JPS63275585A - Sulfur-containing spiroorthocarbonate compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I or II (R represents, 1-10C alkyl, benzyl or acyl; X represents H, Cl, Br, methyl, methoxy, acetyl, nitro or nitrile; n is 1-3). EXAMPLE:A compound expressed by formula III. USE:A raw material for molding and casting materials, adhesives, paints, etc., having especially superior adhesion to basic materials. PREPARATION:A 2,7-bis(halomethyl)-1,4,6,9-tetraoxaspiro[4,4]nonane expressed by formula IV (X represents Cl, Br or I) is reacted with an alkali metal (Na, K) salt of either an alkylthiol expressed by the formula HS-R or an aromatic thiol expressed by formula V at 50-120 deg.C in a polar solvent such as dimethylsulfoxide. The ratio of the alkali metal salt to be blended is preferably 2.05-2.4 equivalents based on equivalent compound expressed by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sulfur-containing biro-orthocardinate compound useful as a raw material for molding materials, casting materials, adhesives, paints, and the like.

[Prior Art] It is known that spiro-orthocargonates having cationic polymerizability have extremely small volumetric contraction or slight volumetric expansion during polymerization, and are useful for eliminating internal strain, improving dimensional accuracy, It is expected to improve adhesive strength. However, the spiro-orthocargonates known so far have a limited number of molecules, consist only of carbon, hydrogen, and oxygen, and have few polar groups, so they can be used in paints, adhesives, etc. When used as a raw material, there was a problem of insufficient adhesion to the base material.

[Problems to be Solved by the Invention] The object of the present invention is to provide a sulfur-containing spiro-orthocarpocarbonate that is useful as a raw material for molding materials, casting materials, adhesives, paints, etc., and has particularly excellent adhesion to base materials. An object of the present invention is to provide a nato compound.

[Means for Solving the Problem] The present invention provides a sulfur-containing spiro-orthocarbonate compound that can achieve the above object.

That is, the present invention is based on the general formula (I1) (wherein, R represents an alkyl group having 1 to 10 carbon atoms, a pencil group, or an acyl group) (wherein, X is Represents hydrogen, chlorine, bromine, methyl group, methoxy group, acetyl group, nitro group or nitrile group, m
The present invention relates to a sulfur-containing spiro-orthocargenate compound represented by ), which represents an integer from 11 to 3.

The compound represented by the general formula (I) and (II) is a 2,7-bis() compound represented by the following general formula (wherein, X represents chlorine and bromine represents iodine). 10 methyl) -1,4,6
゜9-Tetraoxaspiro[4,4]nonane is dissolved in a polar solvent such as dimethyl sulfoxide at 50 to 120°C using the general formula H8-R (wherein, R is an alkyl group having 1 to 10 carbon atoms). or an alkylthiol represented by the following general formula (where X represents hydrogen, chlorine, bromine, methyl group, methoxy group, acetyl group, nitro group or nitrile group) , m
represents an integer from 1 to 3. ) can be easily obtained by reacting with an alkali metal (Na or K) salt of an aromatic thiol. During the reaction, the formula (
The blending ratio of alkyl thiol, pencil thiol, thiol carboxylic acid, h is an alkali metal salt of aromatic thiol (hereinafter abbreviated as alkali metal sulfide) to 1 equivalent of the compound represented by 2) is 2 to 2.5 equivalents. , more preferably 2.05 to 2.4 equivalents. Even if the blending ratio of the alkali metal sulfide is higher or lower than this, it becomes uneconomical and undesirable.

In addition, as another method for obtaining the compound represented by the general formula (I) or (I), 2,7-dimethylene-1,4,6,9-tetraoxaspiro [4.4] Nonane and the above general formula (b)
Alkylthiol, pennorthiol, thiolcal represented by? Examples include a method of carrying out a radical addition reaction with phosphoric acid or an aromatic thiol represented by the general formula (a) above.

As the radical reaction initiator used in the radical addition reaction method, any initiator that can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays can be used.

Examples of radical reaction initiators that can be used in addition reactions using heat, microwaves, and infrared rays include azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, and di-t-butylnoJ? -oxide, alkyloxide, monooxide, such as dicumyloxide, dicumyloxide, etc.
Examples include acyl hydroxycarbonates such as benzoyl peroxide, lauroyl oxide, etc., and acyloxycarbonates such as cyisoglopyroxycarbonate.

Examples of radical reaction initiators that can be used in addition reactions using ultraviolet light include acetophenone, 2,2-dimethoxy-2-thenylacetophenone, 2,2-soethoxyacetophenone, and 4'-isopropyl-2-hydroxy-2. -Methylzorobiophenone, 2-hydroxy-
2-Methylzorobiophenone, 4,4-bis(diethylamino)benzophenone, benzophenone, methyl (0
- carbonyl compounds such as benzoin, benzoin, benzoin methyl ether, benzin ethyl ether, pensoin isoglobil ether, benzoin butyl ether, benzoin octyl ether, benzyl, diacetyl, methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2- Anthraquinone or thioxanthone derivatives such as methylthioxanthone and 2-isozolobylthioxanthone, sulfur compounds such as diphenyl sulfide, diphenyl disulfide, and dithiocarbamate, α-chloromethylnaphthalene,
Examples include anthracene.

The amount of radical reaction initiator to be used is determined by formula (b) and general formula (V
) or (a), the range is from 0.001 to 20 mol, more preferably from 0.01 to 10 mol. If the amount of the radical reaction initiator used is less than 0,001 molty, the addition reaction will not substantially proceed, and if the amount used exceeds 20 molty, it will be uneconomical and undesirable.

The radical addition reaction can also be carried out in a solvent. Examples of solvents that can be used include chlorobenzene, acetonitrile, ethyl acetate, N,N-methylformamide,
Solvents commonly used in lasocal reactions such as dimethyl sulfoxide, nooxane, etc. can be used.

In the above radical addition reaction, the compounding ratio of the thiols represented by the general formula (I) or (I) to 1 equivalent of the compound represented by the formula (B) is in the range of 2 to 2.5 equivalents, and more Preferably it is in the range of 2.05 to 2.4 equivalents. Even if the blending ratio of thiols is higher or lower than this, it becomes uneconomical and undesirable.

Examples of the alkylthiol, benzylthiol or thiol carboxylic acid represented by the general formula (I) include methylmercazotane, ethanethiol, furonocunthiol, butanethiol, kantanethiol, isozolopylthiol, isobutylthiol, Examples include neopentylthiol, benzylthiol, thiolacetic acid, thiolzolopionic acid, thiolbenzoic acid, and the like. Further, as the aromatic thiol represented by the general formula (7),
Thiophenol, 0-thiocresol, p-thiocresol, 2,4-methylthiophenol, 2-chlorothiophenol, 2,4.6-)lichlorothiophenol, 2-bromothiophenol, 2-methoxythiophenol , 2-acetylthiophenol, p-nitrothiophenol, 2,4.6-trinitrothiophenol, p
-Nitrilethiophenol, etc.

The sulfur-containing biro-orthocardinate compound according to the present invention can be polymerized singly or in combination with other compounds having cationic polymerizability using a general cationic polymerization catalyst.

As a cationic polymerization catalyst for polymerization, for example, B
P, , AtCl3, TiC24#5nC14
, FeCl2.

ZnCA2* MgC! Lewis acid of 2nd class; BF, -0
Et2. Lewis acids such as BF, -aniline complex and O,S.

Coordination compound with a compound having N element; oxonium salt, siazonium salt, carbonium salt of Lewis acid; HaCx
Examples include aromatic sulfonium salts such as hydrogen compounds, mixed nitrogen compounds, perhalonic acid derivatives, and the like.

9. Halonium salts as cationic polymerization catalysts by ultraviolet irradiation, aromatic onium salts of Group 1 elements, etc. Nocal of Group 11~Va elements of the Periodic Table, etc.? Nyl complex compounds etc. can be conveniently used.

0.001 to 50 parts by weight, preferably 0, 1
A range of 10 parts by weight is preferred. If the amount of the cationic polymerization catalyst used is less than 0.001 parts by weight, curing will not be sufficient, and if it is more than 50 parts by weight, it is not economical and undesirable. There are no particular restrictions on the curing temperature, and curing is usually carried out at 200°C or lower.

The mixture can also be cured by dissolving it in a solvent. As the solvent used, there can be used solvents commonly used in cationic polymerization, such as aromatic hydrocarbons such as toluene and xylene, and non-loginated hydrocarbons such as methylene chloride and 1°2-dichloroethane.

[Effects of the invention] The sulfur-containing spiro-orthocarbonate compound according to the present invention is useful as a raw material for molding materials, casting materials, adhesives, paints, etc., and is a polymerizable compound with particularly excellent adhesion to base materials. be.

[Example] Hereinafter, the present invention will be explained in more detail by giving Examples, Reference Examples, and Comparative Reference Examples.

In addition, the H-NMR spectral was measured using TMS as an internal standard using a chromator on a JEOL Ltd. FX-100 system. In addition, the infrared absorption spectrum is JASCO Corporation F
It was measured using a 'l'/IR-3 type device.

Example 1 Dimethyl sulfoxide 1501117 was placed in a 300 ml three-bottle flask equipped with a thermometer and a stirrer, and 2,7-bis(chloromethyl')-1,4,6,9 was added to it.
-Tetraoxaspiro[4.4]nonane 22.9 N
(0,10 mol) and ethanethiol sodium salt 17
．． 7. Add li' (0.21 mol), under nitrogen stream,
The mixture was heated to 80 to 100°C and the reaction was carried out for 3 hours. To the obtained reaction solution, 2001R1t of methylene chloride was added, and 22% of water was added.
After extraction three times with 00d, the organic layer was separated and dehydrated by adding magnesium sulfate. Next, the magnesium sulfate was removed and the solvent was removed under reduced pressure to obtain a colorless and transparent liquid 23.
．． I got 8J9.

The structural formula of the obtained compound was as shown below, and the boiling point was 130°C/0.05 wa Hg. In addition, the results of elemental analysis are calculated values: C: 47.12%, H near: 19%, S: 22.87%, actual values;
C: 46.8L%, H: 7.33ch, S: 22
．． It was 47chi.

The IR spectrum of the obtained compound is shown in FIG. Moreover, the 'H-NMR spectrum (in CDC23 solution) is shown in FIG.

Example 2 In a mixture consisting of 1.56 g (0.01 mol) of 2,7-cymethylene-1.4.6.9-tetraoxaspiro[4.4]nonane and 1.49 g (0.024 mol) of ethanethiol , Azobisisobutyronitrile 331Q (0.2 mmol) was added as a radical reaction initiator, and the mixture was reacted in a sealed tube at 60° C. for 24 hours.

The obtained reaction product was purified by distillation under reduced pressure to obtain a colorless and transparent liquid 2.58&.

The IR spectrum and H-NMR spectrum of the obtained compound completely matched each spectrum of the compound obtained in Example 1, confirming that the same compound was obtained.

Example 3 1.56 g (0.01 mol) of 2.7-dimethylene-1,4,6,9-tetraoxaspiro[4.4]nonane and 2.42 # (0,022 mol) of thiophenol were added to chlorobenzene. It was dissolved in 10111. As a radical reaction initiator in this solution, t-butyl monoxide 73In9
(o, s mmol)'t- was added and allowed to react in a sealed tube at 100°C for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, followed by purification by vacuum distillation to obtain white solid 3.3211.

The structural formula of the obtained compound is as shown below, boiling point Fi210C10,25 Cod Hg, melting point 43-45℃
Met. In addition, the results of elemental analysis are calculated values; C: 60
．． 61%, H: 5.35%, S: 17.03%,
Actual measurements: C: 60.64%, H: 5.32%, S:
It was 16.75 cm.

The IR spectrum of the obtained compound is shown in Figure 31.

Further, H-NMR spectrum (CDCt, in solution) is shown in FIG.

Example 4 2.7-S) Methylene-1,4,6,9-tetraoxaspiro[4.4]nonane 1.56N (0.01 mol)
and 2.4.6-)lichlorothiophenol 4.48
9 (0,021 mol) of chlorobenzene xomlvc was dissolved. Add azobisisobutyronitrile 16 to this solution.
m9 (0.1 mmol) was added and reacted for 24 hours at 60° C. in a sealed tube. After the reaction was completed, the solvent was removed under reduced pressure, and the residue was purified by silica sol column chromatography (effluent solution: chloroform/hexane = 1/1 (volume ratio)) to obtain 5.429 of a white solid.

The structural formula of the obtained compound was as shown below, and the melting point was 92 to 93°C. In addition, the results of elemental analysis are
Calculated values: C: 39.13chi, H: 2.42%, 2S:
l 1.00S, C4: 36.48ch, actual value:
C: 39.22%.

H: 2.25 inches, S: 11.12 inches, Ct: 36.31
It was Chi.

IR spectrum data and 'H-NM of the obtained compound
The R spectrum data were as follows.

1R Su-1? Vector: ν(m,X)ctn2900
, 1580, 1490, 1220(s), 11
60.

1120, 840, 780'H-NMR spectrum: δ(CDCt,)pPf!1
2.97 (2H, aa, J-14Hz, 9Hz),
3.25 (2H, dd.

J-14Hz, 5Hz), 3.7-40 (2H, m)
, 4.0-4.7 (4H.

m), 7.48 (4H-d, J-3Hz) Example 5 150WLtt of dimethyl sulfoxide was placed in a 300'R1 three-necked flask equipped with a thermometer and a stirrer, and 2.7-bis(chloromethyl ) -1,4,6,9
-tetraoxaspiro[4.4]nonane 22.911 (
0.10 mol) and neointylthiol potassium salt 2
Add 9.3 # (0.24 mol) and heat to 80-1 under nitrogen stream.
9. Heat to 00°C and react for 5 hours.

Add 200 d of methylene chloride to the obtained nine reaction solution, and add 20 d of water.
After extraction three times at 0d, the entire organic layer was separated and dried by adding magnesium sulfate. Then, magnesium sulfate t-
Remove F and remove the solvent under reduced pressure.

It was further purified by silica sol column chromatography (effluent solution: chloroform/hexane = 476 (volume ratio)),
32.1 g of a colorless and transparent liquid was obtained.

The structural formula of the obtained compound was as shown below, and the boiling point was 10.04 ■Hg or higher (decomposition) at 220°C.

In addition, the results of elemental analysis are calculated values; C: 56.01 yen;
H: 8.85 inches, S: 17.59%, actual value; C: 55
．． 78%, H: 8.92%, S: 17.77%.

IR spectroscopy data and 'H-NM of the compound
There were six RS vector data as follows.

IR system: ν (max) 2950.2910.1450, 2010 (@), 10
60°1040.770'H-NMR spectrum: δ (CDC23) ppm0.
92 (6H, d, J=7Hz), 0.94 (6H
, t , J=7Hz).

1.0-2.0 (6H, m), 2.62 (4H, d
, J=7Hz), 2.64(2H, dd, J
=14Hz t8Hz), 2.93(2H, dd,
J=14Hz, 6Hz) 13.8~4.0 (2H1m
), 4.1 to 4.7 (4H#m) Reference Example 1 and Comparative Reference Example 1 The sulfur-containing spiro-orthocarbonate compound obtained in Example 1 and the conventionally known sulfur-containing compound as a comparative example No subiro-orthocarbonate compound (I,4,6
, 9-tetraoxaspiro[4,4]nonane) with the composition shown in Table 1, an aluminum plate (thickness 0.6 mm
) and cold rolled steel plate JISG-31415PCC
D (thickness: 0.3 m) were bonded together and the T-peel strength was measured.

For thermal curing, BF5/NH2Et is used as a cationic polymerization catalyst.
A cured product was obtained by curing at 120° C. for 4 hours and then at 150° C. for 4 hours. The T-peel strength was measured according to the method of JIS K6854-1977. Note that the adherend used was one that had been degreased with acetone.

From the results shown in Table 1, it can be seen that the composition using the sulfur-containing spiro-orthocarzanate compound according to the present invention is significantly more effective than the composition using the conventional spiro-orthocarzanate compound that does not contain sulfur. It is recognized that it exhibits excellent adhesion.

Reference Column 2 and Comparative Reference Example 2 The sulfur-containing spiro-orthocargenate compound obtained in Example 3 and the conventionally known sulfur-free spiro-orthocargenate compound (2,7-nomethyl- 1.4.6.9-Tetraoxaspiro [4.4
] The T-peel strength was measured in the same manner as in Reference Example 1 and Comparative Reference Example 1 using the same method as in Reference Example 1 and Comparative Reference Example 1. As a result, t-
@Table 2 is a reminder.

Table 2

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum diagram of the sulfur-containing spiro-orthocargonate compound obtained in Example 1, and FIG. 2 is a 'H-NMR spectrum diagram of the same compound. FIG. 3 is an IR spectrum diagram of the sulfur-containing spiro-orthocargonate compound obtained in Example 3, and FIG. 4 is a 1H-NMR spectrum diagram of the same compound.

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group, benzyl group, or acyl group having 1 to 10 carbon atoms.) Or, General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X represents hydrogen, chlorine, bromine, methyl group, methoxy group, acetyl group, nitro group, or nitrile group,
represents an integer from 1 to 3. ) A sulfur-containing spiro-orthocarbonate compound represented by