydroxyphenyl) propane, 1,1 , 3,3-Tetrakis (3,5-difluo-4-hydroxyphenylene) propane, 1,1,3,3-tetrakis (3-methoxy-14-hydroxyphenyl) propane, 1,1 , 3,3-Tetrakis (3,5-dimethoxy-4-hydroxyphenyl), propane, 1,1,3,3-tetra (3-phenylene 4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-1-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-Fluoro-5-methyl-1-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-5-methyl-4-hydroxyphenyl) propane, 1,1,3,3- Tetrakis (3-promo-5-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methoxy-15-methyl-14-hydroxyphenyl) propane, 1,1,3,3 —Tetrakis (3-t_butyl-5-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-phenyl-5-methyl-4-hydroxyphenyl) propane, 1,1, 3, 3—Tetrakis (3—Black mouth 5—Bromo) 4-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-1-5-phenyl-14-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro) Mouth 5—Fenryu 4-Hydroxy (Ciphenyl) propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4- (3-methyl-14-hydroxyphenyl) butane, 1,1,4,4— Tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4- (3,4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3, 5-dichloro-1,4-hydroxyphenylebutane, 1,1,4,4-tetrakis (3-promo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3 , 5-dibutene 4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3_t-butyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-g tert-butyl-4—hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-fluoro-4 (Hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-difluoro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-1-hydroxy) Phenyl) butane, 1,1,4,4-tetrakis (3,5-dimethoxy-14-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-phenyl-14-hydroxyphenyl) butane 1,1,4,4-tetrakis (3,5-diphenyl-14-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-fluoro-5-methyl-1-hydroxyphenyl) butane, 1 , 1,4,4-Tetrakis (3-methyl-5-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-bromo_5_methyl-14-hydroxyphenyl) butane, 1,1 , 4, 4-tetrakis (3-methoxy 5-Methyl-1-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-t-butyl-5-methyl-1-hydroxyphenyl) butane, 1,1,4,4-tetrakis ( 3-phenyl-1-5-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-5-bromo-1-hydroxyphenyl) butane, 1,1,4,4 1-tetrakis (3-chloro-1-5-phenyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrax (3-chloro-5-phenyl 4-hydroxyphenyl) butane, 1, 1,5,5-Tetrakis (4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methyl 4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3 , 5-dimethyl-1-4-hydroxyphenyl) pentane, 1,1,5,5-tetraki (3-chloro-1-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-dichloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-bromo _4-hid Roxyphene) Pentane, 1,1,5,5-tetrakis (3,5-dibromo-14-hydroxy) Pentane, 1,1,5,5-tetrakis (3-t-butyl-1-hydroxyphenyl) Pentane, 1,1,5,5-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-fluoro-4-hydroxyphenyl) pentane, 1 1,1,5,5-tetrakis (3,5-difluoro-4-hydroxyphenylene) pentane, 1,1,5,5-tetrakis (3-methoxy-14-hydroxyphenylyl) pentane, 1,1, 5,5-tetrakis (3,5-dimethyl-1-4-hydroxyphene) pentane, 1,1,5,5-tetrakis (3-phenyl ^ / — 4-hydroxyphenyl) pentane, 1 , 1,5,5-tetrakis (3,5-dihue 2-hydroxy-4-phenyl) pentane, 1,1,5,5-tetrakis (3-fluoro-5-methyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-chloro-5-methyl) L-Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methoxy-1-5-) Methyl-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3—t-butyl-15-methyl-1-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3 —Phenyl-1-5-methy ^ / — 4-Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-chloro-1-5-bromo-4-hydroxyphenyl) pentane, 1,1,5,5 —Tetrakis (3—Mouth 1—Phenyl 1—4—Hee Droxyphenyl) pentane, 1,1,5,5-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) pentane,, a ,,-tetrakis (4-hydroxyphenyl) -ρ-xylene, a, a, ',' -Tetrakis (3_methyl-14-hydroxyphenyl) -p-xylene, a, ,, -tetrakis (3,5-dimethyl-4-hydroxyphenyl) -P-xylene, a,,, -Tetrakis (3-chloro-4-hydroxyphenyl) — P-xylene, 《,, α ′, ′ —tetrakis (3,5-dichloro mouth -4-hydroxyphenyl) -p-xylene, a,, ',' —Tetrakis (3-bromo-1-hydroxyphenyl) 1 p-xylene, a,,, a'-tetrakis (3,5-dibromo-1

4-Hydroxyphenyl) p-xylene, a, a, a, '-tetrakis (3-t_butyl- 4-hydroxyphenyl) p-xylene,, a,, —tetrakis (3,

5-di-tert-butyl 4-hydroxyphenyl) p-xylene, a, a,, Tetrakis (3-fluoro-4-hydroxyphenyl) 1-p-xylene,,,, '-Tetrakis (3,5-difuroleo-4-4-hydroxyphenylisole) 1-p-xylene, α,,,'-Tetrakis (3-Methoxy-1-hydroxyphenyl) _ρ-xylene,, a, a, α'-tetrakis (3,5, -dimethoxy-1-hydroxyphenyl)---xylene, α,,, —tetrakis (3 —Phenyl-1-hydroxyphenyl) 1 ρ-xylene, a,,, —tetrakis (3,5, —diphenyl-1-hydroxydroxyphenyl) p-xylene, a, a, ',' —tetrakis (3 —Fluoro-5-methyl-14-hydroxyphenyl) -p-xylene,, a,, α′-tetraxyl (3-chloro-5-methyl-1-hydroxyphenyl) —p-xylene, a, a, , '-Tetrakis (3-bromo-5-methyl-4 (Hydroxyphenyl) 1-p-xylene,, a,, 1-tetrakis (3-methoxy-5-methyl-14-hydroxyphenyl) — P-xylene,, a,, —tetrakis (3-t-butyl -5) —Methyl—4-hydroxyphenyl) 1 p-xylene, a, a,, α '1-tetrakis (3-phenyl-5-methyl-14-hydroxyphenyl) 1 ρ-xylene, a,,, -tetra Kiss (3-chloro-5-bromo-1-hydroxyphenyl) -p-xylene,, a ,,. A'-tetrakis (3-chloro-1-5-phenyl-4-hydroxyphenyl) -p-xylene ,, A, a, 1-tetrakis (3-chloro-1-5-phenyl 4-hydroxyphenyl) 1-p-xylene, 1,1,2,2-tetrakis (4-carboxyphenyl) pentane 1,1,2,2-tetrakis (3-methyl-1-carboxyphenyl) ethane, 1,1,2,2- Tetrakis (3,5-dimethyl-14-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-1--4-carboxyphenyl) ethane, 1,1,2,2-tetra Lakis (3,5-dichloro-4 mono-loxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-14-carboxyphenyl) ethane, 1,1,2,2-tetrakis ( 3,5-Jib mouth 4- (carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-4-carboxyphenyl) ethane, 1,1,2,2-tetrakis ( 3,5-di-t-butyl-4,4-hydroxyloxyphenyl, 1,1,2,2-tetrakis (3-fluoro4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3 , 5-diphenylo-butoxy 4-propoxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-butoxylipoxy) Phenyl) Etan, 1, 1, 2, 2-tetrakis (3, 5-dimethoxy (I) 4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-phenyloxy) 4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-diphenyl) L-4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-phenyl ^ / ol-5-methyl-1-41-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3- 1,5-, 1-, 2-tetrakis (3-bromo-15-methyl-5-methyl-l-oxyphenyl) ethane, 1,1,2,2-tetrakis (3-) Methoxy-5-methyl_4-propoxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-1-5-methyl-14-propoxyphenyl) .ethane, 1,1,2, 2-tetrax (3-phenyl-1-5-methyl-14-carboxyphenyl) ethane, 1, 1, 2,2-Tetrakis (3-chloro-5-promo 4-carboxyphenyl) ethane, 1,1,2,2 1 Tetrakis (3-chloro-5-phenyl-4,1-potassium lipoxyphenyl) ethane, 1 , 1,2,2-tetrakis (3-chloro-5-phenyl-4,4-hydroxyphenyloxy) ethane, 1,1,2,2-tetrakis (4-aminophenyl) ethane, 1,1,2,2-tetrakis (3 —Methyl-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-14-aminophenyl) ethane, 1,1,2,2-tetrakis (3-chloro-1-amino) Nophenyl) ethane, 1,1,2,2-Tetrakis (3,5-dichloro-1-4-aminophenyl) ethane, 1,1,2,2-Tetrakis (3-bromo-14-aminophenyl) ethane 1,1 , 2,2-tetrakis (3,5-jib-mouth-4-aminophenyl) 1,1,2,2-tetrakis (3-t-butyl-1-aminophenyl) ethane, 1,1,2,2-tetrakis (3,5-di-t-butyl-1-aminophenyl) ethane, 1,1 1,2,2-tetrakis (3-fluoro-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3 —Methoxy-1-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-14-aminophenyl) ethane, 1,1,2,2-tetrakis (3-phenyl-4-aminophenyl) ethane 1,1,2,2-tetrakis (3,5-diphenyl-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-5-methyl-1-aminophenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4 Aminofue two Les) Etan, 1, 1, 2, 2- tetrakis (3-bromo-one 5- Mechire 4 Aminofue sulfonyl) Etan, 1, 1, 2, 2- tetrakis (3-methoxy-5-methyl-4 -Aminophenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-15-methyl-14-aminophenyl) ethane, 1,1,2,2-tetrakis (3-phenyl-1-5-methyl) L-4-aminophenyl) ethane, 1,1,2,2-tetrakis (3-chloro-1-5-promo 4-aminophenyl) ethane, 1,1,2,2-tetrakis (3-chloro-1-5-phenyl) 1,4-aminophenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-14-aminophenyl) ethane, hi,, ','-tetrakis (4-carboxyphenyl) one p— Xylene,, a, a, 1-tetrakis (3-methyl_4-carboxyphenyl) — p-xylene, hi,, α ','-tetrakis (3,5-dimethyl-4-carboxyphenyl) 1 p —Xylene,, a,, '—Tetrakis (3-chloro-1 1-ρ-xylene, 《,,, a'-tetrakis (3,5-dichloro-4-carboxyphenyl) 1-ρ-xylene, a,, α ′, -tetrakis (3-bromo-4 lipoxyphenyl) —Ρ-xylene, ot, a,, tetrakis (3,5-dibutene 4-4-carboxyphenyl) -p-xylene,,,,, a —tetrakis (3-t-butyl-1-4-carboxyphenyl) ) — P-xylene,, a,, α —tetrakis (3,5-di_t-butyl-1-4-carboxyphenyl) -p-xylene,, a, a, α'-tetrakis (3- Fluoro-4-carboxyphenyl) 1-p-xylene,,, ','-tetrakis (3,5-difluoro-4 mono-propyloxyphenyl) 1-p-xylene, ，,, α ', α' -tetrakis (3-methoxy 1 4-carpoxyphenyl) 1 p-xylene, a, a,, (3,5-dimethoxy-1-4-carboxyphenyl) 1-p-xylene,,,, 1-tetrakis (3-phenyl-14-carboxyphenyl) 1 ρ-xylene,,, ', — Tetrakis

(3,5-diphenyl-14-carboxyphenyl) 1 p-xylene, a,,, -tetrakis (3-fluoro-5-methyl-14-carboxyphenyl) 1 p-xylene,, a,, -tetrakis (3-chloro-1-5-methyl-4-carboxyphenyl) -P-xylene, a ,,,, '-tetrakis (3-bromo-15-methyl-14-carboxyphenyl) -p-xylene, ,,, a , —Tetrakis (3-methoxy-5-methyl-4-carboxyphenyl) -p-xylene, a, a,, —tetrakis

(3-t-butyl-5-methyl-4-carboxyphenyl) -ρ-xylene,, a ,,-tetrakis (3-phenyl-15-methyl-14-carboxyphenyl) —p-xylylene ,,,, A '—tetrakis (3-chloro-5-bromo-14-carboxyphenyl) -p-xylene, a, a,,'-tetrakis (3-chloro-5-phenyl-14-carpoxyphenyl J ）) 1-p-xylene, a,,, α-tetrakis (3-chloro-1-5-phenyl-14-carboxyphenyl) ρ-xylene, 《,,,, —tetrakis (4-aminophenyl) 1ρ —Xylene, a,,, α '—tetrakis (3-methyl-4-aminophenyl) -p-xylene, a,, α', '-tetrakis (3,5-dimethyl-14-aminophenyl) p Xylene, α,, ',' —tetrakis (3-chloro-4-aminophenyl) -ρ-xylene, a ,, ', α-tetrakis (3,5-dichloro-4-aminophenyl) -p-xylene, α,,, -tetra Lakis (3-bromo_4-aminophenyl) Len, a,,, —tetrakis (3,5-dibutene 4-aminophenyl) -p-xylene,, a,, —tetrakis (3-t-butyl-14-aminophenyl) p-xylene, (¾,,, —tetrakis (3,5-di-t-butyl-1-4-aminophenyl) -1-p-xylene, α, a, a, α′-tetrakis (3-fluoro-14-aminophenyl) -1-p-xylene, 《, ,, a —tetrakis (3,5-difluoro-4-aminophenyl) -ρ-xylene,, a ,, '-tetrakis (3-methoxy-4-aminophenyl) -p-xylene, a, ,,-tetrakis (3 , 5-Dimethoxy-14-aminophenyl) -P-xylene, CE,, a, a'-Tetrakis (3_phenyl-14-aminophenyl) -P-xylene, a, a,, 'One-tetrakis (3,5- Diphenyl-4-aminophenyl) p-xylene,, a, , —Tetrakis (3-fluoro-5-methyl-1-aminophenyl) _p-xylene, a,,, —Tetrakis (3-chloro-1-5-methyl-14-aminophenyl) — p-xylene,, a,, ' 1-tetrakis (3-bromo-5-methyl-14-aminophenyl) p-xylene, a,,, —tetrakis (3-methoxy-5-methyle 4-aminophenyl) / p-xylene, α,,, '— Tetrakis (3-t-butyl-1-5-methyl-4-aminophenyl) ρ-xylene, α,,, -tetrakis (3-phenyl-15-methyl-1-aminophenyl) p-xylene, α,, ','-tetrakis 3-chloro-1-5-bromo-14-aminophenyl ρ-xylene, α,, ','-tetrakis (3-chloro-1-5-phenyl-4-aminophenyl) ρ-xylene,, a, , (3-chloro-5-phenyl 4-aminophenyl) 1-p-xylene and the like.

The silane coupling agent used in the present invention is a silane compound having an organic functional group having different reactivity in one molecule, and in particular, preferably has a hydrolytic group as one of the organic functional groups. It is not particularly limited as long as it is a compound that functions as a binder between the organic material and the inorganic material, but a silane compound represented by the formula (Π) can be particularly preferably exemplified. '

In the formula (Π), R ₅ is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyl Represents a C 1 -C 8 alkoxy group such as an xy group, an n-hexoxy group, an n-heptoxy group, and an n-octoxy group.

R ₆ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n — C 1 -C 8 alkyl group such as octyl group or methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-benzoxy group , N-hexoxy group, n-heptoxy group, n-octoxy group and the like.

Y is a hydroxyl group, an epoxy group, a formyl group, a propyloxyl group, a 3,4-epoxycyclohexyl group, a glycidyl group, a glycidoxy group, a methacryloxy group, an acryloxy group, an amino group, a phenylamino group, / 3-amino Ethylamino group, butylmethylimino group, ureido group, phenylureido group, mercapto group, isocyanate group, 3- (triethoxysilyl) propyltetrasulfide group; 3-imidazole-1-yl-2-hydroxypropyloxy group; methoxy group, Ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexoxy C1-C6 alkoxy; acetyl , Propanoyl, n-propylcarbonyl, isopropylcarpo C 1 -C 6 alkyl carbonyl groups such as phenyl, n-butyl carbonyl, sec-butyl carbonyl, t-butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, etc .; C 1 -C 6 alexoxyca such as methoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, etc. Luponyl group; acetooxy group, propanoyloxy group, n-propyl carboxy group, isopropyl carbonyloxy group, n-butyl carboxy group, sec-butyl carboxy group, t-butyl carbonyl group, etc. And a group containing at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, such as a C 1 -C 6 alkylcarboxy group.

Examples of the silane coupling agent represented by the compound represented by the formula (II) include, for example, β- (3,4-epoxycyclohexylyl) ethyltrimethoxysilane, and glycidoxypropyl mouth trimethoxysilane. , Aglycidoxypropylmethylethoxysilane, aglycidoxypropyltriethoxysilane, amethacryloxypropylmethyldimethoxysilane, amethacryloxypropyltrimethoxysilane, amethacryloxypropyl methylethoxysilane, τ- Methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, 3-3- (aminoethyl) -1-aminopropylmethyldimethoxysilane, Ν- / 3- (aminoethyl) -1-aminopropyltriamine Methoxysilane, Ν _ β— (amino Ethyl) -r-aminopropyltriethoxysilane, amino-silicyl-1-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-alkenylpropylmethoxydimethoxysilane, mercaptopropyltrimethoxysilane , Bis (3-triethoxysilylpropyl) tetrasulfide, di-isocyanate propyltriethoxysilane, 1- (3-trimethoxysilylpropoxy) -3-imidazole 1-yl-2-hydroxypropane, 1 -(3-Jetoxymethylsilylpropoxy) — 3-imidazole-1-yl-2-hydroxypropane, chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, pinyltriacetoxysilane, hexamethyldisilazane And the like.

The silane coupling agent encapsulated according to the present invention enters into the cavity formed by the host, so that it has better stability in air than a normal silane coupling agent that is not included. Because of the inclusion, volatilization of the silane coupling agent can also be suppressed. Among the silane coupling agents used in the present invention, those which are nocturnal at room temperature become powdered by being included in the host molecules, and are easy to handle. Since the encapsulated silane coupling agent is wrapped with host molecules, it does not react at room temperature even when mixed with highly reactive resin, and it becomes the first time that the guest is released. Can react.

Examples of the resin herein include an epoxy resin, and more specifically, a nopolak epoxy resin such as a nopolak epoxy resin, a cresol nopolak epoxy resin, an aralkyl epoxy resin, Aralkyl epoxy resins, biphenyl epoxy resins, heterocyclic epoxy resins, epoxy resins containing naphthylene rings, bisphenol epoxy resins, triphenol alkane epoxy resins such as triphenol propane epoxy resins, etc. , Can be exemplified. These resins may be used alone or in combination of two or more.

The clathrate compound of the present invention can be easily produced with or without a solvent. When a solvent is used, the host compound is dissolved in a solvent inert to the silane coupling agent, and then the solution is reacted with the silane coupling agent. After the reaction, if necessary, the solvent is evaporated off or cooled, and the inclusion compound precipitates. This precipitate is separated by filtration according to a conventional method to obtain a target clathrate compound. When a solvent is not used, a host compound such as tetrakis (hydroxyphenyl) ethane is directly added to the silane coupling agent and reacted. Thereafter, the precipitated solid matter may be separated in the same manner as in the above method. In both cases, the reaction temperature is from 0 to 100 ° (preferably from 10 to 80 ° C, and the reaction time is from 5 minutes to 24 hours. The clathrate obtained as described above The compound is usually in the form of a powder, and an inclusion compound according to the intended use can be obtained by changing the particle size or forming a molded article having a different shape.

BEST MODE FOR CARRYING OUT THE INVENTION:

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

Production of clathrate compound of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and araminoprovir triethoxysilane

1,1,2,2-Tetrakis (4-hydroxyphenyl) ethane (hereinafter abbreviated as TEP) 43.7 g (llmmol) and araminopropyltriethoxysilane 22.1 g (1 0 mmo 1) was heated and dissolved in a nitrogen atmosphere using dehydrated ethanol solvent 16 Om 1 The mixture was cooled to a warm temperature and further cooled in an ice bath to precipitate crystals. The obtained crystals are filtered and dried in a vacuum dryer.

Dry for 4 hours. (48 g yield, 78% yield)

¹ HNMR of the obtained white powder was measured.

_{^ NMR (CDC 1 3, 270MHz} ) δ 0. 60 (2Η), 1. 18 (9Η), 1. 56 (2Η), 2. 57 (2Η), 3. 79 (6Η), 4. 54 (2Η ), 6.75 (16Η) The chemical shift value indicated that the white powder was a substance having a portion corresponding to ΤΕΡ and α-aminopropyltriethoxysilane. In addition, the thermal analysis (TG-DTA) was measured, and it was found that the weight was reduced from 148 to 180, and a heat phenomenon was observed. When the same thermal analysis was performed for the raw materials Τ Ε Ρ and araminopropyltriethoxysilane, weight loss and endothermic phenomena were observed at 323-348 ° C and 100-132 ° C, respectively. It was found that it was thermally stabilized.

In addition, when powder X-ray analysis (XRD) was performed, characteristic absorptions of 20 and 20 to 25 were observed, and the diffraction pattern was clearly different from that of the raw material TEP.

From the above, it was confirmed that TEP and araminopropyltriethoxysilane form an inclusion compound.

Example 2

The clathrate obtained in Example 1 was left in a Petri dish in the air overnight. The clathrate after standing was soluble in methanol and dimethyl sulfoxide. This suggests that aminopropyltriethoxysilane exists stably even when left in the atmosphere containing moisture. Further, ¹ HNMR of the clathrate compound left unreacted by 1 B was measured, and it was found that 95% or more of T-aminopropyltriethoxysilane remained.

Comparative Example 1

Α-Aminopropyltriethoxysilane was left under the same conditions as in Example 2. The left aminopropyltriethoxysilane was completely whitened, and did not dissolve at all in solvents that normally dissolve aminopropyltriethoxysilane, such as alcohol, chloroform, dimethylsulfoxide, and the like. The IR spectrum of the whitened compound showed that the absorption corresponding to 0-C 2H ₅ was reduced. This suggested that the ethoxy moiety was degraded.

Example 3 Preparation of inclusion compound of TEP and araminoprovir trimethoxysilane

4.37 g (1.lmmo 1) of TEP is weighed into a mortar, and 1.79 g (lmmo 1) of aminopropyltrimethoxysilane containing the same weight of toluene is added thereto. The pestle is placed in a nitrogen atmosphere. And mixed well. After mixing, the mixture was dried with a vacuum dryer at room temperature for 4 hours to remove the used solvent, and a white powder was obtained.

¹ HNMR of the obtained white powder was measured.

_{NMR (CDC 1 3, 270MHz)} δ 0. 60 (2Η), 1. 50 (2Η), 2. 57 (2Η), 3. 32 (9Η), 4. 54 (2Η), 6. 75 (16Η)

From the chemical shift value, it was found that the white powder was a substance having a portion corresponding to TEP and araminopropyltrimethoxysilan. In addition, when powder X-ray analysis (XRD) was performed, a characteristic absorption of 20 was observed at 17.5 to 20, and a diffraction pattern distinctly different from that of the raw material TEP was shown.

Thermal analysis showed no significant difference in weight loss, but significant changes were observed in the spectrum waveform.

Further, similarly to Example 2, when the obtained white powder was left in the air, no change in its properties was observed.

From the above, it was confirmed that TEP and τ-aminopropyltrimethoxysilane formed an inclusion compound.

Industrial applicability:

As described above, the inclusion of an unstable silane coupling agent in the atmosphere containing moisture using TEP or the like makes it possible to stabilize the silane coupling agent. The reactivity of the silane coupling agent can be controlled. Silane coupling agents are useful as a binder for organic and inorganic materials, and can be applied to fields where silane coupling agents could not be used because of their instability. However, industrial applicability is high.

Claims

(In the formula, X represents (CH ₂ ) a or p-phenylene group, a represents 0, 1, 2 or 3, and R ₂ , R ₃ , and R ₄ are each independently Represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group or a phenyl group which may have a substituent, m, n, p, and q each independently represent 0 , 1 or 2.) An inclusion compound comprising a tetrakis (hydroxyphenyl) conjugate represented by the formula: and a silane coupling agent.

2. The silane coupling agent has the formula (II)

(R ₅ represents a C 1 through C 8 alkoxy group, R ₆ represents a C 1 through C 8 alkyl or C 1 through C 8 alkoxy group, t represents an integer of 1 to 6, Y is The clathrate compound according to claim 1, wherein the silane compound is a group containing at least one member selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.