JPS63295585A - Hydroxyspiroorthocarbonate compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is an organic group consisting of 2-5C saturated aliphatic hydrocarbon). EXAMPLE:A compound expressed by formula II. USE:A raw material for producing polyspiroothocarbonates used as a raw material for molding, casting materials, adhesives, coatings, etc., and capable of providing polymers, crosslinkable and curable by use thereof alone and having an extremely small volume change in curing. PREPARATION:3,9-Diallyl-1,5,7,11-tetraoxaspiro[5.5]undecane expressed by formula III and a saturated aliphatic monothioglycol expressed by the formula HO-R-SH are subjected to radical addition reaction.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is useful for producing polyspiroorthocarbonate that can be used as a raw material for molding materials, casting materials, adhesives, paints, etc. The present invention relates to hydroxyspiroorthocarbonate compounds.

[Prior Art] It is known that spiro-orthocarbonates having cationic polymerizability have extremely small volumetric shrinkage or slight volumetric expansion during polymerization, and are useful for eliminating internal strain in molding materials and improving dimensional accuracy. Recently, expectations for practical application have been increasing from the viewpoint of improving adhesive strength. Examples of compounds having such a spiro-orthocarbonate structure include 1,4.8.9-tetraoxaspiro(4.
4) Nonane, 1.5.7.11-tetraoxaspiro (
5.5) Undecane Pond Several compounds are known.

However, the conventionally known compounds having the spiro-orthocarbonate structure cannot be crosslinked and cured when used alone, and in order to be crosslinked and cured, they must be mixed with other resins such as epoxy resins, etc. There was a need.

[Problems to be Solved by the Invention] The object of the present invention is to provide a hydroxyspiro-orthocarbonate useful for producing polysbiro-orthocarbonate which can be cross-linked and cured when used alone and exhibits extremely little volume change during curing. An object of the present invention is to provide orthocarbonate compounds.

[Means for Solving the Problems] As a result of intensive research, the present inventors have found that a compound in which a hydroxy group is introduced as a polymerizable functional group into a spiro-orthocarbonate compound can effectively achieve the above object. This is the heading that led to the present invention.

That is, the present invention provides general formula (I) (hereinafter referred to as blank space)
3,9-diallyl-1,5,7,1 represented by Q
1-Tetraoxaspiro(5.5)undecane is given the general formula (m) HO-R-8H(m) [wherein R represents an organic group consisting of a saturated aliphatic hydrocarbon having 2 to 5 carbon atoms. ] It can be easily obtained by subjecting a saturated aliphatic monothioglycol represented by the following to a radical addition reaction.

The compounding ratio of the saturated aliphatic monothioglycol represented by the above general formula (m) to 1 equivalent of the compound represented by the above formula (II) on the verge of radical addition reaction is within the range of 2 to 2.5 equivalents. , more preferably within the range of 2.05 to 2.2 equivalents. If the blending ratio of saturated aliphatic monothioglycol is higher or lower than this, it is uneconomical and undesirable.

As the radical reaction initiator used in carrying out the radical addition reaction, any initiator can be used as long as it can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays.

Examples of radical reaction initiators that can be used in addition reactions using heat, microwaves, and infrared rays include azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, di-t-butyl peroxide, and dicumyl peroxide. Examples include alkyl peroxides such as oxide, acyl peroxides such as benzoyl peroxide and lauroyl peroxide, and peroxycarbonates such as diisopropyl peroxycarbonate.

Examples of radical reaction initiators that can be used in addition reactions using ultraviolet light include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxyacetophenone, and 4'-isopropyl-2-hydroxy-2-methylpropiodine. Phenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis(
diethylamino)benzophenone, benzophenone, methyl-(0-benzoyl)benzoate, benzoin,
Carbonyl compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, diacetyl, methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. anthraquinone or thioxanthone derivatives, diphenyl sulfide, diphenyl disulfide,
Examples include sulfur compounds such as dithiocarbamates, α-chloromethylnaphthalene, and anthracene.

The amount of the radical reaction initiator to be used is determined by formula (II) and general formula (
0.001 to 2 based on the total amount of compounds represented by m)
It is within the range of 0 mol%, more preferably within the range of 0.01 to 10 mol%. The amount of radical reaction initiator used is o,
If the amount is less than oot mol %, the addition reaction will not substantially proceed, and if it is used in an amount exceeding 20 mol %, it will be uneconomical, which is not preferred.

The radical addition reaction can also be carried out in a solvent. Examples of solvents that can be used include those used in ordinary radical reactions, such as chlorobenzene, acetonitrile, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, dioxane, and the like.

Examples of the saturated aliphatic monothioglycol represented by the general formula (III) include 2-hydroxyethanethiol, 3-hydroxypropanethiol, 2-hydroxypropanethiol, 4-hydroxybutanethiol,
Examples include 2-hydroxybutanethiol, 5-hydroxypentanethiol, 3-hydroxy-2,2-dimethylpropanethiol, and the like.

The hydroxyspiro-orthocarbonate compound of the present invention utilizes the reactivity of the hydroxyl group in the molecule to apply a known polymerization reaction under neutral or basic conditions to produce various polysbirocarbonates. Orthocarbonates can be produced. For example, a polyurethane having a subiro-orthocarbonate structure in the main chain can be produced by carrying out an addition polymerization reaction with a diisocyanate resin using a basic catalyst or an organic tin catalyst. In addition, by polycondensing with a bifunctional acid halogen compound using a basic catalyst etc.,
It is possible to produce polyesters having spiro-orthocarbonate structures in the main chain. Furthermore, it is also possible to produce a hydroxypolyether having a subiro-orthocarbonate structure in the main chain by carrying out a polyaddition reaction with a bifunctional epoxy resin using a basic catalyst or the like.

[Effect of the invention] The hydroxyspiro-orthocarbonate compound according to the present invention utilizes the reactivity of the droxy group in the molecule to
A variety of polyspiroorthocarbonates can be produced. In addition, the polyspiro-orthocarbonate produced in this way has a subbiro-orthocarbonate structure in its main chain, and can be crosslinked and cured without volumetric shrinkage, and can be used as a casting material or a molding material. This resin is useful as a raw material for adhesives, paints, etc. As mentioned above,
The hydroxyspiro-orthocarbonate compound according to the present invention is an extremely useful compound with a wide range of industrial applications.

[Examples] Hereinafter, the present invention will be explained in more detail by referring to Examples and Reference Examples.

The 'H-NMR spectrum was measured using a JEOL FX-100 spectrometer using TMS as an internal standard, and the infrared absorption spectrum was measured using a JEOL IRA spectrometer.
Measured using a Type-2 device.

Example 1 2.40 g (0.01 mol) of 3.9-diallyl-1,5,7,11-tetraoxaspiro(5.5)undecane and 1.84 g (0.01 mol) of 2-hydroxyethanethiol
, 021 mol) was added as a radical reaction initiator, and the mixture was reacted for 24 hours at 60°C in a sealed tube.

The obtained reaction product was subjected to silica gel column chromatography (effluent:
ethyl acetate) to obtain 3.68 g of a white solid.

The structural formula of the obtained compound was as shown below, and the melting point was 42 to 44°C. In addition, the results of elemental analysis are as follows: Calculated values: C: 51.49%, H: 8.13%, S
: 1B, 17%, actual value, C: 51.69%, H: 8.37%, S
: 15.78%.

The IR spectrum of the obtained compound is shown in FIG. Moreover, the 'H-NMR spectrum (in CD0g3 solution) is shown in FIG.

(Leaving space below) Example 2 3.9-diallyl-1,5,7,11-tetraoxaspiro (2.40 g (0.01 mol) of 5.51 undecane and 2.21 g of 3-hydroxypropanethiol (
0,024 mol) was dissolved in 10 ml of chlorobenzene. 73 mg (0.5 mmol) of di-t-butyl peroxide was added to this solution as a radical reaction initiator,
The reaction was carried out 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 silica gel column chromatography (effluent: ethyl acetate) to obtain a white solid 3.
．． 34g was obtained.

The structural formula of the obtained compound was as shown below, and the melting point was 41.5 to 42.0'C. In addition, the results of elemental analysis are as follows: Calculated values: C: 53.74%, H: 8.55%, S
: 15.10%, actual value, C: 53.32%, H: 8.59%, S
: 15.17%.

The IR spectrum of the obtained compound is shown in FIG. In addition, the IH-NMR spectrum (in CD0g3 solution) was
Shown in the figure.

(Left below) ? ? Tomoe S == Example 3 3.9-diallyl-1,5,7,11-tetraoxaspiro[5.5)undecane 2.40 g (0.01 mol) and 3-hydroxy 2.2-dimethylpropane To a mixture consisting of 2.46 g (0.205 mol) of thiol was added 16 mg (0.1 mmol) of azobisisobutyronitrile as a radical reaction initiator, and the mixture was heated at 60°C in a sealed tube.
The reaction was carried out for 24 hours. The obtained reaction product was purified by silica gel column chromatography (effluent: ethyl acetate) to obtain 4.15 g of a white solid.

The structural formula of the obtained compound was as shown below, and the melting point was 47 to 49°C. In addition, the results of elemental analysis are as follows: Calculated values: C: 57.47%, H: 9.23%, S
: 13.34%, actual value, C: 57.34%, H: 9.32%, S
: 13.55%.

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

IR spectrum: ν(wax)cm-'340G,
2900.1380.1200(br), 1040(
br).

'H-NMR spectrum: δ(CD CQ 3 )pp
oro, 92 (1211, s), 1.2-1.7 (
8H, m), 1.7-2.1 (2H, m), 2
．． 32 (2H, t, J-6Hz), 2.54 (411
,t.

J-711z), 2.74 (4H, s), 3.64
(4)1. d, J-6)1z).

3.5~4.1 (8H, a+) (margin below) Q θ)! Reference Example 1 531 mg (1.34 mmol) of the hydroxyspiro-orthocarbonate obtained in Example 1 and 17 mm (0.03 mmol) of dibutyltin dilaurate were dissolved in 2 ml of dimethyl sulfoxide. 334 mg (1.34 mmol) of m-xylylene diisocyanate was added to this solution, and the mixture was reacted at 60° C. for 1 hour. The obtained reaction solution was poured into a large amount of ether to obtain 775 cm of white powdery resin. As a result of analysis, the obtained resin was a polyurethane having a spiro-orthocarbonate structure in its main chain.

500 μl of the obtained polyurethane was dissolved in 2 ml of nitrobenzene, 50 mg of adipoyl chloride was added, and 8
After reacting at 0° C. for 1 hour, a white crosslinked product was obtained.

Based on the density of the resin before and after crosslinking, the volume change was 0.1% expansion.

Reference Example 2 500 aug (1.18 mmol) of hydroxyspiroorthocarbonate obtained in Example 2 and 304 mg (3.0 mmol) of triethylamine were dissolved in 2 ml of dimethyl sulfoxide. Add 239 g (1.18 mmol) of phthaloyl chloride to this solution,
The resulting reaction solution was poured into a large amount of C ether to obtain 613 cm of white powdery resin. As a result of analysis, the resulting resin had a spirool F carbonate structure in its main chain. Made of polyester.

500 mg of the obtained polyester was mixed with 2 nitrobenzene.
ml, add oxalyl chloride lhg to λ80
After reacting at ℃ for 1 hour, a white crosslinked product was obtained. It was found that there was no change in volume from the density of the resin before and after crosslinking.

[Brief explanation of the drawing]

FIG. 1 shows an IR spectrum of the hydroxyspi-orthocarbonate compound obtained in Example 1, and FIG. 2 shows an 'H-NMR spectrum diagram of the same compound. FIG. 3 is an IR spectrum diagram of the todoroxyspiroorthocarbonate compound obtained in Example 2, and FIG. 4 is an LH-NMR spectrum diagram of the same compound. Procedural amendment August 3, 1986

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an organic group consisting of a saturated aliphatic hydrocarbon having 2 to 5 carbon atoms.) Hydroxyspiro-olcarbonate compounds represented.